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The expansion of oxygen deficient zones (ODZs) within the ocean's interior is anticipated to be a major consequence of anthropogenic climate change, but past changes in ODZs are poorly defined. Recent mapping efforts have revealed plumes of the redox‐active metal cobalt within ODZs, driving a basin‐scale correlation between high cobalt and low O2. Here, we investigate the cobalt flux to Equatorial Pacific sediments along the Line Islands Ridge as a novel record of basin‐scale fluctuations in ODZ extent. After accounting for remobilization by diagenesis, we document a ∼40% increase in cobalt accumulation over the last glacial period, with a more pronounced peak during the Last Glacial Maximum, indicative of larger ODZs compared to the Holocene. Our results link ODZ expansion with colder climates and lend support to model‐based assertions that ongoing deoxygenation may reflect a transient response to warming. Plain Language Summary Climate change is linked to a decline in ocean oxygen levels, impacting fish and other organisms that need oxygen to breathe. Knowledge of past changes in ocean oxygen would help put ongoing deoxygenation trends into context. In this study, we investigated changes in oxygen in the Pacific Ocean over the past 145,000 years. Because low‐oxygen waters are enriched in the metal cobalt, we reconstructed the cobalt abundance of the past oceans as a proxy for oxygen. During the past two Ice Ages, when Earth was colder than today, we find evidence for higher cobalt, and therefore an expansion of oxygen‐poor waters. Key Points The cobalt flux to pelagic sediments reflects heightened sources associated with Oxygen Deficient Zones In Equatorial Pacific sediments, cobalt flux increased by ∼40% during the Last Glacial Period, compared to the Holocene Oxygen Deficient Zones likely expanded during the previous two glacial periods

Nearly all iron dissolved in the ocean is complexed by strong organic ligands of unknown composition. The effect of ligand composition on microbial iron acquisition is poorly understood, but amendment experiments using model ligands show they can facilitate or impede iron uptake depending on their identity. Here we show that siderophores, organic compounds synthesized by microbes to facilitate iron uptake, are a dynamic component of the marine ligand pool in the eastern tropical Pacific Ocean. Siderophore concentrations in iron-deficient waters averaged 9 pM, up to fivefold higher than in iron-rich coastal and nutrient-depleted oligotrophic waters, and were dominated by amphibactins, amphiphilic siderophores with cell membrane affinity. Phylogenetic analysis of amphibactin biosynthetic genes suggests that the ability to produce amphibactins has transferred horizontally across multiple Gammaproteobacteria, potentially driven by pressures to compete for iron. In coastal and oligotrophic regions of the eastern Pacific Ocean, amphibactins were replaced with lower concentrations (1–2 pM) of hydrophilic ferrioxamine siderophores. Our results suggest that organic ligand composition changes across the surface ocean in response to environmental pressures. Hydrophilic siderophores are predominantly found across regions of the ocean where iron is not expected to be the limiting nutrient for the microbial community at large. However, in regions with intense competition for iron, some microbes optimize iron acquisition by producing siderophores that minimize diffusive losses to the environment. These siderophores affect iron bioavailability and thus may be an important component of the marine iron cycle.

Biogenic and authigenic particulate iron (pFe) are key components of the marine iron cycle, influencing the fate of Fe in the upper ocean. However, their relative contributions to the total pFe pool are challenging to quantify. The chemical leach commonly used to operationally define “labile” pFe is thought to extract both the biogenic and authigenic phases. To independently determine Fe in biomass, we conducted Fe uptake experiments in the surface mixed layer on 12 cruises in the subtropical North Pacific Ocean. Bulk Fe uptake rates varied ∼ 2.5-fold throughout the year, increasing with higher abundances of Prochlorococcus and picoeukaryotes. We used particulate carbon and phosphorus as biomass estimates in combination with Fe:C uptake ratios, finding that both led to overestimations of the biogenic pFe pool (>200 % of labile pFe in the surface mixed layer). Using the nucleotide adenosine-5'-triphosphate (ATP) as an alternate estimate of living biomass instead suggested that biotic pFe comprised ∼ 60 % of labile pFe in the mixed layer. The remainder of the labile pFe pool, defined as “authigenic + detrital', dominated the labile pFe pool below the euphotic zone, capturing contributions from detrital organic matter, authigenic minerals, and dust. A comparison of Fe phases between Station ALOHA in the North Pacific Subtropical Gyre and the BATS station in the North Atlantic Subtropical Gyre revealed similar concentrations of dissolved Fe and biotic pFe, but higher authigenic pFe concentrations in the North Atlantic, likely reflecting greater dust deposition. The greater role of biotic pFe in the subtropical North Pacific may enable high efficiency Fe recycling, which rivals that observed in Fe-limited ecosystems.

