Multi-model study of mercury dispersion in the atmosphere : Atmospheric processes and model evaluation

Current understanding of mercury (Hg) behavior in the atmosphere contains significant gaps. Some key characteristics of Hg processes, including anthropogenic and geogenic emissions, atmospheric chemistry, and air-surface exchange, are still poorly known. This study provides a complex analysis of processes governing Hg fate in the atmosphere involving both measured data from ground-based sites and simulation results from chemical transport models. A variety of long-term measurements of gaseous elemental Hg (GEM) and reactive Hg (RM) concentration as well as Hg wet deposition flux have been compiled from different global and regional monitoring networks. Four contemporary global-scale transport models for Hg were used, both in their state-of-the-art configurations and for a number of numerical experiments to evaluate particular processes. Results of the model simulations were evaluated against measurements. As follows from the analysis, the interhemispheric GEM gradient is largely formed by the prevailing spatial distribution of anthropogenic emissions in the Northern Hemisphere. The contributions of natural and secondary emissions enhance the south-to-north gradient, but their effect is less significant. Atmospheric chemistry has a limited effect on the spatial distribution and temporal variation of GEM concentration in surface air. In contrast, RM air concentration and wet deposition are largely defined by oxidation chemistry. The Br oxidation mechanism can reproduce successfully the observed seasonal variation of the RM=GEM ratio in the near-surface layer, but it predicts a wet deposition maximum in spring instead of in summer as observed at monitoring sites in North America and Europe. Model runs with OH chemistry correctly simulate both the periods of maximum and minimum values and the amplitude of observed seasonal variation but shift the maximum RM=GEM ratios from spring to summer. O3 chemistry does not predict significant seasonal variation of Hg oxidation. Hence, the performance of the Hg oxidation mechanisms under study differs in the extent to which they can reproduce the various observed parameters. This variation implies possibility of more complex chemistry and multiple Hg oxidation pathways occurring concurrently in various parts of the atmosphere

Marine organic matter in the remote environment of the Cape Verde islands-an introduction and overview to the MarParCloud campaign

The project MarParCloud (Marine biological production, organic aerosol Particles and marine Clouds: a process chain) aims to improve our understanding of the genesis, modification and impact of marine organic matter (OM) from its biological production, to its export to marine aerosol particles and, finally, to its ability to act as ice-nucleating particles (INPs) and cloud condensation nuclei (CCN). A field campaign at the Cape Verde Atmospheric Observatory (CVAO) in the tropics in September-October 2017 formed the core of this project that was jointly performed with the project MARSU (MARine atmospheric Science Unravelled). A suite of chemical, physical, biological and meteorological techniques was applied, and comprehensive measurements of bulk water, the sea surface microlayer (SML), cloud water and ambient aerosol particles collected at a ground-based and a mountain station took place. Key variables comprised the chemical characterization of the atmospherically relevant OM components in the ocean and the atmosphere as well as measurements of INPs and CCN. Moreover, bacterial cell counts, mercury species and trace gases were analyzed. To interpret the results, the measurements were accompanied by various auxiliary parameters such as air mass back-trajectory analysis, vertical atmospheric profile analysis, cloud observations and pigment measurements in seawater. Additional modeling studies supported the experimental analysis. During the campaign, the CVAO exhibited marine air masses with low and partly moderate dust influences. The marine boundary layer was well mixed as indicated by an almost uniform particle number size distribution within the boundary layer. Lipid biomarkers were present in the aerosol particles in typical concentrations of marine background conditions. Accumulation-and coarse-mode particles served as CCN and were efficiently transferred to the cloud water. The ascent of ocean-derived compounds, such as sea salt and sugar-like compounds, to the cloud level, as derived from chemical analysis and atmospheric transfer modeling results, denotes an influence of marine emissions on cloud formation. Organic nitrogen compounds (free amino acids) were enriched by several orders of magnitude in submicron aerosol particles and in cloud water compared to seawater. However, INP measurements also indicated a significant contribution of other non-marine sources to the local INP concentration, as (biologically active) INPs were mainly present in supermicron aerosol particles that are not suggested to undergo strong enrichment during ocean-atmosphere transfer. In addition, the number of CCN at the supersaturation of 0.30 % was about 2.5 times higher during dust periods compared to marine periods. Lipids, sugar-like compounds, UV-absorbing (UV: ultraviolet) humic-like substances and low-molecularweight neutral components were important organic compounds in the seawater, and highly surface-active lipids were enriched within the SML. The selective enrichment of specific organic compounds in the SML needs to be studied in further detail and implemented in an OM source function for emission modeling to better understand transfer patterns, the mechanisms of marine OM transformation in the atmosphere and the role of additional sources. In summary, when looking at particulate mass, we see oceanic compounds transferred to the atmospheric aerosol and to the cloud level, while from a perspective of particle number concentrations, sea spray aerosol (i.e., primary marine aerosol) contributions to both CCN and INPs are rather limited. © Author(s) 2020

