ALBERT

Description: The decay kinetics of superoxide (O2−) reacting with organic matter was examined in oligotrophic waters at, and nearby, the TENATSO ocean observatory adjacent to the Cape Verde archipelago. Superoxide is the short-lived primary photochemical product of colored dissolved organic matter (CDOM) photolysis and also reacts with CDOM or trace metals (Cu, Fe) to form H2O2. In the present work we focused our investigations on reactions between CDOM and superoxide. O2− decay kinetics experiments were performed by adding KO2 to diethylenetriaminepentaacetic acid (DTPA) amended seawater and utilizing an established chemiluminescence technique for the detection of O2− at nM levels. In Cape Verdean waters we found a significant reactivity of superoxide with CDOM with maximal rates adjacent to the chlorophyll maximum, presumably from production of new CDOM from bacteria/phytoplankton. This work highlights a poorly understood process which impacts on the biogeochemical cycling of CDOM and trace metals in the open ocean.

Description: Surface ocean iron (Fe) fertilization can affect the marine primary productivity (MPP), thereby impacting on CO2 exchanges at the atmosphere-ocean interface and eventually on climate. Mineral (aeolian or desert) dust is known to be a major atmospheric source for the surface ocean biogeochemical iron cycle, but the significance of volcanic ash is poorly constrained. We present the results of geochemical experiments aimed at determining the rapid release of Fe upon contact of pristine volcanic ash with seawater, mimicking their dry deposition into the surface ocean. Our data show that volcanic ash from both subduction zone and hot spot volcanoes (n = 44 samples) rapidly mobilized significant amounts of soluble Fe into seawater (35–340 nmol/g ash), with a suggested global mean of 200 ± 50 nmol Fe/g ash. These values are comparable to the range for desert dust in experiments at seawater pH (10–125 nmol Fe/g dust) presented in the literature (Guieu et al., 1996; Spokes et al., 1996). Combining our new Fe release data with the calculated ash flux from a selected major eruption into the ocean as a case study demonstrates that single volcanic eruptions have the potential to significantly increase the surface ocean Fe concentration within an ash fallout area. We also constrain the long-term (millennial-scale) airborne volcanic ash and mineral dust Fe flux into the Pacific Ocean by merging the Fe release data with geological flux estimates. These show that the input of volcanic ash into the Pacific Ocean (128–221 × 1015 g/ka) is within the same order of magnitude as the mineral dust input (39–519 × 1015 g/ka) (Mahowald et al., 2005). From the similarity in both Fe release and particle flux follows that the flux of soluble Fe related to the dry deposition of volcanic ash (3–75 × 109 mol/ka) is comparable to that of mineral dust (1–65 × 109 mol/ka). Our study therefore suggests that airborne volcanic ash is an important but hitherto underestimated atmospheric source for the Pacific surface ocean biogeochemical iron cycle.

Description: Surface delta(15)N(PON) increased 3.92 +/- 0.48 over the course of 20 days following additions of iron (Fe) to an eddy in close proximity to the Antarctic Polar Front in the Atlantic sector of the Southern Ocean. The change in delta(15)N(PON) was associated with an increase in the 〉20 mu m size fraction, leading to a maximal difference of 6.23 between the 〉20 mu m and 〈20 mu m size fractions. Surface delta(13)C(POC) increased 1.18 +/- 0.31 over the same period. After a decrease in particulate organic matter in the surface layer, a second phytoplankton community developed that accumulated less biomass, had a slower growth rate and was characterized by an offset of 1.56 in delta(13)C(POC) relative to the first community. During growth of the second community, surface delta(13)C(POC) further increased 0.83 +/- 0.13. Here we speculate on ways that carboxylation, nitrogen assimilation, substrate pool enrichment and community composition may have contributed to the gradual increase in delta(13)C(POC) associated with phytoplankton biomass accumulation, as well as the systematic offset in delta(13)C(POC) between the two phytoplankton communities.

