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1
Lin, G., J. E. Penner, S. Sillman, D. Taraborrelli, and J. Lelieveld. "Global mechanistic model of SOA formation: effects of different chemical mechanisms." Atmospheric Chemistry and Physics Discussions 11, no. 9 (2011): 26347–413. http://dx.doi.org/10.5194/acpd-11-26347-2011.
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Abstract. Recent experimental findings indicate that Secondary Organic Aerosol (SOA) represents an important and, under many circumstances, the major fraction of the organic aerosol burden. Here, we use a global 3-d model (IMPACT) to test the results of different mechanisms for the production of SOA. The basic mechanism includes SOA formation from organic nitrates and peroxides produced from an explicit chemical formulation, using partition coefficients based on thermodynamic principles. We also include the formation of non-evaporative SOA from the reaction of glyoxal and methylglyoxal on aqueous aerosols and cloud droplets as well as from the reaction of epoxides on aqueous aerosols. A model simulation including these SOA formation mechanisms gives an annual global SOA production of 113.5 Tg. The global production of SOA is substantially decreased to 85.0 Tg yr−1 if the HOx regeneration mechanism proposed by Peeters et al. (2009) is used. Model predictions with and without this HOx regeneration scheme are compared with multiple surface observation datasets, namely: the Interagency Monitoring of Protected Visual Environments (IMPROVE) for the United States, the European Monitoring and Evaluation Programme (EMEP) as well as Aerosol Mass Spectrometry (AMS) data measured in both Northern Hemisphere and tropical forest regions. All model simulations realistically predict the organic carbon mass observed in the Northern Hemisphere, although they tend to overestimate the concentrations in tropical forest regions. This overestimate may result from an unrealistically high uptake rate of glyoxal and methylglyoxal on aqueous aerosols and in cloud drops. The modeled OC in the free troposphere is in agreement with measurements in the ITCT-2K4 aircraft campaign over the North America and in pollution layers in Asia during the INTEX-B campaign, although the model underestimates OC in the free troposphere during the ACE-Asia campaign off the coast of Japan.
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Chen, J. P., T. S. Tsai, and S. C. Liu. "Aerosol nucleation spikes in the planetary boundary layer." Atmospheric Chemistry and Physics Discussions 10, no. 11 (2010): 26931–59. http://dx.doi.org/10.5194/acpd-10-26931-2010.
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Abstract. Photochemically driven nucleation bursts, which typically occur in a few hours after sunrise, often produce strong aerosol number concentration (ANC) fluctuations. The causes of such ANC spikes were investigated using a detailed aerosol model running in the parcel mode. Two potential mechanisms for the ANC spikes are proposed and simulated. The blocking of actinic flux by scattered clouds can significantly influence new particle production, but this does not cause strong fluctuations in the number of aerosols within sizes greater than the detection limit of our measurements. A more plausible mechanism is the turbulence eddy effect. Strong aerosol nucleation may occur in both updrafts and downdrafts, while the cloud formation at the boundary layer top strongly reduces the number of aerosols. As the number of aerosols is sensitive to turbulence eddy and cloud formation properties, a changing turbulence condition would result in large fluctuations in the evolution of ANC similar to that observed at the surface.
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Chen, J. P., T. S. Tsai, and S. C. Liu. "Aerosol nucleation spikes in the planetary boundary layer." Atmospheric Chemistry and Physics 11, no. 14 (2011): 7171–84. http://dx.doi.org/10.5194/acp-11-7171-2011.
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Abstract. Photochemically driven nucleation bursts, which typically occur within a few hours after sunrise, often produce strong aerosol number concentration (ANC) fluctuations. The causes of such ANC spikes were investigated using a detailed aerosol model running in the parcel mode. Two potential mechanisms for the ANC spikes were proposed and simulated. The blocking of actinic flux by scattered clouds can significantly influence new particle production, but this does not cause strong fluctuations in the number of aerosols within sizes greater than the detection limit of our measurements. A more plausible mechanism is the turbulence eddy effect. Strong aerosol nucleation may occur in both updrafts and downdrafts, while the cloud formation at the boundary layer top strongly reduces the number of aerosols. As the number of aerosols is sensitive to turbulence eddy and cloud formation properties, a changing turbulence condition would result in large fluctuations in the evolution of ANC similar to that observed at the surface.
4
Dyson, Joanna E., Graham A. Boustead, Lauren T. Fleming, et al. "Production of HONO from NO<sub>2</sub> uptake on illuminated TiO<sub>2</sub> aerosol particles and following the illumination of mixed TiO<sub>2</sub>∕ammonium nitrate particles." Atmospheric Chemistry and Physics 21, no. 7 (2021): 5755–75. http://dx.doi.org/10.5194/acp-21-5755-2021.
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Abstract. The rate of production of HONO from illuminated TiO2 aerosols in the presence of NO2 was measured using an aerosol flow tube system coupled to a photo-fragmentation laser-induced fluorescence detection apparatus. The reactive uptake coefficient of NO2 to form HONO, γNO2→HONO, was determined for NO2 mixing ratios in the range 34–400 ppb, with γNO2→HONO spanning the range (9.97 ± 3.52) × 10−6 to (1.26 ± 0.17) × 10−4 at a relative humidity of 15 ± 1 % and for a lamp photon flux of (1.63 ± 0.09) ×1016 photons cm−2 s−1 (integrated between 290 and 400 nm), which is similar to midday ambient actinic flux values. γNO2→HONO increased as a function of NO2 mixing ratio at low NO2 before peaking at (1.26 ± 0.17) ×10-4 at ∼ 51 ppb NO2 and then sharply decreasing at higher NO2 mixing ratios rather than levelling off, which would be indicative of surface saturation. The dependence of HONO production on relative humidity was also investigated, with a peak in production of HONO from TiO2 aerosol surfaces found at ∼ 25 % RH. Possible mechanisms consistent with the observed trends in both the HONO production and reactive uptake coefficient were investigated using a zero-dimensional kinetic box model. The modelling studies supported a mechanism for HONO production on the aerosol surface involving two molecules of NO2, as well as a surface HONO loss mechanism which is dependent upon NO2. In a separate experiment, significant production of HONO was observed from illumination of mixed nitrate/TiO2 aerosols in the absence of NO2. However, no production of HONO was seen from the illumination of nitrate aerosols alone. The rate of production of HONO observed from mixed nitrate/TiO2 aerosols was scaled to ambient conditions found at the Cape Verde Atmospheric Observatory (CVAO) in the remote tropical marine boundary layer. The rate of HONO production from aerosol particulate nitrate photolysis containing a photocatalyst was found to be similar to the missing HONO production rate necessary to reproduce observed concentrations of HONO at CVAO. These results provide evidence that particulate nitrate photolysis may have a significant impact on the production of HONO and hence NOx in the marine boundary layer where mixed aerosols containing nitrate and a photocatalytic species such as TiO2, as found in dust, are present.
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Lin, G., J. E. Penner, S. Sillman, D. Taraborrelli, and J. Lelieveld. "Global modeling of SOA formation from dicarbonyls, epoxides, organic nitrates and peroxides." Atmospheric Chemistry and Physics 12, no. 10 (2012): 4743–74. http://dx.doi.org/10.5194/acp-12-4743-2012.
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Abstract. Recent experimental findings indicate that secondary organic aerosol (SOA) represents an important and, under many circumstances, the major fraction of the organic aerosol burden. Here, we use a global 3-D model (IMPACT) to test the results of different mechanisms for the production of SOA. The basic mechanism includes SOA formation from organic nitrates and peroxides produced from an explicit chemical formulation, using partition coefficients based on thermodynamic principles together with assumptions for the rate of formation of low-volatility oligomers. We also include the formation of low-volatility SOA from the reaction of glyoxal and methylglyoxal on aqueous aerosols and cloud droplets as well as from the reaction of epoxides on aqueous aerosols. A model simulation including these SOA formation mechanisms gives an annual global SOA production of 120.5 Tg. The global production of SOA is decreased substantially to 90.8 Tg yr−1 if the HOx regeneration mechanism proposed by Peeters et al. (2009) is used. Model predictions with and without this HOx (OH and HO2 regeneration scheme are compared with multiple surface observation datasets, namely: the Interagency Monitoring of Protected Visual Environments (IMPROVE) for the United States, the European Monitoring and Evaluation Programme (EMEP), and aerosol mass spectrometry (AMS) data measured in both the Northern Hemisphere and tropical forest regions. All model simulations show reasonable agreement with the organic carbon mass observed in the IMPROVE network and the AMS dataset, however observations in Europe are significantly underestimated, which may be caused by an underestimation of primary organic aerosol emissions (POA) in winter and of emissions and/or SOA production in the summer. The modeled organic aerosol concentrations tend to be higher by roughly a factor of three when compared with measurements at three tropical forest sites. This overestimate suggests that more measurements and model studies are needed to examine the formation of organic aerosols in the tropics. The modeled organic carbon (OC) in the free troposphere is in agreement with measurements in the ITCT-2K4 aircraft campaign over North America and in pollution layers off Asia during the INTEX-B campaign, although the model underestimates OC in the free troposphere in comparison with the ACE-Asia campaign off the coast of Japan.
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He, Pengzhen, Becky Alexander, Lei Geng, et al. "Isotopic constraints on heterogeneous sulfate production in Beijing haze." Atmospheric Chemistry and Physics 18, no. 8 (2018): 5515–28. http://dx.doi.org/10.5194/acp-18-5515-2018.
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Abstract. Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter) in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM2.5 sulfate (Δ17O(SO42−)) collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM2.5 concentrations ranged from 16 to 323 µg m−3 with a mean of (141 ± 88 (1σ)) µg m−3, with SO42− representing 8–25 % of PM2.5 mass. The observed Δ17O(SO42−) varied from 0.1 to 1.6 ‰ with a mean of (0.9 ± 0.3) ‰. Δ17O(SO42−) increased with PM2.5 levels in October 2014 while the opposite trend was observed from November 2014 to January 2015. Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM2.5 ≥ 75 µg m−3) of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68 %. During PDs of Cases I and III–V, heterogeneous sulfate production (Phet) was estimated to contribute 41–54 % to total sulfate formation with a mean of (48 ± 5) %. For the specific mechanisms of heterogeneous oxidation of SO2, chemical reaction kinetics calculations suggested S(IV) ( = SO2 ⚫ H2O + HSO3− + SO32−) oxidation by H2O2 in aerosol water accounted for 5–13 % of Phet. The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed Δ17O(SO42−). Heterogeneous sulfate production via S(IV) oxidation by O3 was estimated to contribute 21–22 % of Phet on average. Heterogeneous sulfate production pathways that result in zero-Δ17O(SO42−), such as S(IV) oxidation by NO2 in aerosol water and/or by O2 via a radical chain mechanism, contributed the remaining 66–73 % of Phet. The assumption about the thermodynamic state of aerosols (stable or metastable) was found to significantly influence the calculated aerosol pH (7.6 ± 0.1 or 4.7 ± 1.1, respectively), and thus influence the relative importance of heterogeneous sulfate production via S(IV) oxidation by NO2 and by O2. Our local atmospheric conditions-based calculations suggest sulfate formation via NO2 oxidation can be the dominant pathway in aerosols at high-pH conditions calculated assuming stable state while S(IV) oxidation by O2 can be the dominant pathway providing that highly acidic aerosols (pH ≤ 3) exist. Our local atmospheric-conditions-based calculations illustrate the utility of Δ17O(SO42−) for quantifying sulfate formation pathways, but this estimate may be further improved with future regional modeling work.
