Mechanisms of dissolved and labile particulate iron supply to shelf waters and phytoplankton blooms off South Georgia, Southern Ocean

Abstract. The island of South Georgia is situated in the iron (Fe)-depleted Antarctic Circumpolar Current of the Southern Ocean. Iron emanating from its shelf system fuels large phytoplankton blooms downstream of the island, but the actual supply mechanisms are unclear. To address this, we present an inventory of Fe, manganese (Mn), and aluminium (Al) in shelf sediments, pore waters, and the water column in the vicinity of South Georgia, alongside data on zooplankton-mediated Fe cycling processes, and provide estimates of the relative dissolved Fe (DFe) fluxes from these sources. Seafloor sediments, modified by authigenic Fe precipitation, were the main particulate Fe source to shelf bottom waters as indicated by the similar Fe ∕ Mn and Fe ∕ Al ratios for shelf sediments and suspended particles in the water column. Less than 1 % of the total particulate Fe pool was leachable surface-adsorbed (labile) Fe and therefore potentially available to organisms. Pore waters formed the primary DFe source to shelf bottom waters, supplying 0.1–44 µmol DFe m−2 d−1. However, we estimate that only 0.41±0.26 µmol DFe m−2 d−1 was transferred to the surface mixed layer by vertical diffusive and advective mixing. Other trace metal sources to surface waters included glacial flour released by melting glaciers and via zooplankton egestion and excretion processes. On average 6.5±8.2 µmol m−2 d−1 of labile particulate Fe was supplied to the surface mixed layer via faecal pellets formed by Antarctic krill (Euphausia superba), with a further 1.1±2.2 µmol DFe m−2 d−1 released directly by the krill. The faecal pellets released by krill included seafloor-derived lithogenic and authigenic material and settled algal debris, in addition to freshly ingested suspended phytoplankton cells. The Fe requirement of the phytoplankton blooms ∼ 1250 km downstream of South Georgia was estimated as 0.33±0.11 µmol m−2 d−1, with the DFe supply by horizontal/vertical mixing, deep winter mixing, and aeolian dust estimated as ∼0.12 µmol m−2 d−1. We hypothesize that a substantial contribution of DFe was provided through recycling of biogenically stored Fe following luxury Fe uptake by phytoplankton on the Fe-rich shelf. This process would allow Fe to be retained in the surface mixed layer of waters downstream of South Georgia through continuous recycling and biological uptake, supplying the large downstream phytoplankton blooms. </jats:p

Hydrothermal sediments are a source of water column Fe and Mn in the Bransfield Strait, Antarctica

Short sediment cores were collected from ∼1100 m water depth at the top of Hook Ridge, a submarine volcanic edifice in the Central Basin of the Bransfield Strait, Antarctica, to assess Fe and Mn supply to the water column. Low-temperature hydrothermal fluids advect through these sediments and, in places, subsurface H2S is present at high enough concentrations to support abundant Sclerolinum sp., an infaunal tubeworm that hosts symbiotic thiotrophic bacteria. The water column is fully oxic, and oxygen penetration depths at all sites are 2–5 cmbsf. Pore water Fe and Mn content is high within the subsurface ferruginous zone (max. 565 μmol Fe L−1, >3–7 cmbsf)—14–18 times higher than values measured at a nearby, background site of equivalent water depth. Diffusion and advection of pore waters supply significant Fe and Mn to the surface sediment. Sequential extraction of the sediment demonstrates that there is a significant enrichment in a suite of reactive, authigenic Fe minerals in the upper 0–5 cm of sediment at one site characterised by weathered crusts at the seafloor. At a site with only minor authigenic mineral surface enrichment we infer that leakage of pore water Fe and Mn from the sediment leads to enriched total dissolvable Fe and Mn in bottom waters. An Eh sensor mounted on a towed package mapped a distinct Eh signature above this coring site which is dispersed over several km at the depth of Hook Ridge. We hypothesise that the main mechanism for Fe and Mn efflux from the sediment is breach of the surface oxic layer by the abundant Sclerolinum sp., along with episodic enhancements by physical mixing and resuspension of sediment in this dynamic volcanic environment. We propose that Hook Ridge sediments are an important source of Fe and Mn to the deep waters of the Central Basin in the Bransfield Strait, where concentrations are sustained by the benthic flux, and Fe is stabilised in the water column as either colloidal phases or ligand-bound dissolved species. Entrainment of this water mass into the Drake Passage and thereby the Antarctic Circumpolar Current could provide a significant metal source to this HNLC region of the Southern Ocean if mixing and upwelling occurs before removal of this metal pool to underlying sediments. Sediment-covered volcanic ridges are common within rifted margins and may play a previously overlooked role in the global Fe cycle

