Overlying Water Column Research Articles

The Sinking Dead—Arctic Deep‐Sea Scavengers' Diet Suggests Nekton as Vector in Benthopelagic Coupling

ABSTRACTMany benthic deep‐sea animals rely on carcasses from the overlying water column that sink to the seafloor and form local organic enrichments known as food falls. This flux of organic carbon from the shallow pelagic to the deep sea is part of the biological carbon pump (BCP) and as such contributes to carbon sequestration. For a complete understanding of local carbon budgets, it is crucial to identify the diversity and distribution of sinking carcasses which are difficult to detect by observational methods. Here, we analyzed the diet of the abundant amphipod scavenger, Eurythenes gryllus, by DNA metabarcoding to assess their potential to identify food falls in the Fram Strait, a gateway to the Arctic. E. gryllus scavenges on nekton but so far it was not certain whether this represents their main diet. We detected dietary taxa (26 in total) in 20 out of 101 analyzed amphipods. We found that amphipods primarily fed on larger nekton including fish, cephalopods, and mammals, with bony fish being the most targeted food source in terms of diversity and abundance. Only one amphipod had fed on a gelatinous organism. These results support the hypothesis that E. gryllus targets mostly nekton food falls. The diversity of dietary taxa differed between the Eastern and Western Fram Strait, which suggests regional variability in food falls availability. We also detected, for the first time in E. gryllus, infections with the parasitic dinoflagellate Hematodinium. This detection demonstrates the potential of metabarcoding for revealing both food web dynamics and host–parasite interactions in the deep sea. E. gryllus seems a promising “natural sampler” to monitor the diversity of deep‐sea food falls which will help to investigate the importance of medium‐sized food falls in local vertical carbon export in a rapidly changing Arctic Ocean.

Characteristics of Phosphate Sorption on Surface Sediments: A Study in Kendari Bay

Phosphate adsorption and desorption are significant processes that influence the presence of phosphate in aquatic ecosystems and regulate the concentration of phosphate at the water-sediment interface. This research aims to investigate the characteristics of phosphate adsorption and desorption in Kendari Bay sediments, study the relationship between adsorption capacity and sediment characteristics and its phosphorus fraction, and evaluate its potential contribution to the overlying water column. Physicochemical measurements of the water and sediments were performed in the sampling location and the laboratory. Two types of adsorption-desorption kinetics models and two types of isothermal adsorption models were used to estimate the adsorption rate and capacity of the surface sediments. Adsorption kinetics and desorption kinetics experiments produced pseudo-second-order kinetic model equations with regression coefficients (R2) of 0.865–0.936 and 0.886–0.947, respectively. The isothermal adsorption experiment follows the Langmuir equation model with R2 = 0.964. The maximum adsorption capacity (Qmax) value was 156.3–227.3 mg/kg, and the phosphate concentration value at zero equilibrium (EPC0) was 0.0026–0.0047 mgP/L. Notably, the EPC0 value was higher than the SRP concentration, indicating that the resuspension of phosphate ions from sediment into the water column could occur. Furthermore, there was a correlation between Qmax values with OP, Al-P, Fe-P, clay particles, and organic materials. Potential practical applications may include integrating sediment adsorption capacity data into ecosystem models to inform nutrient management strategies and promote sustainable coastal development in Kendari Bay and beyond.

Linkages Between Mineral Element Composition of Soils and Sediments With Hyporheic Zone Dissolved Organic Matter Chemistry Across the Contiguous United States

AbstractThe hyporheic zone is a hotspot for biogeochemical cycling where interactions with mineral metals preserve the release and biodegradation of organic matter (OM). A small fraction of OM can still be exchanged between localized sediments and the overlying water column, and recent evidence suggests there exists a longitudinal structuring in sediment dissolved OM (DOM) chemistry across the continental United States (CONUS). In this study, we tested a hypothesis that water extractable sediment DOM chemistry could be explained by sediment metal contents and integrative watershed scale features at the CONUS scale. Crowdsourced samples were characterized for high resolution mass spectrometry and coupled with sediment metals determined via x‐ray fluorescence as well as with land cover and soil elemental information obtained from national databases. Our results highlight weak relationships between DOM chemistry and elemental composition at the CONUS scale indicating limited transferability of organo‐metal linkages into multi‐scale hydrobiogeochemical models.

