Long-term chemical characterization of aerosols at CVAO from 2007 to 2011

The first long-term aerosol sampling and chemical characterization results from measurements at the Cape Verde Atmospheric Observatory (CVAO) on the island of São Vicente are presented and are discussed with respect to air mass origin and seasonal trends. In total 671 samples were collected using a high-volume PM10 sampler on quartz fiber filters from January 2007 to December 2011. The samples were analyzed for their aerosol chemical composition, including their ionic and organic constituents. Back trajectory analyses showed that the aerosol at CVAO was strongly influenced by emissions from Europe and Africa, with the latter often responsible for high mineral dust loading. Sea salt and mineral dust dominated the aerosol mass and made up in total about 80% of the aerosol mass. The 5-year PM10 mean was 47.1 ± 55.5 µg/m**2, while the mineral dust and sea salt means were 27.9 ± 48.7 and 11.1 ± 5.5 µg/m**2, respectively. Non-sea-salt (nss) sulfate made up 62% of the total sulfate and originated from both long-range transport from Africa or Europe and marine sources. Strong seasonal variation was observed for the aerosol components. While nitrate showed no clear seasonal variation with an annual mean of 1.1 ± 0.6 µg/m**3, the aerosol mass, OC (organic carbon) and EC (elemental carbon), showed strong winter maxima due to strong influence of African air mass inflow. Additionally during summer, elevated concentrations of OM were observed originating from marine emissions. A summer maximum was observed for non-sea-salt sulfate and was connected to periods when air mass inflow was predominantly of marine origin, indicating that marine biogenic emissions were a significant source. Ammonium showed a distinct maximum in spring and coincided with ocean surface water chlorophyll a concentrations. Good correlations were also observed between nss-sulfate and oxalate during the summer and winter seasons, indicating a likely photochemical in-cloud processing of the marine and anthropogenic precursors of these species. High temporal variability was observed in both chloride and bromide depletion, differing significantly within the seasons, air mass history and Saharan dust concentration. Chloride (bromide) depletion varied from 8.8 ± 8.5% (62 ± 42%) in Saharan-dust-dominated air mass to 30 ± 12% (87 ± 11%) in polluted Europe air masses. During summer, bromide depletion often reached 100% in marine as well as in polluted continental samples. In addition to the influence of the aerosol acidic components, photochemistry was one of the main drivers of halogenide depletion during the summer; while during dust events, displacement reaction with nitric acid was found to be the dominant mechanism. Positive matrix factorization (PMF) analysis identified three major aerosol sources: sea salt, aged sea salt and long-range transport. The ionic budget was dominated by the first two of these factors, while the long-range transport factor could only account for about 14% of the total observed ionic mass.

(Table 2) Seasonal flux data and percentages of major bulk components of total flux at the mesotrophic sediment trap site CB from 1988 - 2012

A more than two-decadal sediment trap record from the Eastern Boundary Upwelling Ecosystem (EBUE) off Cape Blanc, Mauritania, is analysed with respect to deep ocean mass fluxes, flux components and their variability on seasonal to decadal timescales. The total mass flux revealed interannual fluctuations which were superimposed by fluctuations on decadal timescales. High winter fluxes of biogenic silica (BSi), used as a measure of marine production (mostly by diatoms) largely correspond to a positive North Atlantic Oscillation (NAO) index (December-March). However, this relationship is weak. The highest positive BSi anomaly was in winter 2004-2005 when the NAO was in a neutral state. More episodic BSi sedimentation events occurred in several summer seasons between 2001 and 2005, when the previous winter NAO was neutral or even negative. We suggest that distinct dust outbreaks and deposition in the surface ocean in winter and occasionally in summer/autumn enhanced particle sedimentation and carbon export on short timescales via the ballasting effect. Episodic perturbations of the marine carbon cycle by dust outbreaks (e.g. in 2005) might have weakened the relationships between fluxes and large-scale climatic oscillations. As phytoplankton biomass is high throughout the year, any dry (in winter) or wet (in summer) deposition of fine-grained dust particles is assumed to enhance the efficiency of the biological pump by incorporating dust into dense and fast settling organic-rich aggregates. A good correspondence between BSi and dust fluxes was observed for the dusty year 2005, following a period of rather dry conditions in the Sahara/Sahel region. Large changes of all bulk fluxes occurred during the strongest El Niño-Southern Oscillation (ENSO) in 1997-1999 where low fluxes were obtained for almost 1 year during the warm El Niño and high fluxes in the following cold La Niña phase. For decadal timescales, Bakun (1990) suggested an intensification of coastal upwelling due to increased winds (''Bakun upwelling intensification hypothesis''; Cropper et al., 2014) and global climate change. We did not observe an increase of any flux component off Cape Blanc during the past 2 and a half decades which might support this. Furthermore, fluxes of mineral dust did not show any positive or negative trends over time which might suggest enhanced desertification or ''Saharan greening'' during the last few decades.