Marine organic matter in the remote environment of the Cape Verde islands – an introduction and overview to the MarParCloud campaign

The project MarParCloud (Marine biological production, organic aerosol Particles and marine Clouds: a process chain) aims to improve our understanding of the genesis, modification and impact of marine organic matter (OM) from its biological production, to its export to marine aerosol particles and, finally, to its ability to act as ice-nucleating particles (INPs) and cloud condensation nuclei (CCN). A field campaign at the Cape Verde Atmospheric Observatory (CVAO) in the tropics in September–October 2017 formed the core of this project that was jointly performed with the project MARSU (MARine atmospheric Science Unravelled). A suite of chemical, physical, biological and meteorological techniques was applied, and comprehensive measurements of bulk water, the sea surface microlayer (SML), cloud water and ambient aerosol particles collected at a ground-based and a mountain station took place. Key variables comprised the chemical characterization of the atmospherically relevant OM components in the ocean and the atmosphere as well as measurements of INPs and CCN. Moreover, bacterial cell counts, mercury species and trace gases were analyzed. To interpret the results, the measurements were accompanied by various auxiliary parameters such as air mass back-trajectory analysis, vertical atmospheric profile analysis, cloud observations and pigment measurements in seawater. Additional modeling studies supported the experimental analysis. During the campaign, the CVAO exhibited marine air masses with low and partly moderate dust influences. The marine boundary layer was well mixed as indicated by an almost uniform particle number size distribution within the boundary layer. Lipid biomarkers were present in the aerosol particles in typical concentrations of marine background conditions. Accumulation- and coarse-mode particles served as CCN and were efficiently transferred to the cloud water. The ascent of ocean-derived compounds, such as sea salt and sugar-like compounds, to the cloud level, as derived from chemical analysis and atmospheric transfer modeling results, denotes an influence of marine emissions on cloud formation. Organic nitrogen compounds (free amino acids) were enriched by several orders of magnitude in submicron aerosol particles and in cloud water compared to seawater. However, INP measurements also indicated a significant contribution of other non-marine sources to the local INP concentration, as (biologically active) INPs were mainly present in supermicron aerosol particles that are not suggested to undergo strong enrichment during ocean–atmosphere transfer. In addition, the number of CCN at the supersaturation of 0.30 % was about 2.5 times higher during dust periods compared to marine periods. Lipids, sugar-like compounds, UV-absorbing (UV: ultraviolet) humic-like substances and low-molecular-weight neutral components were important organic compounds in the seawater, and highly surface-active lipids were enriched within the SML. The selective enrichment of specific organic compounds in the SML needs to be studied in further detail and implemented in an OM source function for emission modeling to better understand transfer patterns, the mechanisms of marine OM transformation in the atmosphere and the role of additional sources. In summary, when looking at particulate mass, we see oceanic compounds transferred to the atmospheric aerosol and to the cloud level, while from a perspective of particle number concentrations, sea spray aerosol (i.e., primary marine aerosol) contributions to both CCN and INPs are rather limited

Extensive field evidence for the release of HONO from the photolysis of nitrate aerosols

Particulate nitrate ([Formula: see text]) has long been considered a permanent sink for NO(x) (NO and NO(2)), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of [Formula: see text] can recycle HONO and NO(x) back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in “renoxification” photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of [Formula: see text] , thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O(3) in both polluted and clean environments

Volatile organic carbon (VOC) chemistry in remote atmospheres

EThOS - Electronic Theses Online ServiceGBUnited Kingdo