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ABSTRACT The microbial recycling of organic matter in marine sediments depends upon electron acceptors that are utilized based on availability and energetic yield. Since sulfate is the most abundant oxidant once oxygen has been depleted, the sulfide produced after sulfate reduction becomes an important electron donor for autotrophic microbes. The ability of sulfide to be re‐oxidized through multiple metabolic pathways and intermediates with variable oxidation states prompts investigation into which species are preferentially utilized and what are the factors that determine the fate of reduced sulfur species. Quantifying these sulfur intermediates in porewaters is a critical first step towards achieving a more complete understanding of the oxidative sulfur cycle, yet this has been accomplished in very few studies, none of which include oligotrophic sedimentary environments in the open ocean. Here we present profiles of porewater sulfur intermediates from sediments underlying oligotrophic regions of the ocean, which encompass about 75% of the ocean's surface and are characterized by low nutrient levels and productivity. Aiming at addressing uncertainties about if and how sulfide produced by the degradation of scarce sedimentary organic matter plays a role in carbon fixation in the sediment, we determine depth profiles of redox‐sensitive metals and sulfate isotope compositions and integrate these datasets with 16S rRNA microbial community composition data and solid‐phase sulfur concentrations. We did not find significant correlations between sulfur species or trace metals and specific sulfur cycling taxa, which suggests that microorganisms in pelagic and oxic sediments may be generalists utilizing flexible metabolisms to oxidize organic matter through different electron acceptors. 

Abstract The cycling of marine particulate matter is critical for sequestering carbon in the deep ocean and in marine sediments. Biogenic minerals such as calcium carbonate (CaCO₃) and opal add density to more buoyant organic material, facilitating particle sinking and export. Here, we compile and analyze a global data set of particulate organic carbon (POC), particulate inorganic carbon (PIC, or CaCO₃), and biogenic silica (bSi, or opal) concentrations collected using large volume pumps (LVPs). We analyze the distribution of all three biogenic phases in the small (1–53 μm) and large (>53 μm) size classes. Over the entire water column 76% of POC exists in the small size fraction. Similarly, the small size class contains 82% of PIC, indicating the importance of small‐sized coccolithophores to the PIC budget of the ocean. In contrast, 50% of bSi exists in the large size fraction, reflecting the larger size of diatoms and radiolarians compared with coccolithophores. We use PIC:POC and bSi:POC ratios in the upper ocean to document a consistent signal of shallow mineral dissolution, likely linked to biologically mediated processes. Sediment trap PIC:POC and bSi:POC are elevated with respect to LVP samples and increase strongly with depth, indicating the concentration of mineral phases and/or a deficit of POC in large sinking particles. We suggest that future sampling campaigns pair LVPs with sediment traps to capture the full particulate field, especially the large aggregates that contribute to mineral‐rich deep ocean fluxes, and may be missed by LVPs. 

Marine dissolved organic matter (DOM) is a major reservoir that links global carbon, nitrogen, and phosphorus. DOM is also important for marine sulfur biogeochemistry as the largest water column reservoir of organic sulfur. Dissolved organic sulfur (DOS) can originate from phytoplankton-derived biomolecules in the surface ocean or from abiotically “sulfurized” organic matter diffusing from sulfidic sediments. These sources differ in 34S/32S isotope ratios (δ34S values), with phytoplankton-produced DOS tracking marine sulfate (21‰) and sulfurized DOS mirroring sedimentary porewater sulfide (∼0 to –10‰). We measured the δ34S values of solid-phase extracted (SPE) DOM from marine water columns and porewater from sulfidic sediments. Marine DOM_SPE δ34S values ranged from 14.9‰ to 19.9‰ and C:S ratios from 153 to 303, with lower δ34S values corresponding to higher C:S ratios. Marine DOM_SPE samples showed consistent trends with depth: δ34S values decreased, C:S ratios increased, and δ13C values were constant. Porewater DOM_SPE was 34S-depleted (∼-0.6‰) and sulfur-rich (C:S ∼37) compared with water column samples. We interpret these trends as reflecting at most 20% (and on average ∼8%) contribution of abiotic sulfurized sources to marine DOS_SPE and conclude that sulfurized porewater is not a main component of oceanic DOS and DOM. We hypothesize that heterogeneity in δ34S values and C:S ratios reflects the combination of sulfurized porewater inputs and preferential microbial scavenging of sulfur relative to carbon without isotope fractionation. Our findings strengthen links between oceanic sulfur and carbon cycling, supporting a realization that organic sulfur, not just sulfate, is important to marine biogeochemistry. 