Raised water temperature enhances benthopelagic links via intensified bioturbation and benthos-mediated nutrient cycling

Sediment reworking by benthic infauna, namely bioturbation, is of pivotal importance in expansive soft-sediment environments such as the Wadden Sea. Bioturbating fauna facilitate ecosystem functions such as bentho-pelagic coupling and sediment nutrient remineralization capacities. Yet, these benthic fauna are expected to be profoundly affected by current observed rising sea temperatures. In order to predict future changes in ecosystem functioning in soft-sediment environments like the Wadden Sea, knowledge on the underlying processes such as sediment reworking, is crucial. Here, we tested how temperature affects bioturbation and its associated ecosystem processes, such as benthic nutrient fluxes and sediment oxygen consumption, using luminophore tracers and sediment incubation cores. We used a controlled mesocosm experiment set-up with key Wadden Sea benthos species: the burrowing polychaetes Arenicola marina and Hediste diversicolor, the bivalve Cerastoderma edule, and the tube-building polychaete Lanice conchilega. The highest bioturbation rates were observed from A. marina, reaching up to 375 cm2yr−1; followed by H. diversicolor, with 124 cm2yr−1 being the peak bioturbation rate for the ragworm. Additionally, the sediment reworking activity of A. marina facilitated nearly double the amount of silicate efflux compared to any other species. Arenicola marina and H. diversicolor accordingly facilitated stronger nutrient effluxes under a warmer temperature than L. conchilega and C. edule. The oxygen uptake of A. marina and H. diversicolor within the sediment incubation cores was correspondingly enhanced with a higher temperature. Thus, increases in sea temperatures may initially be beneficial to ecosystem functioning in the Wadden Sea as faunal bioturbation is definitely expedited, leading to a tighter coupling between the sediment and overlying water column. The enhanced bioturbation activity, oxygen consumption, and facilitated nutrient effluxes from these invertebrates themselves, will aid in the ongoing high levels of primary productivity and organic matter production.

Spatial Distribution, Ecological Risk Assessment, and Source Identification of Metals in Sediments of the Krka River Estuary (Croatia)

To evaluate the level of contamination and predict the potential toxicity risk, selected metal concentrations (Cd, Pb, Cr, Mn, Co, Ni, Cu, Zn, and As) were determined in 40 surface sediment samples from the stratified karstic Krka River estuary (Croatia). In addition, diffusive gradients in thin films (DGT) probes were deployed in situ to understand the mobilization mechanisms and bioavailability of metals in the sediment. The results show significant spatial differences between the upper and lower estuary, with the latter being more affected by anthropogenic pollution. The pollution assessment using the enrichment factor (EF), the geoaccumulation index (Igeo), and the pollution load index (PLI) showed a strong enrichment of metals in the lower part of the estuary, especially of Mn, Cu, Zn, Pb, and As. The statistical analysis (PCA) revealed the former ferromanganese factory and the port as major sources of pollution in the area. Nickel, Co, and Cr, although slightly elevated, may be attributed to the natural origin. The metal mobility in the estuarine sediment was primarily governed by early diagenetic processes (aerobic organic matter mineralization, Fe and Mn oxyhydroxide reduction), which caused the release of metals from the sediment into the pore water and subsequently into the overlying water column.