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Swanson, William F., Chris D. Holmes, William R. Simpson, et al. "Comparison of model and ground observations finds snowpack and blowing snow aerosols both contribute to Arctic tropospheric reactive bromine." Atmospheric Chemistry and Physics 22, no. 22 (2022): 14467–88. http://dx.doi.org/10.5194/acp-22-14467-2022.
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Abstract. Reactive halogens play a prominent role in the atmospheric chemistry of the Arctic during springtime. Field measurements and modeling studies suggest that halogens are emitted into the atmosphere from snowpack and reactions on wind-blown snow-sourced aerosols. The relative importance of snowpack and blowing snow sources is still debated, both at local scales and regionally throughout the Arctic. To understand the implications of these halogen sources on a pan-Arctic scale, we simulate Arctic reactive bromine chemistry in the atmospheric chemical transport model GEOS-Chem. Two mechanisms are included: (1) a blowing snow sea salt aerosol formation mechanism and (2) a snowpack mechanism assuming uniform molecular bromine production from all snow surfaces. We compare simulations including neither mechanism, each mechanism individually, and both mechanisms to examine conditions where one process may dominate or the mechanisms may interact. We compare the models using these mechanisms to observations of bromine monoxide (BrO) derived from multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instruments on O-Buoy platforms on the sea ice and at a coastal site in Utqiaġvik, Alaska, during spring 2015. Model estimations of hourly and monthly average BrO are improved by assuming a constant yield of 0.1 % molecular bromine from all snowpack surfaces on ozone deposition. The blowing snow aerosol mechanism increases modeled BrO by providing more bromide-rich aerosol surface area for reactive bromine recycling. The snowpack mechanism led to increased model BrO across the Arctic Ocean with maximum production in coastal regions, whereas the blowing snow aerosol mechanism increases BrO in specific areas due to high surface wind speeds. Our uniform snowpack source has a greater impact on BrO mixing ratios than the blowing snow source. Model results best replicate several features of BrO observations during spring 2015 when using both mechanisms in conjunction, adding evidence that these mechanisms are both active during the Arctic spring. Extending our transport model throughout the entire year leads to predictions of enhanced fall BrO that are not supported by observations.
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Song, Shaojie, Meng Gao, Weiqi Xu, et al. "Possible heterogeneous chemistry of hydroxymethanesulfonate (HMS) in northern China winter haze." Atmospheric Chemistry and Physics 19, no. 2 (2019): 1357–71. http://dx.doi.org/10.5194/acp-19-1357-2019.
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Abstract. The chemical mechanisms responsible for rapid sulfate production, an important driver of winter haze formation in northern China, remain unclear. Here, we propose a potentially important heterogeneous hydroxymethanesulfonate (HMS) chemical mechanism. Through analyzing field measurements with aerosol mass spectrometry, we show evidence for a possible significant existence in haze aerosols of organosulfur primarily as HMS, misidentified as sulfate in previous observations. We estimate that HMS can account for up to about one-third of the sulfate concentrations unexplained by current air quality models. Heterogeneous production of HMS by SO2 and formaldehyde is favored under northern China winter haze conditions due to high aerosol water content, moderately acidic pH values, high gaseous precursor levels, and low temperature. These analyses identify an unappreciated importance of formaldehyde in secondary aerosol formation and call for more research on sources and on the chemistry of formaldehyde in northern China winter.
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Flores, J. M., G. Bourdin, O. Altaratz, et al. "Tara Pacific Expedition’s Atmospheric Measurements of Marine Aerosols across the Atlantic and Pacific Oceans: Overview and Preliminary Results." Bulletin of the American Meteorological Society 101, no. 5 (2020): E536—E554. http://dx.doi.org/10.1175/bams-d-18-0224.1.
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Abstract Marine aerosols play a significant role in the global radiative budget, in clouds’ processes, and in the chemistry of the marine atmosphere. There is a critical need to better understand their production mechanisms, composition, chemical properties, and the contribution of ocean-derived biogenic matter to their mass and number concentration. Here we present an overview of a new dataset of in situ measurements of marine aerosols conducted over the 2.5-yr Tara Pacific Expedition over 110,000 km across the Atlantic and Pacific Oceans. Preliminary results are presented here to describe the new dataset that will be built using this novel set of measurements. It will characterize marine aerosols properties in detail and will open a new window to study the marine aerosol link to the water properties and environmental conditions.
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Li, Siyuan, Dantong Liu, Shaofei Kong, et al. "Evolution of source attributed organic aerosols and gases in a megacity of central China." Atmospheric Chemistry and Physics 22, no. 10 (2022): 6937–51. http://dx.doi.org/10.5194/acp-22-6937-2022.
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Abstract. The secondary production of oxygenated organic aerosol (OOA) impacts air quality, climate, and human health. The importance of various sources in contributing to the OOA loading and associated different ageing mechanisms remains to be elucidated. Here we present a concurrent observation and factorization analysis on the mass spectra of organic aerosol (OA) by a high-resolution aerosol mass spectrometer and volatile organic compounds (VOCs) by a proton transfer reaction mass spectrometer in Wuhan, a megacity in central China, during autumn. The full mass spectra of organics with two principle anthropogenic sources were identified as the traffic and cooking sources, for their primary emission profiles in aerosol and gas phases, the evolutions, and their respective roles in producing OOA and secondary VOCs. Primary emissions in gas and aerosol phases both contributed to the production of OOA. The photooxidation of traffic sources from the morning rush hour caused a 2.5 fold increase in OOA mass in a higher oxidation state (oxygen-to-carbon ratio as O/C =0.72), co-producing gas phase carboxylic acids, while, at night, cooking aerosols and VOCs (particularly acrolein and hexanal) importantly caused the nocturnal formation of oxygenated intermediate VOCs, increasing OOA mass by a factor of 1.7 (O/C =0.42). The daytime and nighttime formation of secondary aerosols, as contributed by different sources, was found to be modulated by solar radiation and air moisture, respectively. The environmental policy should, therefore, consider the primary emissions and their respective ageing mechanisms influenced by meteorological conditions.
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Sarwar, G., J. Godowitch, B. Henderson, et al. "A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms." Atmospheric Chemistry and Physics Discussions 13, no. 3 (2013): 6923–69. http://dx.doi.org/10.5194/acpd-13-6923-2013.
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Abstract. We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 predictions generally agree better with the observed data than the CB05TU predictions. RACM2 enhances ozone for all ambient levels leading to higher bias at low (< 60 ppbv) concentrations but improved performance at high (>70 ppbv) concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. While RACM2 enhances ozone and secondary aerosols by relatively large margins, control strategies developed for ozone or fine particles using the two mechanisms do not differ appreciably.
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Sarwar, G., J. Godowitch, B. H. Henderson, et al. "A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms." Atmospheric Chemistry and Physics 13, no. 19 (2013): 9695–712. http://dx.doi.org/10.5194/acp-13-9695-2013.
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Abstract. We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 enhances ozone compared to CB05TU at all ambient levels. Although it exhibited greater overestimates at lower observed concentrations, it displayed an improved performance at higher observed concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. Any air pollution control strategies developed using the two mechanisms do not differ appreciably.
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Shao, Jingyuan, Qianjie Chen, Yuxuan Wang, et al. "Heterogeneous sulfate aerosol formation mechanisms during wintertime Chinese haze events: air quality model assessment using observations of sulfate oxygen isotopes in Beijing." Atmospheric Chemistry and Physics 19, no. 9 (2019): 6107–23. http://dx.doi.org/10.5194/acp-19-6107-2019.
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Abstract. Air quality models have not been able to reproduce the magnitude of the observed concentrations of fine particulate matter (PM2.5) during wintertime Chinese haze events. The discrepancy has been at least partly attributed to low biases in modeled sulfate production rates, due to the lack of heterogeneous sulfate production on aerosols in the models. In this study, we explicitly implement four heterogeneous sulfate formation mechanisms into a regional chemical transport model, in addition to gas-phase and in-cloud sulfate production. We compare the model results with observations of sulfate concentrations and oxygen isotopes, Δ17O(SO42-), in the winter of 2014–2015, the latter of which is highly sensitive to the relative importance of different sulfate production mechanisms. Model results suggest that heterogeneous sulfate production on aerosols accounts for about 20 % of sulfate production in clean and polluted conditions, partially reducing the modeled low bias in sulfate concentrations. Model sensitivity studies in comparison with the Δ17O(SO42-) observations suggest that heterogeneous sulfate formation is dominated by transition metal ion-catalyzed oxidation of SO2.
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Ezhova, Ekaterina, Ilona Ylivinkka, Joel Kuusk, et al. "Direct effect of aerosols on solar radiation and gross primary production in boreal and hemiboreal forests." Atmospheric Chemistry and Physics 18, no. 24 (2018): 17863–81. http://dx.doi.org/10.5194/acp-18-17863-2018.
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Abstract. The effect of aerosol loading on solar radiation and the subsequent effect on photosynthesis is a relevant question for estimating climate feedback mechanisms. This effect is quantified in the present study using ground-based measurements from five remote sites in boreal and hemiboreal (coniferous and mixed) forests of Eurasia. The diffuse fraction of global radiation associated with the direct effect of aerosols, i.e. excluding the effect of clouds, increases with an increase in the aerosol loading. The increase in the diffuse fraction of global radiation from approximately 0.11 on days characterized by low aerosol loading to 0.2–0.27 on days with relatively high aerosol loading leads to an increase in gross primary production (GPP) between 6 % and 14 % at all sites. The largest increase in GPP (relative to days with low aerosol loading) is observed for two types of ecosystems: a coniferous forest at high latitudes and a mixed forest at the middle latitudes. For the former ecosystem the change in GPP due to the relatively large increase in the diffuse radiation is compensated for by the moderate increase in the light use efficiency. For the latter ecosystem, the increase in the diffuse radiation is smaller for the same aerosol loading, but the smaller change in GPP due to this relationship between radiation and aerosol loading is compensated for by the higher increase in the light use efficiency. The dependence of GPP on the diffuse fraction of solar radiation has a weakly pronounced maximum related to clouds.
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Kiliyanpilakkil, V. P., and N. Meskhidze. "Deriving the effect of wind speed on clean maritime aerosol optical properties using the A-Train satellites." Atmospheric Chemistry and Physics Discussions 11, no. 2 (2011): 4599–630. http://dx.doi.org/10.5194/acpd-11-4599-2011.
