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: Investigations into Fe(II) cycling during two Southern Ocean mesoscale iron enrichment experiments, SOFeX and EIFeX, clearly show the importance of Fe(II) to iron speciation during these experiments. In both cases the added Fe(II) persisted significantly longer than its expected oxidation time indicating a significant Fe reduction process at work. During EIFeX diel studies showed a strong photochemically induced cycle in Fe(II) production in sunlit surface waters. Our results suggest that the photochemical cycling of iron may also be important in unfertilized waters of the Southern Ocean.

Description: Comparison of eight iron experiments shows that maximum Chl a, the maximum DIC removal, and the overall DIC/Fe efficiency all scale inversely with depth of the wind mixed layer (WML) defining the light environment. Moreover, lateral patch dilution, sea surface irradiance, temperature, and grazing play additional roles. The Southern Ocean experiments were most influenced by very deep WMLs. In contrast, light conditions were most favorable during SEEDS and SERIES as well as during IronEx-2. The two extreme experiments, EisenEx and SEEDS, can be linked via EisenEx bottle incubations with shallower simulated WML depth. Large diatoms always benefit the most from Fe addition, where a remarkably small group of thriving diatom species is dominated by universal response of Pseudo-nitzschia spp. Significant response of these moderate (10–30 μm), medium (30–60 μm), and large (〉60 μm) diatoms is consistent with growth physiology determined for single species in natural seawater. The minimum level of “dissolved” Fe (filtrate 〈 0.2 μm) maintained during an experiment determines the dominant diatom size class. However, this is further complicated by continuous transfer of original truly dissolved reduced Fe(II) into the colloidal pool, which may constitute some 75% of the “dissolved” pool. Depth integration of carbon inventory changes partly compensates the adverse effects of a deep WML due to its greater integration depths, decreasing the differences in responses between the eight experiments. About half of depth-integrated overall primary productivity is reflected in a decrease of DIC. The overall C/Fe efficiency of DIC uptake is DIC/Fe ∼ 5600 for all eight experiments. The increase of particulate organic carbon is about a quarter of the primary production, suggesting food web losses for the other three quarters. Replenishment of DIC by air/sea exchange tends to be a minor few percent of primary CO2 fixation but will continue well after observations have stopped. Export of carbon into deeper waters is difficult to assess and is until now firmly proven and quite modest in only two experiments.

Description: During the 13 day Southern Ocean Iron RE-lease Experiment (SOIREE), dissolved iron concentrations decreased rapidly following each of three iron-enrichments, but remained high (〉1 nM, up to 80% as FeII) after the fourth and final enrichment on day 8. The former trend was mainly due to dilution (spreading of iron-fertilized waters) and particle scavenging. The latter may only be explained by a joint production-maintenance mechanism; photoreduction is the only candidate process able to produce sufficiently high FeII, but as such levels persisted overnight (8 hr dark period) —ten times the half—life for this species—a maintenance mechanism (complexation of FeII) is required, and is supported by evidence of increased ligand concentrations on day 12. The source of these ligands and their affinity for FeII is not known. This retention of iron probably permitted the longevity of this bloom raising fundamental questions about iron cycling in HNLC (High Nitrate Low Chlorophyll) Polar waters.

Description: An improved knowledge of iron biogeochemistry is needed to better understand key controls on the functioning of high-nitrate low-chlorophyll (HNLC) oceanic regions. Iron budgets for HNLC waters have been constructed using data from disparate sources ranging from laboratory algal cultures to ocean physics. In summer 2003 we conducted FeCycle, a 10-day mesoscale tracer release in HNLC waters SE of New Zealand, and measured concurrently all sources (with the exception of aerosol deposition) to, sinks of iron from, and rates of iron recycling within, the surface mixed layer. A pelagic iron budget (timescale of days) indicated that oceanic supply terms (lateral advection and vertical diffusion) were relatively small compared to the main sink (downward particulate export). Remote sensing and terrestrial monitoring reveal 13 dust or wildfire events in Australia, prior to and during FeCycle, one of which may have deposited iron at the study location. However, iron deposition rates cannot be derived from such observations, illustrating the difficulties in closing iron budgets without quantification of episodic atmospheric supply. Despite the threefold uncertainties reported for rates of aerosol deposition (Duce et al., 1991), published atmospheric iron supply for the New Zealand region is ∼50-fold (i.e., 7- to 150-fold) greater than the oceanic iron supply measured in our budget, and thus was comparable (i.e., a third to threefold) to our estimates of downward export of particulate iron. During FeCycle, the fluxes due to short term (hours) biological iron uptake and regeneration were indicative of rapid recycling and were tenfold greater than for new iron (i.e. estimated atmospheric and measured oceanic supply), giving an “fe” ratio (uptake of new iron/uptake of new + regenerated iron) of 0.17 (i.e., a range of 0.06 to 0.51 due to uncertainties on aerosol iron supply), and an “Fe” ratio (biogenic Fe export/uptake of new + regenerated iron) of 0.09 (i.e., 0.03 to 0.24).

Description: Hydrogen peroxide (H2O2) is an important oxidant for many bio-relevant trace metals and organic compounds and has potential as a tracer for mixing in near surface waters. In this study we combine H2O2 and bio-optical measurements with satellite data for a meridional transect from 46 degrees N to 26 degrees S in the eastern Atlantic in order to determine the key processes affecting its distribution. Surface H2O2 ranged from 21 - 123 nmol L-1, with maximum inventories (0 - 200 m) of 5.5 - 5.9 mmol m(-2) found at 30 degrees N and 25 degrees S. Analyses showed a strong positive correlation of surface H2O2 with daily irradiances and recent precipitation, though poor correlations with CDOM suggest sunlight is the limiting reactant for H2O2 formation. Vertical distributions of H2O2 were controlled by a combination of mixing processes and phytoplankton activity. The present study highlights processes controlling global H2O2 distributions and points towards the development of parameterization schemes for prediction via satellite data. Citation: Steigenberger, S., and P. L. Croot (2008), Identifying the processes controlling the distribution of H2O2 in surface waters along a meridional transect in the eastern Atlantic.

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: H2O2 was measured in the upper water column (0–200 m) along a west-east transect through the Equatorial Atlantic as part of the German SOLAS (Surface Ocean Lower Atmosphere) cruise Meteor 55 (M55). Vertical profiles of H2O2 showed characteristic exponential decay consistent with light profiles and rainwater inputs. Integrated (0–100 m) water column H2O2 inventories ranged from 1.1–8.9 mmol m−2 with the highest values in the Amazon Plume. H2O2 inventories were also higher at the Equatorial Upwelling and after heavy rain showers in the region of the Inter Tropical Convergence Zone (ITCZ). Analysis of rain water samples collected during the cruise gave a volume weighted mean of 10.8 μmol L−1 (range 1.5–22.3 μmol L−1). This work highlights the importance of rainwater as a major source for H2O2 in the surface waters under the ITCZ.

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