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Transport processes along the river-ocean continuum influence delivery of nutrients, carbon and trace metals from terrestrial systems to the marine environment, impacting coastal primary productivity and water quality. Although trace metal transformations have been studied extensively in the Mississippi River Delta region of the Northern Gulf of Mexico, investigations of manganese (Mn) and the presence of ligand-stabilized, dissolved manganese (Mn(III)-L) and its role in the transformation of trace elements and organic matter during riverine transport and estuarine mixing have not been considered. This study examined the chemical speciation of dissolved and particulate Mn in the water column and sediment porewaters in the Mississippi River and Northern Gulf of Mexico in March of 2021 to explore transformations in Mn speciation along the river-ocean continuum and the impact of different processes on the distribution of Mn. Total dissolved Mn concentrations were highest in the Mississippi River and decreased offshore, while Mn(III)-L contributed most to the dissolved Mn pool in near-shore waters. Porewater profiles indicated that ligand stabilization prevented dissolved Mn(III) reduction below the depth of oxygen penetration and in the presence of equimolar dissolved iron(II). Dissolved Mn(III)-L was enriched in bottom waters at all Northern Gulf of Mexico stations, and diffusive flux modelling of porewater dissolved Mn suggested that reducing sediments were a source of dissolved Mn to the overlying water column in the form of both reduced Mn(II) and Mn(III)-L. A simple box model of the Mn cycle in the Northern Gulf of Mexico indicates that Mn(III)-L is required to balance the Mn budget in this region and is an integral, and previously unconsidered, piece of the Mn cycle in the Northern Gulf of Mexico. The presence of Mn(III)-L in this system likely has an outsized impact on trace element scavenging rates, oxidative capacity, and the carbon cycle that have not been previously appreciated. 

Key Points Black carbon fluxes were 0.1 g cm −2  year −1 at both Northeast shelf sites, accounting for 8%–22% of total carbon North Carolina had mostly old black carbon ( 14 C fraction modern 14%–31%), likely from fossil fuel combustion Black carbon in the Florida Strait sediment was mostly biomass‐derived ( 14 C fraction modern ∼70%), likely reflecting biomass burning 

Nitrogen is a major limiting element for biological productivity, and thus understanding past variations in nitrogen cycling is central to understanding past and future ocean biogeochemical cycling, global climate cycles, and biodiversity. Organic nitrogen encapsulated in fossil biominerals is generally protected from alteration, making it an important archive of the marine nitrogen cycle on seasonal to million-year timescales. The isotopic composition of fossil-bound nitrogen reflects variations in the large-scale nitrogen inventory, local sources and processing, and ecological and physiological traits of organisms. The ability to measure trace amounts of fossil-bound nitrogen has expanded with recent method developments. In this article, we review the foundations and ground truthing for three important fossil-bound proxy types: diatoms, foraminifera, and corals. We highlight their utility with examples of high-resolution evidence for anthropogenic inputs of nitrogen to the oceans, glacial–interglacial-scale assessments of nitrogen inventory change, and evidence for enhanced CO 2 drawdown in the high-latitude ocean. Future directions include expanded method development, characterization of ecological and physiological variation, and exploration of extended timescales to push reconstructions further back in Earth's history. 

Abstract Submarine groundwater discharge is increasingly recognized as an important component of the oceanic geochemical budget, but knowledge of the distribution of this phenomenon is limited. To date, reports of meteoric inputs to marine sediments are typically limited to shallow shelf and coastal environments, whereas contributions of freshwater along deeper sections of tectonically active margins have generally been attributed to silicate diagenesis, mineral dehydration, or methane hydrate dissociation. Here, using geochemical fingerprinting of pore water data from Site J1003 recovered from the Chilean Margin during D/V JOIDES Resolution Expedition 379 T, we show that substantial offshore freshening reflects deep and focused contributions of meteorically modified geothermal groundwater, which is likely sourced from a reservoir ~2.8 km deep in the Aysén region of Patagonia and infiltrated marine sediments during or shortly after the last glacial period. Emplacement of fossil groundwaters reflects an apparently ubiquitous phenomenon in margin sediments globally, but our results now identify an unappreciated locus of deep submarine groundwater discharge along active margins with potential implications for coastal biogeochemical processes and tectonic instability. 

Abstract Sedimentary nitrogen isotope (as δ¹⁵N) records from the Southern Ocean provide critical constraints on surface nutrient consumption in the past and the role of Southern Ocean biophysical changes in setting atmosphericpCO₂. We present a field assessment of how surface nitrate consumption is reflected in δ¹⁵N values of total nitrogen and diatom‐bound nitrogen pools of particles and sediments across the Southern Ocean along 170°W during late austral summer. Mixed layer nitrate δ¹⁵N values increase northwards associated with greater nitrate drawdown. Particles and sediments are expected to follow this trend. Contrary to expectations, surface ocean particle total nitrogen and diatom‐bound δ¹⁵N values decreased northward during the late summer, likely due to recycling of nitrogen and the assimilation of regenerated ammonium, as well as nitrate. The relationship between δ¹⁵N values of the total nitrogen and diatom‐bound pools remains relatively constant across this Southern Ocean transect, suggesting that the isotopic composition of these two surface ocean nitrogen pools are largely set by the δ¹⁵N value(s) of the assimilated nutrient(s). Surface sediment δ¹⁵N values do increase away from the region of maximum biogenic silica deposition, suggesting that the recycled nitrogen isotopic signal observed in late summer particles may not significantly impact the sedimentary record. However, the enrichment in δ¹⁵N values of the diatom‐bound pool is greater than what is expected from progressive utilization of the surface nitrate alone and not yet explained. 

Abstract The meridional variability of the Subtropical Front (STF) in the Southern Hemisphere, linked to expansions or contractions of the Southern Ocean, may have played an important role in global ocean circulation by moderating the magnitude of water exchange at the Indian‐Atlantic Ocean Gateway, so called Agulhas Leakage. Here we present new biomarker records of upper water column temperature (and) and primary productivity (chlorins and alkenones) from marine sediments at IODP Site U1475 on the Agulhas Plateau, near the STF and within the Agulhas retroflection pathway. We use these multiproxy time‐series records from 1.4 to 0.3 Ma to examine implied changes in the upper oceanographic conditions at the mid‐Pleistocene transition (MPT, ca. 1.2–0.8 Ma). Our reconstructions, combined with prior evidence of migrations of the STF over the last 350 ka, suggest that in the Southwestern Indian Ocean the STF may have been further south from the Agulhas Plateau during the mid‐Pleistocene Interim State (MPIS, MIS 23–12) and reached its northernmost position during MIS 34–24 and MIS 10. Comparison to aGloborotalia menardii‐derived Agulhas Leakage reconstruction from the Cape Basin suggests that only the most extreme northward migrations of the STF are associated with reduced Agulhas Leakage. During the MPIS, STF migrations do not appear to control Agulhas Leakage variability, we suggest previously modeled shifting westerly winds may be responsible for the patterns observed. A detachment between STF migrations and Agulhas Leakage, in addition to invoking shifting westerly winds may also help explain changes in CO₂ventilation seen during the MPIS.