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Abstract. Relationship between "clean marine" aerosol optical properties and ocean surface wind speed is explored using remotely sensed data from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) on board the CALIPSO satellite and the Advanced Microwave Scanning Radiometer (AMSR-E) on board the AQUA satellite. Detailed data analyses are carried out over 15 regions selected to be representative of different areas of the global ocean for the time period from June 2006 to June 2010. Based on remotely sensed optical properties the CALIPSO algorithm is capable of discriminating "clean marine" aerosols from other types often present over the ocean (such as urban/industrial pollution, desert dust and biomass burning). The global mean optical depth of "clean marine" aerosol at 532 nm (AOD532) is found to be 0.052 ± 0.038. The mean layer integrated volume depolarization ratio of marine aerosols is 0.016 ± 0.012, the value representative of sea salt crystals. Integrated attenuated backscatter and color ratio of marine aerosols at 532 nm were obtained to be 0.003 ± 0.002 sr−1 and 0.530 ± 0.149, respectively. A logistic regression between AOD532 and 10-meter surface wind speed (U10) revealed three distinct regions. For surface winds lower than 4 m s−1, the mean CALIPSO-derived AOD532 is found to be 0.02 ± 0.003 with little dependency on the surface wind speed. For surface winds from 4 m s−1 to 12 m s−1, representing the dominant fraction of all available data, marine aerosol optical depth is linearly correlated with the U10, with a slope of 0.0062 s m−1. In this intermediate wind speed region, the AOD532 vs. U10 regression derived here is comparable to previously reported relationships. At very high wind speed values (U10 > 18 m s−1), the AOD532-wind speed relationship showed a tendency toward leveling off, suggesting the existence of some maximum value for maritime AOD. Results of our calculations suggest that considerable improvements to both optical properties of marine aerosols and their production mechanisms can be achieved by discriminating "clean marine" aerosols (or sea salt particles) from all other types of aerosols present over the ocean.
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Chen, Qianjie, Lei Geng, Johan A. Schmidt, et al. "Isotopic constraints on the role of hypohalous acids in sulfate aerosol formation in the remote marine boundary layer." Atmospheric Chemistry and Physics 16, no. 17 (2016): 11433–50. http://dx.doi.org/10.5194/acp-16-11433-2016.
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Abstract. Sulfate is an important component of global atmospheric aerosol, and has partially compensated for greenhouse gas-induced warming during the industrial period. The magnitude of direct and indirect radiative forcing of aerosols since preindustrial times is a large uncertainty in climate models, which has been attributed largely to uncertainties in the preindustrial environment. Here, we report observations of the oxygen isotopic composition (Δ17O) of sulfate aerosol collected in the remote marine boundary layer (MBL) in spring and summer in order to evaluate sulfate production mechanisms in pristine-like environments. Model-aided analysis of the observations suggests that 33–50 % of sulfate in the MBL is formed via oxidation by hypohalous acids (HOX = HOBr + HOCl), a production mechanism typically excluded in large-scale models due to uncertainties in the reaction rates, which are due mainly to uncertainties in reactive halogen concentrations. Based on the estimated fraction of sulfate formed via HOX oxidation, we further estimate that daily-averaged HOX mixing ratios on the order of 0.01–0.1 parts per trillion (ppt = pmol/mol) in the remote MBL during spring and summer are sufficient to explain the observations.
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Wang, Yao, Yue Zhao, Yuchen Wang, et al. "Organosulfates in atmospheric aerosols in Shanghai, China: seasonal and interannual variability, origin, and formation mechanisms." Atmospheric Chemistry and Physics 21, no. 4 (2021): 2959–80. http://dx.doi.org/10.5194/acp-21-2959-2021.
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Abstract. Organosulfates (OSs) are ubiquitous in the atmosphere and serve as important tracers for secondary organic aerosols (SOAs). Despite intense research over the years, the abundance, origin, and formation mechanisms of OSs in ambient aerosols, particularly in regions with severe anthropogenic pollution, are still not well understood. In this study, we collected filter samples of ambient fine particulate matter (PM2.5) over four seasons in both 2015–2016 and 2018–2019 at an urban site in Shanghai, China, and comprehensively characterized the OS species in these PM2.5 samples using an ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometer equipped with an electrospray ionization (ESI) source (UPLC-ESI-QToFMS). Overall, we find that while the concentration of organic aerosols (OAs) decreased by 29 % in 2018–2019 compared to that in 2015–2016, mainly as a result of the reduction of anthropogenic pollutant emissions in eastern China, the annually averaged concentrations of 35 quantified OSs were similar in both years (65.5 ± 77.5 ng m−3, 0.57 % ± 0.56 % of OA in 2015–2016 vs. 59.4 ± 79.7 ng m−3, 0.66 % ± 0.56 % of OA in 2018–2019), suggesting an increased contribution of SOAs to OAs in 2018–2019 compared to 2015–2016. Isoprene- and monoterpene-derived OSs were the two most abundant OS families, on average, accounting for 36.3 % and 31.0 % of the quantified OS concentrations, respectively, during both sampling years, suggesting an important contribution of biogenic emissions to the production of OSs and SOAs in Shanghai. The abundance of biogenic OSs, particularly those arising from isoprene, exhibited strong seasonality (peaked in summer) but no significant interannual variability. In contrast, the quantified anthropogenic OSs had little seasonal variability and declined in 2018–2019 compared with those in 2015–2016. The C2 and C3 OS species that have both biogenic and anthropogenic origins contributed, on average, 19.0 % of the quantified OSs, with C2H3O6S−, C3H5O5S−, and C3H5O6S− being the most abundant species, together accounting for 76 % of the C2 and C3 OS concentrations in 2015–2016 and 2018–2019. 2-Methyltetrol sulfate (2-MTS, C5H11O7S−) and monoterpene-derived C10H16NO7S− were the most abundant OSs and nitrooxy OSs in summer, on average, contributing 31 % and 5 % of the quantified OSs, respectively, during the summertime of the sampling years. The substantially larger concentration ratio of 2-MTS to 2-methylglyceric acid sulfate (2-MAS, C4H7O7S−) in summer (6.8–7.8) compared to the other seasons (0.31–0.78) implies that low-NOx oxidation pathways played a dominant role in isoprene-derived SOA formation in summer, while high-NOx reaction pathways were more important in other seasons. We further find that the production of OSs was largely controlled by the level of Ox (Ox= O3+ NO2), namely the photochemistry of OS precursors, particularly in summer, though sulfate concentration, aerosol acidity, and aerosol liquid water content (ALWC) that could affect the heterogeneous chemistry of reactive intermediates leading to OS formation also played a role. Our study provides valuable insights into the characteristics and mechanisms of OS formation in a typical Chinese megacity and implies that the mitigation of Ox pollution can effectively reduce the production of OSs and SOAs in eastern China.
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Crosswhite, Mark R., Lena N. Jeong, Patrick C. Bailey, et al. "Non-Targeted Chemical Characterization of JUUL-Menthol-Flavored Aerosols Using Liquid and Gas Chromatography." Separations 9, no. 11 (2022): 367. http://dx.doi.org/10.3390/separations9110367.
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The aerosol constituents generated from JUUL Menthol pods with 3.0% and 5.0% nicotine by weight (Me3 and Me5) are characterized by a non-targeted approach, which was developed to detect aerosol constituents that are not known to be present beforehand or that may be measured with targeted methods. Three replicates from three production batches (n = 9) were aerosolized using two puffing regimens (intense and non-intense). Each of the 18 samples were analyzed by gas chromatography electron ionization mass spectrometry and by liquid chromatography electrospray ionization high-resolving power mass spectrometry. All chemical constituents determined to differ from control were identified and semi-quantified. To have a complete understanding of the aerosol constituents and chemistry, each chemical constituent was categorized into one of five groups: (1) flavorants, (2) harmful and potentially harmful constituents, (3) leachables, (4) reaction products, and (5) chemical constituents that were unable to be identified or rationalized (e.g., chemical constituents that could not be categorized in groups (1–4). Under intense puffing, 74 chemical constituents were identified in Me3 aerosols and 68 under non-intense puffing, with 53 chemical constituents common between both regimens. Eighty-three chemical constituents were identified in Me5 aerosol using an intense puffing regimen and seventy-five with a non-intense puffing regimen, with sixty-two chemical constituents in common. Excluding primary constituents, reaction products accounted for the greatest number of chemical constituents (approximately 60% in all cases, ranging from about 0.05% to 0.1% by mass), and flavorants—excluding menthol—comprised the second largest number of chemical constituents (approximately 25%, ranging consistently around 0.01% by mass). The chemical constituents detected in JUUL aerosols were then compared to known constituents from cigarette smoke to determine the relative chemical complexities and commonalities/differences between the two. This revealed (1) a substantial decrease in the chemical complexity of JUUL aerosols vs. cigarette smoke and (2) that there are between 55 (Me3) and 61 (Me5) unique chemical constituents in JUUL aerosols not reported in cigarette smoke. Understanding the chemical complexity of JUUL aerosols is important because the health effects of combustible cigarette smoke are related to the combined effect of these chemical constituents through multiple mechanisms, not just the effects of any single smoke constituent.
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Prashanth, Prakash, Sebastian D. Eastham, Raymond L. Speth, and Steven R. H. Barrett. "Aerosol formation pathways from aviation emissions." Environmental Research Communications 4, no. 2 (2022): 021002. http://dx.doi.org/10.1088/2515-7620/ac5229.
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Abstract Aviation emissions are responsible for an estimated 24,000 premature mortalities annually and 3.5% of anthropogenic radiative forcing (RF). Emissions of nitrogen and sulfur oxides (NOx and SOx) contribute to these impacts. However, the relative contributions and mechanisms linking these emissions to formation and impacts of secondary aerosols (as opposed to direct aerosol emissions) have not been quantified, including how short-lived aerosol precursors at altitude can increase surface-level aerosol concentrations. We apply global chemistry transport modeling to identify and quantify the different chemical pathways to aerosol formation from aviation emissions, including the resulting impact on radiative forcing. We estimate a net aerosol radiative forcing of –8.3 mWm−2, of which –0.67 and –7.8 mWm−2 result from nitrate and sulfate aerosols respectively. We find that aviation NOx causes –1.7 mWm−2 through nitrate aerosol forcing but also –1.6 mWm−2 of sulfate aerosol forcing by promoting oxidation of SO2 to sulfate aerosol. This accounts for 21% of the total sulfate forcing, and oxidation of SO2 due to aviation NOx is responsible for 47% of the net aviation NOx attributable RF. Aviation NOx emissions in turn account for 41% of net aviation-aerosol-attributable RF (non-contrail). This is due to ozone-mediated oxidation of background sulfur and the ‘nitrate bounce-back’ effect, which reduces the net impact of sulfur emissions. The ozone-mediated mechanism also explains the ability of cruise aviation emissions to significantly affect surface aerosol concentrations. We find that aviation NOx emissions cause 72% of aviation-attributable, near-surface aerosol loading by mass, compared to 27% from aviation SOx emissions and less than 0.1% from direct emission of black carbon. We conclude that aviation NOx and SOx emissions are the dominant cause of aviation-attributable secondary inorganic aerosol radiative forcing, and that conversion of background aerosol precursors at all altitudes is amplified by enhanced production of aviation attributable oxidants at cruise altitudes.
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Karl, M., K. Tsigaridis, E. Vignati, and F. Dentener. "Formation of secondary organic aerosol from isoprene oxidation over Europe." Atmospheric Chemistry and Physics Discussions 9, no. 1 (2009): 2855–915. http://dx.doi.org/10.5194/acpd-9-2855-2009.
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Abstract. The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr−1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of particulate organic matter (POM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates POM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr−1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Tropospheric isoprene SOA production over Europe in summer more than doubles when, in addition to pre-existing carbonaceous aerosols, condensation of semi volatile vapours on ammonium and sulphate aerosols is considered. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights in isoprene SOA formation mechanisms reduces the tropospheric production of isoprene derived SOA over Europe from 0.4 Tg yr−1 in our reference simulation to 0.1 Tg yr−1.
