Description: As part of the Bonus-GoodHope (BGH) campaign, 15N-labelled nitrate, ammonium and urea uptake measurements were made along the BGH transect from Cape Town to ~60° S in late austral summer, 2008. Our results are categorised according to distinct hydrographic regions defined by oceanic fronts and open ocean zones. High regenerated nitrate uptake rate in the oligotrophic Subtropical Zone (STZ) resulted in low f-ratios (f = 0.2) with nitrogen uptake being dominated by ρurea, which contributed up to 70 % of total nitrogen uptake. Size fractionated chlorophyll data showed that the greatest contribution (〉50 %) of picophytoplankton (〈2 μm) were found in the STZ, consistent with a community based on regenerated production. The Subantarctic Zone (SAZ) showed the greatest total integrated nitrogen uptake (10.3 mmol m−2 d−1), mainly due to enhanced nutrient supply within an anticyclonic eddy observed in this region. A decrease in the contribution of smaller size classes to the phytoplankton community was observed with increasing latitude, concurrent with a decrease in the contribution of regenerated production. Higher f-ratios observed in the SAZ (f = 0.49), Polar Frontal Zone (f= 0.41) and Antarctic Zone (f = 0.45) relative to the STZ (f = 0.24), indicate a higher contribution of NO3−-uptake relative to total nitrogen and potentially higher export production. High ambient regenerated nutrient concentrations are indicative of active regeneration processes throughout the transect and ascribed to late summer season sampling. Higher depth integrated uptake rates also correspond with higher surface iron concentrations. No clear correlation was observed between carbon export estimates derived from new production and 234Th flux. In addition, export derived from 15N estimates were 2–20 times greater than those based on 234Th flux. Variability in the magnitude of export is likely due to intrinsically different methods, compounded by differences in integration time scales for the two proxies of carbon export.

Description: Atmospheric iron and underway sea-surface dissolved (〈0.2 μm) iron (DFe) concentrations were investigated along a north-south transect in the eastern Atlantic Ocean (27°N/16°W-19°S/5°E). Fe concentrations in aerosols and dry deposition fluxes of soluble Fe were at least two orders of magnitude higher in the Saharan dust plume than at the equator or at the extreme south of the transect. A weaker source of atmospheric Fe was also observed in the South Atlantic, possibly originating in southern Africa via the north-easterly outflow of the Angolan plume. Estimations of total atmospheric deposition fluxes (dry plus wet) of soluble Fe suggested that wet deposition dominated in the intertropical convergence zone, due to the very high amount of precipitation and to the fact that a substantial part of Fe was delivered in dissolved form. On the other hand, dry deposition dominated in the other regions of the transect (73-97), where rainfall rates were much lower. Underway sea-surface DFe concentrations ranged 0.02-1.1 nM. Such low values (0.02 nM) are reported for the first time in the Atlantic Ocean and may be (co)-limiting for primary production. A significant correlation (Spearman's rho = 0.862, p〈0.01) was observed between mean DFe concentrations and total atmospheric deposition fluxes, confirming the importance of atmospheric deposition on the iron cycle in the Atlantic. Residence time of DFe in the surface waters relative to atmospheric inputs were estimated in the northern part of our study area (17 ± 8 to 28 ± 16 d). These values confirmed the rapid removal of Fe from the surface waters, possibly by colloidal aggregation. © 2003 Elsevier Ltd. All rights reserved.

Description: A shipboard analytical intercomparison of dissolved (〈0.2 μm) iron in the surface waters of the Atlantic Ocean was undertaken during October 2000. A single underway surface (1-2 m) seawater sampling and filtration protocol was used, in order to minimise differences from possible sample contamination. Over 200 samples (1/h) were collected over 12 days and analysed immediately using four different analytical methods, based on three variants of flow injection with luminol chemiluminescence (FI-CL) and cathodic stripping voltammetry (CSV). Dissolved iron concentrations varied between 0.02 and 1.61 nM during the intercomparison. On average, CSV Electroanalysis 12 (2000) 565 measured 0.08 nM higher iron concentrations than one FI-CL method Anal. Chim. Acta 361 (1998) 189, which measured 0.13 nM higher iron values than the other two Anal. Chem. 65 (1993) 1524; Anal. Chim. Acta 377 (1998) 113, Statistical analyses (paired two-tailed t-test) showed that each analytical method gave significantly different dissolved iron concentrations at the 95% confidence interval. These data however, represent a significant improvement over earlier intercomparison exercises for iron. The data have been evaluated with respect to accuracy and overall inter-laboratory replicate precision, which was generally better than the 95% confidence intervals reported for the NASS Certified Reference Materials. Systematic differences between analytical methods were probably due to the extraction of different physico-chemical forms of iron during preconcentration, either on the micro-column resin (in the FI methods) or with competing ligand equilibration (in the CSV method). Small systematic concentration differences may also have resulted from protocols used for quantification of the analytical blank and instrument calibration. © 2003 Elsevier B.V All rights reserved.

