Bottom Water Oxygen Concentrations Research Articles

Alkaline mineral addition to anoxic to hypoxic Baltic Sea sediments as a potentially efficient CO2-removal technique

Recent studies have begun to explore the potential of enhanced benthic weathering (EBW) in the Baltic Sea as a measure for climate change mitigation. To augment the understanding of EBW under seasonally changing conditions, this study aims to investigate weathering processes under anoxia to hypoxia in corrosive bottom waters, which reflect late summer conditions in the Baltic Sea. Dunite and calcite were added to sediment cores retrieved from Eckernförde Bay (Western Baltic Sea) with a constant flow-through of deoxygenated, CO2-enriched Baltic Sea bottom water. The addition of both materials increased benthic alkalinity release by 2.94 μmol cm−2 d−1 (calcite) and 1.12 μmol cm−2 d−1 (dunite), compared to the unamended control experiment. These excess fluxes are significantly higher than those obtained under winter conditions. The comparison with bottom water oxygen concentrations emphasizes that highest fluxes of alkalinity were associated with anoxic phases of the experiment. An increase in Ca and Si fluxes showed that the enhanced alkalinity fluxes could be attributed to calcite and dunite weathering. First order rate constants calculated based on these data were close to rates published in previous studies conducted under different conditions. This highlights the suitability of these proxies for mineral dissolution and justifies the use of these rate constants in modeling studies investigating EBW in the Baltic Sea and areas with similar chemical conditions. Generally stable pH profiles over the course of the experiment, together with the fact that the added minerals remained on the sediment surface, suggest that corrosive bottom waters were the main driving factor for the dissolution of the added minerals. These factors have important implications for the choice of mineral and timing for EBW as a possible marine carbon dioxide removal method in seasonally hypoxic to anoxic regions of the Baltic Sea.

Early Diagenetic Controls on Sedimentary Iodine Release and Iodine‐To‐Organic Carbon Ratios in the Paleo‐Record

AbstractIodine cycling in the ocean is closely linked to productivity, organic carbon export, and oxygenation. However, iodine sources and sinks at the seafloor are poorly constrained, which limits the applicability of iodine as a biogeochemical tracer. We present pore water and solid phase iodine data for sediment cores from the Peruvian continental margin, which cover a range of bottom water oxygen concentrations, organic carbon rain rates and sedimentation rates. By applying a numerical reaction‐transport model, we evaluate how these parameters determine benthic iodine fluxes and sedimentary iodine‐to‐organic carbon ratios (I:Corg) in the paleo‐record. Iodine is delivered to the sediment with organic material and released into the pore water as iodide (I−) during early diagenesis. Under anoxic conditions in the bottom water, most of the iodine delivered is recycled, which can explain the presence of excess dissolved iodine in near‐shore anoxic seawater. According to our model, the benthic I− efflux in anoxic areas is mainly determined by the organic carbon rain rate. Under oxic conditions, pore water dissolved I− is oxidized and precipitated at the sediment surface. Much of the precipitated iodine re‐dissolves during early diagenesis and only a fraction is buried. Particulate iodine burial efficiency and I:Corg burial ratios do increase with bottom water oxygen. However, multiple combinations of bottom water oxygen, organic carbon rain rate and sedimentation rate can lead to identical I:Corg, which limits the utility of I:Corg as a quantitative oxygenation proxy. Our findings may help to better constrain the ocean's iodine mass balance, both today and in the geological past.