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Saleeby, Stephen M., Stephen R. Herbener, Susan C. van den Heever, and Tristan L’Ecuyer. "Impacts of Cloud Droplet–Nucleating Aerosols on Shallow Tropical Convection." Journal of the Atmospheric Sciences 72, no. 4 (2015): 1369–85. http://dx.doi.org/10.1175/jas-d-14-0153.1.
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Abstract Low-level warm-phase clouds cover a substantial portion of Earth’s oceans and play an important role in the global water and energy budgets. The characteristics of these clouds are controlled by the large-scale environment, boundary layer conditions, and cloud microphysics. Variability in the concentration of aerosols can alter cloud microphysical and precipitation processes that subsequently impact the system dynamics and thermodynamics and thereby create aerosol–cloud dynamic–thermodynamic feedback effects. In this study, three distinct cloud regimes were simulated, including stratocumulus, low-level cumulus (cumulus under stratocumulus), and deeper cumulus clouds. The simulations were conducted without environmental large-scale forcing, thereby allowing all three cloud types to freely interact with the environmental state in an undamped fashion. Increases in aerosol concentration in these unforced, warm-phase, tropical cloud simulations lead to the production of fewer low-level cumuli; thinning and erosion of the widespread stratocumulus layer; and the development of deeper, inversion-penetrating cumuli. The mechanisms for these changes are explored. Despite the development of deeper, more heavily precipitating cumuli, the reduction of the widespread moderately precipitating stratocumulus clouds leads to an overall reduction in domainwide accumulated precipitation when aerosol concentrations are enhanced.
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Shayakhmetov, Salim F., Victor S. Rukavishnikov, Lyudmila G. Lisetskaya, and Alexey V. Merinov. "Characteristics of generated aerosol suspensions-complexes at traditional and modernized aluminum electrolysis technologies." Russian Journal of Occupational Health and Industrial Ecology 62, no. 7 (2022): 452–58. http://dx.doi.org/10.31089/1026-9428-2022-62-7-452-458.
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Introduction. Assessment of occupational risk and mechanisms of workers' health disorders due to exposure to complex aerosol suspensions determines the need for in-depth study of the physicochemical properties of dust particles in the air. The study aim was the assessment of the dispersion and chemical composition of complex aerosol suspensions affecting workers in traditional and modernized aluminum production technologies. Materials and methods. The monitoring of air pollution of the working area with soluble and insoluble fluorides, aluminum trioxide aerosols was carried out using standard analysis methods, the dispersed and chemical composition of aerosol suspensions was studied using scanning electron microscopy and energy dispersive X-ray microanalysis. Results. The highest average shift concentration of fluorides, exceeding the occupational exposure limit by 4.7-12.5 times, are observed in the working area of professions serving electrolyzers and anodes, with a predominance of insoluble fluorides over soluble ones. Cases of exceeding the occupational exposure limit of aluminum trioxide by 1.9-2.6 times were noted. Dust suspended in the air of the working area consists of highly and ultradispersed aerosol mixtures of various chemical nature, including particles of the nanoscale range, impurities of heavy metals and toxic compounds. Highly dispersed dust particles, mainly alumina and fluorocarbon compounds, dominated in the air of workshops with traditional aluminum electrolysis technology, while micro- and nanoparticles, consisting mainly of cryolite and a mixture of aluminum fluoride with alumina, dominated in the modernized one. Conclusion. The exposure of complex multicomponent aerosol mixtures of aluminum production can pose a danger to the health of workers, which requires an in-depth analysis of the chemical and dispersed composition of aerosols when assessing the exposure of the dust factor and improving the complexes of preventive measures to prevent the development of diseases.
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Sun, Yele, Wei Du, Pingqing Fu, et al. "Primary and secondary aerosols in Beijing in winter: sources, variations and processes." Atmospheric Chemistry and Physics 16, no. 13 (2016): 8309–29. http://dx.doi.org/10.5194/acp-16-8309-2016.
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Abstract. Winter has the worst air pollution of the year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge of the sources, formation mechanisms and evolution of aerosol particles is not complete. Here we have a comprehensive characterization of the sources, variations and processes of submicron aerosols that were measured by an Aerodyne high-resolution aerosol mass spectrometer from 17 December 2013 to 17 January 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was generally similar across the winter of different years and was mainly composed of organics (60 %), sulfate (15 %) and nitrate (11 %). Positive matrix factorization of high- and unit-mass resolution spectra identified four primary organic aerosol (POA) factors from traffic, cooking, biomass burning (BBOA) and coal combustion (CCOA) emissions as well as two secondary OA (SOA) factors. POA dominated OA, on average accounting for 56 %, with CCOA being the largest contributor (20 %). Both CCOA and BBOA showed distinct polycyclic aromatic hydrocarbons (PAHs) spectral signatures, indicating that PAHs in winter were mainly from coal combustion (66 %) and biomass burning emissions (18 %). BBOA was highly correlated with levoglucosan, a tracer compound for biomass burning (r2 = 0.93), and made a considerable contribution to OA in winter (9 %). An aqueous-phase-processed SOA (aq-OOA) that was strongly correlated with particle liquid water content, sulfate and S-containing ions (e.g. CH2SO2+) was identified. On average aq-OOA contributed 12 % to the total OA and played a dominant role in increasing oxidation degrees of OA at high RH levels (> 50 %). Our results illustrate that aqueous-phase processing can enhance SOA production and oxidation states of OA as well in winter. Further episode analyses highlighted the significant impacts of meteorological parameters on aerosol composition, size distributions, oxidation states of OA and evolutionary processes of secondary aerosols.
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Xia, Men, Xiang Peng, Weihao Wang, et al. "Significant production of ClNO<sub>2</sub> and possible source of Cl<sub>2</sub> from N<sub>2</sub>O<sub>5</sub> uptake at a suburban site in eastern China." Atmospheric Chemistry and Physics 20, no. 10 (2020): 6147–58. http://dx.doi.org/10.5194/acp-20-6147-2020.
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Abstract. ClNO2 and Cl2 can affect atmospheric oxidation and thereby the formation of ozone and secondary aerosols, yet their sources and production mechanisms are not well understood or quantified. In this study we present field observations of ClNO2 and Cl2 at a suburban site in eastern China during April 2018. Persistent high levels of ClNO2 (maximum: ∼3.7 ppbv; 1 min average) were frequently observed at night, due to the high ClNO2 yield (φ (ClNO2), 0.56±0.20) inferred from the measurements. The φ (ClNO2) value showed a positive correlation with the [Cl−] / [H2O] ratio, and its parameterization was improved at low to median yields (0–0.75) by the incorporation of [Cl−] / [H2O] and the suppression effect of aerosol organics. ClNO2 and Cl2 showed a significant correlation on most nights. We show that the Cl2 at our site was more likely a co-product with ClNO2 from N2O5 uptake on acidic aerosols that contain chloride than being produced by ClNO2 uptake as previously suggested. We propose a mechanism in which NO2+ can react with Cl− to produce Cl2 and ClNO2 simultaneously. Under a new framework which regards Cl2, ClNO2, and nitrate as products of N2O5 uptake, the Cl2 yield (φ (Cl2)) was derived using ambient data. φ (Cl2) exhibited significant correlations with [Cl−] and [H+], based on which a parameterization of φ (Cl2) was developed. The derived parameterizations of φ (ClNO2) and φ (Cl2) can be used in models to evaluate the nighttime production of ClNO2 and Cl2 and their impact on the next day's photochemistry.
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Noël, Alexandra, and Ginette Truchon. "Inhaled Titanium Dioxide Nanoparticles: A Review of Their Pulmonary Responses with Particular Focus on the Agglomeration State." Nano LIFE 05, no. 01 (2015): 1450008. http://dx.doi.org/10.1142/s1793984414500081.
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Nanotechnology represents major scientific and economic issues for the future. TiO 2 is used as a reference nanoparticle (NP) for research and workplace exposure assessments due to its important industrial production. However, to date little consistent information exists about its human health effects. Approximately 50% of all TiO 2in vivo studies targeting the respiratory tract have been by inhalation and these exposures are often in the form of agglomerates rather than as individual NPs. Therefore, the size of the NP agglomerates represents the effective size interacting with the biological material and could thereby influence the NP mechanisms of action. Thus, interpretation of nanotoxicological data without considering the agglomeration state could partly explain the heterogeneous results found in the scientific literature for TiO 2 NPs. The objective of this review is to examine the literature concerning the importance of TiO 2 aerosol characterization in the assessment of pulmonary toxicity in rodents. In this way, this review reveals that the pulmonary responses following inhalation of TiO 2 NPs might not depend solely on the primary NP size, but also on the crystal phase, the NP agglomerate size, its structure and the mass concentration. It also shows that TiO 2 NPs may exert their toxicity mechanisms specifically because of the size of their agglomerates in aerosols, thus supporting the concept that aerosols composed essentially of small (< 100 nm) or large (> 100 nm) NP agglomerates do not seem to follow the same pulmonary toxicity mechanisms.
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Rindelaub, Joel D., Carlos H. Borca, Matthew A. Hostetler та ін. "The acid-catalyzed hydrolysis of an <i>α</i>-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact". Atmospheric Chemistry and Physics 16, № 23 (2016): 15425–32. http://dx.doi.org/10.5194/acp-16-15425-2016.
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Abstract. The production of atmospheric organic nitrates (RONO2) has a large impact on air quality and climate due to their contribution to secondary organic aerosol and influence on tropospheric ozone concentrations. Since organic nitrates control the fate of gas phase NOx (NO + NO2), a byproduct of anthropogenic combustion processes, their atmospheric production and reactivity is of great interest. While the atmospheric reactivity of many relevant organic nitrates is still uncertain, one significant reactive pathway, condensed phase hydrolysis, has recently been identified as a potential sink for organic nitrate species. The partitioning of gas phase organic nitrates to aerosol particles and subsequent hydrolysis likely removes the oxidized nitrogen from further atmospheric processing, due to large organic nitrate uptake to aerosols and proposed hydrolysis lifetimes, which may impact long-range transport of NOx, a tropospheric ozone precursor. Despite the atmospheric importance, the hydrolysis rates and reaction mechanisms for atmospherically derived organic nitrates are almost completely unknown, including those derived from α-pinene, a biogenic volatile organic compound (BVOC) that is one of the most significant precursors to biogenic secondary organic aerosol (BSOA). To better understand the chemistry that governs the fate of particle phase organic nitrates, the hydrolysis mechanism and rate constants were elucidated for several organic nitrates, including an α-pinene-derived organic nitrate (APN). A positive trend in hydrolysis rate constants was observed with increasing solution acidity for all organic nitrates studied, with the tertiary APN lifetime ranging from 8.3 min at acidic pH (0.25) to 8.8 h at neutral pH (6.9). Since ambient fine aerosol pH values are observed to be acidic, the reported lifetimes, which are much shorter than that of atmospheric fine aerosol, provide important insight into the fate of particle phase organic nitrates. Along with rate constant data, product identification confirms that a unimolecular specific acid-catalyzed mechanism is responsible for organic nitrate hydrolysis under acidic conditions. The free energies and enthalpies of the isobutyl nitrate hydrolysis intermediates and products were calculated using a hybrid density functional (ωB97X-V) to support the proposed mechanisms. These findings provide valuable information regarding the organic nitrate hydrolysis mechanism and its contribution to the fate of atmospheric NOx, aerosol phase processing, and BSOA composition.
