scholarly journals Sensitivities of sulfate aerosol formation and oxidation pathways on the chemical mechanism employed in simulations

2012 ◽  
Vol 12 (18) ◽  
pp. 8567-8574 ◽  
Author(s):  
A. F. Stein ◽  
R. D. Saylor
Keyword(s):  
Sulfur Dioxide ◽  
Radiative Forcing ◽  
Chemical Mechanism ◽  
Test Model ◽  
Aerosol Formation ◽  
Radiative Balance ◽  
Chemical Mechanisms ◽  
Photochemical Model ◽  
Sulfate Formation ◽  
Primary Emissions

Abstract. The processes of aerosol sulfate formation are vital components in the scientific understanding of perturbations of earth's radiative balance via aerosol direct and indirect effects. In this work, an analysis of the influence of changes in oxidant levels and sulfur dioxide oxidation pathways was performed to study the underlying pathways for sulfate formation. Sensitivities of this constituent were calculated from a series of photochemical model simulations with varying rates of NOx and VOC emissions to produce variations in oxidant abundances using a photochemical model (CMAQ) that covers the eastern US for part of the ICARTT 2004 campaign. Three different chemical mechanisms (CBIV, CB05, and SAPRC99) were used to test model responses to changes in NOx and VOC concentrations. Comparison of modeled results and measurements demonstrates that the simulations with all three chemical mechanisms capture the levels of sulfate reasonably well. However, the three mechanisms are shown to have significantly different responses in sulfate formation when the emissions of NOx and/or VOC are altered, reflecting different photochemical regimes under which the formation of sulfate occurs. Also, an analysis of the oxidation pathways that contribute to sulfur dioxide conversion to sulfate reveals substantial differences in the importance of the various pathways among the three chemical mechanisms. These findings suggest that estimations of the influence that future changes in primary emissions or other changes which perturb SO2 oxidants have on sulfate abundances, and on its direct and indirect radiative forcing effects, may be dependent on the chemical mechanism employed in the model analysis.

scholarly journals Sensitivities of sulfate aerosol formation and oxidation pathways on the chemical mechanism employed in simulations

2012 ◽  
Vol 12 (3) ◽  
pp. 8169-8182 ◽  
Author(s):  
A. F. Stein ◽  
R. D. Saylor
Keyword(s):  
Sulfur Dioxide ◽  
Radiative Forcing ◽  
Chemical Mechanism ◽  
Test Model ◽  
Aerosol Formation ◽  
Radiative Balance ◽  
Chemical Mechanisms ◽  
Photochemical Model ◽  
Sulfate Formation ◽  
Primary Emissions

Abstract. The processes of aerosol sulfate formation are vital components in the scientific understanding of perturbations of earth's radiative balance via aerosol direct and indirect effects. In this work, an analysis of the influence of changes in oxidant levels and sulfur dioxide oxidation pathways was performed to study the underlying pathways for sulfate formation. Sensitivities of this constituent were calculated from a series of photochemical model simulations with varying rates of NOx and VOC emissions to produce variations in oxidant abundances using a photochemical model (CMAQ) that covers the Eastern US for the ICARTT 2004 campaign. Three different chemical mechanisms (CBIV, CB05, and SAPRC99) were used to test model responses to changes in NOx and VOC levels. Comparison of modeled results and measurements demonstrates that the simulations with all three chemical mechanisms capture the levels of sulfate reasonably well. However, the three mechanisms are shown to have significantly different responses in sulfate formation when the emissions of NOx and/or VOC are altered, reflecting different photochemical regimes under which the formation of sulfate occurs. Also, an analysis of the oxidation pathways that contribute to sulfur dioxide conversion to sulfate reveals substantial differences in the importance of the various pathways among the three chemical mechanisms. These findings suggest that estimations of the influence that future changes in primary emissions or other changes which perturb SO2 oxidants have on sulfate abundances, and on its direct and indirect radiative forcing effects, may be dependent on the chemical mechanism employed in the model analysis.

scholarly journals Reviews and syntheses: Marine biogenic aerosols and the ecophysiology of coral reefs

2019 ◽  
Author(s):  
Rebecca Jackson ◽  
Albert Gabric ◽  
Roger Cropp ◽  
Matthew Woodhouse
Keyword(s):  
Climate Change ◽  
Coral Reefs ◽  
Social Services ◽  
Radiative Forcing ◽  
Marine Boundary Layer ◽  
Global Climate ◽  
Aerosol Formation ◽  
Radiative Balance ◽  
Cloud Properties