Ocean Oxygen, Preformed Nutrients, and the Cause of the Lower Carbon Dioxide Concentration in the Atmosphere of the Last Glacial Maximum

AbstractAll else equal, if the ocean's “biological [carbon] pump” strengthens, the dissolved oxygen (O2) content of the ocean interior declines. Confidence is now high that the ocean interior as a whole contained less oxygen during the ice ages. This is strong evidence that the ocean's biological pump stored more carbon in the ocean interior during the ice ages, providing the core of an explanation for the lower atmospheric carbon dioxide (CO2) concentrations of the ice ages. Vollmer et al. (2022, https://doi.org/10.1029/2021PA004339) combine proxies for the oxygen and nutrient content of bottom waters to show that the ocean nutrient reservoir was more completely harnessed by the biological pump during the Last Glacial Maximum, with an increase in the proportion of dissolved nutrients in the ocean interior that were “regenerated” (transported as sinking organic matter from the ocean surface to the interior) rather than “preformed” (transported to the interior as dissolved nutrients by ocean circulation). This points to changes in the Southern Ocean, the dominant source of preformed nutrients in the modern ocean, with an apparent additional contribution from a decline in the preformed nutrient content of North Atlantic‐formed interior water. Vollmer et al. also find a lack of LGM‐to‐Holocene difference in the preformed 13C/12C ratio of dissolved inorganic carbon. This finding may allow future studies to resolve which of the proposed Southern Ocean mechanisms was most responsible for enhanced ocean CO2 storage during the ice ages: (a) coupled changes in ocean circulation and biological productivity, or (b) physical limitations on air‐sea gas exchange.

The role of seasonal hypoxia and benthic boundary layer exchange on iron redox cycling on the Oregon shelf

AbstractWidespread hypoxia occurs seasonally across the Oregon continental shelf, and the duration, intensity, and frequency of hypoxic events have increased in recent years. In hypoxic regions, iron reduction can liberate dissolved Fe(II) from continental shelf sediments. Fe(II) was measured in the water column across the continental shelf and slope on the Oregon coast during summer 2022 using both a trace metal clean rosette and a high‐resolution benthic gradient sampler. In the summer, Fe(II) concentrations were exceptionally high (40–60 nM) within bottom waters and ubiquitous across the Oregon shelf, reflecting the low oxygen condition (40–70 μM) at that time. The observed inverse correlation between Fe(II) and bottom water oxygen concentrations is in agreement with expectations based on previous work that demonstrates oxygen is a major determinant of benthic Fe fluxes. Rapid attenuation of Fe(II) from the benthic boundary layer (within 1 m of the seafloor) probably reflects efficient cross‐shelf advection. One region, centered around Heceta Bank (~ 44°N) acts a hotspot for Fe release on the Oregon continental shelf, likely due to its semi‐retentive nature and high percent mud content in sediment. The results suggest that hypoxia is an important determinant of the inventory of iron is Oregon shelf waters and thus ultimately controls the importance of continental margin‐derived iron to the interior of the North Pacific Basin.

Revisiting the relationship between the pore water carbon isotope gradient and bottom water oxygen concentrations

Reconstructing the oxygen content at the ocean floor provides insight into ocean circulation, ventilation, and carbon storage in the deep sea. The microbial breakdown of organic carbon within marine sediment through aerobic respiration consumes oxygen in the pore fluid and releases dissolved inorganic carbon. The offset in the carbon isotopic composition, δ13C, of epifaunal and infaunal foraminifera, Δδ13C, is considered to reflect the aerobic respiration of organic carbon and can be used to reconstruct the oxygen content of the bottom water. Previous work provided an empirical calibration that was suggested to be valid for oxygen reconstructions between 55 and 235 μmol kg−1. In this study, we apply a biogeochemical reactive transport model (RTM) to extend and update this calibration, allowing for the reconstruction of oxygen concentrations ([O2]) up to ∼300 μmol kg−1. Using the RTM and new bottom water [O2] and pore fluid measurements from Iberian Margin sediment cores, we also demonstrate that the calibration between the Δδ13C and bottom water [O2] must account for the coupled changes in the carbon system due to the respiration of organic carbon in the overlying ocean including the concentration and carbon isotopic composition of the dissolved inorganic carbon, and the δ13C of the organic carbon within the sediment column. We apply the improved calibration to reconstruct the changes in oxygen content at International Ocean Discovery Program (IODP) Site U1385 in the deep North Atlantic over the past 1.5 Myr.

