Beschreibung: Our study followed the seasonal cycling of soluble (SFe), colloidal (CFe), dissolved (DFe), total dissolvable (TDFe), labile particulate (LPFe) and total particulate (TPFe) iron in the Celtic Sea (NE Atlantic Ocean). Preferential uptake of SFe occurred during the spring bloom, preceding the removal of CFe. Uptake and export of Fe during the spring bloom, coupled with a reduction in vertical exchange, led to Fe deplete surface waters (〈0.2 nM DFe; 0.11 nM LPFe, 0.45 nM TDFe, 1.84 nM TPFe) during summer stratification. Below the seasonal thermocline, DFe concentrations increased from spring to autumn, mirroring NO3- and consistent with supply from remineralised sinking organic material, and cycled independently of particulate Fe over seasonal timescales. These results demonstrate that summer Fe availability is comparable to the seasonally Fe limited Ross Sea shelf, and therefore is likely low enough to affect phytoplankton growth and species composition.

Beschreibung: Iron (Fe), cobalt (Co), and vitamin B12 addition experiments were performed in the eastern Equatorial Pacific/Peruvian upwelling zone during the 2015 El Niño event. Near the Peruvian coastline, apparent photosystem II photochemical efficiencies (Fv/Fm) were unchanged by nutrient addition and chlorophyll‐a tripled in untreated controls over two days, indicating nutrient replete conditions. Conversely, Fe amendment further away from the coastline in the high nitrate, low Fe zone significantly increased Fv/Fm and chlorophyll‐a concentrations. Mean chlorophyll‐a was further enhanced following supply of Fe+Co and Fe+B12 relative to Fe alone, but this was not statistically significant; further offshore, reported Co depletion relative to Fe could enhance responses. The persistence of Fe limitation in this system under a developing El Niño, as previously demonstrated under non‐El Niño conditions, suggests that diminished upwelled Fe is likely an important factor driving reductions in offshore phytoplankton productivity during these events.

Beschreibung: Anthropogenic activities have resulted in enhanced lead (Pb) emissions to the environment over the past century, mainly through the combustion of leaded gasoline. Here, we present the first combined dissolved (DPb), labile (LpPb) and particulate (PPb) Pb dataset from the Northeast Atlantic (Celtic Sea) since the phasing out of leaded gasoline in Europe. Concentrations of DPb in surface waters have decreased by 4-fold over the last four decades. We demonstrate that anthropogenic Pb is transported from the Mediterranean Sea over long distances (〉2500 km). Benthic DPb fluxes exceeded the atmospheric Pb flux in the region, indicating the importance of sediments as a contemporary Pb source. A strong positive correlation between DPb, PPb and LpPb indicates a dynamic equilibrium between the phases and the potential for particles to ‘buffer’ the DPb pool. This study provides insights into Pb biogeochemical cycling and demonstrates the potential of Pb in constraining ocean circulation patterns.

Beschreibung: Concentrations of heme b, the iron-containing component of b-type hemoproteins, ranged from 〈 0.4 to 5.3 pM with an average of 1.18 ± 0.8 pM (± 1σ; n = 86) in the Iceland Basin (IB), from 〈 0.4 to 19.1 pM with an average of 2.24 ± 1.67 pM (n = 269) in the tropical northeast Atlantic (TNA) and from 0.6 to 21 pM with an average of 5.1 ± 4.8 pM (n = 34) in the Scotia Sea (SS). Heme b concentrations were enhanced in the photic zone and decreased with depth. Heme b concentrations correlated positively with chlorophyll a (chl a) in the TNA (r = 0.41, p 〈 0.01, n = 269). Heme b did not correlate with chl a in the IB or SS. In the IB and SS, stations with high-chlorophyll and low-nutrient (Fe and/or Si) concentrations exhibited low heme b concentrations relative to particulate organic carbon (〈 0.1 μmol mol−1), and high chl a:heme b ratios (〉 500). High chl a:heme b ratios resulted from relative decreases in heme b, suggesting proteins such as cytochrome b6f, the core complex of photosystem II, and eukaryotic nitrate reductase were depleted relative to proteins containing chlorophyll such as the eukaryotic light-harvesting antenna. Relative variations in heme b, particulate organic carbon, and chl a can thus be indicative of a physiological response of the phytoplankton community to the prevailing growth conditions, within the context of large-scale changes in phytoplankton community composition.