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Rasch, Philip J., Simone Tilmes, Richard P. Turco, et al. "An overview of geoengineering of climate using stratospheric sulphate aerosols." Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 366, no. 1882 (2008): 4007–37. http://dx.doi.org/10.1098/rsta.2008.0131.
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We provide an overview of geoengineering by stratospheric sulphate aerosols. The state of understanding about this topic as of early 2008 is reviewed, summarizing the past 30 years of work in the area, highlighting some very recent studies using climate models, and discussing methods used to deliver sulphur species to the stratosphere. The studies reviewed here suggest that sulphate aerosols can counteract the globally averaged temperature increase associated with increasing greenhouse gases, and reduce changes to some other components of the Earth system. There are likely to be remaining regional climate changes after geoengineering, with some regions experiencing significant changes in temperature or precipitation. The aerosols also serve as surfaces for heterogeneous chemistry resulting in increased ozone depletion. The delivery of sulphur species to the stratosphere in a way that will produce particles of the right size is shown to be a complex and potentially very difficult task. Two simple delivery scenarios are explored, but similar exercises will be needed for other suggested delivery mechanisms. While the introduction of the geoengineering source of sulphate aerosol will perturb the sulphur cycle of the stratosphere signicantly, it is a small perturbation to the total (stratosphere and troposphere) sulphur cycle. The geoengineering source would thus be a small contributor to the total global source of ‘acid rain’ that could be compensated for through improved pollution control of anthropogenic tropospheric sources. Some areas of research remain unexplored. Although ozone may be depleted, with a consequent increase to solar ultraviolet-B (UVB) energy reaching the surface and a potential impact on health and biological populations, the aerosols will also scatter and attenuate this part of the energy spectrum, and this may compensate the UVB enhancement associated with ozone depletion. The aerosol will also change the ratio of diffuse to direct energy reaching the surface, and this may influence ecosystems. The impact of geoengineering on these components of the Earth system has not yet been studied. Representations for the formation, evolution and removal of aerosol and distribution of particle size are still very crude, and more work will be needed to gain confidence in our understanding of the deliberate production of this class of aerosols and their role in the climate system.
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Kiliyanpilakkil, V. P., and N. Meskhidze. "Deriving the effect of wind speed on clean marine aerosol optical properties using the A-Train satellites." Atmospheric Chemistry and Physics 11, no. 22 (2011): 11401–13. http://dx.doi.org/10.5194/acp-11-11401-2011.
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Abstract. The relationship between "clean marine" aerosol optical properties and ocean surface wind speed is explored using remotely sensed data from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) on board the CALIPSO satellite and the Advanced Microwave Scanning Radiometer (AMSR-E) on board the AQUA satellite. Detailed data analyses are carried out over 15 regions selected to be representative of different areas of the global ocean for the time period from June 2006 to April 2011. Based on remotely sensed optical properties the CALIPSO algorithm is capable of discriminating "clean marine" aerosols from other types often present over the ocean (such as urban/industrial pollution, desert dust and biomass burning). The global mean optical depth of "clean marine" aerosol at 532 nm (AOD532) is found to be 0.052 ± 0.038 (mean plus or minus standard deviation). The mean layer integrated particulate depolarization ratio of marine aerosols is 0.02 ± 0.016. Integrated attenuated backscatter and color ratio of marine aerosols at 532 nm were found to be 0.003 ± 0.002 sr−1 and 0.530 ± 0.149, respectively. A logistic regression between AOD532 and 10-m surface wind speed (U10) revealed three distinct regimes. For U10 ≤ 4 m s−1 the mean CALIPSO-derived AOD532 is found to be 0.02 ± 0.003 with little dependency on the surface wind speed. For 4 < U10 ≤ 12 m s−1, representing the dominant fraction of all available data, marine aerosol optical depth is linearly correlated with the surface wind speed values, with a slope of 0.006 s m−1. In this intermediate wind speed region, the AOD532 vs. U10 regression slope derived here is comparable to previously reported values. At very high wind speed values (U10 > 18 m s−1), the AOD532-wind speed relationship showed a tendency toward leveling off, asymptotically approaching value of 0.15. The conclusions of this study regarding the aerosol extinction vs. wind speed relationship may have been influenced by the constant lidar ratio used for CALIPSO-derived AOD532. Nevertheless, active satellite sensor used in this study that allows separation of maritime wind induced component of AOD from the total AOD over the ocean could lead to improvements in optical properties of sea spray aerosols and their production mechanisms.
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Paulot, Fabien, David Paynter, Paul Ginoux, Vaishali Naik, and Larry W. Horowitz. "Changes in the aerosol direct radiative forcing from 2001 to 2015: observational constraints and regional mechanisms." Atmospheric Chemistry and Physics 18, no. 17 (2018): 13265–81. http://dx.doi.org/10.5194/acp-18-13265-2018.
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Abstract. We present estimates of changes in the direct aerosol effects (DRE) and its anthropogenic component (DRF) from 2001 to 2015 using the GFDL chemistry–climate model AM3 driven by CMIP6 historical emissions. AM3 is evaluated against observed changes in the clear-sky shortwave direct aerosol effect (DREswclr) derived from the Clouds and the Earth's Radiant Energy System (CERES) over polluted regions. From 2001 to 2015, observations suggest that DREclrsw increases (i.e., less radiation is scattered to space by aerosols) over western Europe (0.7–1 W m−2 decade−1) and the eastern US (0.9–1.4 W m−2 decade−1), decreases over India (−1 to −1.6 W m−2 decade−1), and does not change significantly over eastern China. AM3 captures these observed regional changes in DREclrsw well in the US and western Europe, where they are dominated by the decline of sulfate aerosols, but not in Asia, where the model overestimates the decrease of DREclrsw. Over India, the model bias can be partly attributed to a decrease of the dust optical depth, which is not captured by our model and offsets some of the increase of anthropogenic aerosols. Over China, we find that the decline of SO2 emissions after 2007 is not represented in the CMIP6 emission inventory. Accounting for this decline, using the Modular Emission Inventory for China, and for the heterogeneous oxidation of SO2 significantly reduces the model bias. For both India and China, our simulations indicate that nitrate and black carbon contribute more to changes in DREclrsw than in the US and Europe. Indeed, our model suggests that black carbon (+0.12 W m−2) dominates the relatively weak change in DRF from 2001 to 2015 (+0.03 W m−2). Over this period, the changes in the forcing from nitrate and sulfate are both small and of the same magnitude (−0.03 W m−2 each). This is in sharp contrast to the forcing from 1850 to 2001 in which forcings by sulfate and black carbon largely cancel each other out, with minor contributions from nitrate. The differences between these time periods can be well understood from changes in emissions alone for black carbon but not for nitrate and sulfate; this reflects non-linear changes in the photochemical production of nitrate and sulfate associated with changes in both the magnitude and spatial distribution of anthropogenic emissions.
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Mironova, I. A., I. G. Usoskin, G. A. Kovaltsov, and S. V. Petelina. "Possible effect of extreme solar energetic particle event of 20 January 2005 on polar stratospheric aerosols: direct observational evidence." Atmospheric Chemistry and Physics 12, no. 2 (2012): 769–78. http://dx.doi.org/10.5194/acp-12-769-2012.
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Abstract. Energetic cosmic rays are the main source of ionization of the low-middle atmosphere, leading to associated changes in atmospheric properties. Via the hypothetical influence of ionization on aerosol growth and facilitated formation of clouds, this may be an important indirect link relating solar variability to climate. This effect is highly debated, however, since the proposed theoretical mechanisms still remain illusive and qualitative, and observational evidence is inconclusive and controversial. Therefore, important questions regarding the existence and magnitude of the effect, and particularly the fraction of aerosol particles that can form and grow, are still open. Here we present empirical evidence of the possible effect caused by cosmic rays upon polar stratospheric aerosols, based on a case study of an extreme solar energetic particle (SEP) event of 20 January 2005. Using aerosol data obtained over polar regions from different satellites with optical instruments that were operating during January 2005, such as the Stratospheric Aerosol and Gas Experiment III (SAGE III), and Optical Spectrograph and Infrared Imaging System (OSIRIS), we found a significant simultaneous change in aerosol properties in both the Southern and Northern Polar regions in temporal association with the SEP event. We speculate that ionization of the atmosphere, which was abnormally high in the lower stratosphere during the extreme SEP event, might have led to formation of new particles and/or growth of preexisting ultrafine particles in the polar stratospheric region. However, a detailed interpretation of the effect is left for subsequent studies. This is the first time high vertical resolution measurements have been used to discuss possible production of stratospheric aerosols under the influence of cosmic ray induced ionization. The observed effect is marginally detectable for the analyzed severe SEP event and can be undetectable for the majority of weak-moderate events. The present interpretation serves as a conservative upper limit of solar energetic particle effect upon polar stratospheric aerosols.
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Meskhidze, Nicholas, Markus D. Petters, Kostas Tsigaridis, et al. "Production mechanisms, number concentration, size distribution, chemical composition, and optical properties of sea spray aerosols." Atmospheric Science Letters 14, no. 4 (2013): 207–13. http://dx.doi.org/10.1002/asl2.441.
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O'Dowd, Colin D., and Thorsten Hoffmann. "Coastal New Particle Formation: A Review of the Current State-Of-The-Art." Environmental Chemistry 2, no. 4 (2005): 245. http://dx.doi.org/10.1071/en05077.
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Environmental Context.Atmospheric aerosols play an important role in determining the earth’s radiative budget, climate change and air quality levels. Much effort has been spent on quantifying the impact of aerosols on climate change; however, the largest gap in our knowledge relates to quantifying natural aerosol systems and the new particle formation process associated with these systems. The marine aerosol system is of particular interest due to the 70% ocean coverage of the earth’s surface. Coastal new particle formation events are though to be more frequent and of stronger intensity compared with open ocean events and thus have been studied in detail to identify possible processes leading to open ocean new particle production. Abstract.New particle formation via secondary gas-to-particle conversion processes over the oceans is one of the main mechanisms controlling the marine aerosol number population; however, despite extensive effort over the years, this phenomenon is still not well quantified. Coastal new particle formation events are more frequent than open ocean events and consequently have been studied in greater detail. This review article summarizes the recent studies into coastal new particle formation events and summarizes the linkage of these events to iodine emissions and ultimate particle formation via iodine oxide nucleation processes. The current state of knowledge may be summarized by concluding that, in general, coastal nucleation events are driven by biogenic emissions of iodine vapours that undergo rapid chemical reactions to produce condensable iodine oxides leading to nucleation and growth of new particles. The primary source of the condensable iodine vapours is thought to be molecular iodine (I2). The role of iodine oxides in open-ocean new particle production still remains an open question and is the most pressing next step to undertake.
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Tritscher, T., J. Dommen, P. F. DeCarlo, et al. "Volatility and hygroscopicity of aging secondary organic aerosol in a smog chamber." Atmospheric Chemistry and Physics 11, no. 22 (2011): 11477–96. http://dx.doi.org/10.5194/acp-11-11477-2011.
