Regeneration of Fe(II) during EIFeX and SOFeX

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

The role of airborne volcanic ash for the surface ocean biogeochemical iron-cycle: a review

Iron is a key micronutrient for phytoplankton growth in the surface ocean. Yet the significance of volcanism for the marine biogeochemical iron-cycle is poorly constrained. Recent studies, however, suggest that offshore deposition of airborne ash from volcanic eruptions is a way to inject significant amounts of bio-available iron into the surface ocean. Volcanic ash may be transported up to several tens of kilometers high into the atmosphere during large-scale eruptions and fine ash may stay aloft for days to weeks, thereby reaching even the remotest and most iron-starved oceanic regions. Scientific ocean drilling demonstrates that volcanic ash layers and dispersed ash particles are frequently found in marine sediments and that therefore volcanic ash deposition and iron-injection into the oceans took place throughout much of the Earth's history. Natural evidence and the data now available from geochemical and biological experiments and satellite techniques suggest that volcanic ash is a so far underestimated source for iron in the surface ocean, possibly of similar importance as aeolian dust. Here we summarise the development of and the knowledge in this fairly young research field. The paper covers a wide range of chemical and biological issues and we make recommendations for future directions in these areas. The review paper may thus be helpful to improve our understanding of the role of volcanic ash for the marine biogeochemical iron-cycle, marine primary productivity and the ocean-atmosphere exchange of CO2 and other gases relevant for climate in the Earth's history

Physical mixing effects on iron biogeochemical cycling: FeCycle experiment

The effects of physical processes on the distribution, speciation, and sources/sinks for Fe in a high-nutrient low-chlorophyll (HNLC) region were assessed during FeCycle, a mesoscale SF6 tracer release during February 2003 (austral summer) to the SE of New Zealand. Physical mixing processes were prevalent during FeCycle with rapid patch growth (strain rate γ = 0.17–0.20 d−1) from a circular shape (50 km2) into a long filament of ∼400 km2 by day 10. Slippage between layers saw the patch-head overlying noninfused waters while the tail was capped by adjacent surface waters resulting in a SF6 maximum at depth. As the patch developed it entrained adjacent waters containing higher chlorophyll concentrations, but similar dissolved iron (DFe) levels, than the initial infused patch. DFe was low ∼60 pmol L−1 in surface waters during FeCycle and was dominated by organic complexation. Nighttime measurements of Fe(II) ∼20 pmol L−1 suggest the presence of Fe(II) organic complexes in the absence of an identifiable fast Fe(III) reduction process. Combining residence times and phytoplankton uptake fluxes for DFe it is cycled through the biota 140–280 times before leaving the winter mixed layer (WML). This strong Fe demand throughout the euphotic zone coupled with the low Fe:NO3 − (11.9 μmol:mol) below the ferricline suggests that vertical diffusion of Fe is insufficient to relieve chronic iron limitation, indicating the importance of atmospheric inputs of Fe to this region

A luminescent whole-cell cyanobacterial bioreporter for measuring Fe availability in diverse marine environments

A Synechococcus sp. strain PCC 7002 Fe bioreporter was constructed containing the isiAB promoter fused to the Vibrio harveyi luxAB genes. Bioreporter luminescence was characterized with respect to the free ferric ion concentration in trace metal-buffered synthetic medium. The applicability of the Fe bioreporter to assess Fe availability in the natural environment was tested by using samples collected from the Baltic Sea and from the high-nutrient, low-chlorophyll subarctic Pacific Ocean. Parallel assessment of dissolved Fe and bioreporter response confirmed that direct chemical measurements of dissolved Fe should not be considered alone when assessing Fe availability to phytoplankton

A luminescent whole-cell cyanobacterial bioreporter for measuring Fe availability in diverse marine environments

A Synechococcus sp. strain PCC 7002 Fe bioreporter was constructed containing the isiAB promoter fused to the Vibrio harveyi luxAB genes. Bioreporter luminescence was characterized with respect to the free ferric ion concentration in trace metal-buffered synthetic medium. The applicability of the Fe bioreporter to assess Fe availability in the natural environment was tested by using samples collected from the Baltic Sea and from the high-nutrient, low-chlorophyll subarctic Pacific Ocean. Parallel assessment of dissolved Fe and bioreporter response confirmed that direct chemical measurements of dissolved Fe should not be considered alone when assessing Fe availability to phytoplankton

Iron biogeochemistry across marine systems progress from the past decade

Based on an international workshop (Gothenburg, 14–16 May 2008), this review article aims to combine interdisciplinary knowledge from coastal and open ocean research on iron biogeochemistry. The major scientific findings of the past decade are structured into sections on natural and artificial iron fertilization, iron inputs into coastal and estuarine systems, colloidal iron and organic matter, and biological processes. Potential effects of global climate change, particularly ocean acidification, on iron biogeochemistry are discussed. The findings are synthesized into recommendations for future research areas

Pathways of Superoxide (O2-) decay in the Eastern Tropical North Atlantic

Superoxide (O2-: IUPAC name dioxide (•1−)) is an important transient reactive oxygen species (ROS) in the ocean formed as an intermediate in the redox transformation of oxygen (O2) into hydrogen peroxide (H2O2) and vice versa. This highly reactive and very short-lived radical anion can be produced both via photochemical and biological processes in the ocean. In this paper we examine the decomposition rate of O2- throughout the water column, using new data collected in the Eastern Tropical North Atlantic (ETNA) Ocean. For this approach we applied a semi factorial experimental design, to identify and quantify the pathways of the major identified sinks in the ocean. In this work we occupied 6 stations, 2 on the West African continental shelf and 4 open ocean stations, including the CVOO time series site adjacent to Cape Verde. Our results indicate that in the surface ocean, impacted by Saharan aerosols and sediment resuspension, the main decay pathways for superoxide is via reactions with Mn(II) and organic matter

Iron uptake and physiological response of phytoplankton during a mesoscale Southern Ocean Iron enrichment.

Iron supply is thought to regulate primary production in high nitrate, low chlorophyll (HNLC) regions of the sea in both the past and the present. A critical aspect of this relationship is acquisition of iron (Fe) by phytoplankton, which occurs through a complex series of extracellular reactions that are influenced by Fe chemistry and speciation. During the first in situ mesoscale Fe-enrichment experiment in the Southern Ocean (Southern Ocean iron release experiment [SOIREE]), we monitored the uptake of Fe by three size classes of plankton and their ensuing physiological response to the Fe enrichment. Rates of Fe uptake from both inorganic Fe (Fe') and organic Fe complexes (FeL) were initially fast, indicative of Fe-limitation. After Fe enrichment phytoplankton down-regulated Fe uptake and optimized physiological performance, but by day 12 they had greatly increased their capacity to acquire Fe from FeL. The increase in Fe uptake from FeL coincided with a sixfold decrease in Fe' that followed the production of Fe-binding organic ligands. Phytoplankton were able to use organically bound Fe at rates sufficient to maintain net growth for more than 42 d. Adaptation to such shifts in Fe chemistry may contribute to bloom longevity in these polar HNLC waters