Beschreibung: The major part of dissolved iron (DFe) in seawater is bound to organic matter, which prevents iron from adsorptive removal by sinking particles and essentially regulates the residence time of DFe and its availability for marine biota. Characteristics of iron‐binding ligands highly depend on their biological origin and physico‐chemical properties of seawater which may intensely alter under ongoing climate change. To understand environmental controls on the iron binding, we applied a function of pH and dissolved organic carbon (DOC) to describe changes in the binding strength of organic ligands in a global biogeochemical model (REcoM). This function was derived based on calculations using a thermodynamic chemical speciation model NICA. This parameterization considerably improved the modeled DFe distribution, particularly in the surface Pacific and the global mesopelagic and deep waters, compared to our previous model simulations with a constant ligand or one prognostic ligand. This indicates that the organic binding of iron is apparently controlled by seawater pH in addition to its link to organic matter. We tested further the response of this control to environmental changes in a simulation with future pH of a high emission scenario. The response of the binding potential shows a complex pattern in different regions and is regulated by factors that have opposite effects on the binding potential. The relative contributions of these factors can change over time by a continual change of environmental conditions. A dynamic feedback system therefore needs to be considered to predict the marine iron cycle under ongoing climate change.

Beschreibung: Upwelling ocean currents associated with oxygen minimum zones (OMZs) supply nutrients fuelling intense marine productivity. Perturbations in the extent and intensity of OMZs are projected in the future, but it is currently uncertain how this will impact fluxes of redox‐sensitive trace metal micronutrients to the surface ocean. Here we report seawater concentrations of Fe, Mn, Co, Cd, and Ni alongside the redox indicator iodide/iodate in the Peruvian OMZ during the 2015 El Niño event. The El Niño drove atypical upwelling of oxygen‐enriched water over the Peruvian Shelf, resulting in oxidized iodine and strongly depleted Fe (II), total dissolved Fe, and reactive particulate Fe concentrations relative to non‐El Niño conditions. Observations of Fe were matched by the redox‐sensitive micronutrients Co and Mn, but not by non‐redox‐sensitive Cd and Ni. These observations demonstrate that oxygenation of OMZs significantly reduces water column inventories of redox‐sensitive micronutrients, with potential impacts on ocean productivity. Plain Language Summary Some trace metals, including iron, are essential micronutrients for phytoplankton growth. However, the solubility of iron is very low under oxygenated conditions. Consequently, restricted iron availability in oxygen‐rich seawater can limit phytoplankton growth in the ocean, including in the Eastern Tropical South Pacific. Under typical conditions, depleted oxygen on the South American continental shelf is generally thought to enhance iron supply to the ocean, fuelling phytoplankton productivity in overlying waters. However, the impact of changes in oxygenation, which are predicted to occur in the future, are not known. The 2015 El Niño event led to unusually high oxygen on the Peruvian shelf, offering a system‐scale test on how oxygen influences seawater iron concentrations. We show that El Niño‐driven oxygenation resulted in marked decreases in iron and other metals sensitive to oxygen (cobalt and manganese), whilst metals not sensitive to oxygen (cadmium and nickel) were unaffected. The measured reductions in iron may have led to decreased phytoplankton productivity.

Beschreibung: Reactive iron (Fe) oxides in marine sediments may represent a source of bioavailable Fe to the ocean via reductive dissolution and sedimentary Fe release or can promote organic carbon preservation and long-term burial. Furthermore, enrichments of reactive Fe (sum of Fe oxides, carbonates and sulfides normalized to total Fe) in ancient sediments are utilized as a paleo-proxy for anoxic conditions. Considering the general importance of reactive Fe oxides in marine biogeochemistry, it is important to quantify their terrestrial sources and fate at the land-ocean interface. We applied sequential Fe extractions to sediments from the Amazon shelf to investigate the transformation of river-derived Fe oxides during early diagenesis. We found that ∼22 % of the Amazon River-derived Fe oxides are converted to Fe-containing clay minerals in Amazon shelf sediments. The incorporation of reactive Fe into authigenic clay minerals (commonly referred to as reverse weathering) is substantiated by the relationship between Fe oxide loss and potassium (K) uptake from sedimentary pore waters, which is in agreement with the previously reported Fe/K stoichiometry of authigenic clay minerals. Mass balance calculations suggest that widely applied sequential extractions do not separate Fe-rich authigenic clay minerals from reactive Fe oxides and carbonates. We conclude that the balance between terrestrial supply of reactive Fe and reverse weathering in continental margin sediments has to be taken into account in the interpretation of sedimentary Fe speciation data. Key Points - Reactive Fe is transferred from river-derived Fe oxides into Fe-containing silicate minerals during early diagenesis - Standard sequential extraction schemes do not separate Fe oxides and carbonates from authigenic silicate minerals in Amazon shelf sediments - Terrigenous supply of reactive Fe and reverse weathering need to be considered in the interpretation of sedimentary Fe speciation