Diagenetic imprints in the reservoirs of Agbada Formation, Niger Delta Basin: Implication for reservoir quality and appraisal of calcite cement

The main exploration targets for hydrocarbons in the Niger Delta Basin are within the Agbada sandstone reservoirs. The current study utilizes a multitechnical approach (SEM-MLA, SEM-EDS, XRD and LA-ICP-MS) to evaluate the roles of framework composition and diagenetic processes, particularly calcite cementation on reservoir quality in Miocene intervals of the Agbada Formation sandstone, Niger Delta Basin. Petrographic analysis reveals that the sandstones are feldspatho-quartzose to quartzose sandstones, with a preponderance of quartzose sandstones. The overall diagenetic imprints suggest minimal compaction and lack of pervasive cement, which have contributed significantly to the high porosity. Although the degree of mechanical compaction is generally low, it has comparatively exercised a better control on porosity than the growth of cement, excluding some intervals with considerable cementation (siderite and ferroan calcite) where compactional porosity-loss was minimal. The occurrence of ferroan calcite cement (CaCO3 = 95.9 ± 0.4, MgCO3 = 0.8 ± 0.1, FeCO3 = 2.9 ± 0.2 mol%) is generally small, probably discontinuous and unlikely to represent significant barriers to fluid flow with their localized influence, but understanding their locally significant influence may still contribute to building good reservoir models. Petrographic observations suggest that the precipitation of “poikilitic” calcite was early, but the shale normalized REY patterns do not mimic seawater patterns (Y/Ho ratios; 36.3 ± 1.6) due to possible contributions from clastic or detrital grains and/or incorporation of particulate matter that can preferentially scavenge LREEs from the overlying water column. A possible concern during reservoir production is the occurrence of clay mineral matrix (mostly kaolinitic) anticipated to cause the production of fines and formation damage, but this can be mitigated with proper reservoir management.

Mercury Mobility in Epibenthic Waters of a Deltaic Environment

AbstractMercury (Hg) cycling at the sediment‐water interfaces (SWI) encompasses multiple homogeneous and heterogeneous biogeochemical reactions whose result is not yet elucidated. Estuarine SWIs, where the organic matter mineralization is active, constitute experimental sites particularly suitable for scrutinizing Hg speciation and mobilization. Here, we present high‐resolution vertical concentration profiles of Hg species, including inorganic divalent Hg () and monomethyl Hg (MMHg) in solid and dissolved (<0.22 μm) phases, on both sides of the SWI of the proximal part of the Rhône prodelta (northwestern Mediterranean Sea) using sediment cores and dialyzers implemented for a 67‐day‐long period. Concentrations of the dissolved species were <0.10 nM in the sediment pore waters but reached up to 0.58 nM in the epibenthic water zone, a concentration level that is ∼200 times higher than that of the water column. Conversely, MMHg concentrations were low (<0.5 pM) above the SWI and increased to up to 4.6 pM in the sulfate‐reducing zones of the sediment. The dynamic of the Hg species interconversions was explored using one‐dimensional transport‐reaction equations. This model allowed us to constrain the depth intervals where various species are produced or consumed and to approximate the reaction rates. We conclude that the epibenthic zone of the Rhône prodelta is a location of intense mobilization of inorganic HgII associated with organic matter mineralization and MMHg distribution in pore water is controlled by microbiological in situ reactions, but sedimentary MMHg does not diffuse in the overlying water column.

Sediment capping technology for eutrophication control and its potential for application in Indonesian lakes: a review

Eutrophication occurs when the lakes become enriched with nutrients. Some nitrogen and phosphorus fractions will settle in sediment, and others will be released back into the overlying water column. Excess nutrients in water bodies resulting in hypoxic to anoxic conditions that can cause a mass fish death. Hence, we need a sediment management strategy to minimize resuspension and transport of sediment back into the water column. Sediment capping is a containment technology to reduce the release of nutrients from sediment as a strategy for eutrophication control. This study aims to provide insight into sediment capping technology, including several considerations in capping design, as well as information on several active materials that have been applied as capping materials and their efficiencies. Capping materials such as calcite, zeolite, bentonite, activated carbon, sludge, biochar, and gypsum from previous studies showed the efficiency of 54–99 % nutrient reduction with capping duration of 10–300 days in some eutrophic lakes. Sediment capping technology has successfully promoted lake ecosystem restoration in other countries, and this technology has the potential to be applied in Indonesian eutrophic lakes as a strategy for eutrophication control and sustainable management of lake ecosystems by considering the selection of the most effective, efficient, easy, inexpensive, and eco-friendly capping materials.

