Continuous 25-years aerosol records at coastal Antarctica: Part I. Variability and climate implications of ionic compounds

The aerosol climatology at the coastal Antarctic Neumayer Station (NM) was investigated based on continuous, 25-yr long observations of biogenic sulphur components (methanesulfonate and non-sea salt sulphate), sea salt and nitrate. Although significant long-term trends could only be detected for nitrate (-3.6 ± 2.5% per year between 1983 and 1993 and +4.0 ± 3.2% per year from 1993-2007), non-harmonic periodicities between 2 and 5 yr were typical for all species. Dedicated time series analyses revealed that relations to sea ice extent and various circulation indices are weak at best or not significant. In particular, no consistent link between sea ice extent and sea salt loadings was evident suggesting only a rather local relevance of the NM sea salt record. Nevertheless, a higher Southern Annular Mode index tended to entail a lower biogenic sulphur signal. In examining the spatial uniformity of the NM findings we contrasted them to respective 17 yr records from the coastal Dumont d'Urville Station. We found similar long-term trends for nitrate, indicating an Antarctic-wide but not identifiable atmospheric signal, although any significant impact of solar activity or pollution could be ruled out. No inter-site variability on the multiannual scale was evident for the other ionic compounds.

Trace elements in the aerosol at Neumayer Station, Antarctica

Atmospheric trace element concentrations were measured from March 1999 through December 2003 at the Air Chemistry Observatory of the German Antarctic station Neumayer by inductively coupled plasma - quadrupol mass spectrometry (ICP-QMS) and ion chromatogra-phy (IC). This continuous five year long record derived from weekly aerosol sampling re-vealed a distinct seasonal summer maximum for elements linked with mineral dust entry (Al, La, Ce, Nd) and a winter maximum for the mostly sea salt derived elements Li, Na, K, Mg, Ca, and Sr. The relative seasonal amplitude was around 1.7 and 1.4 for mineral dust (La) and sea salt aerosol (Na), respectively. On average a significant deviation regarding mean ocean water composition was apparent for Li, Mg, and Sr which could hardly be explained by mir-abilite precipitation on freshly formed sea ice. In addition we observed all over the year a not clarified high variability of element ratios Li/Na, K/Na, Mg/Na, Ca/Na, and Sr/Na. We found an intriguing co-variation of Se concentrations with biogenic sulfur aerosols (methane sul-fonate and non-sea salt sulfate), indicating a dominant marine biogenic source for this element linked with the marine biogenic sulfur source.

Chemical characterization of marine sub-micrometer aerosol particles during the MERIAN cruise MSM18/3 from the Cape Verde island Sao Vicente to Gabun (Atlantic Ocean)

Sub-micron marine aerosol particles (PM1) were collected during the MERIAN cruise MSM 18/3 between 22 June 2011 and 21 July 2011 from the Cape Verde island Sao Vicente to Gabun crossing the tropical Atlantic Ocean and passing equatorial upwelling areas. According to air mass origin and chemical composition of the aerosol particles, three main regimes could be established. Aerosol particles in the first part of the cruise were mainly of marine origin, in the second part was marine and slightly biomass burning influenced (increasing tendency) and in the in last part of the cruise, approaching the African mainland, biomass burning influences became dominant. Generally aerosols were dominated by sulfate (caverage = 1.99 µg/m**3) and ammonium ions (caverage = 0.72 µg/m**3) that are well correlated and slightly increasing along the cruise. High concentrations of water insoluble organic carbon (WISOC) averaging 0.51 µg/m**3 were found probably attributed to the high oceanic productivity in this region. Water soluble organic carbon (WSOC) was strongly increasing along the cruise from concentrations of 0.26 µg/m**3 in the mainly marine influenced part to concentrations up to 3.3 µg/m**3 that are probably caused by biomass burning influences. Major organic constituents were oxalic acid, methansulfonic acid (MSA) and aliphatic amines. MSA concentrations were quite constant along the cruise (caverage = 43 ng/m**3). While aliphatic amines were more abundant in the first mainly marine influenced part with concentrations of about 20 ng/m**3, oxalic acid showed the opposite pattern with average concentrations of 12 ng/m**3 in the marine and 158 ng/m**3 in the biomass burning influenced part. The alpha dicarbonyl compounds glyoxal and methylglyoxal were detected in the aerosol particles in the low ng/m**3 range and followed oxalic acid closely. MSA and aliphatic amines accounted for biogenic marine (secondary) aerosol constituents whereas oxalic acid and the alpha dicarbonyl compounds were believed to result mainly from biomass burning. N-alkane concentrations increased along the cruise from 0.81 to 4.66 ng/m**3, PAHs and hopanes were abundant in the last part of the cruise (caverage of PAHs = 0.13 ng/m**3, caverage of hopanes = 0.19 ng/m**3). Levoglucosan was identified in several samples of the last part of the cruise in concentrations around 2 ng/m**3, pointing to (aged) biomass burning influences. The investigated organic compounds could explain 9.5% of WSOC in the mainly marine influenced part (dominating compounds: aliphatic amines and MSA) and 2.7% of WSOC in the biomass burning influenced part (dominating compound: oxalic acid) of the cruise.