Abstract Quantifying variability in, and identifying the mechanisms behind, East Asian dust production and transport across the last several million years is essential for constraining future dust emissions and deposition. Our current understanding of East Asian dust dynamics through the Quaternary is primarily limited to low‐resolution records from the North Pacific Ocean, those from the Chinese Loess Plateau (CLP), and paleoenvironmental reconstructions from arid basins. All are susceptible to sediment winnowing and focusing as well as input of poorly constrained or unidentified non‐dust detrital material. To avoid these limitations, we examine high‐resolution, constant flux proxy‐derived dust fluxes from the North Pacific and find evidence for higher glacial dust fluxes in the late Pliocene‐early Pleistocene compared to the late Pleistocene‐Holocene. Our results suggest decreasing dust transported to the mid‐latitude North Pacific Ocean from eastern Asia across the Quaternary. This observation is ostensibly at odds with previous dust records from marine sediments and the CLP, and with the perception of higher East Asian dust production and transport during the late Pleistocene associated with the amplification of glaciations. We provide three possible scenarios to describe the ∼2,700‐ky evolution of eastern Asia glacial dust dynamics, and discuss them in the context of sediment production, availability, and atmospheric circulation. Our data and proposed driving mechanisms not only raise questions about the framework typically used to interpret dust archives from East Asia and the North Pacific Ocean, but also provide a roadmap for hypothesis testing and future work necessary to produce better‐constrained records of paleo‐dust fluxes. 

Abstract The deep ocean has long been recognized as the reservoir that stores the carbon dioxide (CO₂) removed from the atmosphere during Pleistocene glacial periods. The removal of glacial atmospheric CO₂into the ocean is likely modulated by an increase in the degree of utilization of macronutrients at the sea surface and enhanced storage of respired CO₂in the deep ocean, known as enhanced efficiency of the biological pump. Enhanced biological pump efficiency during glacial periods is most easily documented in the deep ocean using proxies for oxygen concentrations, which are directly linked to respiratory CO₂levels. We document the enhanced storage of respired CO₂during the Last Glacial Maximum (LGM) in the Pacific Southern Ocean and deepest Equatorial Pacific using records of deglacial authigenic manganese, which form as relict peaks during increases in bottom water oxygen (BWO) concentration. These peaks are found at depths and regions where other oxygenation histories have been ambiguous, due to diagenetic alteration of authigenic uranium, another proxy for BWO. Our results require that the entirety of the abyssal Pacific below approximately 1,000 m was enriched in respired CO₂and depleted in oxygen during the LGM. The presence of authigenic Mn enrichment in the deep Equatorial Pacific for each of the last five deglaciations suggests that the storage of respired CO₂in the deep ocean is a ubiquitous feature of late‐Pleistocene ice ages. 

Abstract Processes controlling dissolved barium (dBa) were investigated along the GEOTRACES GA03 North Atlantic and GP16 Eastern Tropical Pacific transects, which traversed similar physical and biogeochemical provinces. Dissolved Ba concentrations are lowest in surface waters (∼35–50 nmol kg⁻¹) and increase to 70–80 and 140–150 nmol kg⁻¹in deep waters of the Atlantic and Pacific transects, respectively. Using water mass mixing models, we estimate conservative mixing that accounts for most of dBa variability in both transects. To examine nonconservative processes, particulate excess Ba (pBa_xs) formation and dissolution rates were tracked by normalizing particulate excess²³⁰Th activities. Th‐normalized pBa_xsfluxes, with barite as the likely phase, have subsurface maxima in the top 1,000 m (∼100–200 μmol m⁻² year⁻¹average) in both basins. Barite precipitation depletes dBa within oxygen minimum zones from concentrations predicted by water mass mixing, whereas inputs from continental margins, particle dissolution in the water column, and benthic diffusive flux raise dBa above predications. Average pBa_xsburial efficiencies along GA03 and GP16 are ∼37% and 17%–100%, respectively, and do not seem to be predicated on barite saturation indices in the overlying water column. Using published values, we reevaluate the global freshwater dBa river input as 6.6 ± 3.9 Gmol year⁻¹. Estuarine mixing processes may add another 3–13 Gmol year⁻¹. Dissolved Ba inputs from broad shallow continental margins, previously unaccounted for in global marine summaries, are substantial (∼17 Gmol year⁻¹), exceeding terrestrial freshwater inputs. Revising river and shelf dBa inputs may help bring the marine Ba isotope budget more into balance.