Artificial reef biofouling community impacts on ecosystem metabolism and biogeochemical cycling in estuarine waters of the northern Gulf of Mexico

Artificial reefs increase hard bottom habitat and bolster shoreline protection in coastal waters. Reefs are rapidly colonized by biofouling communities which can potentially alter ecosystem metabolism. Despite the high biomass and ubiquitous nature of biofouling communities, little is known about their ecosystem metabolism or role in biogeochemical nutrient cycling. Using a combination of laboratory and field-based methods, this study focused on the metabolic activity of artificial reef biofouling communities and their potential to contribute to water column hypoxia in a shallow subtropical estuary. Study objectives aimed to (1) measure in situ dissolved oxygen (DO) concentrations in surface and bottom waters along reef transects during summer months when episodic hypoxic events typically occur, (2) estimate respiration rates in relation to nutrient regeneration in the absence versus presence of biofouling communities, and (3) examine seasonal shifts in trophic structure by relating elemental C:N ratios and stable nitrogen isotope (δ15N) values of the biofouling community across eight sample periods. In situ DO in bottom waters was low near high profile reefs. Water column respiration and nutrient regeneration rates were comparable to other estuaries. Respiration and regeneration rates of ammonium and phosphate were all manifestly higher in the presence of a biofouling community. Biofouling metabolic-driven processes were higher at low profile reefs than at high profile reefs. Seasonal shifts in biofouling elemental composition indicated by higher C:N and lower δ15N during cooler months and lower C:N and higher δ15N during warmer months reflected a transition from a more autotrophic community in winter to a more heterotrophic community during the rest of the year. Our results demonstrate that artificial reef biofouling communities can potentially contribute to hypoxic conditions in coastal waters of the northern Gulf of Mexico.

Paleoproductivity and deep-sea oxygenation in Cosmonaut Sea since the last glacial maximum: impact on atmospheric CO2

The paleoproductivity in the Southern Ocean plays a crucial role in controlling the atmospheric CO2 concentration. Here, we present the sediment record of gravity core ANT37-C5/6-07, which was retrieved from the Cosmonaut Sea (CS), Indian Ocean sector of the Southern Ocean. We found that the change in the oxygen concentration in the CS bottom water is strongly correlated with the atmospheric CO2 fluctuations since the Last Glacial Maximum (LGM). Based on the change in the export production, we reconstructed the evolution history of the deep-water ventilation/upwelling in the study area. During the LGM, a large amount of respiratory carbon was stored in the deep Southern Ocean due to the effect of the low export productivity and restricted ventilation. The oxygen concentration was also low at this time. Despite the increase in paleoproductivity, the biological pump efficiency remained at a low level during the Last Deglaciation. Vast quantities of CO2 were released into the atmosphere through enhanced upwelling. The recovery of ventilation during this period facilitated the supply of oxygen-rich surface water to the deep ocean. Moreover, signals were identified during the transitions between the Heinrich Stage 1 (HS1), Antarctic Cold Reverse (ACR), and Younger Drays (YD) periods. During the Holocene, the productivity increased overall, and the oxygen in the bottom water was consumed but still remained at a high level. This may have been caused by the enhanced ventilation and/or the prevalence of East Cosmonaut Polynya (ECP) near Cape Ann.

Sedimentary molybdenum and uranium cycling under seasonally contrasting redox conditions on the Namibian Shelf