High potential but low achievement: Frequent disturbance constrains the light use efficiency of river ecosystems

AbstractWe rarely consider light limitation in ecosystem productivity, yet light limitation is a major constraint on river autotrophy. Because the light that reaches benthic autotrophs must first pass through terrestrial vegetation and an overlying water column that can be loaded with sediments or colored organic material, there is strong selection for river autotrophs to have high light use efficiencies (LUEs), that is, the efficiency at which light energy is converted to biomass. In contrast to prior studies that have estimated river LUE on single days, we calculated continuous LUE over more than 6 full years for 64 free‐flowing rivers across the United States. This dataset represents the largest compilation of continuous estimates of daily rates of gross primary productivity (GPP) and daily light inputs from which we calculated daily estimates of LUE. Early estimates of LUE in rivers found that clearwater springs with stable flows could achieve LUEs of 4%, much higher than LUEs reported for terrestrial plants. We found that 53% of the rivers in our dataset have LUEs that exceed 4% on at least one day of their time series. Because of the high variability in daily LUE, measurements taken on any given day may misrepresent a river ecosystem's annual LUE. Though most rivers share a high potential, the mean annual LUE of all rivers in our dataset is much lower, only 0.5%. We found that rivers with more variable flow regimes had lower annual LUEs, which indicates that LUE is constrained by hydrologic disturbances that remove, bury, or shade autotrophic biomass. Comparisons of LUE across ecosystems allow us to reframe our view of rivers, by recognizing the high efficiency with which they convert light to biomass compared with lentic, marine, and terrestrial ecosystems.

Role of marine algal blooms in the release of arsenic at the sediment-seawater interface: Evidence from microcosm experiments

Algal blooms can aggravate arsenic (As) release from sediments and thus pose a pollution risk in the marine environment. However, the driving mechanism of algal blooms on sedimentary As cycling remains unclear. This study undertakes the first comprehensive examination of As release mechanisms under algal bloom conditions based on the evidence provided by temporal and depth profile changes of As species in the overlying water column, porewater and sediment, as well as As-related functional genes over the course of a 30-day incubation experiment using algal addition. The higher rate of increase of dissolved total As (dTAs) concentrations in a high biomass algal group (HAG) than an experimental control group (CG) suggested that algal degradation promoted the release of sedimentary As. The solid phase in all experimental groups remained rich in As(V), while in porewater As(III) and As(V) were the dominant As species during the initial rapid and subsequent slow degradation phases of organic matter, respectively, indicating that microbial reduction of As(V) and Fe(III) controlled the release of As during these two periods. A pronounced increase in arrA gene copies, and not a corresponding increase in the Geobacter copies, in HAG relative to CG supported the notion that algal blooms promoted microbial As(V) reduction. Additionally, the lower concentration of dissolved As(III) and cumulative dTAs flux in the sterilized-HAG treatment than in the sterilized-CG one further suggested that geochemically-mediated processes were not the main pathways of As release. Finally, it is estimated that summer algal blooms in the Changjiang Estuary can cause the release of 1440 kg of sedimentary As into the overlying water.

The impact of volcanic ash deposition and the Storegga Slide on organic carbon preservation processes in marine sediments near Iceland

The burial of organic carbon (OC) in marine sediments is a considerable sink for carbon, removing OC from the active ocean-atmosphere system. Both the total OC buried, and the proportion of OC retained in sediments after burial, varies by location, with some areas of the ocean floor known to be ‘hotspots’ of OC sequestration. Two potential such hotspots may be sediments containing high proportions of tephra (the unconsolidated products of explosive volcanism), and locations of turbidite deposition, but knowledge of specific burial regimes in such locations remains poorly constrained. To fully investigate these processes, we performed a holistic (organic and inorganic) geochemical analysis of samples from the Aegir Ridge, which contain both tephra layers and material from the Storegga Slide, a large turbidite. We show sediments found between the Storegga Slide and the tephra are a location of high OC preservation, linked to reducing conditions caused by the rapidly deposited slide layer sealing the sediments from overlying water column O2. We see little evidence for tephra positively affecting OC preservation at our site, but this is likely a feature of specific burial conditions, with the responsible mechanisms depending highly on the nature of the tephra. Our findings demonstrate how even in locations proposed as OC burial hotpots, the processes controlling this burial are highly complex, and that levels of sedimentary OC burial must be assessed on a case-by-case basis.