Stability of dissolved and soluble Fe(II) in shelf sediment pore waters and release to an oxic water column

Shelf sediments underlying temperate and oxic waters of the Celtic Sea (NW European Shelf) were found to have shallow oxygen penetrations depths from late spring to late summer (2.2–5.8 mm below seafloor) with the shallowest during/after the spring-bloom (mid-April to mid-May) when the organic carbon content was highest. Sediment porewater dissolved iron (dFe, 85%) consisted of Fe(II) and gradually increased from 0.4 to 15 μM at the sediment surface to ~100–170 µM at about 6 cm depth. During the late spring this Fe(II) was found to be mainly present as soluble Fe(II) (>85% sFe, 7 h. Iron(II) oxidation experiments in core top and bottom waters also showed removal from solution but at rates up to 5-times slower than predicted from theoretical reaction kinetics. These data imply the presence of ligands capable of complexing Fe(II) and supressing oxidation. The lower oxidation rate allows more time for the diffusion of Fe(II) from the sediments into the overlying water column. Modelling indicates significant diffusive fluxes of Fe(II) (on the order of 23–31 µmol m−2 day−1) are possible during late spring when oxygen penetration depths are shallow, and pore water Fe(II) concentrations are highest. In the water column this stabilised Fe(II) will gradually be oxidised and become part of the dFe(III) pool. Thus oxic continental shelves can supply dFe to the water column, which is enhanced during a small period of the year after phytoplankton bloom events when organic matter is transferred to the seafloor. This input is based on conservative assumptions for solute exchange (diffusion-reaction), whereas (bio)physical advection and resuspension events are likely to accelerate these solute exchanges in shelf-seas

An approach for the identification of exemplar sites for scaling up targeted field observations of benthic biogeochemistry in heterogeneous environments

Continental shelf sediments are globally important for biogeochemical activity. Quantification of shelf-scale stocks and fluxes of carbon and nutrients requires the extrapolation of observations made at limited points in space and time. The procedure for selecting exemplar sites to form the basis of this up-scaling is discussed in relation to a UK-funded research programme investigating biogeochemistry in shelf seas. A three-step selection process is proposed in which (1) a target area representative of UK shelf sediment heterogeneity is selected, (2) the target area is assessed for spatial heterogeneity in sediment and habitat type, bed and water column structure and hydrodynamic forcing, and (3) study sites are selected within this target area encompassing the range of spatial heterogeneity required to address key scientific questions regarding shelf scale biogeochemistry, and minimise confounding variables. This led to the selection of four sites within the Celtic Sea that are significantly different in terms of their sediment, bed structure, and macrofaunal, meiofaunal and microbial community structures and diversity, but have minimal variations in water depth, tidal and wave magnitudes and directions, temperature and salinity. They form the basis of a research cruise programme of observation, sampling and experimentation encompassing the spring bloom cycle. Typical variation in key biogeochemical, sediment, biological and hydrodynamic parameters over a pre to post bloom period are presented, with a discussion of anthropogenic influences in the region. This methodology ensures the best likelihood of site-specific work being useful for up-scaling activities, increasing our understanding of benthic biogeochemistry at the UK-shelf scale

Constraints on the Cycling of Iron Isotopes From a Global Ocean Model

Although iron (Fe) is a key regulator of primary production over much of the ocean, many components of the marine iron cycle are poorly constrained, which undermines our understanding of climate change impacts. In recent years, a growing number of studies (often part of GEOTRACES) have used Fe isotopic signatures (δ56Fe) to disentangle different aspects of the marine Fe cycle. Characteristic δ56Fe endmembers of external sources and assumed isotopic fractionation during biological Fe uptake or recycling have been used to estimate relative source contributions and investigate internal transformations, respectively. However, different external sources and fractionation processes often overlap and act simultaneously, complicating the interpretation of oceanic Fe isotope observations. Here we investigate the driving forces behind the marine dissolved Fe isotopic signature (δ56Fediss) distribution by incorporating Fe isotopes into the global ocean biogeochemical model PISCES. We find that distinct external source endmembers acting alongside fractionation during organic complexation and phytoplankton uptake are required to reproduce δ56Fediss observations along GEOTRACES transects. δ56Fediss distributions through the water column result from regional imbalances of remineralization and abiotic removal processes. They modify δ56Fediss directly and transfer surface ocean signals to the interior with opposing effects. Although attributing crustal compositions to sedimentary Fe sources in regions with low organic carbon fluxes improves our isotope model, δ56Fediss signals from hydrothermal or sediment sources cannot be reproduced accurately by simply adjusting δ56Fe endmember values. This highlights that additional processes must govern the exchange and/or speciation of Fe supplied by these sources to the ocean