Sedimentary molybdenum (Mo) and uranium (U) enrichments have been widely used as a proxy for redox conditions in oxygen-depleted marine paleo-environments. However, in a dynamic upwelling system the seasonal fluctuations from oxic to completely anoxic-sulfidic bottom waters and lateral sediment transport can modify the primary Mo and U signal of the sediment, which in turn may impact paleo-redox interpretations. In this study we present pore water and solid phase data collected at two cross shelf transects during the ‘more oxygenated’ austral winter and ‘anoxic’ austral summer to study the influence of spatially and seasonally contrasting redox conditions on the formation of authigenic Mo and U enrichments in organic carbon (TOC) rich mud belt sediments on the Namibian shelf. A mass balance was established for each element based on diffusive fluxes and element mass accumulation rates to evaluate the respective mechanisms of trace metal delivery, accumulation and recycling.Mo is delivered to the sediment in its dissolved form via diffusion across the sediment–water interface, especially during austral summer when bottom waters are anoxic and surface sediments are highly sulfidic. In the center of the inner shelf mud belt, the benthic Mo fluxes of up to 37 nmol cm−2 yr−1 into sulfidic surface sediments are the highest ever reported for reducing sulfidic systems and agree with the rate of Mo accumulation in the solid phase. Concurrently, high sedimentation rates and low terrigenous input limit solid phase Mo accumulation on the Namibian shelf. In ancient marine sediments, this mode of Mo cycling can be identified by low Mo/TOC ratios of ∼2 similar to those found in sediments deposited below the perennial oxygen minimum zone on the Peruvian shelf and to those found in deposits of the Cretaceous Oceanic Anoxic Event 2. Diffusive U fluxes into the sediment are generally too low to account for the sedimentary enrichment leading to the conclusion that U is delivered mainly in particulate form. In areas with anoxic bottom water, shallow dissolved U maxima directly below the sediment water interface and rather low sedimentary U content indicate that particulate U is recycled and largely released back into the bottom water. At sites where bottom water oxygen concentrations vary from anoxic to completely oxic on seasonal timescales, the depth at which Mo and U are removed from pore waters moves vertically within the sediment column thus defining a layer between the sediment surface and ∼20 cm depth, in which Mo and U accumulate in the solid phase. Our results emphasize the importance of short-term redox fluctuations in the bottom waters and underlying sediments, as well as lateral sediment transport for the authigenic enrichment of redox-sensitive trace metals in reducing shelf sediments. The relative enrichment patterns identified might be useful for the reconstruction of open marine anoxia in the geological past.

Distribution of modern benthic foraminiferal assemblages across the Northeast Greenland continental shelf

Analysis of benthic foraminifera in surface samples from 23 sites on the Northeast Greenland continental shelf reveal key assemblage differences between sites. Cluster analysis creates two clear geographical faunal assemblage zones: the 1) inner shelf, and 2) mid and outer shelf sites. These assemblages differ significantly, with the inner shelf sites being characterised by a high percentage and concentration of calcareous species, whilst the mid and outer shelf sites are dominated by agglutinated taxa. At almost all sites, the calcareous assemblages are dominated by Cassidulina neoteretis and Cassidulina reniforme, suggesting that they thrive across the shelf. Stetsonia horvathi, Oridorsalis tener, as well as Glomulina oculus and other miliolid species are found to be key calcareous species at many sites in the inner shelf zone, but they are rare-to-absent on the mid and outer shelf. Canonical correspondence analysis shows that September sea-ice cover and bottom water oxygen content are positively correlated with benthic foraminiferal assemblages at inner shelf sites, whereas organic carbon content is correlated with those in the mid and outer shelf. The formation of seasonal sea-ice and the Northeast Water polynya rejects brine into surrounding waters and transports CO2 to the seafloor, creating a highly corrosive environment for calcium carbonate. These environments are also highly productive, as indicated by the high organic carbon content and low bottom water oxygen content. The oxidation of this organic material creates CO2. We propose that these processes are key drivers in the dissolution of calcareous tests. In contrast, extensive sea-ice, high bottom water oxygen content and low primary productivity in the glacier-proximal region facilitates carbonate preservation.

Multi-proxy reconstruction of climate changes in the Lower St. Lawrence Estuary, Canada, during the Middle and Late-Holocene