Year-round chemical aerosol records at Kohnen, Antarctica obtained by automatic samplings

Aimed at year-round recording of the chemical aerosol composition in central Antarctica, an unattended operating aerosol sampler was successfully deployed at the EPICA deep drilling site in Dronning Maud Land (Kohnen Station). Analyses of teflon/nylon filter packs consecutively collected over bi-weekly intervals during the February 2003 to December 2005 period allowed to evaluate seasonal concentration variations of methane sulphonate (MS), Cl-, NO3-, non-sea salt (nss-)SO4**2- and Na+, while NH4+ and mineral dust related ion results remained below detection limits. For MS and nss-SO4**2 distinct late summer maxima around 44 and 200 ng/m**3, respectively, were found, while (total) NO3- showed a broad November maximum of about 52 ng m**-3. In contrast, the highest concentrations of Na+ with peak values of up to 160 ng/m**3 were observed during the winter half year. The seasonality of these species broadly coincided with long-term observations at the coastal Neumayer Station, including surprisingly comparable NO3- levels. However, the biogenic sulphur and sea salt concentrations were lower at Kohnen by typically a factor of 2-3 and 10, respectively. The arrival of sea ice derived sea salt particles at Kohnen could not clearly detected, since even during mid-winter the nss-SO4**2- to Na+ ratio was generally too high to unambiguously identify a sulphur depleted sea salt SO4**2- fraction.

A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.

Integrated Data Sets of the EU FP5 Research Project ORFOIS: Origin and fate of biogenic particle fluxes in the ocean and their interactions with atmospheric CO2 concentrations as well as the marine sediment

For a reliable simulation of the time and space dependent CO2 redistribution between ocean and atmosphere an appropriate time dependent simulation of particle dynamics processes is essential but has not been carried out so far. The major difficulties were the lack of suitable modules for particle dynamics and early diagenesis (in order to close the carbon and nutrient budget) in ocean general circulation models, and the lack of an understanding of biogeochemical processes, such as the partial dissolution of calcareous particles in oversaturated water. The main target of ORFOIS was to fill in this gap in our knowledge and prediction capability infrastructure. This goal has been achieved step by step. At first comprehensive data bases (already existing data) of observations of relevance for the three major types of biogenic particles, organic carbon (POC), calcium carbonate (CaCO3), and biogenic silica (BSi or opal), as well as for refractory particles of terrestrial origin were collated and made publicly available.

(Table 1) Insoluble aerosol concentrations and vertical fluxes at the eastern shelf of the Black Sea during breeze circulation in October 1987

Amounts of aerosols transported to the shelf surface were calculated on the basis of in situ measurements of concentrations of eolian matter (insoluble aerosol fraction) and vertical fluxes of settling dust in five areas of the Black Sea shelf from the Danube delta to the Inguri River mouth. More than 8.3 mln t of eolian matter are annually transported from the land over the shelf of the former USSR. At the same time more than 5.4 mln t are supplied to the northwestern shelf area, 1.7 mln t are supplied to the Crimean area, about 0.8 mln t are supplied to the Kerch-Taman' area, and about 0.45 mln t are supplied to the Caucasian area.