Beschreibung: An insufficient supply of the micronutrient iron (Fe) limits phytoplankton growth across large parts of the ocean. Ambient Fe speciation and solubility are largely dependent on seawater physico-chemical properties. We calculated the apparent Fe solubility (SFe(III)app) at equilibrium for ambient conditions, where SFe(III)app is defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to organic matter formed at a free Fe3+ concentration equal to the solubility of Fe hydroxide. We compared the SFe(III)app to measured dissolved Fe (dFe) in the Atlantic and Pacific Oceans. The SFe(III)app was overall ∼2 to 4-fold higher than observed dFe at depths less than 1000 m, ∼2-fold higher than the dFe between 1000-4000 m and ∼3-fold higher than dFe below 4000 m. Within the range of used parameters, our results showed that there was a similar trend in the vertical distributions of horizontally averaged SFe(III)app and dFe. Our results suggest that vertical dFe distributions are underpinned by changes in SFe(III)app which are driven by relative changes in ambient pH and temperature. Since both pH and temperature are essential parameters controlling ambient Fe speciation, these should be accounted for in investigations of changing Fe dynamics, particularly in the context of ocean acidification and warming. Key Points Apparent iron solubility is driven by ambient pH, temperature (T) and dissolved organic carbon (DOC), and showed a 6-fold variation between surface (pH= 8.05 on the total scale, DOC= 71.8 µmol L-1, T= 20.4 °C) and deep oceanic waters (pH= 7.82, DOC= 38.6 µmol L-1, T= 1.1°C). Higher values of apparent iron solubility were determined for deep Atlantic and Pacific waters, with lower values in subtropical gyres. Calculated apparent iron solubility showed a similar trend in vertical distribution to dissolved iron, highlighting the importance of considering the impact of changes in ambient physico-chemical conditions on seawater iron chemistry.

Beschreibung: The marine cyanobacterium Trichodesmium has the remarkable ability to interact with and utilize air‐borne dust as a nutrient source. However, dust may adversely affect Trichodesmium through buoyancy loss and exposure to toxic metals. Our study explored the effect of desert dust on buoyancy and mortality of natural Red Sea puff‐shaped Trichodesmium thiebautii . Sinking velocities and ability of individual colonies to stay afloat with increasing dust loads were studied in sedimentation chambers. Low dust loads of up to ∼400 ng per colony did not impact initial sinking velocity and colonies remained afloat in the chamber. Above this threshold, sinking velocity increased linearly with the colony dust load at a slope matching prediction based on Stoke's law. The potential toxicity of dust was assessed with regards to metal dissolution kinetics, differentiating between rapidly released metals, which may impact surface blooms, and gradually released metals that may impact dust‐centering colonies. Incubations with increasing dust concentrations revealed colony death, but the observed lethal dose far exceeded dust concentrations measured in coastal and open ocean systems. Removal of toxic particles as a mechanism to reduce toxicity was explored using SEM‐EDX imaging of colonies incubated with Cu‐minerals, yet observations did not support this pathway. Combining our current and former experiments, we suggest that in natural settings the nutritional benefits gained by Trichodesmium via dust collection outweigh the risks of buoyancy loss and toxicity. Our data and concepts feed into the growing recognition of the significance of dust for Trichodesmium 's ecology and subsequently to ocean productivity. Plain Language Summary Trichodesmium spp. are abundant cyanobacteria, forming extensive blooms in low latitude warm oceans, and contribute significantly to carbon (C) and nitrogen (N) fixation, recycling and export. Desert dust deposited on the ocean surface was shown to supply Trichodesmium with the scarce micronutrient iron. Spherical, millimeter‐sized colonies of Trichodesmium from different ocean basins were reported to actively accumulate dust in their cores. While dust accumulation likely helps Trichodesmium obtain nutrients, it may come at a cost. Metals released from dust may induce toxicity and the dust weight could send Trichodesmium to the ocean depth. Our experimental study with natural Red Sea colonies examined some trade‐offs of dust accumulation. Links between dust load and colony buoyancy were examined in sedimentation experiments. Toxicity thresholds for surface blooms and dust‐accumulating colonies were determined from mortality assays and dust dissolution measurements. We found that metal‐induced toxicity to Trichodesmium is unlikely at typical oceanic dust fluxes, and that dust‐containing colonies can remain buoyant. At high loads, dust weight determined the colony's sinking velocity. Our findings and concepts can be extended to additional aerosols and Trichodesmium ‐rich habitats, and may assist in assessing Trichodesmium 's distribution, ecophysiology, and contribution to C or N transport to the deep ocean. Key Points Dust collected by Trichodesmium colonies from seawater as a nutrient source may result in metal toxification and buoyancy loss At moderate dust loads, colonies kept their buoyancy, but above 400 ng, sinking velocities increased linearly with dust loads Desert dust induced Trichodesmium mortality through toxic metal release, yet the lethal dose far exceeded oceanic dust concentrations