The micropaleontological and palynological content, and geochemical and isotopic composition of a marine sediment core collected off Pointe-des-Monts in eastern Québec, Canada, reveal regional palaeoclimatic and paleoceanographic conditions in the Lower St. Lawrence Estuary over the last ~8200 years. The pollen and spore content allows comparison with the terrestrial palynostratigraphy, whereas dinoflagellate cysts and benthic foraminifera are used to reconstruct sea-surface conditions and bottom water properties, respectively. The dinocyst-based reconstructions indicate shifts between estuarine and oceanic conditions with important changes in sea-surface temperature, salinity, and primary productivity. Both the dinocyst assemblages and the quantitative sea-surface estimates highlight a distinct transition at ca. 4200 cal years BP. It is notably marked by a change towards higher salinity, which suggests reduced freshwater discharge, hence lower precipitation in the watershed, during the Late-Holocene. The isotopic composition (δ18O and δ13C) and assemblages of the benthic foraminifera indicate centennial to millennial frequency variability of bottom water properties, over a general trend towards decreasing temperatures and increasing ventilation from the beginning of the Middle Holocene until the last century. Since then, reverse trends with abrupt warming and decreasing dissolved oxygen content in bottom water have been observed.

Reconstructing ocean oxygenation changes from U/Ca and U/Mn in foraminiferal coatings: Proxy validation and constraints on glacial oxygenation changes

Deep-sea oxygen concentrations reflect combined effects of air-sea exchange in high-latitude surface waters, ventilation through ocean circulation and the organic carbon remineralization at depth. Reconstruction of past bottom water oxygen (BWO) concentrations has been challenging due to limitations of each existing BWO proxy whose fidelity may be complicated by diagenetic or depositional factors. Therefore, evaluations on BWO changes with multi-proxy approach are always preferred. In this study, we exploit the authigenic uranium content on mixed planktonic foraminiferal coatings as a BWO proxy by presenting new foraminiferal U/Ca and U/Mn ratios of the Holocene and last glacial maximum (LGM) sediments from 54 sites throughout the Pacific Ocean, covering a range of modern BWO from 8 to 210 μmol/kg. Distinct correlation between Holocene foraminiferal U/Ca and U/Mn with BWO is observed in the modern Pacific Ocean, which has not been obscured by other complicating factors such as sedimentation rate and organic carbon flux. Based on the comparison of our foraminiferal U/Ca and U/Mn ratios between the Holocene and LGM and existing redox proxy data, we provide new constraints on Equatorial and South Pacific oxygenation changes during the LGM. First, the boundary between better oxygenated upper ocean and less oxygenated deeper ocean in the Eastern Equatorial Pacific was limited to a narrower water depth range between ∼0.6 and 0.7 km surrounding the Panama Basin. Second, our data imply better oxygenation in the upper and bottom waters of the Pacific Ocean and mid-depth deoxygenation, which contrasts with findings in the deep Atlantic and Indian Oceans. After excluding influences from other factors such as sedimentation rates and productivity, our study demonstrates foraminiferal U/Ca and U/Mn provide a useful proxy for BWO reconstruction in the Pacific, thus helping to constrain the glacial-interglacial oceanic carbon cycle.

Trace metals as a redox proxy in Arabian Sea sediments in and below the oxygen minimum zone

Sedimentary trace metals are widely used to reconstruct past bottom water redox conditions. The calibration of trace metals as a redox proxy for oxygen minimum zones (OMZs) can still be improved. Here, we combine pore water and solid phase Mo, U, Re and V profiles with Fe and Mn data for ten sites along a bottom water oxygen (2 to 83 μmol L−1 O2) and water depth gradient (885 to 3010 m) in and below the perennial OMZ in the northern Arabian Sea (Murray Ridge). Trends in sedimentary Mo, U and Re contents generally follow ambient bottom water redox conditions, with the highest enrichments in OMZ sediments, supporting the validity of these trace metals as redox proxies. Vanadium and Fe are exclusively enriched in the sediments of the most anoxic OMZ site and do not capture further redox changes in and below the OMZ. We attribute the absence of a redox trend in sedimentary Fe content to the mildly reducing conditions in the sediments, with little FeS formation and benthic release of Fe. Manganese, in contrast, is depleted in the OMZ sediments and enriched in sediments below the OMZ, in accordance with loss from OMZ sediments and transfer of Mn to deeper sites (“Mn shuttling”). Manganese oxides are likely a key carrier of Mo and V to the sediments, especially below the OMZ, while diffusion across the sediment-water interface supplies U. Sedimentary Mo, U and V contents in the present-day Arabian Sea OMZ are generally lower than observed in other perennial OMZs. This may be related to a lower input of organic matter in this part of the Arabian Sea when compared to other OMZs, and hence, less anaerobic degradation of organic matter and less authigenic fixation of metals, even at the same bottom water oxygen concentrations. Our results have implications for the detection of OMZs in the geological record, implying that thresholds in trace metal concentrations for perennial OMZs may be lower than previously considered. Comparison of our Mo, U, Re and V data to trace metal records from 15 to 200 ka for the same Arabian Sea region suggests that the OMZ was periodically wider and more reducing in the past.