Description: Comprehensive synoptic datasets (surface water down to 4000 m) of dissolved cadmium (Cd), copper (Cu), manganese (Mn), lead (Pb) and silver (Ag) are presented along a section between 34° S and 57° S in the southeastern Atlantic Ocean and the Southern Ocean to the south off South Africa. The vertical distributions of Cu and Ag display nutrient-like profiles similar to silicic acid, and of Cd similar to phosphate. The distribution of Mn shows a subsurface maximum in the oxygen minimum zone, whereas Pb concentrations are rather invariable with depth. Dry deposition of aerosols is thought to be an important source of Pb to surface waters close to South Africa, and dry deposition and snowfall may have been significant sources of Cu and Mn at the higher latitudes. Furthermore, the advection of water masses enriched in trace metals following contact with continental margins appeared to be an important source of trace elements to the surface, intermediate and deep waters in the southeastern Atlantic Ocean and the Antarctic Circumpolar Current. Hydrothermal inputs may have formed a source of trace metals to the deep waters over the Bouvet Triple Junction ridge crest, as suggested by relatively enhanced dissolved Mn concentrations. The biological utilization of Cu and Ag was proportional to that of silicic acid across the section, suggesting that diatoms formed an important control over the removal of Cu and Ag from surface waters. However, uptake by dino- and nano-flagellates may have influenced the distribution of Cu and Ag in the surface waters of the subtropical Atlantic domain. Cadmium correlated strongly with phosphate (P), yielding lower Cd / P ratios in the subtropical surface waters where phosphate concentrations were below 0.95 μM. The greater depletion of Cd relative to P observed in the Weddell Gyre compared to the Antarctic Circumpolar Current could be due to increase Cd uptake induced by iron-limiting conditions in these high-nutrient–low-chlorophyll waters. Similarly, an increase of Mn uptake under Fe-depleted conditions may have caused the highest depletion of Mn relative to P in the surface waters of the Weddell Gyre. In addition, a cellular Mn-transport channel of Cd was possibly activated in the Weddell Gyre, which in turn may have yielded depletion of both Mn and Cd in these surface waters.

Description: Meridional and vertical distributions of several biogeochemical parameters were studied along a section in the southeastern Atlantic and the Southern Ocean south of South Africa during the austral summer 2008 of the International Polar Year to characterize the biogeochemical provinces and to assess the seasonal net diatom production. Based on analyses of macro-nutrients, ammonium (NH4), chlorophyll a, (Chl a), phaeopigments, biogenic silica (BSi), particulate inorganic carbon (PIC), and particulate organic carbon and nitrogen (POC and PON, respectively), four biogeochemical domains were distinguished along the section: the subtropical Atlantic, the confluence zone of the subtropical and subantarctic domains, the Polar Frontal Zone (PFZ) in the Antarctic Circumpolar Current (ACC), and the north-eastern branch of the Weddell Gyre. The subtropical region displayed extremely low nutrient concentrations featuring oligotrophic conditions, and sub-surface maxima of Chl a and phaeopigments never exceeded 0.5 µg L−1 and 0.25 µg L−1, respectively. The anticyclonic and cyclonic eddies crossed in the Cape Basin were characterized by a deepening and a rise, respectively, of the nutrients isoclines. The confluence zone of the subtropical domain and the northern side of the ACC within the subantarctic domain displayed remnant nitrate and phosphate levels, whereas silicate concentrations kept to extremely low levels. In this area, Chl a level of 0.4–0.5 µg L−1 distributed homogenously within the mixed layer, and POC and PON accumulated to values up to 10 µM and 1.5 µM, respectively, indicative of biomass accumulation along the confluence zone during the late productive period. In the ACC domain, the Polar Frontal Zone was marked by a post-bloom of diatoms that extended beyond the Polar Front (PF) during this late summer condition, as primarily evidenced by the massive depletion of silicic acid in the surface waters. The accumulation of NH4 to values up to 1.25 µM at 100 m depth centred on the PF and the accumulation of BSi up to 0.5 µM in the surface waters of the central part of the PFZ also featured a late stage of the seasonal diatom bloom. The silica daily net production rate based on the seasonal depletion of silicic acid was estimated to be 11.9 ± 6.5 mmol m−2 d−1 in the domain of the vast diatom post-bloom, agreeing well with the previously recorded values in this province. The Weddell Gyre occasionally displayed relative surface depletion of silicic acid, suggesting a late stage of a relatively minor diatom bloom possibly driven by iceberg drifting releases of iron. In this domain the estimated range of silica daily net production rate (e.g. 21.1 ± 8.8 mmol m−2 d−1) is consistent with previous studies, but was not significantly higher than that in the Polar Front region.