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Abstract. The evolution of secondary organic aerosols (SOA) during (photo-)chemical aging processes was investigated in a smog chamber. Fresh SOA from ozonolysis of 10 to 40 ppb α-pinene was formed followed by aging with OH radicals. The particles' volatility and hygroscopicity (expressed as volume fraction remaining (VFR) and hygroscopicity parameter κ) were measured in parallel with a volatility and hygroscopicity tandem differential mobility analyzer (V/H-TDMA). An aerosol mass spectrometer (AMS) was used for the chemical characterization of the aerosol. These measurements were used as sensitive parameters to reveal the mechanisms possibly responsible for the changes in the SOA composition during aging. A change of VFR and/or κ during processing of atmospheric aerosols may occur either by addition of SOA mass (by condensation) or by a change of SOA composition leading to different aerosol properties. The latter may occur either by heterogeneous reactions on the surface of the SOA particles, by condensed phase reactions like oligomerization or by an evaporation – gas-phase oxidation – recondensation cycle. The condensation mechanism showed to be dominant when there is a substantial change in the aerosol mass by addition of new molecules to the aerosol phase with time. Experiments could be divided into four periods based on the temporal evolution (qualitative changes) of VFR, κ and organic mass: O3 induced condensation, ripening, and OH induced chemical aging first with substantial mass gain and then without significant mass gain. During the O3 induced condensation the particles' volatility decreased (increasing VFR) while the hygroscopicity increased. Thereafter, in the course of ripening volatility continued to decrease, but hygroscopicity stayed roughly constant. After exposing the SOA to OH radicals an OH induced chemical aging with substantial mass gain started resulting in the production of at least 50 % more SOA mass. This new SOA mass was highly volatile and oxidized. This period was then followed by further OH induced chemical aging without significant mass gain leading to a decrease of volatility while hygroscopicity and SOA mass stayed roughly constant.
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Lin, Yu-Chi, Yan-Lin Zhang, Mei-Yi Fan, and Mengying Bao. "Heterogeneous formation of particulate nitrate under ammonium-rich regimes during the high-PM<sub>2.5</sub> events in Nanjing, China." Atmospheric Chemistry and Physics 20, no. 6 (2020): 3999–4011. http://dx.doi.org/10.5194/acp-20-3999-2020.
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Abstract. Particulate nitrate (NO3-) not only influences regional climates but also contributes to the acidification of terrestrial and aquatic ecosystems. In 2016 and 2017, four intensive online measurements of water-soluble ions in PM2.5 were conducted in Nanjing City in order to investigate the potential formation mechanisms of particulate nitrate. During the sampling periods, NO3- was the predominant species, accounting approximately for 35 % of the total water-soluble inorganic ions, followed by SO42- (33 %) and NH4+ (24 %). Significant enhancements of nitrate aerosols in terms of both absolute concentrations and relative abundances suggested that NO3- was a major contributing species to high-PM2.5 events (hourly PM2.5≥150 µg m−3). High NO3- concentrations mainly occurred under NH4+-rich conditions, implying that the formation of nitrate aerosols in Nanjing involved NH3. During the high-PM2.5 events, the nitrogen conversion ratios (Fn) were positively correlated with the aerosol liquid water content (ALWC; R>0.72 and p<0.05). Meanwhile, increasing NO3- concentrations regularly coincided with increasing ALWC and decreasing Ox (Ox=O3+NO2). These results suggested that the heterogeneous reaction was probably a major mechanism of nitrate formation during the high-PM2.5 events. Moreover, the average production rate of NO3- by heterogeneous processes was estimated to be 12.6 % h−1 (4.1 µg m−3 h−1), which was much higher than that (2.5 % h−1; 0.8 µg m−3 h−1) of gas-phase reactions. This can also explain the abrupt increases in nitrate concentrations during the high-PM2.5 events. Utilizing the ISORROPIA II model, we found that nitrate aerosol formation in Nanjing during the high-PM2.5 events was HNO3 limited. This indicated that control of NOx emissions will be able to efficiently reduce airborne particulate nitrate concentrations and improve the air quality in this industrial city.
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Zhao, Jian, Wei Du, Yingjie Zhang, et al. "Insights into aerosol chemistry during the 2015 China Victory Day parade: results from simultaneous measurements at ground level and 260 m in Beijing." Atmospheric Chemistry and Physics 17, no. 4 (2017): 3215–32. http://dx.doi.org/10.5194/acp-17-3215-2017.
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Abstract. Strict emission controls were implemented in Beijing and adjacent provinces to ensure good air quality during the 2015 China Victory Day parade. Here, we conducted synchronous measurements of submicron aerosols (PM1) at ground level and 260 m on a meteorological tower by using a high-resolution aerosol mass spectrometer and an aerosol chemical speciation monitor, respectively, in Beijing from 22 August to 30 September. Our results showed that the average PM1 concentrations are 19.3 and 14.8 µg m−3 at ground level and 260 m, respectively, during the control period (20 August–3 September), which are 57 and 50 % lower than those after the control period (4–30 September). Organic aerosols (OAs) dominated PM1 during the control period at both ground level and 260 m (55 and 53 %, respectively), while their contribution showed substantial decreases (∼ 40 %) associated with an increase in secondary inorganic aerosols (SIAs) after the parade, indicating a larger impact of emission controls on SIA than OA. Positive matrix factorization of OA further illustrated that primary OA (POA) showed similar decreases as secondary OA (SOA) at both ground level (40 % vs. 42 %) and 260 m (35 % vs. 36 %). However, we also observed significant changes in SOA composition at ground level. While the more oxidized SOA showed a large decrease by 75 %, the less oxidized SOA was comparable during (5.6 µg m−3) and after the control periods (6.5 µg m−3). Our results demonstrated that the changes in meteorological conditions and PM loadings have affected SOA formation mechanisms, and the photochemical production of fresh SOA was more important during the control period. By isolating the influences of meteorological conditions and footprint regions in polluted episodes, we found that regional emission controls on average reduced PM levels by 44–45 %, and the reductions were close among SIA, SOA and POA at 260 m, whereas primary species showed relatively more reductions (55–67 %) than secondary aerosol species (33–44 %) at ground level.
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Pace, G., A. di Sarra, D. Meloni, S. Piacentino, and P. Chamard. "Aerosol optical properties at Lampedusa (Central Mediterranean) – 1. Influence of transport and identification of different aerosol types." Atmospheric Chemistry and Physics Discussions 5, no. 4 (2005): 4929–69. http://dx.doi.org/10.5194/acpd-5-4929-2005.
Full textAbstract:
Abstract. Aerosol optical depth and Ångström exponent were obtained from multi filter rotating shadowband radiometer (MFRSR) observations carried out at the island of Lampedusa, in the Central Mediterranean, in the period July 2001–September 2003. The average aerosol optical depth at 495.7 nm, τ, is 0.24±0.14; the average Ångström exponent, α, is 0.86±0.63. The observed values of τ range from 0.03 to 1.13, and the values of α vary from −0.32 to 2.05, indicating a large variability in aerosol content and size. In cloud-free conditions, 36% of the airmasses come from Africa, 25% from Central-Eastern Europe, and 19% from Western France, Spain and the North Atlantic. In summer, 42% of the airmasses are of African origin. In almost all cases African aerosols display high values of τ and low values of α, typical of Saharan dust (average values of τ and α are 0.36 and 0.42, respectively). Particles originating from Central-Eastern Europe show relatively large average values of τ and α (0.23 and 1.5, respectively), while particles from Western France, Spain and the North Atlantic show the lowest average values of τ (0.15), and relatively small values of α (0.92). Intermediate values of α are often connected with relatively fast changes of the airmass originating sector, suggesting the contemporary presence of different types of particles in the air column. The largest values of α (about 2) were observed in August 2003, when large scale forest fires in Southern Europe produced consistent amounts of fine combustion particles that were transported to the Central Mediterranean by a persistent high pressure system over Central Europe. Smoke particles in some cases mix with desert dust, producing intermediate values of α. The seasonal distribution of the meteorological patterns over the Mediterranean, the efficiency of the aerosol production mechanisms, and the variability of the particles' residence time produce a distinct seasonal cycle of aerosol optical depths and Ångström exponent values. Particles originating from all sectors show a summer maximum in aerosol optical depth. The summer increase in optical depth for European aerosols is linked with an increment in the values of α that indicates an enhancement in the number of fine particles. The summer maximum of τ for African particles is associated with a weak reduction in the Ångström exponent, suggesting an increase in the total number of particles and a relatively more intense transport of large particles. The observations were classified according to the aerosol optical properties, and two main classes have been identified: desert dust and biomass burning/urban-industrial aerosols. Values of τ and α averaged over the whole observing period are 0.37 and 0.15 for desert dust, and 0.27 and 1.77 for urban-industrial/biomass burning aerosols. Lampedusa reveals a stronger influence of desert dust compared to other Mediterranean sites (mostly located on the coasts of Europe).
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Johnson, David, Michael E. Jenkin, Klaus Wirtz, and Montserrat Martin-Reviejo. "Simulating the Formation of Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons." Environmental Chemistry 2, no. 1 (2005): 35. http://dx.doi.org/10.1071/en04079.
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Environmental Context. Atmospheric particulate material can affect the radiative balance of the atmosphere and is believed to be detrimental to human health. Secondary organic aerosols (SOA), which make a significant contribution to the total atmospheric burden of fine particulate material, are formed in situ following the photochemical transformation of organic pollutants into relatively less-volatile, oxygenated compounds which can subsequently transfer from the gas phase to a particle phase. SOA formation from the atmospheric photooxidation of aromatic hydrocarbons—present, for example, as a result of automobile use—is believed to be important in the urban environment and yet the mechanisms are not well understood. For example, even the reasons for observed variations in the relative propensity for SOA formation, from the photooxidation of various simple aromatic hydrocarbons, are not clear. Abstract. The formation and composition of secondary organic aerosol (SOA) from the photooxidation of benzene, p-xylene, and 1,3,5-trimethylbenzene has been simulated using the Master Chemical Mechanism version 3.1 (MCM v3.1) coupled to a representation of the transfer of organic material from the gas to particle phase. The combined mechanism was tested against data obtained from a series of experiments conducted at the European Photoreactor (EUPHORE) outdoor smog chamber in Valencia, Spain. Simulated aerosol mass concentrations compared reasonably well with the measured SOA data only after absorptive partitioning coefficients were increased by a factor of between 5 and 30. The requirement of such scaling was interpreted in terms of the occurrence of unaccounted-for association reactions in the condensed organic phase leading to the production of relatively more nonvolatile species. Comparisons were made between the relative aerosol forming efficiencies of benzene, toluene, p-xylene, and 1,3,5-trimethylbenzene, and differences in the OH-initiated degradation mechanisms of these aromatic hydrocarbons. A strong, nonlinear relationship was observed between measured (reference) yields of SOA and (proportional) yields of unsaturated dicarbonyl aldehyde species resulting from ring-fragmenting pathways. This observation, and the results of the simulations, is strongly suggestive of the involvement of reactive aldehyde species in association reactions occurring in the aerosol phase, thus promoting SOA formation and growth. The effect of NOx concentrations on SOA formation efficiencies (and formation mechanisms) is discussed.