Bioturbation and the δ56Fe signature of dissolved iron fluxes from marine sediments.

We developed a reaction-transport model capable of tracing iron isotopes in marine sediments to quantify the influence of bioturbation on the isotopic signature of the benthic dissolved (DFe) flux. By fitting the model to published data from marine sediments, we calibrated effective overall fractionation factors for iron reduction (-1.3‰), oxidation (+0.4‰), iron-sulfide precipitation (+0.5‰) and dissolution (-0.5‰) and pyrite precipitation (-0.7‰) that agree with literature values. Results show that for bottom-water oxygen concentrations greater than 50 µM, higher bioturbation increased the benthic DFe flux and its δ 56Fe signature. By contrast, for oxygen concentrations less than 50 µM, higher bioturbation decreased the benthic DFe flux and its δ 56Fe signature. The expressed overall fractionation of the benthic DFe flux relative to the δ 56Fe of the iron oxides entering the sediment ranges from -1.67‰ to 0.0‰. On a global scale, the presence of bioturbation increases sedimentary DFe release from approximately 70 G mol DFe yr-1 to approximately 160 G mol DFe yr-1 and decreases the δ 56Fe signature of the DFe flux.

Marine sedimentary uranium to barium ratios as a potential quantitative proxy for Pleistocene bottom water oxygen concentrations

Oxygen is essential for marine ecosystems, and it is linked by respiration to carbon storage in the deep ocean. Reconstructing oxygen concentrations in the past has been limited by the absence of quantitative, rather than qualitative, proxies, but several new (semi-) quantitative oxygen proxies have recently been developed. In this study we explore the possibility of adding bulk sedimentary uranium (U) to this list by normalizing it to barium (Ba). First, U/Ba and bottom water oxygen concentrations are compared on a global scale, using a core top database, in pelagic environments greater than 200 m water depth. Then, the relationships between U/Ba and bottom water oxygen are examined on smaller spatial scales: within each ocean basin and regionally within the Eastern Equatorial Pacific, the Arabian Sea, and Western Equatorial Atlantic. At this regional scale, where secondary influences on the behavior of both U and Ba may be more spatially uniform, empirical piecewise linear calibrations are developed and subsequently tested on downcore records. U/Ba-based oxygen reconstructions generally agree with those derived from previously published alkenone preservation and benthic foraminiferal surface porosity records. Several limitations to the utility of U/Ba as a proxy for oxygen have also been identified. The proxy should only be applied in the uppermost sedimentary intervals that contain porewater sulfate to minimize barite diagenesis, and phosphorus contents should be monitored for the potential influence of apatite on uranium content. U/Ba is more successful at recording oxygen concentrations during mean glacial and interglacial periods than during climate transitions, when the timing and amplitude may be more sensitive to burndown and smoothing. Conservative errors on the calibrations result in the greatest utility of U/Ba in regions with relatively high oxygen concentrations (e.g., >50 μmol/kg) and large oxygen variability (±10 s of μmol/kg). Even with these caveats, U/Ba is only one of two quantitative oxygen proxies potentially capable of recording variability above 50 μmol/kg, and further investigation into its functionality in different environmental settings is worthwhile in the endeavor to reconstruct the full marine range of oxygen concentrations in the past.