Description: An in situ iron enrichment experiment was carried out in the Southern Ocean Polar Frontal Zone and fertilized a patch of water within an eddy of the Antarctic Circumpolar Current (EisenEx, Nov. 2000). During the experiment, a physical speciation technique was used for iron analysis in order to understand the changes in iron distribution and size-fractionations, including soluble Fe (〈200 kDa), colloidal Fe (200 kDa–0.2 μm) and labile particle Fe (〉0.2 μm), throughout the development of the phytoplankton bloom. Prior to the first infusion of iron, dissolved (〈0.2 μm) iron concentrations in the ambient surface seawater were extremely low (0.06±0.015 nM) with colloidal iron being a minor fraction. For the iron addition, an acidified FeSO4 solution was released three times over a 23-day period to the eddy. High levels of dissolved iron concentrations (2.0±1.1 nM) were measured in the surface water until 4 days after the first iron infusion. After every iron infusion, when high iron concentrations were observed before storm events, there was a significant correlation between colloidal and dissolved iron concentrations ([Colloidal Fe]=0.7627[Dissolved Fe]+0.0519, R2=0.9346). These results indicate that a roughly constant proportion of colloidal vs. dissolved iron was observed after iron infusion (∼76%). Storm events caused a significant decrease in iron concentrations (〈0.61 nM in dissolved iron) and changed the proportions of the three iron size-fractions (soluble, colloidal and labile particle). The changes in each iron size-fraction indicate that colloidal iron was eliminated from surface mixed layer more easily than particulate and soluble fractions. Therefore, particle and soluble iron efficiently remain in the mixed layer, probably due to the presence of suspended particles and naturally dissolved organic ligands. Our data suggest that iron removal through colloidal aggregation during phytoplankton bloom should be considered in the oceanic iron cycle.

Description: The speciation of strongly chelated iron during the 22-day course of an iron enrichment experiment in the Atlantic sector of the Southern Ocean deviates strongly from ambient natural waters. Three iron additions (ferrous sulfate solution) were conducted, resulting in elevated dissolved iron concentrations (Nishioka, J., Takeda, S., de Baar, H.J.W., Croot, P.L., Boye, M., Laan, P., Timmermans, K.R., in press. Changes in the concentration of iron in different size fractions during an iron enrichment experiment in the open Southern Ocean. Marine Chemistry.) and significant Fe(II) levels (Croot, P.L., Laan, P., Nishioka, J., Strass, V., Cisewski, B., Boye, M., Timmermans, K.R., Bellerby, R.G., Goldson, L., Nightingale, P., de Baar, H.J.W., in press. Spatial and Temporal distribution of Fe(II) and H2O2 during EisenEx, an open ocean mescoscale iron enrichment. Marine Chemistry.). Repeated vertical profiles for dissolved (filtrate 〈 0.2 μm) Fe(III)-binding ligands indicated a production of chelators in the upper water column induced by iron fertilizations. Abiotic processes (chemical reactions) and an inductive biologically mediated mechanism were the likely sources of the dissolved ligands which existed either as inorganic amorphous phases and/or as strong organic chelators. Discrete analysis on ultra-filtered samples (〈 200 kDa) suggested that the produced ligands would be principally colloidal in size (〉 200 kDa–〈 0.2 μm), as opposed to the soluble fraction (〈 200 kDa) which dominated prior to the iron infusions. Yet these colloidal ligands would exist in a more transient nature than soluble ligands which may have a longer residence time. The production of dissolved Fe-chelators was generally smaller than the overall increase in dissolved iron in the surface infused mixed layer, leaving a fraction (about 13–40%) of dissolved Fe not bound by these dissolved Fe-chelators. It is suggested that this fraction would be inorganic colloids. The unexpected persistence of such high inorganic colloids concentrations above inorganic Fe-solubility limits illustrates the peculiar features of the chemical iron cycling in these waters. Obviously, the artificial about hundred-fold increase of overall Fe levels by addition of dissolved inorganic Fe(II) ions yields a major disruption of the natural physical–chemical abundances and reactivity of Fe in seawater. Hence the ensuing responses of the plankton ecosystem, while in itself significant, are not necessarily representative for a natural enrichment, for example by dry or wet deposition of aeolian dust. Ultimately, the temporal changes of the Fe(III)-binding ligand and iron concentrations were dominated by the mixing events that occurred during EISENEX, with storms leading to more than an order of magnitude dilution of the dissolved ligands and iron concentrations. This had strongest impact on the colloidal size class (〉 200 kDa–〈 0.2 μm) where a dramatic decrease of both the colloidal ligand and the colloidal iron levels (Nishioka, J., Takeda, S., de Baar, H.J.W., Croot, P.L., Boye, M., Laan, P., Timmermans, K.R., in press. Changes in the concentration of iron in different size fractions during an iron enrichment experiment in the open Southern Ocean. Marine Chemistry.) was observed.