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Ji, Yuemeng, Qiuju Shi, Yixin Li, et al. "Carbenium ion-mediated oligomerization of methylglyoxal for secondary organic aerosol formation." Proceedings of the National Academy of Sciences 117, no. 24 (2020): 13294–99. http://dx.doi.org/10.1073/pnas.1912235117.
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Secondary organic aerosol (SOA) represents a major constituent of tropospheric fine particulate matter, with profound implications for human health and climate. However, the chemical mechanisms leading to SOA formation remain uncertain, and atmospheric models consistently underpredict the global SOA budget. Small α-dicarbonyls, such as methylglyoxal, are ubiquitous in the atmosphere because of their significant production from photooxidation of aromatic hydrocarbons from traffic and industrial sources as well as from biogenic isoprene. Current experimental and theoretical results on the roles of methylglyoxal in SOA formation are conflicting. Using quantum chemical calculations, we show cationic oligomerization of methylglyoxal in aqueous media. Initial protonation and hydration of methylglyoxal lead to formation of diols/tetrol, and subsequent protonation and dehydration of diols/tetrol yield carbenium ions, which represent the key intermediates for formation and propagation of oligomerization. On the other hand, our results reveal that the previously proposed oligomerization via hydration for methylglyoxal is kinetically and thermodynamically implausible. The carbenium ion-mediated mechanism occurs barrierlessly on weakly acidic aerosols and cloud/fog droplets and likely provides a key pathway for SOA formation from biogenic and anthropogenic emissions.
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Lv, Shuang, Feng-Yang Bai, Xiu-Mei Pan, and Liang Zhao. "Theoretical insight into the role of urea in the hydrolysis reaction of NO2 as a source of HONO and aerosols." Environmental Chemistry 15, no. 6 (2018): 372. http://dx.doi.org/10.1071/en18083.
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Environmental contextUrea is an important component of dissolved organic nitrogen in rainfall and aerosols, but the sources and the mechanisms of its production are not well understood. This computational study explores the effects of urea and water on the hydrolysis of NO2 and urea nitrate production. The results will aid our interpretation of the role of urea in the formation of atmospheric secondary nitrogen contaminants and aerosols. AbstractThe effects of urea on the hydrolysis reaction 2NO2 + mH2O (m = 1–3) have been investigated by theoretical calculations. The energy barrier (−2.67 kcal mol−1) of the urea-promoted reaction is lower than the naked reaction by 14.37 kcal mol−1. Urea also has a better catalytic effect on the reaction than methylamine and ammonia. Urea acts as a catalyst and proton transfer medium in this process, and the produced HONO may serve as a source of atmospheric nitrous acid. In addition, the subsequent reactions include clusters of nitrite, urea, and nitric acid. Then urea nitrate (UN), which is a typical HNO3 aerosol, can be formed in the subsequent reactions. The production of the acid-base complex (UN-2) is more favourable with an energy barrier of 0.10 kcal mol−1, which is 3.88 kcal mol−1 lower than that of the zwitterions NH2CONH3+NO3− (UN-1). The formation of zwitterions and the hydrolysis reaction are affected by humidity. The multi water-promoted hydrolysis reactions exhibit better thermodynamic stability when the humidity is increased. The extra water molecules act as solvent molecules to reduce the energy barrier. The natural bond orbital (NBO) analysis is employed to describe the donor-acceptor interactions of the complexes. The hydrogen bond interaction between the urea carbonyl and nitric acid of UN-2 is the strongest. The potential distribution maps of the urea nitrate and hydrate are examined, and the result shows that they tend to form zwitterions.
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Fan, Jiwen, and Renyi Zhang. "Atmospheric Oxidation Mechanism of Isoprene." Environmental Chemistry 1, no. 3 (2004): 140. http://dx.doi.org/10.1071/en04045.
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Environmental Context. Many plant species biosynthesize and emit the volatile hydrocarbon isoprene. Once in the atmosphere, isoprene is susceptible to a range of reactions involving potentially hundred of products and intermediate compounds. The products of these reactions in turn may pose a risk to human and plant health and impact the climate through the generation of acids, ozone, and atmospheric aerosols. Abstract. The atmospheric oxidation mechanism of isoprene initiated by OH, O3, NO3, and Cl, which incorporates the most recent laboratory and theoretical studies, is described. A box model intercomparison between the new mechanism and previous available isoprene oxidation mechanisms has been performed. Ozone and OH concentrations are compared with predictions by the previous mechanisms in high and low NOx scenarios. The O3 and OH sensitivities to the chlorine−isoprene reactions have also been investigated by comparing the box model results with and without the chlorine−isoprene reactions, showing that the ozone production rate and OH concentrations are slightly impacted. The new mechanism facilitates more accurate modelling of isoprene photochemistry in the atmosphere.
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Pace, G., A. di Sarra, D. Meloni, S. Piacentino, and P. Chamard. "Aerosol optical properties at Lampedusa (Central Mediterranean). 1. Influence of transport and identification of different aerosol types." Atmospheric Chemistry and Physics 6, no. 3 (2006): 697–713. http://dx.doi.org/10.5194/acp-6-697-2006.
Full textAbstract:
Abstract. Aerosol optical depth and Ångström exponent were obtained from multi filter rotating shadowband radiometer (MFRSR) observations carried out at the island of Lampedusa, in the Central Mediterranean, in the period July 2001–September 2003. The average aerosol optical depth at 495.7 nm, τ, is 0.24±0.14; the average Ångström exponent, α, is 0.86±0.63. The observed values of τ range from 0.03 to 1.13, and the values of α vary from −0.32 to 2.05, indicating a large variability in aerosol content and size. In cloud-free conditions, 36% of the airmasses come from Africa, 25% from Central-Eastern Europe, and 19% from Western France, Spain and the North Atlantic. In summer, 42% of the airmasses is of African origin. In almost all cases African aerosols display high values of τ and low values of α, typical of Saharan dust (average values of τ and α are 0.36 and 0.42, respectively). Particles originating from Central-Eastern Europe show relatively large average values of τ and α (0.23 and 1.5, respectively), while particles from Western France, Spain and the North Atlantic show the lowest average values of τ (0.15), and relatively small values of α (0.92). Intermediate values of α are often connected with relatively fast changes of the airmass originating sector, suggesting the contemporary presence of different types of particles in the air column. Clean marine conditions are rare at Lampedusa, and are generally associated with subsidence of the airmasses reaching the island. Average values of τ and α for clean marine conditions are 0.11 and 0.86, respectively. The largest values of α (about 2) were observed in August 2003, when large scale forest fires in Southern Europe produced consistent amounts of fine combustion particles, that were transported to the Central Mediterranean by a persistent high pressure system over Central Europe. Smoke particles in some cases mix with desert dust, producing intermediate values of α. The seasonal distribution of the meteorological patterns over the Mediterranean, the efficiency of the aerosol production mechanisms, and the variability of the particles' residence time produce a distinct seasonal cycle of aerosol optical depths and Ångström exponent values. Particles originating from all sectors show a summer maximum in aerosol optical depth. The summer increase in optical depth for European aerosols is linked with an increment in the values of α, that indicates an enhancement in the number of fine particles. The summer maximum of τ for African particles is associated with a weak reduction in the Ångström exponent, suggesting an increase in the total number of particles and a relatively more intense transport of large particles. The observations were classified according to the aerosol optical properties, and two main classes have been identified: desert dust and biomass burning/urban-industrial aerosols. Values of τ and α averaged over the whole observing period are 0.37 and 0.15 for desert dust, and 0.27 and 1.77 for urban-industrial/biomass burning aerosols.
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Karl, M., K. Tsigaridis, E. Vignati, and F. Dentener. "Formation of secondary organic aerosol from isoprene oxidation over Europe." Atmospheric Chemistry and Physics 9, no. 18 (2009): 7003–30. http://dx.doi.org/10.5194/acp-9-7003-2009.
Full textAbstract:
Abstract. The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr−1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr−1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights in isoprene SOA formation mechanisms reduces the tropospheric production of isoprene derived SOA over Europe from 0.4 Tg yr−1 in our reference simulation to 0.1 Tg yr−1.
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Lebonnois, Sebastien, Pascal Rannou, and Frederic Hourdin. "The coupling of winds, aerosols and chemistry in Titan's atmosphere." Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 367, no. 1889 (2008): 665–82. http://dx.doi.org/10.1098/rsta.2008.0243.
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The atmosphere of Titan is a complex system, where thermal structure, radiative transfer, dynamics, microphysics and photochemistry are strongly coupled together. The global climate model developed over the past 15 years at the Pierre-Simon Laplace Institute has been exploring these different couplings, and has demonstrated how they can help to interpret the observed atmospheric structure of Titan's lower atmosphere (mainly in the stratosphere and troposphere). This review discusses these interactions, and our current understanding of their role in the context of this model, but also of other available works. The recent Cassini results, and the importance of the production mechanisms for Titan's haze, have put forward the need to explore the mesosphere and the couplings between upper and lower atmosphere, as well as the current limits of available models.
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Grythe, H., J. Ström, R. Krejci, P. Quinn, and A. Stohl. "A review of sea-spray aerosol source functions using a large global set of sea salt aerosol concentration measurements." Atmospheric Chemistry and Physics 14, no. 3 (2014): 1277–97. http://dx.doi.org/10.5194/acp-14-1277-2014.
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Abstract. Sea-spray aerosols (SSA) are an important part of the climate system because of their effects on the global radiative budget – both directly as scatterers and absorbers of solar and terrestrial radiation, and indirectly as cloud condensation nuclei (CCN) influencing cloud formation, lifetime, and precipitation. In terms of their global mass, SSA have the largest uncertainty of all aerosols. In this study we review 21 SSA source functions from the literature, several of which are used in current climate models. In addition, we propose a~new function. Even excluding outliers, the global annual SSA mass produced spans roughly 3–70 Pg yr−1 for the different source functions, for particles with dry diameter Dp < 10 μm, with relatively little interannual variability for a given function. The FLEXPART Lagrangian particle dispersion model was run in backward mode for a large global set of observed SSA concentrations, comprised of several station networks and ship cruise measurement campaigns. FLEXPART backward calculations produce gridded emission sensitivity fields, which can subsequently be multiplied with gridded SSA production fluxes in order to obtain modeled SSA concentrations. This allowed us to efficiently and simultaneously evaluate all 21 source functions against the measurements. Another advantage of this method is that source-region information on wind speed and sea surface temperatures (SSTs) could be stored and used for improving the SSA source function parameterizations. The best source functions reproduced as much as 70% of the observed SSA concentration variability at several stations, which is comparable with "state of the art" aerosol models. The main driver of SSA production is wind, and we found that the best fit to the observation data could be obtained when the SSA production is proportional to U103.5, where U10 is the source region averaged 10 m wind speed. A strong influence of SST on SSA production, with higher temperatures leading to higher production, could be detected as well, although the underlying physical mechanisms of the SST influence remains unclear. Our new source function with wind speed and temperature dependence gives a global SSA production for particles smaller than Dp < 10 μm of 9 Pg yr−1, and is the best fit to the observed concentrations.
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Crosbie, Ewan, Luke D. Ziemba, Michael A. Shook, et al. "Measurement report: Closure analysis of aerosol–cloud composition in tropical maritime warm convection." Atmospheric Chemistry and Physics 22, no. 20 (2022): 13269–302. http://dx.doi.org/10.5194/acp-22-13269-2022.
