Transport Of Organic Carbon Research Articles

How is particulate organic carbon transported through the river-fed submarine Congo Canyon to the deep sea?

Abstract. The transfer of carbon from land to the near-coastal ocean is increasingly being recognized in global carbon budgets. However, a more direct transfer of terrestrial organic carbon to the deep sea is comparatively overlooked. Among systems that connect coastal to deep-sea environments, the submarine Congo Canyon is of particular interest since the canyon head starts 30 km into the Congo River estuary, which delivers ∼7 % of the dissolved and particulate organic carbon from the world's rivers. However, sediment and particulate organic carbon transport mechanisms that operate in the Congo Canyon and submarine canyons more globally are poorly constrained compared to rivers because monitoring of deep-sea canyons remains challenging. Using a novel array of acoustic instruments, sediment traps, and cores, this study seeks to understand the hydrodynamic processes that control delivery of particulate organic carbon via the submarine Congo Canyon to the deep sea. We show that particulate organic carbon transport in the canyon axis is modulated by two processes. First, we observe periods where the canyon dynamics are dominated by tides, which induce a background oscillatory flow (speeds of up to 0.15 m s−1) through the water column, keeping muds in suspension, with a net upslope transport direction. Second, fast-moving (up to 8 m s−1) turbidity currents occur for 35 % of the time during monitoring periods and transport particulate organic carbon with mud and sand at an estimated transit flux that is more than 3 to 6 times the flux induced by tides. Organic carbon transported and deposited in the submarine canyon has a similar isotopic composition to organic carbon in the Congo River and in the deep-sea fan at 5 km of water depth. Episodic turbidity currents thus promote efficient transfer of river-derived particulate organic carbon in the Congo submarine fan, leading to some of the highest terrestrial carbon preservation rates observed in marine sediments globally.

Sourcing and long-range transport of particulate organic matter in river bedload: Río Bermejo, Argentina

Abstract. Fluvial transport of organic carbon from the terrestrial biosphere to the oceans is an important term in the global carbon cycle. Traditionally, the long-term burial flux of fluvial particulate organic carbon (POC) is estimated using river suspended sediment flux; however, organic carbon can also travel in river bedload as coarse particulate organic matter (POMBed). Estimates of fluvial POC export to the ocean are highly uncertain because few studies document POMbed sources, flux, and evolution during long-range fluvial transport from uplands to ocean basins. This knowledge gap limits our ability to determine the global terrestrial organic carbon burial flux. In this study we investigate the flux, sources, and transformations of POMBed during fluvial transport over a ∼1300 km long reach of the Río Bermejo, Argentina, which has no tributary inputs. To constrain sourcing of POMBed, we analyzed the composition and stable hydrogen and carbon isotope ratios (δ2H, δ13C) of plant wax biomarkers from POMBed at six locations along the Río Bermejo and compared this to samples of suspended sediment, soil, leaf litter, and floating organic debris (POMfloat) from both the lowland and headwater river system. Across all samples, we found no discernible differences in n-alkane average chain length or nC29 δ13C, indicting a common origin for all sampled POMBed. Leaf litter and POMfloat nC29 δ2H values decrease with elevation, making it a useful proxy for POMBed source elevation. Biomarker δ2H values suggest that POMBed is a mix of distally derived headwater and locally recruited floodplain sources at all sampling locations. These results indicate that POMBed can be preserved during transport through lowland rivers for hundreds of kilometers. However, the POMBed flux decreases with increasing transport distance, suggesting mechanical comminution of these coarse organic particles and progressive transfer into the suspended load. Our provisional estimates suggest that the carbon flux from POMBed comprises less than 1 % of the suspended load POC flux in the Río Bermejo. While this represents a small portion of the river POC flux, this coarse, high-density material likely has a higher probability of deposition and burial in sedimentary basins, potentially allowing it to be more effective in long-term CO2 drawdown relative to fine suspended particles. Because the rate and ratio of POMBed transport versus comminution likely vary across tectonic and climatic settings, additional research is needed to determine the importance of POMBed in the global carbon cycle.

Carbon Reduction Associated with Sediment Reworking through Burrows of the Thalassinid Mud Shrimp Laomedia sp. (Crustacea: Laomediidae) from Korean Intertidal Sediments

This study evaluated the biotic and abiotic factors influencing the sediment reworking rate (SRR) of Laomedia sp. through in situ measurements and assessed the organic carbon reduction by comparing carbon concentrations between particles collected from the water column and reworked sediments. The SRR was significantly correlated with the duration of submergence at high elevation, whereas it showed a stronger correlation with mound height than with the duration of submergence at low elevation. The organic carbon content of suspended particles was reduced by 68% by the sediment reworking of Laomedia sp., with a mean organic carbon reduction of 0.01 gC ind.−1 d−1. This reduction resulted from particle selection by the inhabitant and by accumulation along the burrow walls. The estimated annual organic carbon reduction associated with the sediment reworking was 12.8 gC m−2 yr−1. The transport of organic carbon from the burrows into the water column was comparatively high relative to other species. These findings suggest that Laomedia sp. plays a significant role in enhancing the carbon cycle as an important bioturbator, with its burrows acting as carbon sinks by trapping organic carbon in intertidal sediments. Therefore, bioturbation by macroinvertebrates should be considered when evaluating carbon sequestration in intertidal sediments.

