Low‐Volatility Vapors and New Particle Formation Over the Southern Ocean During the Antarctic Circumnavigation Expedition

During summer, the Southern Ocean is largely unaffected by anthropogenic emissions, which makes this region an ideal place to investigate marine natural aerosol sources and processes. A better understanding of natural aerosol is key to constrain the preindustrial aerosol state and reduce the aerosol radiative forcing uncertainty in global climate models. We report the concentrations of gaseous sulfuric acid, iodic acid, and methanesulfonic acid (MSA) together with a characterization of new particle formation (NPF) events over a large stretch of the Southern Ocean. Measurements were conducted on board the Russian icebreaker Akademik Tryoshnikov from January to March 2017. Iodic acid is characterized by a particular diurnal cycle with reduced concentration around noon, suggesting a lower formation yield when solar irradiance is higher. Gaseous MSA does not have a diurnal cycle and measured concentrations in gas and condensed phase are compatible with this species being primarily produced via heterogeneous oxidation of dimethyl sulfide and subsequent partitioning into the gas phase. We also found that NPF in the boundary layer is mainly driven by sulfuric acid but it occurred very rarely over the vast geographical area probed and did not contribute to the cloud condensation nuclei budget in a directly observable manner. Despite the near absence of NPF events in the boundary layer, Aitken mode particles were frequently measured, supporting the hypothesis of a free tropospheric source. Iodic acid and MSA were not found to participate in nucleation, however, MSA may contribute to aerosol growth via heterogeneous formation in the aqueous phase.

Aerosol Transport and Distribution

Quentin Bourgeois

The fourth report of the Intergovernmental Panel of Climate Change (IPCC) unambiguously indicates that the climate is changing. Climate change is induced by changes in atmospheric abundances of greenhouse gases and aerosols, solar radiation and land surface properties, which all alter the radiative balance of the Earth. Among them, greenhouse gases and aerosols are likely the compounds affecting the climate the most. While greenhouse gases warm the Earth, aerosols influence its radiative balance by scattering and absorbing solar radiation (the direct effect), and by modifying cloud amount and properties (the indirect effect). The radiative forcing of aerosols on the climate is however the less understood among the various forcings currently considered in the IPCC assessment. This is likely related to the lack of comprehensive and accurate observations of aerosols (and in particular of their vertical distribution) which thus makes global aerosol models difficult to constrain. Recent model intercomparisons have indicated that different assumptions regarding aerosol emissions, formation and growing properties, and removal processes generate large diversities within models. These large diversities are found in particular in the Arctic and the upper troposphere region where extreme surrounding conditions take place, limiting instrument sensitivity and accuracy. The objectives of this thesis are to better quantify the processes driving the aerosol distribution in regions where the uncertainties are the largest, including the Arctic region and the upper troposphere, and to assess the quality of CALIOP observations. For this purpose, we used the fully coupled global climate-aerosol-chemistry ECHAM5-HAMMOZ model conjointly with a suite of remote sensing observations including the CALIOP satellite instrument, which provides the vertical distribution of aerosols. The model predicts the size distribution and composition of aerosols as well as the number concentration of cloud droplets and ice crystals. We first investigated the processes that drive the transport of soluble and insoluble compounds toward the Arctic in the ECHAM5-HAMMOZ model. Recognizing that scavenging processes may be an issue in global models, we "re-visited" their properties in ECHAM5-HAMMOZ. We find that the model better reproduces the aerosol vertical distribution in the northern mid- and high-latitudes, especially in the free troposphere, by decreasing aerosol scavenging coefficients in the model. Using smaller aerosol scavenging coefficients results in an increase of aerosol burden and lifetime, especially in the Arctic. In addition, the Arctic haze phenomenon is better represented in the simulation using decreased aerosol scavenging coefficients. The relative contributions of different processes governing the transport of aerosols from the midlatitudes toward the Arctic together with the relative contributions of different geopolitical source regions were then quantified. We find that Europe and Siberia contribute the most to the Arctic pollution even though Asian anthropogenic emissions are much larger. The model suggests that BC emitted in Siberia and Europe is ten times more efficiently deposited onto the Arctic than BC emitted in Asia. We next investigated an aerosol layer that forms in the vicinity of the tropical tropopause layer (TTL) over the southern Asian and Indian Ocean region. Aerosols in this layer are observed with the CALIOP instrument even though ice clouds partly mask their signal. The aerosol layer follows the Inter Tropical Convergence Zone (ITCZ), which indicates that these aerosols are likely transported during convective processes. The ECHAM5.5-HAM2 model reproduces such an aerosol layer in the TTL over the same region but clearly overestimates CALIOP data. Model results suggest that aerosols in this layer are mostly sulfate particles transported during convective processes and originating from natural sources. The shortwave forcing of this aerosol layer is estimated. Finally, we assessed the accuracy of aerosol extinction retrievals from the CALIOP satellite instrument by comparing them with remote sensing observations such as AERONET, MODIS and MISR over the last four years. Overall, standard CALIOP products underestimate by 50% observed aerosol extinctions. However, this comparison is substantially improved by screening CALIOP data. The comparison of the CALIOP screened product with the ECHAM5.5-HAM2 model shows large disparities in model results. The model reproduces quite well the observed interannual variability and vertical distribution of aerosols in Europe and North Africa while it underestimates them in America and Asia. This is likely due to an underestimate of dust and anthropogenic emissions in North America and Asia.