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Abstract. Cloud droplet chemical composition is a key observable property that can aid understanding of how aerosols and clouds interact. As part of the Clouds, Aerosols and Monsoon Processes – Philippines Experiment (CAMP2Ex), three case studies were analyzed involving collocated airborne sampling of relevant clear and cloudy air masses associated with maritime warm convection. Two of the cases represented a polluted marine background, with signatures of transported East Asian regional pollution, aged over water for several days, while the third case comprised a major smoke transport event from Kalimantan fires. Sea salt was a dominant component of cloud droplet composition, in spite of fine particulate enhancement from regional anthropogenic sources. Furthermore, the proportion of sea salt was enhanced relative to sulfate in rainwater and may indicate both a propensity for sea salt to aid warm rain production and an increased collection efficiency of large sea salt particles by rain in subsaturated environments. Amongst cases, as precipitation became more significant, so too did the variability in the sea salt to (non-sea salt) sulfate ratio. Across cases, nitrate and ammonium were fractionally greater in cloud water than fine-mode aerosol particles; however, a strong covariability in cloud water nitrate and sea salt was suggestive of prior uptake of nitrate on large salt particles. A mass-based closure analysis of non-sea salt sulfate compared the cloud water air-equivalent mass concentration to the concentration of aerosol particles serving as cloud condensation nuclei for droplet activation. While sulfate found in cloud was generally constrained by the sub-cloud aerosol concentration, there was significant intra-cloud variability that was attributed to entrainment – causing evaporation of sulfate-containing droplets – and losses due to precipitation. In addition, precipitation tended to promote mesoscale variability in the sub-cloud aerosol through a combination of removal, convective downdrafts, and dynamically driven convergence. Physical mechanisms exerted such strong control over the cloud water compositional budget that it was not possible to isolate any signature of chemical production/loss using in-cloud observations. The cloud-free environment surrounding the non-precipitating smoke case indicated sulfate enhancement compared to convective mixing quantified by a stable gas tracer; however, this was not observed in the cloud water (either through use of ratios or the mass closure), perhaps implying that the warm convective cloud timescale was too short for chemical production to be a leading-order budgetary term and because precursors had already been predominantly exhausted. Closure of other species was truncated by incomplete characterization of coarse aerosol (e.g., it was found that only 10 %–50 % of sea salt mass found in cloud was captured during clear-air sampling) and unmeasured gas-phase abundances affecting closure of semi-volatile aerosol species (e.g., ammonium, nitrate and organic) and soluble volatile organic compound contributions to total organic carbon in cloud water.
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Grythe, H., J. Ström, R. Krejci, P. Quinn, and A. Stohl. "A review of sea spray aerosol source functions using a large global set of sea salt aerosol concentration measurements." Atmospheric Chemistry and Physics Discussions 13, no. 8 (2013): 20729–81. http://dx.doi.org/10.5194/acpd-13-20729-2013.
Full textAbstract:
Abstract. Sea spray aerosols (SSA) are an important part of the climate system through their effects on the global radiative budget both directly as scatterers and absorbers of solar and terrestrial radiation, and indirectly as cloud condensation nuclei (CCN) influencing cloud formation, lifetime and precipitation. In terms of their global mass, SSA have the largest uncertainty of all aerosols. In this study we review 21 SSA source functions from the literature, several of which are used in current climate models, and we also propose a new function. Even excluding outliers, the global annual SSA mass produced by these source functions spans roughly 3–70 Pg yr-1 for the different source functions, with relatively little interannual variability for a given function. The FLEXPART Lagrangian model was run in backward mode for a large global set of observed SSA concentrations, comprised of several station networks and ship cruise measurement campaigns. FLEXPART backward calculations produce gridded emission sensitivity fields, which can subsequently be multiplied with gridded SSA production fluxes to obtain modeled SSA concentrations. This allowed to efficiently evaluate all 21source functions at the same time against the measurements. Another advantage of this method is that source-region information on wind speed and sea surface temperatures (SSTs) could be stored and used for improving the SSA source function parameterizations. The best source functions reproduced as much as 70% of the observed SSA concentration variability at several stations, which is comparable with "state of the art" aerosol models. The main driver of SSA production is wind, and we found that the best fit to the observation data could be obtained when the SSA production is proportional to U103.5 where U10 is the source region averaged 10 m wind speed, to the power of 3.5. A strong influence of SST on SSA production could be detected as well, although the underlying physical mechanisms of the SST influence remains unclear. Our new source function gives a global SSA production for particles smaller than 10 μm of 9 Pg yr-1 and is the best fit to the observed concentrations.
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Mironova, I. A., I. G. Usoskin, G. A. Kovaltsov, and S. V. Petelina. "Possible effect of extreme solar energetic particle event of 20 January 2005 on polar stratospheric aerosols: direct observational evidence." Atmospheric Chemistry and Physics Discussions 11, no. 5 (2011): 14003–29. http://dx.doi.org/10.5194/acpd-11-14003-2011.
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Abstract. Energetic cosmic rays are the main source of ionization of the low-middle atmosphere, leading to associated changes in atmospheric properties. Via the hypothetical influence of ionization on aerosol growth and facilitated formation of cloud condensation nuclei, this may be an important indirect link relating solar variability to climate. This effect is highly debated, however, since the proposed theoretical mechanisms still remain illusive and qualitative, and observational evidence is inconclusive and controversial. Therefore, important questions regarding the existence and magnitude of the effect, and particularly the fraction of aerosol particles that can be formed and grow large enough to influence cloud condensation nuclei (CCN), are still open. Here we present empirical evidence of the possible effect caused by cosmic rays upon polar stratospheric aerosols, based on a case study of an extreme solar energetic particle (SEP) event of 20 January 2005. Using aerosol data obtained over polar regions from different satellites with optical instruments that were operating during January 2005, such as the Stratospheric Aerosol and Gas Experiment III (SAGE III), and Optical Spectrograph and Infrared Imaging System (OSIRIS), we found a significant simultaneous change in aerosol properties in both the southern and northern polar regions in temporal association with the SEP event. We speculate that ionization of the atmosphere, which was abnormally high during this extreme SEP event, might have led to formation of new particles and/or growth of preexisting ultrafine particles up to the size of CCN. However, a detailed interpretation of the effect is left for subsequent studies. This is the first time high vertical resolution measurements have been used to provide evidence for the probable production of stratospheric CCN from cosmic ray induced ionization.
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Tsigaridis, K., J. Lathière, M. Kanakidou, and D. A. Hauglustaine. "Naturally driven variability in the global secondary organic aerosol over a decade." Atmospheric Chemistry and Physics Discussions 5, no. 2 (2005): 1255–83. http://dx.doi.org/10.5194/acpd-5-1255-2005.
Full textAbstract:
Abstract. In order to investigate the variability of the secondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been applied. The response of the global budget of SOA to temperature and moisture changes as well as to biogenic emission changes over a decade (1984–1993) has been evaluated. The considered emissions of biogenic non-methane volatile organic compounds (VOC) are driven by temperature, light and vegetation. They vary between 756 and 810 TgC y-1 and are therefore about 5.5 times higher than the anthropogenic VOC emissions. All secondary aerosols (sulphuric, nitrates and organics) are computed on-line together with the aerosol associated water. Over the studied decade, the computed natural variations (8%) in the chemical SOA production from biogenic VOC oxidation equal the chemical SOA production from anthropogenic VOC oxidation. This computed variability results from a 7% increase in biogenic VOC emissions combined with 8.5% and 6% increases in the wet and dry deposition of SOA and leads to about 11.5% increase in the SOA burden of biogenic origin. The present study also demonstrates the importance of the hydrological cycle in determining the built up and fate of SOA in the atmosphere. It also reveals the existence of significant positive and negative feedback mechanisms in the atmosphere responsible for the non linear relationship between emissions of biogenic VOC and SOA burden.
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Tsai, I. C., J. P. Chen, P. Y. Lin, W. C. Wang, and I. S. A. Isaksen. "Sulfur cycle and sulfate radiative forcing simulated from a coupled global climate-chemistry model." Atmospheric Chemistry and Physics Discussions 9, no. 5 (2009): 22365–406. http://dx.doi.org/10.5194/acpd-9-22365-2009.
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Abstract. The sulfur cycle and radiative effects of sulfate aerosol on climate are studied with a Global tropospheric Climate-Chemistry Model in which chemistry, radiation and dynamics are fully coupled. Production and removal mechanisms of sulfate are analyzed for the conditions of natural and anthropogenic sulfur emissions. Results show that the 1985 anthropogenic emission doubled the global SO2 and sulfate loadings from its natural value of 0.15 and 0.27 Tg S, respectively. Under natural conditions, the fraction of sulfate produced in-cloud is 87%, and the lifetime of SO2 and sulfate are 1.8 and 4.0 days, respectively; whereas with anthropogenic emissions, changes in in-cloud sulfate production are small, while SO2 and sulfate lifetimes are significant reduced (1.0 and 2.4 days, respectively). The doubling of sulfate results in a direct radiative forcing of −0.32 and −0.14 W m−2 under clear-sky and all-sky conditions, respectively, and a significant first indirect forcing of −1.69 W m−2. The first indirect forcing is sensitive to the relationship between aerosol concentration and cloud droplet number concentration. Two aspects of chemistry-climate interaction are addressed. Firstly, the coupling effects lead to 10% and 2% decreases in sulfate loading, respectively, for the cases of natural and anthropogenic added sulfur emissions. Secondly, only the indirect effect of sulfate aerosols yields significantly stronger signals in changes of near surface temperature and sulfate loading than changes due to intrinsic climate variability, while other responses to the indirect effect and all responses to the direct effect are weak.
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Sun, Jiming, Parisa A. Ariya, Henry G. Leighton, and Man Kong Yau. "Modeling Study of Ice Formation in Warm-Based Precipitating Shallow Cumulus Clouds." Journal of the Atmospheric Sciences 69, no. 11 (2012): 3315–35. http://dx.doi.org/10.1175/jas-d-11-0344.1.
Full textAbstract:
Abstract Observations of large concentrations of ice particles in the dissipating stage of warm-based precipitating shallow cumulus clouds point to the limitations of scientists’ understanding of the physics of such clouds and the possible role of cloud dynamics. The most commonly accepted mechanisms of ice splinter production in the riming process have limitations to properly explain the rapid production of ice bursts. A more detailed description of the temporal and spatial evolution of hydrometeors and their interaction with cloud condensation nuclei and ice nuclei is needed to understand this phenomenon. A cloud model with bin-resolved microphysics can describe the time-dependent evolution of liquid droplets and ice particles and provide insights into how the physics and dynamics and their interaction may result in ice initiation and ice multiplication. The authors developed a 1.5-dimensional nonhydrostatic convective cloud and aerosol interaction model with spectral (bin) microphysics. The number and mass concentrations of aerosols, including ice nuclei and cloud condensation nuclei, were explicitly followed. Since both in situ observations of bioaerosols and laboratory experiments pointed to efficient nucleation capabilities at relative warm temperatures, it was assumed that ice-nucleating bioaerosols are involved in primary ice particle formation in condensation and immersion modes. Results show that bioaerosols can be the source of primary ice pellets, which in turn lead to high ice concentrations.