FUN Azores: a FUNctional trait database for the meio-, macro-, and megafauna from the Azores Marine Park (Mid-Atlantic Ridge)

Trait-based approaches that complement taxonomy-based studies have increased in popularity among the scientific community over the last decades. The collection of biological and ecological characteristics of species (i.e., traits) provides insight into species and ecosystem vulnerability to environmental and anthropogenic changes, as well as ecosystem functioning. Here, we present the FUN Azores trait database, describe our approach, evaluate its scope, compare it to other marine trait databases, and explore the spatial distribution of its traits with “functional maps.” While most of the available trait databases to date contain essential information to understand the functional diversity of a taxonomic or functional group, our ecosystem-based approach provides a comprehensive assessment of diverse fauna (i.e., meio-, macro-, and megafauna) from benthic and pelagic environments in the Azores Marine Park; including ridges, seamounts, hydrothermal vents, and the overlying water column. We used a collaborative approach involving 30 researchers with different expertise to develop the FUN Azores database, which contains compiled data on 14 traits representing morphological, behavioral, and life history characteristics for 1,210 species across 10 phyla. The “functional maps” show a distinct distribution of the two most common size classes, suggesting different communities with different functionalities. The following traits had the best scoring coverage (i.e., >95% of the species scored): maximum body size, body form, skeleton material, feeding structure, motility, environmental position, substratum affinity, distribution, and depth range; while traits related to species behavior (e.g., sociability or aggregation tendencies) and life history (e.g., developmental mechanism) had lower scoring coverage, highlighting the need for further research to fill these knowledge gaps. We found a larger number of species in the benthic compared to the pelagic environment and differing species composition between areas within the Azores Marine Park resulting from varying biodiversity, ecosystem types, sampling effort, and methodologies used. The FUN Azores database will foster and facilitate trait-based approaches in the area, develop a framework for expansion of cross-ecosystem and cross-taxa trait databases elsewhere, and improve our ecological understanding of the Azores Marine Park and its conservation requirements.

Major fine-scale spatial heterogeneity in accumulation of gelatinous carbon fluxes on the deep seabed

Abyssal plain communities rely on the overlying water column for a settling flux of organic matter. The origin and rate of this flux as well as the controls on its fine-scale spatial distribution following seafloor settlement are largely unquantified. This is particularly true across regions where anthropogenically-induced seafloor disturbance has occurred. Here, we observed, quantified and mapped a mass deposition event of gelatinous zooplankton carcasses (pyrosomes) in July-September 2015 across one such physically disturbed region in the Peru Basin polymetallic nodule province (4150 m). Seafloor in this area was disturbed with a plough harrow in 1989 (as part of the DISCOL experiment) causing troughs in the sediment. Other parts were disturbed with an epibenthic sled (EBS) during a cruise in 2015 resulting in steep-walled, U-shaped troughs. We investigated two hypotheses: a) gelatinous food falls contribute significantly to the abyssal plain carbon pump and b) physical seafloor disturbance influences abyssal distribution of organic matter. We combined optical and bathymetric seafloor observations, to analyze pyrosome distribution on seabeds with different levels of disturbance. 2954 pyrosome colonies and associated taxa were detected in > 14,000 seafloor images. The mean regional carbon (C) deposition associated with pyrosome carcasses was significant compared to the flux of particulate organic C (182 to 1543%), and the total respired benthic C flux in the DISCOL Experimental Area (39 to 184%). EBS-disturbed seafloor tracks contained 72 times more pyrosome-associated C than an undisturbed reference site, and up to 4 times more than an area disturbed in 1989. Deposited pyrosomes collected had a higher proportion of labile fatty acids compared to the sediment. We document the temporal and spatial extent of an abyssal food fall event with unprecedented detail and show that physical seafloor disturbance results in the accumulation of detrital material. Such accumulation may reduce oxygen availability and alter benthic community structure. Understanding both the relevance of large food falls and the fine scale topography of the seafloor, is necessary for impact assessment of technologies altering seafloor integrity (e.g. as a result of bottom-trawling or deep seabed mining) and may improve their management on a global scale.