Corrigendum to “Opposing controls on the isotopic signature of dissolved iron in hydrothermal plumes” [Geochim. Cosmochim Acta 202 (2017) 1–20](S0016703716307311)(10.1016/j.gca.2016.12.022)

The authors regret a mistake in Eq. (1) of Section 2.5 where the numerator and denominator of the Fe isotope ratios are inverted as published. The equation should read: [Formula presented] The authors would like to apologise for any inconvenience caused.</p

Long-term organic carbon preservation enhanced by iron and manganese

The balance between degradation and preservation of sedimentary organic carbon (OC) is important for global carbon and oxygen cycles 1 . The relative importance of different mechanisms and environmental conditions contributing to marine sedimentary OC preservation, however, remains unclear 2–8 . Simple organic molecules can be geopolymerized into recalcitrant forms by means of the Maillard reaction 5 , although reaction kinetics at marine sedimentary temperatures are thought to be slow 9,10 . More recent work in terrestrial systems suggests that the reaction can be catalysed by manganese minerals 11–13 , but the potential for the promotion of geopolymerized OC formation at marine sedimentary temperatures is uncertain. Here we present incubation experiments and find that iron and manganese ions and minerals abiotically catalyse the Maillard reaction by up to two orders of magnitude at temperatures relevant to continental margins where most preservation occurs 4 . Furthermore, the chemical signature of the reaction products closely resembles dissolved and total OC found in continental margin sediments globally. With the aid of a pore-water model 14 , we estimate that iron- and manganese-catalysed transformation of simple organic molecules into complex macromolecules might generate on the order of approximately 4.1 Tg C yr −1 for preservation in marine sediments. In the context of perhaps only about 63 Tg C yr −1 variation in sedimentary organic preservation over the past 300 million years 6 , we propose that variable iron and manganese inputs to the ocean could exert a substantial but hitherto unexplored impact on global OC preservation over geological time

Authigenic mineral phases as a driver of the upper-ocean iron cycle

International audienceIron is important in regulating the ocean carbon cycle1. Although several dissolved and particulate species participate in oceanic iron cycling, current understanding emphasizes the importance of complexation by organic ligands in stabilizing oceanic dissolved iron concentrations2-6. However, it is difficult to reconcile this view of ligands as a primary control on dissolved iron cycling with the observed size partitioning of dissolved iron species, inefficient dissolved iron regeneration at depth or the potential importance of authigenic iron phases in particulate iron observational datasets7-12. Here we present a new dissolved iron, ligand and particulate iron seasonal dataset from the Bermuda Atlantic Time-series Study (BATS) region. We find that upper-ocean dissolved iron dynamics were decoupled from those of ligands, which necessitates a process by which dissolved iron escapes ligand stabilization to generate a reservoir of authigenic iron particles that settle to depth. When this `colloidal shunt' mechanism was implemented in a global-scale biogeochemical model, it reproduced both seasonal iron-cycle dynamics observations and independent global datasets when previous models failed13-15. Overall, we argue that the turnover of authigenic particulate iron phases must be considered alongside biological activity and ligands in controlling ocean-dissolved iron distributions and the coupling between dissolved and particulate iron pools

Evidence of dark oxygen production at the abyssal seafloor

Deep-seafloor organisms consume oxygen, which can be measured by in situ benthic chamber experiments. Here we report such experiments at the polymetallic nodule-covered abyssal seafloor in the Pacific Ocean in which oxygen increased over two days to more than three times the background concentration, which from ex situ incubations we attribute to the polymetallic nodules. Given high voltage potentials (up to 0.95 V) on nodule surfaces, we hypothesize that seawater electrolysis may contribute to this dark oxygen production.</p

Coastal ocean and shelf-sea biogeochemical cycling of trace elements and isotopes : lessons learned from GEOTRACES

Unidad de excelencia María de Maeztu MdM-2015-0552Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T⅟₂ = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf ²²⁸Ra fluxes are combined with TEI/ ²²⁸Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean