A global compilation of dissolved iron measurements: focus on distributions and processes in the Southern Ocean

Due to its importance as a limiting nutrient for phytoplankton growth in large regions of the world's oceans, ocean water column observations of concentration of the trace-metal iron (Fe) have increased markedly over recent decades. Here we compile >13 000 global measurements of dissolved Fe (dFe) and make this available to the community. We then conduct a synthesis study focussed on the Southern Ocean, where dFe plays a fundamental role in governing the carbon cycle, using four regions, six basins and five depth intervals as a framework. Our analysis highlights depth-dependent trends in the properties of dFe between different regions and basins. In general, surface dFe is highest in the Atlantic basin and the Antarctic region. While attributing drivers to these patterns is uncertain, inter-basin patterns in surface dFe might be linked to differing degrees of dFe inputs, while variability in biological consumption between regions covaries with the associated surface dFe differences. Opposite to the surface, dFe concentrations at depth are typically higher in the Indian basin and the Subantarctic region. The inter-region trends can be reconciled with similar ligand variability (although only from one cruise), and the inter-basin difference might be explained by differences in hydrothermal inputs suggested by modelling studies (Tagliabue et al., 2010) that await observational confirmation. We find that even in regions where many dFe measurements exist, the processes governing the seasonal evolution of dFe remain enigmatic, suggesting that, aside from broad Subantarctic - Antarctic trends, biological consumption might not be the major driver of dFe variability. This highlights the apparent importance of other processes such as exogenous inputs, physical transport/mixing or dFe recycling processes. Nevertheless, missing measurements during key seasonal transitions make it difficult to better quantify and understand surface water replenishment processes and the seasonal Fe cycle. Finally, we detail the degree of seasonal coverage by region, basin and depth. By synthesising prior measurements, we suggest a role for different processes and highlight key gaps in understanding, which we hope can help structure future research efforts in the Southern Ocean

Size-fractionated labile trace elements in the Northwest Pacific and Southern Oceans

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Marine Chemistry 126 (2011): 108-113, doi:10.1016/j.marchem.2011.04.004.Photosynthesis by marine phytoplankton requires bioavailable forms of several trace elements that are found in extremely low concentrations in the open ocean. We have compared the concentration, lability and size distribution (< 1 nm and < 10 nm) of a suite of trace elements that are thought to be limiting to primary productivity as well as a toxic element (Pb) in two High Nutrient Low Chlorophyll (HNLC) regions using a new dynamic speciation technique, Diffusive Gradients in Thin-film (DGT). The labile species trapped within the DGT probes have a size that is smaller or similar than the pore size of algal cell walls and thus present a proxy for bioavailable species. Total Dissolvable trace element concentrations (TD concentration) varied between 0.05 nM (Co) and 4.0 nM (Ni) at K2 (Northwest Pacific Ocean) and between 0.026 nM (Co) and 4.7 nM (Ni) in the Southern Ocean. The smallest size fractionated labile concentrations (< 1 nm) observed at Southern Ocean sampling stations ranged between 0.002 nM (Co) and 2.1 nM (Ni). Moreover, large differences in bioavailable fractions (ratio of labile to TD concentration) were observed between the trace elements. In the Northwest Pacific Ocean Fe, Cu and Mn had lower labile fractions (between 10 and 44%) than Co, Cd, Ni and Pb (between 80 and 100%). In the Southern Ocean a similar trend was observed, and in addition: (1) Co, Cd, Ni and Pb have lower labile fractions in the Southern Ocean than in the Northwest Pacific and (2) the ratios of <1nm to dissolvable element concentrations at some Southern Ocean stations were very low and varied between 4 and16 %.This research was supported by Federal Science Policy Office, Brussels, through contracts EV/03/7A, SD/CA/03A, the Research Foundation Flanders through grant G.0021.04 and Vrije Universiteit Brussel via grant GOA 22, as well as for K2, the VERTIGO program funding primarily by the US National Science Foundation programs in Chemical and Biological Oceanograph

Oceanography of the subantarctic and Polar Frontal Zones south of Australia during summer: Setting for the SAZ-Sense study

This paper provides a description of the physical and chemical properties (temperature, salinity, macro-nutrient, and oxygen concentrations) and bulk biomass indicators (chlorophyll and beam attenuation) prevailing in the subantarctic zone and polar front zones south of Tasmania (Australia) during the 'Sensitivity of the subantarctic zone to environmental change' (SAZ-Sense) expedition carried out in the austral summer of 2007. Phytoplankton biomass showed a characteristic north-south gradient of decreasing chlorophyll from the subantarctic zone to Polar Frontal Zone, as well as a zonal gradient in the northern subantarctic zone, with an increase in chlorophyll from southwest to southeast of Tasmania. The representativeness of the observations was assessed by comparison to previous studies including satellite observation of chlorophyll biomass over a 10-year period. We consider the possible role of spatial differences in: (i) ocean water masses and frontal systems, (ii) upper mixed layer stratification at three process stations, and (iii) nutrient availability, in controlling the observed variations in phytoplankton biomass in the region. Zonal gradients of the basic oceanographic physical and chemical conditions in the subantarctic zone were relatively small and therefore unlikely to control the three-fold west-to-east differences observed in the accumulation of phytoplankton biomass. The zonal variation in subantarctic zone chlorophyll biomass appears to be driven at least partly by greater micro-nutrient (iron) supply to the waters east of Tasmania, as reported also by others (Bowie et al., 2009; Mongin et al., 2011a). Despite this condition, the region of higher phytoplankton biomass to the southeast of Tasmania was only marginally more productive than the region of lower biomass west of Tasmania and south of the polar front, and exported less particulate carbon than the lower biomass waters (Jacquet et al., 2011)

Design of an automated flow injection - chemiluminescence instrument for monitoring picomolar concentrations of iron in seawater

A flow-injection (FI)-based instrument under LabVIEW control for monitoring iron in marine waters is described. The instrument incorporates a miniature, low-power photomultiplier tube (PMT), and a number of microelectric and solenoid actuated valves and peristaltic pumps. The software allows full control of all flow injection components and processing of the data from the PMT. The optimised system is capable of 20 injections per hour, including preconcentration and wash steps. The detection limit (3 sd of the blank) is 21 pM at sea and the linear range is 21–2000 pM with a 60-second sample load time. Typical precision between replicate FI peaks is 5.9 ± 3.2 % (n =4) over the linear range

Determination of Cobalt and Iron in Estuarine and Coastal Water using Flow Injection with Chemiluminescence Detection

Flow injection with chemiluminescence detection (FI-CL) was used to determine cobalt and iron in estuarine and coastal waters. Cobalt(II) was determined by means of a pyrogallol-hydrogen peroxide-sodium hydroxide reaction in the presence of methanol and the surfactant cetyltrimethylammonium bromide (CTAB). With pyrogallol, the sensitivity was enhanced compared with the traditional reagent, gallic acid. The practical limit of detection in sea-water was 5 pM (3s) and there was good agreement with certified values for the sea-water CRMs NASS-5 (0.16 ± 0.01 nM), CASS-3 (0.60 ± 0.09 nM) and SLEW-2 (0.93 ± 0.13 nM). Results for an Irish Sea sample gave good agreement with data obtained using cathodic stripping voltammetry. Iron(II + III) was determined using a luminol reaction with dissolved oxygen as the oxidant. The practical limit of detection was 40 pM (3s) and results from shipboard analysis of the CRM NASS-4 (1.95 ± 0.14 nM) were in good agreement with the certified value (1.88 ± 0.29 nM). Field evaluation of the instrumentation and analytical methods was achieved through a series of local surveys in the Tamar Estuary (UK), from which environmental data are presented

Distribution of Fe and other trace elements (Al, Co and Ni) in the Atlantic Ocean

Iron and other trace metals (Al, Co, Ni) were measured through the upper water column during two north–south transects of the Atlantic Ocean (approximately 50°N–50°S), from the United Kingdom (UK) to the Falkland Islands (September/October 1996) and from South Africa to the UK (May/June 1998). Total dissolvable iron (TD-Fe) concentrations in the surface layers (&lt;200 m) of the open Atlantic Ocean averaged 0.95±0.67 nM (n=142) during the 1996 cruise and 1.08±0.59 nM (n=160) during the 1998 cruise, with increased values in shelf waters at both extremes of the transects. Iron enrichments, fingerprinted via correlation with other trace metals, macronutrients and hydrography, correlated well with dry aerosol deposition off the west African continent and wet deposition in the Inter-Tropical Convergence Zone (ITCZ), with levels &gt;2.2 nM observed in surface waters in these regions. Benthic fluxes provided a significant amount of Fe (2–38 nM) to the base of the water column in coastal zones. In addition, samples collected from one Atlantic Meridional Transect (AMT) expedition were re-analysed after a 16 month acidification period and showed significant increases over shipboard analyses (average values increasing to 2.26±1.50 nM), indicating the extended release of Fe from leachable particulate material in the stored samples. Detailed profiling through the euphotic zone revealed TD-Fe distributions that exhibited strong relationships with biological uptake, regeneration and water column hydrography. In equatorial and tropical North Atlantic waters, trace elemental distributions showed evidence of recent atmospheric deposition through a history of stratified mixed layers