EPFL2012

Iodic acid, sulfuric acid and methanesulfonic acid collected during the Arctic Ocean 2018 expedition

Andrea Baccarini, Julia Schmale

Measurements of iodic acid, sulfuric acid and methanesulfonic acid concentration in the gas phase obtained with a nitrate chemical ionization mass spectrometer (we used an APi-TOF mass spectrometer produced by Tofwerk AG coupled with a Chemical ionization inlet A70 produced by Airmodus). These three species are of fundamental importance in the atmosphere because they participate in both new particle formation and growth affecting the Earth radiative balance and cloud properties. Iodic acid is mainly produced from the oxidation of the iodine molecule whereas both sulfuric and methanesulfonic acid are produced from the oxidation of dimethyl sulfide. Measurements were performed on the 4th deck of icebreaker Oden during August and September 2018 along the track of the expedition. Concentrations are reported as molecules per cubic centimeter in ten minutes averages.

2020

Overview of the Antarctic Circumnavigation Expedition: Study of Preindustrial-like Aerosols and Their Climate Effects (ACE-SPACE)

Andrea Baccarini, Sebastian Johannes Heinz-Josef Landwehr, Robin Lewis Modini, Julia Schmale

Uncertainty in radiative forcing caused by aerosol–cloud interactions is about twice as large as for CO2 and remains the least well understood anthropogenic contribution to climate change. A major cause of uncertainty is the poorly quantified state of aerosols in the pristine preindustrial atmosphere, which defines the baseline against which anthropogenic effects are calculated. The Southern Ocean is one of the few remaining near-pristine aerosol environments on Earth, but there are very few measurements to help evaluate models. The Antarctic Circumnavigation Expedition: Study of Preindustrial-like Aerosols and their Climate Effects (ACE-SPACE) took place between December 2016 and March 2017 and covered the entire Southern Ocean region (Indian, Pacific, and Atlantic Oceans; length of ship track >33,000 km) including previously unexplored areas. In situ measurements covered aerosol characteristics [e.g., chemical composition, size distributions, and cloud condensation nuclei (CCN) number concentrations], trace gases, and meteorological variables. Remote sensing observations of cloud properties, the physical and microbial ocean state, and back trajectory analyses are used to interpret the in situ data. The contribution of sea spray to CCN in the westerly wind belt can be larger than 50%. The abundance of methanesulfonic acid indicates local and regional microbial influence on CCN abundance in Antarctic coastal waters and in the open ocean. We use the in situ data to evaluate simulated CCN concentrations from a global aerosol model. The extensive, available ACE-SPACE dataset (https://zenodo.org/communities/spi-ace?page=1&size=20) provides an unprecedented opportunity to evaluate models and to reduce the uncertainty in radiative forcing associated with the natural processes of aerosol emission, formation, transport, and processing occurring over the pristine Southern Ocean.