Abstract. Coral reefs are being threatened by global climate change, with ocean warming and acidification, compounded by declining water quality in many coastal systems, adversely affecting coral health and cover. This is of great concern as coral reefs provide numerous ecosystem, economic and social services. Corals are also recognized as being amongst the strongest individual sources of natural atmospheric sulfur, through stress-induced emissions of dimethylsulfide (DMS). In the clean marine boundary layer, biogenic sulfates contribute to new aerosol formation and the growth of existing particles, with important implications for the radiative balance. Evidence suggests that DMS is not only directly involved in the coral stress response, alleviating oxidative stress, but may create an ocean thermostat which suppresses sea surface temperature (SST) through changes to aerosol and cloud properties. This review provides a summary of the current major threats facing coral reefs and describes the role of dimethylated sulfur compounds in coral physiology and climate. The role of coral reefs as a source of climatically important compounds is an emerging topic of research however, the window of opportunity to understand the complex biogeophysical processes involved is closing with ongoing degradation of the world's coral reefs. The greatest uncertainty in our estimates of radiative forcing and climate change are derived from natural aerosol sources, such as marine DMS, which constitutes the largest flux of oceanic reduced sulfur to the atmosphere. Gaining a better understanding of the role of coral reef DMS emissions is crucial to predicting the future climate of our planet.

scholarly journals The sensitivity of the oxygen isotopes of ice core sulfate to changing oxidant concentrations since the preindustrial

2010 ◽  
Vol 10 (8) ◽  
pp. 20607-20623 ◽  
Author(s):  
E. D. Sofen ◽  
B. Alexander ◽  
S. A. Kunasek
Keyword(s):  
Oxygen Isotopes ◽  
Radiative Forcing ◽  
Transport Model ◽  
Ice Core ◽  
Ice Cores ◽  
The Arctic ◽  
Aerosol Formation ◽  
Chemical Transport Model ◽  
Sensitivity Studies ◽  
Sulfate Formation

Abstract. Changes in tropospheric oxidant concentrations since preindustrial times have implications for the ozone radiative forcing, lifetimes of reduced trace gases, aerosol formation, and human health but are highly uncertain. Measurements of the triple oxygen isotopes of sulfate in ice cores (described by Δ17OSO4 = δ17O − 0.52 × δ18O) provide one of the few constraints on paleo-oxidants. We use the GEOS-Chem global atmospheric chemical transport model to simulate changes in oxidant concentrations and the Δ17OSO4 between 1850 and 1990 to assess the sensitivity of Δ17OSO4 measurements in Greenland and Antarctic ice cores to changing tropospheric oxidant concentrations. The model indicates a 42% increase in the concentration of global mean tropospheric O3, a 10% decrease in OH, and a 58% increase in H2O2 between the preindustrial and present. Modeled Δ17OSO4 is consistent with measurements from ice core and aerosol samples. Model results indicate that the observed decrease in the Arctic Δ17OSO4 in spite of increasing O3 is due to the combined effects of increased sulfate formation by O2 catalyzed by anthropogenic transition metals and increased cloud water acidity. In Antarctica, the Δ17OSO4 is sensitive to relative changes of oxidant concentrations, but in a nonlinear fashion. Sensitivity studies explore the uncertainties in preindustrial emissions of oxidant precursors.

scholarly journals Influence of isoprene chemical mechanism on modelled changes in tropospheric ozone due to climate and land use over the 21st century

2015 ◽  
Vol 15 (9) ◽  
pp. 5123-5143 ◽  
Author(s):  
O. J. Squire ◽  
A. T. Archibald ◽  
P. T. Griffiths ◽  
M. E. Jenkin ◽  
D. Smith ◽  
...  
Keyword(s):  
Land Use ◽  
Tropospheric Ozone ◽  
Global Model ◽  
Box Model ◽  
Chemical Mechanism ◽  
Anthropogenic Activity ◽  
Aerosol Formation ◽  
Chemical Mechanisms ◽  
Reservoir Species ◽  
Isoprene Oxidation