Early diagenesis and benthic fluxes of redox-sensitive metals in eastern China shelf sediments

Thirteen Short sediment cores (30-50 cm) were collected from Bohai Sea, Yellow Sea and Changjiang Estuary in China, and the early diagenesis of several redox sensitive metals (Fe, Mn, Mo, U and V, referring to as RSMs) in sediment were studied. The recycling process of Mo and Mn was closely correlated with each other, generating benthic fluxes diffusing upward from sediment to overlying water column, and the flux rates are related to the organic carbon oxidation rates. The recycling of U and V were more tightly coupled with Fe oxides, generating benthic fluxes going downward into the sediment in most cores. Significant authigenic accumulation of U, in contrary to little to no accumulation of Mo and V, were found in the study region, even in Changjiang Estuary where hypoxic condition was often found during summer. Benthic diffusive fluxes were compared with authigenic mass accumulate rates (MAR), which indicated that, besides the benthic diffusion process, there are other processes controlling the authigenic accumulation of the RSMs. The close relationships between authigenic accumulation of RSMs with OCburial and OCburial with Sburial, indicating the authigenic accumulation of RSMs is a consequence of redox environment in shelf sediment, which directly influencing the organic carbon degradation process. Compared with other continental margin, moderate enrichment of U was found in China continental sediment. The authigenic U accumulation in BS and NYS sediments accounted for 20 - 68% of the Yellow River input, whilst in SYS sediments accounted for ~ 64% of the Yellow River and Changjiang River input, which acting as important U sinks that cannot be ignored.

Compositions and sources of sedimentary organic carbon on the tropical epicontinental sea

The deposition of fluvially derived terrestrial organic carbon (OC) together with marine OC in marine sediments has important implications for the global carbon cycle. However, dispersal extent and fates of terrestrial soil and petrogenic OC on the continental shelf have remained unclear and debated. Here, we present OC compositions and mineral properties of marine sediments from the Gulf of Thailand and the adjacent Mekong shelf, as well as river sediments from continents surrounding them in order to determine the provenance of sedimentary OC in this tropical epicontinental sea. We find that stable carbon isotope composition (δ13C) and radiocarbon activity (Δ14C) of sedimentary OC fall between those of marine OC and of river sediments, mainly composed of C3 plant-dominated pre-aged soil and petrogenic OC. Mixing model reveals that the OC in river sediments is predominantly sourced from pre-aged deep soils, accounting for 73 ± 5%, with the remaining consisting of modern surface soil (25 ± 6%) and bedrock (2 ± 1%). The sedimentary OC on the shelf is primarily derived from marine OC, accounting for 65 ± 15%, with terrestrial soil OC and petrogenic OC contributing 24 ± 14% and 10 ± 5%, respectively. The sources, degradation, and aging of OC and mineral surface area determine the spatial pattern of sedimentary OC compositions in the Gulf of Thailand and the Mekong shelf. The contents of marine, soil, and petrogenic OC decrease with increasing distance offshore, consistent with changes in spatial patterns of sedimentation rate of terrestrial materials and of marine primary production in the overlying water column. Extensive degradation of terrestrial OC and extremely low OC burial rate in this tropical epicontinental sea suggest a minor role on OC sequestration in marine sediments, but an important CO2 source to the atmosphere in the context of the global carbon cycle.

Persistence of E. coli in Streambed Sediment Contaminated with Faeces from Dairy Cows, Geese, and Deer: Legacy Risks to Environment and Health.