Fossil-fuel emissions may impact phytoplankton primary productivity and carbon cycling by supplying bioavailable Fe to remote areas of the ocean via atmospheric aerosols. However, this path-way has not been confirmed by field observations of anthropogenic Fe in seawater. Here we present high-resolution trace-metal concentrations across the North Pacific Ocean (158°W from 25°to 42°N). A dissolved Fe maximum was observed around 35°N, coincident with high dissolved Pb and Pb isotope ratios matching Asian industrial sources and confirming recent aerosol deposition. Ironstable isotopes reveal in situ evidence of anthropogenic Fe in seawater, with low δ56Fe (−0.23‰ > δ56Fe > −0.65‰) observed in the region that is most influenced by aerosol deposition. An isotope mass balance suggests that anthropogenic Fe contributes 21–59% of dissolved Fe measured between 35° and 40°N. Thus, anthropogenic aerosol Fe is likely to be an important Fe source to the North Pacific Ocean.

Scarce dissolved surface ocean concentrations of the essential algal micronutrient zinc suggest that Zn may influence the growth of phytoplankton such as diatoms, which are major contributors to marine primary productivity. However, the specific mechanisms by which diatoms acclimate to Zn deficiency are poorly understood. Using global proteomic analysis, we identified two proteins (ZCRP-A/B, Zn/Co Responsive Protein A/B) among four diatom species that became abundant under Zn/Co limitation. Characterization using reverse genetic techniques and homology data suggests putative Zn/Co chaperone and membrane-bound transport complex component roles for ZCRP-A (a COG0523 domain protein) and ZCRP-B, respectively. Metaproteomic detection of ZCRPs along a Pacific Ocean transect revealed increased abundances at the surface (<200 m) where dZn and dCo were scarcest, implying Zn nutritional stress in marine algae is more prevalent than previously recognized. These results demonstrate multiple adaptive responses to Zn scarcity in marine diatoms that are deployed in low Zn regions of the Pacific Ocean. Here the authors identify two zinc/cobalt responsive proteins (ZCRPs) in marine diatoms, determining their functional roles in trace metal transport and homeostasis, as well as their application as an indicator of oceanic Zn stress.

Cobalt is a nutrient to phytoplankton, but knowledge about its biogeochemical cycling is limited, especially in the Pacific Ocean. Here, we report sections of dissolved cobalt and labile dissolved cobalt from the US GEOTRACES GP16 transect in the South Pacific. The cobalt distribution is closely tied to the extent and intensity of the oxygen minimum zone in the eastern South Pacific with highest concentrations measured at the oxycline near the Peru margin. Below 200 m, remineralization and circulation produce an inverse relationship between cobalt and dissolved oxygen that extends throughout the basin. Within the oxygen minimum zone, elevated concentrations of labile cobalt are generated by input from coastal sources and reduced scavenging at low O2. As these high cobalt waters are upwelled and advected offshore, phytoplankton export returns cobalt to low-oxygen water masses underneath. West of the Peru upwelling region, dissolved cobalt is less than 10 pM in the euphotic zone and strongly bound by organic ligands. Because the cobalt nutricline within the South Pacific gyre is deeper than in oligotrophic regions in the North and South Atlantic, cobalt involved in sustaining phytoplankton productivity in the gyre is heavily recycled and ultimately arrives from lateral transport of upwelled waters from the eastern margin. In contrast to large coastal inputs, atmospheric deposition and hydrothermal vents along the East Pacific Rise appear to be minor sources of cobalt. Overall, these results demonstrate that oxygen biogeochemistry exerts a strong influence on cobalt cycling.