Abstract. Isoprene is a~precursor to tropospheric ozone, a key pollutant and greenhouse gas. Anthropogenic activity over the coming century is likely to cause large changes in atmospheric CO2 levels, climate and land use, all of which will alter the global vegetation distribution leading to changes in isoprene emissions. Previous studies have used global chemistry–climate models to assess how possible changes in climate and land use could affect isoprene emissions and hence tropospheric ozone. The chemistry of isoprene oxidation, which can alter the concentration of ozone, is highly complex, therefore it must be parameterised in these models. In this work, we compare the effect of four different reduced isoprene chemical mechanisms, all currently used in Earth system models, on tropospheric ozone. Using a box model we compare ozone in these reduced schemes to that in a more explicit scheme (the Master Chemical Mechanism) over a range of NOx and isoprene emissions, through the use of O3 isopleths. We find that there is some variability, especially at high isoprene emissions, caused by differences in isoprene-derived NOx reservoir species. A global model is then used to examine how the different reduced schemes respond to potential future changes in climate, isoprene emissions, anthropogenic emissions and land use change. We find that, particularly in isoprene-rich regions, the response of the schemes varies considerably. The wide-ranging response is due to differences in the model descriptions of the peroxy radical chemistry, particularly their relative rates of reaction towards NO, leading to ozone formation, or HO2, leading to termination. Also important is the yield of isoprene nitrates and peroxyacyl nitrate precursors from isoprene oxidation. Those schemes that produce less of these NOx reservoir species, tend to produce more ozone locally and less away from the source region. We also note changes in other key oxidants such as NO3 and OH (due to the inclusion of additional isoprene-derived HOx recycling pathways). These have implications for secondary organic aerosol formation, as does the inclusion of an epoxide formation pathway in one of the mechanisms. By combining the emissions and O3 data from all of the global model integrations, we are able to construct isopleth plots comparable to those from the box model analysis. We find that the global and box model isopleths show good qualitative agreement, suggesting that comparing chemical mechanisms with a box model in this framework is a useful tool for assessing mechanistic performance in complex global models. We conclude that as the choice of reduced isoprene mechanism may alter both the magnitude and sign of the ozone response, how isoprene chemistry is parameterised in perturbation experiments such as these is a crucially important consideration. More measurements and laboratory studies are needed to validate these reduced mechanisms especially under high-volatile-organic-compound, low-NOx conditions.

scholarly journals Possible heterogeneous hydroxymethanesulfonate (HMS) chemistry in northern China winter haze and implications for rapid sulfate formation

2018 ◽  
Author(s):  
Shaojie Song ◽  
Meng Gao ◽  
Weiqi Xu ◽  
Yele Sun ◽  
Douglas R. Worsnop ◽  
...  
Keyword(s):  
Field Measurements ◽  
Northern China ◽  
Chemical Mechanism ◽  
Aerosol Formation ◽  
Sulfate Production ◽  
Aerosol Mass ◽  
Show Evidence ◽  
Sulfate Formation ◽  
Gaseous Precursor ◽  
Haze Formation

Abstract. 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. In addition, HMS in the presence of hydroxyl radicals can trigger rapid sulfate production in aerosol water. 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 calls for more research on sources and on the chemistry of formaldehyde in northern China winter.

scholarly journals Dimethylsulfide (DMS), marine biogenic aerosols and the ecophysiology of coral reefs

2020 ◽  
Vol 17 (8) ◽  
pp. 2181-2204
Author(s):  
Rebecca L. Jackson ◽  
Albert J. Gabric ◽  
Roger Cropp ◽  
Matthew T. Woodhouse
Keyword(s):  
Climate Change ◽  
Coral Reefs ◽  
Social Services ◽  
Radiative Forcing ◽  
Marine Boundary Layer ◽  
Global Climate ◽  
Aerosol Formation ◽  
Local Climate ◽  
Radiative Balance