Predicted Episode of Submarine Groundwater Discharge Onto the South Carolina, USA, Continental Shelf and Its Effect on Dissolved Oxygen

AbstractSubmarine groundwater discharge (SGD) may directly influence the dissolved oxygen (DO) content of coastal bottom waters. Here, we report a predicted episode of enhanced SGD that caused low DO concentrations on the South Carolina continental shelf. The prediction model linked episodes of SGD to upwelling‐favorable winds. The data revealed these waters were a factor of 2–6 higher in 226Ra and 228Ra compared to typical bottom water values and were significantly depleted in DO (<130 μM). The tight 228Ra:226Ra correlation of these data was similar to values during a strong hypoxic event off SC in 2012. Water ages from 224Ra and 223Ra indicated the event occurred 2–9 days before sampling. The success of the prediction lends added credence to the correlation of upwelling‐favorable winds—but not necessarily accompanied by upwelling—to episodic SGD events. This prediction from wind data represents a major advance for quantifying SGD in the region.

Decadal Time‐Series Depletion of Dissolved Oxygen at Abyssal Depths in the Northeast Pacific

AbstractDissolved oxygen depletion in the global ocean is well documented over several decades from the surface ocean to abyssal depths. This decline is especially prevalent in the Northeast Pacific. A significant decline in dissolved oxygen has been measured over 30 years at 4,000–4,100 m depth (Station M) beneath the California Current off central California. Three principal hypotheses examined the relationship of declining oxygen with biological and physical factors over the 30‐year time series. Annual resolution revealed Ekman pumping, coastal upwelling, particulate matter flux, and sediment community oxygen consumption having significant correlations with bottom water dissolved oxygen concentration. Coastal upwelling accounted for 65% of the annual variation in bottom water oxygen concentration. Stepwise regression yielded descriptive models of bottom water dissolved oxygen using coastal upwelling, wind stress and primary production variables. Is continued oxygen depletion in the Northeast Pacific indicative of abyssal regions in the world ocean?

The Peruvian oxygen minimum zone was similar in extent but weaker during the Last Glacial Maximum than Late Holocene

Quantifying past oxygen concentrations in oceans is crucial to improving understanding of current global ocean deoxygenation. Here, we use a record of pore density of the epibenthic foraminifer Planulina limbata from the Peruvian Oxygen Minimum Zone to reconstruct oxygen concentrations in bottom waters from the Last Glacial Maximum to the Late Holocene at 17.5°S about 500 meters below the sea surface. We found that oxygen levels were 40% lower during the Last Glacial Maximum than during the Late Holocene (about 6.7 versus 11.1 µmol/kg, respectively). A comparison with other reconstructions of oxygen concentrations in the region reveals a shallow Oxygen Minimum Zone during the Last Glacial Maximum that was similar in water depth and extent but weaker than during the Late Holocene. Increased glacial oxygen concentrations are probably related to lower temperatures (higher oxygen solubility), decreased nutrient and increased oxygen supply by source waters, and a decrease in coastal upwelling.

Sedimentary molybdenum and uranium: Improving proxies for deoxygenation in coastal depositional environments