Description: Iron (Fe) is a limiting nutrient for phytoplankton productivity in many different oceanic regions. A critical aspect underlying iron limitation is its low solubility in seawater as this controls the distribution and transport of iron through the ocean. Processes which enhance the solubility of iron in seawater, either through redox reactions or organic complexation, are central to understanding the biogeochemical cycling of iron. In this work we combined iron solubility measurements with parallel factor (PARAFAC) data analysis of CDOM fluorescence along a meridional transect through the Atlantic (PS ANT XXVI-4) to examine the hypothesis that marine humic fluorescence is a potential proxy for iron solubility in the surface ocean. PARAFAC analysis revealed 4 components, two humic like substances and two protein-like. Overall none of the 4 components were significantly correlated with iron solubility, though humic-like components were weakly correlated with iron solubility in iron replete waters. Our analysis suggests that the ligands responsible for maintaining iron in solution in the euphotic zone are sourced from both remineralisation processes and specific ligands produced in response to iron stress and are not easily related to bulk CDOM properties. The humic fluorescence signal was sharply attenuated in surface waters presumably most likely due to photo bleaching, though there was only a weak correlation with the transient photo product H2O2, suggesting longer lifetimes in the photic zone for the fluorescent components identified here. Key Points: - humic-like components correlated with Fe solubility in iron repleted water - ligands are sourced from remineralisation processes produced to Fe stress - humic flu sharply attenuated in surface waters, but only weak corr. with H2O2

Description: Surface water distributions of dissolved Al (dAl) and dissolved Ti (dTi) were investigated along a meridional Atlantic transect and related to dust deposition estimates. In the zone of Saharan dust deposition, highest dAl concentrations occurred in the tropical salinity minimum and suggest increasing Al dissolution from Saharan aerosols with wet deposition. By contrast, the dTi distribution is not related to precipitation but agrees with the pattern of annual dust deposition. In the zone of Patagonian dust deposition, elevated dTi concentrations contrasted with decreased dAl concentrations, indicating excess dAl scavenging onto biogenic particles in surface waters. Estimated residence times range from months to years for dAl and are ∼10 times higher for dTi. This suggests that dAl reflects seasonal changes in dust deposition, while dTi is related to longer temporal scales. However, spatial variations in input and removal processes complicate the quantification of dust deposition from surface water concentrations.

Description: Seventeen inorganic germanium and silicon concentration profiles collected from the Atlantic, southwest Pacific, and Southern oceans are presented. A plot of germanium concentration versus silicon concentration produced a near-linear line with a slope of 0.760 × 10−6 (±0.004) and an intercept of 1.27 (±0.24) pmol L−1 (r2 = 0.993, p 〈 0.001). When the germanium-to-silicon ratios (Ge/Si) were plotted versus depth and/or silicon concentrations, higher values are observed in surface waters (low in silicon) and decreased with depth (high in silicon). Germanium-to-silicon ratios in diatoms (0.608–1.03 × 10−6) and coupled seawater samples (0.471–7.46 × 10−6) collected from the Southern Ocean are also presented and show clear evidence for Ge/Si fractionation between the water and opal phases. Using a 10 box model (based on PANDORA), Ge/Si fractionation was modeled using three assumptions: (1) no fractionation, (2) fractionation using a constant distribution coefficient (KD) between the water and solid phase, and (3) fractionation simulated using Michaelis-Menten uptake kinetics for germanium and silicon via the silicon uptake system. Model runs indicated that only Ge/Si fractionation based on differences in the Michaelis-Menten uptake kinetics for germanium and silicon can adequately describe the data. The model output using this fractionation process produced a near linear line with a slope of 0.76 × 10−6 and an intercept of 0.92 (±0.28) pmol L−1, thus reflecting the oceanic data set. This result indicates that Ge/Si fractionation in the global ocean occurs as a result of subtle differences in the uptake of germanium and silicon via diatoms in surface waters.