Abstract. Global climate change and the impacts of ocean warming, ocean acidification and declining water quality are adversely affecting coral-reef ecosystems. This is of great concern, as coral reefs provide numerous ecosystem, economic and social services. Corals are also recognised as being amongst the strongest individual sources of natural atmospheric sulfur, through stress-induced emissions of dimethylsulfide (DMS). In the clean marine boundary layer, biogenic sulfates contribute to new aerosol formation and the growth of existing particles, with important implications for the radiative balance over the ocean. Evidence suggests that DMS is not only directly involved in the coral stress response, alleviating oxidative stress, but also may create an “ocean thermostat” which suppresses sea surface temperature through changes to aerosol and cloud properties. This review provides a summary of the current major threats facing coral reefs and describes the role of dimethylated sulfur compounds in coral ecophysiology and the potential influence on climate. The role of coral reefs as a source of climatically important compounds is an emerging topic of research; however the window of opportunity to understand the complex biogeophysical processes involved is closing with ongoing degradation of the world's coral reefs. The greatest uncertainty in our estimates of radiative forcing and climate change is derived from natural aerosol sources, such as marine DMS, which constitute the largest flux of oceanic reduced sulfur to the atmosphere. Given the increasing frequency of coral bleaching events, it is crucial that we gain a better understanding of the role of DMS in local climate of coral reefs.

Automatic generation from MCM of reduced mechanisms to study the formation and evolution of SOA in 3D air quality models 

2021 ◽  
Author(s):  
Zhizhao Wang ◽  
Florian Couvidat ◽  
Karine Sartelet
Keyword(s):  
Molecular Structure ◽  
Air Quality ◽  
Large Scale ◽  
Automatic Generation ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Aerosol Formation ◽  
Quality Models ◽  
Chemical Mechanisms ◽  
Formation And Evolution

<p>As secondary organic aerosols (SOA) largely contribute to the mass of particles and may strongly affect health, it is essential to represent them as accurately as possible in air quality models (AQM). Their formation and aging involve multi-generation oxidations of numerous volatile organic compounds (VOC) combined with gas-particle partitioning processes.<br> <br>Tracking the non-linear relationship between VOC emissions and aerosol formation demands comprehensive chemical mechanisms, which take into account the whole complexity of the SOA precursor oxidation to simulate aerosols under various conditions.<br>However, the use of explicit gas-phase chemical mechanism (e.g., MCM, GECKO-A) or molecular structure-limited parameterization (e.g., VBS, SOM, FGOM) could be problematical in large-scale SOA modeling, as the former is overwhelmingly computational expensive while the latter loses tracks of VOC oxidation products after few generations and specific properties relying on aerosol formation.<br> <br>Consequently, we have developed semi-explicit SOA chemical mechanisms designed to model the SOA formation and evolution in 3D AQM. These mechanisms are reduced based on simulations of the near-explicit master chemical mechanism (MCM) performed under various conditions representative of ambient conditions and different lumping strategies. The new mechanisms integrate the crucial SOA species/reactions with different mechanism complexities. The mechanisms, therefore, preserve the complexity of the oxidation chemistry (dependence on NOx of the SOA formation, the influence of radical concentrations, humidity, photolysis, etc..) as well as the molecular composition of the organic aerosol. The mechanisms are implemented in a novel 0D aerosol model SSH-aerosol, which can use the molecular structure of lumped compounds to estimate the influence of non-ideality on SOA formation.</p><p>The current application has been conducted on the MCM degradation scheme of beta-caryophyllene (C<sub>15</sub>H<sub>24</sub>), the most representative sesquiterpene. A reduction of the average 90% CPU time and up to 92% number of S/IVOCs species has been achieved compared to the original MCM mechanism.</p>

scholarly journals Impacts of primary emissions and secondary aerosol formation on air pollution in an urban area of China during the COVID-19 lockdown

2021 ◽  
Vol 150 ◽  
pp. 106426
Author(s):  
Jie Tian ◽  
Qiyuan Wang ◽  
Yong Zhang ◽  
Mengyuan Yan ◽  
Huikun Liu ◽  
...  
Keyword(s):  
Air Pollution ◽  
Urban Area ◽  
Aerosol Formation ◽  
Secondary Aerosol ◽  
Primary Emissions

scholarly journals Decadal increase in Arctic dimethylsulfide emission

2019 ◽  
Vol 116 (39) ◽  
pp. 19311-19317 ◽  
Author(s):  
Martí Galí ◽  
Emmanuel Devred ◽  
Marcel Babin ◽  
Maurice Levasseur
Keyword(s):  
Sea Ice ◽  
Radiative Forcing ◽  
Positive Trend ◽  
Aerosol Formation ◽  
Atmospheric Measurements ◽  
Sea Ice Extent ◽  
Phytoplankton Productivity ◽  
Physical Forcing ◽  
Ice Retreat ◽  
Aerosol Cloud Interactions