Cobalt is the scarcest of metallic micronutrients and displays a complex biogeochemical cycle. This study examines the distribution, chemical speciation, and biogeochemistry of dissolved cobalt during the US North Atlantic GEOTRACES transect expeditions (GA03/3_e), which took place in the fall of 2010 and 2011. Two major subsurface sources of cobalt to the North Atlantic were identified. The more prominent of the two was a large plume of cobalt emanating from the African coast off the eastern tropical North Atlantic coincident with the oxygen minimum zone (OMZ) likely due to reductive dissolution, biouptake and remineralization, and aeolian dust deposition. The occurrence of this plume in an OMZ with oxygen above suboxic levels implies a high threshold for persistence of dissolved cobalt plumes. The other major subsurface source came from Upper Labrador Seawater, which may carry high cobalt concentrations due to the interaction of this water mass with resuspended sediment at the western margin or from transport further upstream. Minor sources of cobalt came from dust, coastal surface waters and hydrothermal systems along the Mid-Atlantic Ridge. The full depth section of cobalt chemical speciation revealed near-complete complexation in surface waters, even within regions of high dust deposition. However, labile cobalt observed below the euphotic zone demonstrated that strong cobalt-binding ligands were not present in excess of the total cobalt concentration there, implying that mesopelagic labile cobalt was sourced from the remineralization of sinking organic matter. In the upper water column, correlations were observed between total cobalt and phosphate, and between labile cobalt and phosphate, demonstrating a strong biological influence on cobalt cycling. Along the western margin off the North American coast, this correlation with phosphate was no longer observed and instead a relationship between cobalt and salinity was observed, reflecting the importance of coastal input processes on cobalt distributions. In deep waters, both total and labile cobalt concentrations were lower than in intermediate depth waters, demonstrating that scavenging may remove labile cobalt from the water column. Total and labile cobalt distributions were also compared to a previously published South Atlantic GEOTRACES-compliant zonal transect (CoFeMUG, GAc01) to discern regional biogeochemical differences. Together, these Atlantic sectional studies highlight the dynamic ecological stoichiometry of total and labile cobalt. As increasing anthropogenic use and subsequent release of cobalt poses the potential to overpower natural cobalt signals in the oceans, it is more important than ever to establish a baseline understanding of cobalt distributions in the ocean.

Bioactive trace metals are critical micronutrients for marine microorganisms due to their role in mediating biological redox reactions, and complex biogeochemical processes control their distributions. Hydrothermal vents may represent an important source of metals to microorganisms, especially those inhabiting low-iron waters, such as in the southwest Pacific Ocean. Previous measurements of primordial 3He indicate a significant hydrothermal source originating in the northeastern (NE) Lau Basin, with the plume advecting into the southwest Pacific Ocean at 1500–2000 m depth (Lupton et al., 2004). Studies investigating the long-range transport of trace metals associated with such dispersing plumes are rare, and the biogeochemical impacts on local microbial physiology have not yet been described. Here we quantified dissolved metals and assessed microbial metaproteomes across a transect spanning the tropical and equatorial Pacific with a focus on the hydrothermally active NE Lau Basin and report elevated iron and manganese concentrations across 441 km of the southwest Pacific. The most intense signal was detected near the Mangatolo Triple Junction (MTJ) and Northeast Lau Spreading Center (NELSC), in close proximity to the previously reported 3He signature. Protein content in distal-plume-influenced seawater, which was high in metals, was overall similar to background locations, though key prokaryotic proteins involved in metal and organic uptake, protein degradation, and chemoautotrophy were abundant compared to deep waters outside of the distal plume. Our results demonstrate that trace metals derived from the NE Lau Basin are transported over appreciable distances into the southwest Pacific Ocean and that bioactive chemical resources released from submarine vent systems are utilized by surrounding deep-sea microbes, influencing both their physiology and their contributions to ocean biogeochemical cycling.

