Salinity and SO4 and Br enrichment of seawater and frost flowers near Barrow, Alaska

Frost flowers have been proposed to be the major source of sea-salt aerosol to the atmosphere during polar winter and a source of reactive bromine during polar springtime. However little is known about their bulk chemical composition or microstructure, two important factors that may affect their ability to produce aerosols and provide chemically reactive surfaces for exchange with the atmosphere. Therefore, we chemically analyzed 28 samples of frost flowers and parts of frost flowers collected from sea ice off of northern Alaska. Our results support the proposed mechanism for frost flower growth that suggests water vapor deposition forms an ice skeleton that wicks brine present on newly grown sea ice. We measured a high variability in sulfate enrichment factors (with respect to chloride) in frost flowers and seawater from the vicinity of freezing sea ice. The variability in sulfate indicates that mirabilite precipitation (Na2SO4 x 10 H2O) occurs during frost flower growth. Brine wicked up by frost flowers is typically sulfate depleted, in agreement with the theory that frost flowers are related to sulfate-depleted aerosol observed in Antarctica. The bromide enrichment factors we measured in frost flowers are within error of seawater composition, constraining the direct reactive losses of bromide from frost flowers. We combined the chemical composition measurements with temperature observations to create a conceptual model of possible scenarios for frost flower microstructure development.

Chemical concentrations and fluxes from EPICA ice cores EDML and EDC

Continuous sea salt and mineral dust aerosol records have been studied on the two EPICA (European Project for Ice Coring in Antarctica) deep ice cores. The joint use of these records from opposite sides of the East Antarctic plateau allows for an estimate of changes in dust transport and emission intensity as well as for the identification of regional differences in the sea salt aerosol source. The mineral dust flux records at both sites show a strong coherency over the last 150 kyr related to dust emission changes in the glacial Patagonian dust source with three times higher dust fluxes in the Atlantic compared to the Indian Ocean sector of the Southern Ocean (SO). Using a simple conceptual transport model this indicates that transport can explain only 40% of the atmospheric dust concentration changes in Antarctica, while factor 5-10 changes occurred. Accordingly, the main cause for the strong glacial dust flux changes in Antarctica must lie in environmental changes in Patagonia. Dust emissions, hence environmental conditions in Patagonia, were very similar during the last two glacials and interglacials, respectively, despite 2-4 °C warmer temperatures recorded in Antarctica during the penultimate interglacial than today. 2-3 times higher sea salt fluxes found in both ice cores in the glacial compared to the Holocene are difficult to reconcile with a largely unchanged transport intensity and the distant open ocean source. The substantial glacial enhancements in sea salt aerosol fluxes can be readily explained assuming sea ice formation as the main sea salt aerosol source with a significantly larger expansion of (summer) sea ice in the Weddell Sea than in the Indian Ocean sector. During the penultimate interglacial, our sea salt records point to a 50% reduction of winter sea ice coverage compared to the Holocene both in the Indian and Atlantic Ocean sector of the SO. However, from 20 to 80 ka before present sea salt fluxes show only very subdued millennial changes despite pronounced temperature fluctuations, likely due to the large distance of the sea ice salt source to our drill sites.

Mineralogy and geochemistry of aerosols from the Western Pacific

Aerosols collected by net method over the Western Pacific were investigated. Distribution of eolian material, its mineral and chemical compositions are controlled by the climatic and circumcontinental zonalities. It was stated that Fe and Mn were bound with mineral components of aerosols, while trace elements are bound with organogenic matter. Fluxes of aerosols and their components on the ocean surface were determined.

Characteristics and aldehyde concentrations of diamond dust events near Barrow, Alaska

Diamond dust (DD) refers to tiny ice crystals that form frequently in the Polar troposphere under clear sky conditions. They provide surfaces for chemical reactions and scatter light. We have measured the specific surface area (SSA) of DD at Barrow in March-April 2009. We have also measured its chemical composition in mineral and organic ions, dissolved organic carbon (DOC), aldehydes, H2O2, and the absorption spectra of water-soluble chromophores. Mercury concentrations were also measured in spring 2006, when conditions were similar. The SSA of DD ranges from 79.9 to 223 m**2/kg . The calculated ice surface area in the atmosphere reaches 11000 (±70%) µm**2/cm**3, much higher than the aerosol surface area. However, the impact of DD on the downwelling and upwelling light fluxes in the UV and visible is negligible. The composition of DD is markedly different from that of snow on the surface. Its concentrations in mineral ions are much lower, and its overall composition is acidic. Its concentrations in aldehydes, DOC, H2O2 and mercury are much higher than in surface snows. Our interpretation is that DOC from the oceanic surface microlayer, coming from open leads in the ice off of Barrow, is taken up by DD. Active chemistry in the atmosphere takes place on DD crystal surfaces, explaining its high concentrations in aldehydes and mercury. After deposition, active photochemistry modifies DD composition, as seen from the modifications in its absorption spectra and aldehyde and H2O2 content. This probably leads to the emissions of reactive species to the atmosphere.

Atmospheric nitrate concentrations and isotope composition for samples collected in the marine boundary layer in 2006 and 2007

The comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the d15N of nitrate mostly deriving from anthropogenically emitted NOx is found to be significantly different (from 0 to 6 per mil) from nitrate sampled in locations influenced by natural NOx sources (-4 ± 2) per mil. The effects on d15N(NO3-) of different NOx sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (D17O = d17O - 0.52 × d18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NOx sinks. Different D17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low d15N values (down to -40 per mil) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NOx from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores.

(Table 4) Seasonal variation of sea spray sodium concentrations during 2004-2007 at Concordia Station, Antarctica

From November 2004 to December 2007, size-segregated aerosol samples were collected all-year-round at Dome C (East Antarctica) by using PM10 and PM2.5 samplers, and multi-stage impactors. The data set obtained from the chemical analysis provided the longest and the most time-resolved record of sea spray aerosol (sea salt Na+) in inner Antarctica. Sea spray showed a sharp seasonal pattern. The highest values measured in winter (Apr-Nov) were about ten times larger than in summer (Dec-Mar). For the first time, a size-distribution seasonal pattern was also shown: in winter, sea spray particles are mainly submicrometric, while their summer size-mode is around 1-2 µm. Meteorological analysis on a synoptic scale allowed the definition of atmospheric conditions leading sea spray to Dome C. An extreme-value approach along with specific environmental based criteria was taken to yield stronger fingerprints linking atmospheric circulation (means and anomalies) to extreme sea spray events. Air mass back-trajectory analyses for some high sea spray events allowed the identification of two major air mass pathways, reflecting different size distributions: micrometric fractions for transport from the closer Indian-Pacific sector, and sub-micrometric particles for longer trajectories over the Antarctic Plateau. The seasonal pattern of the SO4**2- /Na+ ratio enabled the identification of few events depleted in sulphate, with respect to the seawater composition. By using methanesulphonic acid (MSA) profile to evaluate the biogenic SO4**2- contribution, a more reliable sea salt sulphate was calculated. In this way, few events (mainly in April and in September) were identified originating probably from the "frost flower" source. A comparison with daily-collected superficial snow samples revealed that there is a temporal shift between aerosol and snow sea spray trends. This feature could imply a more complex deposition processes of sea spray, involving significant contribution of wet and diamond dust deposition, but further work has to be carried out to rule out the effect of wind re-distribution and to have more statistic significance.