Dimethylsulfide (DMS), a gas produced by marine microbial food webs, promotes aerosol formation in pristine atmospheres, altering cloud radiative forcing and precipitation. Recent studies suggest that DMS controls aerosol formation in the summertime Arctic atmosphere and call for an assessment of pan-Arctic DMS emission (EDMS) in a context of dramatic ecosystem changes. Using a remote sensing algorithm, we show that summertime EDMS from ice-free waters increased at a mean rate of 13.3 ± 6.7 Gg S decade−1 (∼33% decade−1) north of 70°N between 1998 and 2016. This trend, mostly explained by the reduction in sea-ice extent, is consistent with independent atmospheric measurements showing an increasing trend of methane sulfonic acid, a DMS oxidation product. Extrapolation to an ice-free Arctic summer could imply a 2.4-fold (±1.2) increase in EDMS compared to present emission. However, unexpected regime shifts in Arctic geo- and ecosystems could result in future EDMS departure from the predicted range. Superimposed on the positive trend, EDMS shows substantial interannual changes and nonmonotonic multiyear trends, reflecting the interplay between physical forcing, ice retreat patterns, and phytoplankton productivity. Our results provide key constraints to determine whether increasing marine sulfur emissions, and resulting aerosol–cloud interactions, will moderate or accelerate Arctic warming in the context of sea-ice retreat and increasing low-level cloud cover.

scholarly journals Enhanced SOA formation from mixed anthropogenic and biogenic emissions during the CARES campaign

2013 ◽  
Vol 13 (4) ◽  
pp. 2091-2113 ◽  
Author(s):  
J. E. Shilling ◽  
R. A. Zaveri ◽  
J. D. Fast ◽  
L. Kleinman ◽  
M. L. Alexander ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Organic Aerosol ◽  
Proton Transfer Reaction ◽  
Chemical Mechanism ◽  
Biogenic Emissions ◽  
Anthropogenic Emissions ◽  
Radiation Balance ◽  
Particle Phase ◽  
Aerosol Formation ◽  
Research Aircraft

Abstract. The CARES campaign was conducted during June, 2010 in the vicinity of Sacramento, California to study aerosol formation and aging in a region where anthropogenic and biogenic emissions regularly mix. Here, we describe measurements from an Aerodyne High Resolution Aerosol Mass Spectrometer (AMS), an Ionicon Proton Transfer Reaction Mass Spectrometer (PTR-MS), and trace gas detectors (CO, NO, NOx) deployed on the G-1 research aircraft to investigate ambient gas- and particle-phase chemical composition. AMS measurements showed that the particle phase is dominated by organic aerosol (OA) (85% on average) with smaller concentrations of sulfate (5%), nitrate (6%) and ammonium (3%) observed. PTR-MS data showed that isoprene dominated the biogenic volatile organic compound concentrations (BVOCs), with monoterpene concentrations generally below the detection limit. Using two different metrics, median OA concentrations and the slope of plots of OA vs. CO concentrations (i.e., ΔOA/ΔCO), we contrast organic aerosol evolution on flight days with different prevailing meteorological conditions to elucidate the role of anthropogenic and biogenic emissions on OA formation. Airmasses influenced predominantly by biogenic emissions had median OA concentrations of 2.2 μg m−3 and near zero ΔOA/ΔCO. Those influenced predominantly by anthropogenic emissions had median OA concentrations of 4.7 μg m−3 and ΔOA/ΔCO ratios of 35–44 μg m−3 ppmv. But, when biogenic and anthropogenic emissions mixed, OA levels were enhanced, with median OA concentrations of 11.4 μg m−3 and ΔOA/ΔCO ratios of 77–157 μg m−3 ppmv. Taken together, our observations show that production of OA was enhanced when anthropogenic emissions from Sacramento mixed with isoprene-rich air from the foothills. After considering several anthropogenic/biogenic interaction mechanisms, we conclude that NOx concentrations play a strong role in enhancing SOA formation from isoprene, though the chemical mechanism for the enhancement remains unclear. If these observations are found to be robust in other seasons and in areas outside of Sacramento, regional and global aerosol modules will need to incorporate more complex representations of NOx-dependent SOA mechanisms and yields into their algorithms. Ultimately, accurately predicting OA mass concentrations and their effect on radiation balance will require a mechanistically-based treatment of the interactions of biogenic and anthropogenic emissions.

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