Legacy stores of faecal pollution in streambed sediments can result in delayed impacts on environmental quality and human health if resuspended into the overlying water column. Different catchment sources of faecal pollution can contribute to a legacy store of microbial pollutants, with size of stores influenced by microbial die-off and faecal accrual rates in the streambed. The aim of this study was to use a mesocosm experiment to characterise the persistence of E. coli derived from faeces of dairy cows, deer, and geese once introduced to streambed sediment under different temperature regimes. The settling rate of solid constituents of faecal material into streambed sediment once delivered into an aquatic environment was also quantified. The persistence patterns of E. coli in streambed sediment were found to vary as a function of faecal source and temperature; die-off of E. coli in sediment contaminated with goose faeces was more rapid than in sediments contaminated with dairy cow or deer faeces. Goose faeces also recorded a more rapid settling rate of faecal particles through the water column relative to dairy cow and deer faeces, suggesting a more efficient delivery of E. coli to streambed sediments associated with this faecal source. Our findings provide new evidence to improve understanding of the potential longer-term risks to both the environment and public health posed by sediments when contaminated with livestock, wildlife, and wildfowl faeces.

Evidence for abundant organic matter in a Neoarchean banded iron formation

Abstract Microbial Fe(II) oxidation has been proposed as a major source of Fe minerals during deposition of banded iron formations (BIFs) in the Archean and Proterozoic Eons. The conspicuous absence of organic matter or graphitic carbon from BIFs, however, has given rise to divergent views on the importance of such a biologically mediated iron cycle. Here, we present mineral associations, major element concentrations, total carbon contents and carbon isotope compositions for a set of lower amphibolite-facies BIF samples from the Neoarchean Zhalanzhangzi BIF in the Qinglonghe supracrustal sequence, Eastern Hebei, China. Graphite grains with crystallization temperatures (~470 °C) that are comparable to that predicted for the regional metamorphic grade are widely distributed, despite highly variable iron (12.9 to 54.0 wt%) and total organic carbon (0.19 to 1.10 wt%) contents. The crystalline graphite is interpreted to represent the metamorphosed product of syngenetic bio-mass, based on its co-occurrence with apatite rosettes and negative bulk rock δ13Corganic values (–23.8 to –15.4‰). Moreover, the crystalline graphite is unevenly distributed between iron- and silica-rich bands. In the iron-rich bands, abundant graphite relicts are closely associated with magnetite and/or are preserved within carbonate minerals (i.e., siderite, ankerite, and calcite) with highly negative bulk rock δ13Ccarb values (–16.73 to –6.33‰), indicating incomplete reduction of primary ferric (oxyhydr) oxides by organic matter. By comparison, only minor graphite grains are observed in the silica-rich bands. Normally, these grains are preserved within quartz or silicate minerals and thus did not undergo oxidation by Fe(III). In addition, the close association of graphite with iron-bearing phases indicates that ferric (oxyhydr)oxides may have exerted a first order control on the abundance of organic matter. Combined, the biological oxidation of Fe(II) in the oceanic photic zone and subsequent burial of ferric (oxyhydr)oxides and biomass in sediments to form BIFs, suggests that a BIF-dependent carbon cycle was important in the Archean Eon. Although significant re-adsorption of phosphorus to ferric (oxyhydr)oxides and the formation of authigenic phosphate minerals at the sediment-water interface would be expected, oxidation of biomass in BIFs may have recycled at least a portion of the P (and other nutrients) released from reactions between organic matter and ferric (oxyhydr)oxides to the overlying water column, potentially promoting further primary productivity.