Sedimentary molybdenum (Mo) and uranium (U) enrichments are widely used to reconstruct changes in bottom water oxygen conditions in aquatic environments. Until now, most studies using Mo and U have focused on restricted suboxic-euxinic basins and continental margin oxygen minimum zones (OMZs), leaving mildly reducing and oxic (but eutrophic) coastal depositional environments vastly understudied. Currently, it is unknown: (1) to what extent Mo and U enrichment factors (Mo- and U-EFs) can accurately reconstruct oxygen conditions in coastal sites experiencing mild deoxygenation, and (2) to what degree secondary (depositional environmental) factors impact Mo- and U-EFs. Here we investigate 18 coastal sites with varying bottom water redox conditions, which we define by means of five “redox bins”, ranging from persistently oxic to persistently euxinic, from a variety of depositional environments. Our results demonstrate that Mo- and U-EF-based redox proxies and sedimentary Mo and U contents can be used to differentiate bottom water oxygen concentration among a range of modern coastal depositional environments. This is underpinned by the contrasting EFs of Mo and U along the redox gradient, which shows a substantial difference of Mo-EFs between redox bins 3–5 (ir/regularly suboxic – ir/regularly dysoxic – persistently oxic) and of U-EFs between redox bins 1–2 (persistently euxinic – ir/regularly euxinic). Surprisingly, we observe comparatively low redox proxy potential for U in environments of mild deoxygenation (redox bins 3–5). Further, we found that secondary factors can bias Mo-and U-EFs to such an extent that EFs do not reliably reflect bottom water redox conditions. We investigate the impact of limited Mo sedimentary sequestration in sulfidic depositional environments (i.e., the “basin reservoir effect”, equilibrium with FeMoS4), Fe/Mn-(oxy)(hydr)oxide “shuttling”, oxidative dissolution, the sulfate methane transition zone in the sediment, sedimentation rate, and the local Al background on Mo- and U-EFs.

Impacts of bioturbation on iron biogeochemistry and microbial communities in coastal sediment mesocosms under varying degrees of hypoxia

Coastal sediments are important sources of dissolved iron (dFe) that make the coastal ocean iron replete, and contribute an important supply of dFe to the photic regions of the adjacent open ocean. The biogeochemical processes that dictate sedimentary dFe flux are a complex interplay of microbial activities related to reduction-oxidation condition, Fe and S cycling, and sediment bio-mixing and bio-irrigation by benthic fauna. We investigated the effect of bottom water oxygen concentration on iron dynamics in laboratory mesocosms in the presence and absence of the common polychaete Nereis diversicolor. Mesocosms were established using sediment obtained from a local intertidal mudflat, maintained with varying levels of hypoxia (defined as <63 μM dissolved O2), and monitored for changes in iron biogeochemistry. At the end of the experiment, subcores were taken to measure solid phase Fe species and microbial community analysis via 16S rDNA gene sequencing. Bioturbation played an important role in increasing the quantity of poorly crystalline Fe(III)-oxides within the sediments, but decreasing the flux of Fe(II) across the sediment-water interface. These results further demonstrate the importance of bioturbation for sedimentary Fe-cycling and show a complex response to hypoxia involving both animal behavior and microbial response.

Cable Bacteria Activity Modulates Arsenic Release From Sediments in a Seasonally Hypoxic Marine Basin.

Eutrophication and global change are increasing the occurrence of seasonal hypoxia (bottom-water oxygen concentration <63 μM) in coastal systems worldwide. In extreme cases, the bottom water can become completely anoxic, allowing sulfide to escape from the sediments and leading to the development of bottom-water euxinia. In seasonally hypoxic coastal basins, electrogenic sulfur oxidation by long, filamentous cable bacteria has been shown to stimulate the formation of an iron oxide layer near the sediment-water interface, while the bottom waters are oxygenated. Upon the development of bottom-water anoxia, this iron oxide “firewall” prevents the sedimentary release of sulfide. Iron oxides also act as an adsorption trap for elements such as arsenic. Arsenic is a toxic trace metal, and its release from sediments can have a negative impact on marine ecosystems. Yet, it is currently unknown how electrogenic sulfur oxidation impacts arsenic cycling in seasonally hypoxic basins. In this study, we presented results from a seasonal field study of an uncontaminated marine lake, complemented with a long-term sediment core incubation experiment, which reveals that cable bacteria have a strong impact on the arsenic cycle in a seasonally hypoxic system. Electrogenic sulfur oxidation significantly modulates the arsenic fluxes over a seasonal time scale by enriching arsenic in the iron oxide layer near the sediment-water interface in the oxic period and pulse-releasing arsenic during the anoxic period. Fluxes as large as 20 μmol m−2 day−1 were measured, which are comparable to As fluxes reported from highly contaminated sediments. Since cable bacteria are recognized as active components of the microbial community in seasonally hypoxic systems worldwide, this seasonal amplification of arsenic fluxes is likely a widespread phenomenon.