Cobalt (Co) is an important bioactive trace metal that is the metal cofactor in cobalamin (vitamin B12) which can limit or co-limit phytoplankton growth in many regions of the ocean. Total dissolved and labile Co measurements in the Canadian sector of the Arctic Ocean during the U.S. GEOTRACES Arctic expedition (GN01) and the Canadian International Polar Year GEOTRACES expedition (GIPY14) revealed a dynamic biogeochemical cycle for Co in this basin. The major sources of Co in the Arctic were from shelf regions and rivers, with only minimal contributions from other freshwater sources (sea ice, snow) and eolian deposition. The most striking feature was the extremely high concentrations of dissolved Co in the upper 100 m, with concentrations routinely exceeding 800 pmol L−1 over the shelf regions. This plume of high Co persisted throughout the Arctic basin and extended to the North Pole, where sources of Co shifted from primarily shelf-derived to riverine, as freshwater from Arctic rivers was entrained in the Transpolar Drift. Dissolved Co was also strongly organically complexed in the Arctic, ranging from 70 % to 100 % complexed in the surface and deep ocean, respectively. Deep-water concentrations of dissolved Co were remarkably consistent throughout the basin (∼55 pmol L−1), with concentrations reflecting those of deep Atlantic water and deep-ocean scavenging of dissolved Co. A biogeochemical model of Co cycling was used to support the hypothesis that the majority of the high surface Co in the Arctic was emanating from the shelf. The model showed that the high concentrations of Co observed were due to the large shelf area of the Arctic, as well as to dampened scavenging of Co by manganese-oxidizing (Mn-oxidizing) bacteria due to the lower temperatures. The majority of this scavenging appears to have occurred in the upper 200 m, with minimal additional scavenging below this depth. Evidence suggests that both dissolved Co (dCo) and labile Co (LCo) are increasing over time on the Arctic shelf, and these limited temporal results are consistent with other tracers in the Arctic. These elevated surface concentrations of Co likely lead to a net flux of Co out of the Arctic, with implications for downstream biological uptake of Co in the North Atlantic and elevated Co in North Atlantic Deep Water. Understanding the current distributions of Co in the Arctic will be important for constraining changes to Co inputs resulting from regional intensification of freshwater fluxes from ice and permafrost melt in response to ongoing climate change.

Organic ligands form strong complexes with many trace elements in seawater. Various metals can compete for the same ligand chelation sites, and the final speciation of bound metals is determined by relative binding affinities, concentrations of binding sites, uncomplexed metal concentrations, and association/dissociation kinetics. Different ligands have a wide range of metal affinities and specificities. However, the chemical composition of these ligands in the marine environment remains poorly constrained, which has hindered progress in modeling marine metal speciation. In this study, we detected and characterized natural ligands that bind copper (Cu) and nickel (Ni) in the eastern South Pacific Ocean with liquid chromatography tandem inductively coupled plasma mass spectrometry (LC-ICPMS), and high resolution electrospray ionization mass spectrometry (ESIMS). Dissolved Cu, Ni, and ligand concentrations were highest near the coast. Chromatographically unresolved polar compounds dominated ligands isolated near the coast by solid phase extraction. Offshore, metal and ligand concentrations decreased, but several new ligands appeared. One major ligand was detected that bound both Cu2+ and Ni2+. Based on accurate mass and fragmentation measurements, this compound has a molecular formula of [C20H21N4O8S2 + M]+ (M = metal isotope) and contains several azole-like metal binding groups. Additional lipophilic Ni complexes were also present only in oligotrophic waters, with masses of 649, 698, and 712 m/z (corresponding to the 58Ni metal complex). Molecular formulae of [C32H54N3O6S2Ni]+ and [C33H56N3O6S2Ni]+ were determined for two of these compounds. Addition of Cu and Ni to the samples also revealed the presence of additional compounds that can bind both Ni and Cu. Although these specific compounds represent a small fraction of the total dissolved Cu and Ni pool, they highlight the compositional diversity and spatial heterogeneity of marine Ni and Cu ligands, as well as variability in the extent to which different metals in the same environment compete for ligand binding.