Precessional pacing of early Proterozoic redox cycles

Regularly alternating reduction-oxidation (redox) patterns attributed to variations in the Earth's orbit and axis (Milankovitch cycles) are widely recorded in marine sediment successions of the Phanerozoic and attest to a dynamic history of biospheric oxygen in response to astronomically forced climate change. To date, however, such astronomical redox control remains elusive for much older, Precambrian intervals of the geological record that were characterized by a globally anoxic and iron-rich ocean, i.e., prior to Earth's atmospheric oxygenation (ca. 2.4–2.2 billion years ago). Here we report a detailed cyclostratigraphic and geochemical investigation of marine-sedimentary redox cycles identified in the ca. 2.46 billion-year-old Joffre Member of the Brockman Iron Formation, NW Australia, suggesting the imprint of Earth's climatic precession cycle. Around the base and top of regularly intercalated mudrock layers, we identify sharp enrichments in redox sensitive elements (Fe, S, Ca, P) that appear to represent chemical reaction fronts formed during nonsteady state diagenesis. Using a reactive transport model, we find that the formation of characteristic double S peaks required periods of increased organic matter deposition, coupled to strongly declining Fe2+ concentrations in the overlying water column. This combination, in turn, implies a periodic deepening of the iron chemocline due to enhanced oxygenic photosynthesis in marine surface waters, and is interpreted as the result of precession-induced changes in monsoonal intensity that drove variations in runoff and associated nutrient delivery. Our study results point to a dynamic redox evolution of Precambrian oceanic margin environments in response to Milankovitch forcing, and offer a temporal framework to investigate linkages between biological activity and the early build-up of oxygen in Earth's ocean-atmosphere system.

Storm-driven variations in depositional environments modify pyrite sulfur isotope records

The sulfur isotopic composition of marine pyrite (δ34Spyr) is one of the major geochemical tools to reconstruct global changes in Earth's surface environment. Storm-driven variations in depositional environments, however, can play key roles in modifying the δ34Spyr signal. Here we present δ34Spyr values in a complete Holocene muddy storm deposit on the East China coastal plain, which is identified by comprehensive analyses of sediment components, organic matter composition, bulk organic carbon isotopic ratios, carbon and oxygen isotopic ratios of carbonates and trace element concentrations. We find that positive (+5.8‰ to +15.8‰) and negative (−9.0‰ to −19.7‰) δ34Spyr values were preserved in two successive intervals of the muddy storm deposit (ca. 62 cm long), corresponding to the high-energy storm peak phase (HESPP) and the waning-energy late storm phase (WELSP), respectively. We propose that the 34S enrichment in pyrite from the HESPP is most likely due to a combination of storm reworking of sediments and high sedimentation rates, which involves various physical and chemical processes leading to the accumulation of 34S-enriched pyrite, such as oxidation of near-surface sulfides, reduced exchange of sulfate between sediment pore fluids and the overlying water column, and/or input of excess reactive iron minerals. In contrast, lower sedimentation rates and limited sedimentary remobilization during the WELSP allow the isotopic signal of early-formed 32S-enriched pyrite to be preserved. The striking shift in δ34Spyr values, therefore, reflects a dramatic change in the local depositional environment between the HESPP and WELSP, suggesting that non-steady-state deposition induced by storm activity facilitates the formation of isotopically “heavy” pyrite. This sharp shift can be further generalized as a characteristic feature of δ34Spyr values in storm deposits. Our work highlights the critical impact of weather- and climate-event-driven depositional variations on δ34Spyr values, adding to the growing evidence emphasizing the local environmental and diagenetic controls on these records.

Predicting Coral Reef Carbonate Chemistry Through Statistical Modeling: Constraining Nearshore Residence Time Around Guam

To accurately predict the impacts of ocean acidification on shallow-water ecosystems, we must account for the biogeochemical impact of local benthic communities, as well as the connectivity between offshore and onshore water masses. Estimation of residence time can help quantify this connectivity and determine the degree to which the benthos can influence the chemistry of the overlying water column. We present estimates of nearshore residence time for Guam and utilize these estimates to model the effects of benthic ecosystem metabolism on the coral reef carbonate system. Control volume and particle tracking approaches were used to estimate nearshore residence time. These estimates were paired with observed patterns in the reef carbonate system around Guam using water samples collected by NOAA’s National Coral Reef Monitoring Program. Model performance results suggest that when considering the effects of benthic metabolism on the carbonate system, it is paramount to represent the contact time of the water volume with the benthos. Even coarse estimates of residence time significantly increase model skill. We observed the highest predictive skill in models including control volume derived estimates of residence time, but only when those estimates were included as an interaction with benthic composition. This work shows that not only is residence time critically important to better predict biogeochemical variability in coral reef environments, but that even coarse hydrodynamic models can provide useful residence time estimates at management relevant, whole-ecosystem scales.