High sensitivity of dissolved organic carbon transport during hydrological events in a small subtropical karst catchment

Dissolved organic carbon (DOC) and discharge are often tightly coupled, though these relationships in karst environments remain poorly constrained. In this study, DOC dynamics over 13 hydrological events, alongside monthly monitoring over an entire hydrological year were monitored in a small karst catchment, SW China. The concurrent analyses of power-law model and hysteresis patterns reveal that DOC behavior is generally transport-limited due to flushing effects of increased discharge but highly variable at both intra- and inter-event scales. The initial discharge at event onset and discharge-weighted mean concentration of DOC ([DOC]DW) of individual events can explain 37.7 % and 19.9 % of the variance of DOC behavior among events, respectively. The sustained dry-cold antecedent conditions make DOC hysteresis behavior during the earliest event complex and different from subsequent events. At event scale, the variability in DOC export is primarily controlled by [DOC]DW (explaining 64.3 %) and the yield of total dissolved solutes (YTDS, explaining 30.4 %), reflecting the impacts of variable hydrological connectivity and intense soil-water-rock interactions in this karst catchment. On an annual scale, DOC yield (YDOC, 222.86 kg C km−2) was mostly derived during the wet season (98.19 %) under the hydrological driving force. The difference in annual YDOC between this karst catchment and other regions can be well explained by annual water yield (Ywater, explaining 24.2 %) and [DOC] (explaining 35.4 %), whereas the variance in DOC export efficiency among catchments is almost exclusively controlled by [DOC] alone, independent of drainage area and annual Ywater. This study highlights the necessity of high-frequency sampling for modeling carbon biogeochemical processes and the particularity of the earliest hydrological events occurred after a long cold-dry period in karst catchments. Under the changing climate, whether DOC dynamics in karst catchments will present source-limited patterns during more extreme hydrological events merits further study.

Fate and partition of perfluoroalkyl acids (PFAAs) driven by particles in mangrove ecosystems: Mechanistic insights and environmental implications

A critical gap in understanding emerging pollutants in mangrove ecosystems should be addressed. Despite their ecological importance, the state of environmental quality in fragmented mangrove patches, especially emerging contaminants, remains largely uncharted. Our research presented an in-depth analysis of the distribution of perfluoroalkyl acids (PFAAs) across porewater, suspended particles, and sediment in these small, fragmented mangroves, revealing the mechanisms behind their distribution. The findings indicated that PFAA concentrations in sediments were generally lower than in suspended particles, except for C12–C14 perfluorinated carboxylic acids (PFCAs) and C4–C6 perfluorinated sulfonic acids (PFSAs). A comparison of contamination levels in different mangrove patches concurred with conventional water quality assessments and crab burrow surveys, showing that large artificially planted patches were less contaminated, while areas with intense human activity were more polluted. Notably, no significant differences were observed in the concentrations of long-chain PFAAs and PFCAs between patches (p > 0.1). Elevated crab burrowing activity and higher concentrations of perfluorobutanoic acid (PFBA) and perfluorohexane sulfonic acid (PFHxS) in suspended particles in low intertidal zones suggested that seafood, particularly crabs and shellfish, might be at risk of PFAA pollution. Rainfall-runoff was identified as the primary source of PFAA pollution in porewater and suspended particle systems in these areas. The transport of PFAAs and organic carbon in mangroves was influenced by the concentrations and properties of suspended particles. These insights were critical for developing targeted environmental management strategies to mitigate the impact of PFAAs and preserve the ecological integrity of mangrove ecosystems.

Integrated Effects of Site Hydrology and Vegetation on Exchange Fluxes and Nutrient Cycling at a Coastal Terrestrial‐Aquatic Interface

AbstractThe complex interactions among soil, vegetation, and site hydrologic conditions driven by precipitation and tidal cycles control the biogeochemical transformations and bi‐directional exchange of carbon and nutrients across the terrestrial–aquatic interfaces (TAIs) in coastal regions. This study uses a highly mechanistic model, Advanced Terrestrial Simulator (ATS)‐PFLOTRAN, to explore how these interactions affect exchanges of materials and carbon and nitrogen cycling. We used a transect in the Chesapeake Bay region that spans zones of open water, coastal wetland, transition, and upland forest. We designed several simulation scenarios to parse the effects of the individual controlling factors and the sensitivity of carbon cycling to reaction rate parameters derived from laboratory experiments. Our simulations reveal an active zone for carbon cycling under the transition zones between the wetland and the upland. Evapotranspiration is found to enhance the exchange fluxes between the surface and subsurface domains, resulting in a higher dissolved oxygen concentration in the TAIs. The transport of organic carbon derived from plant leaves and roots provide an additional source of organic carbon needed for the aerobic respiration and denitrification processes in the TAIs. The variability in reaction rate parameters associated with microbial activities is also found to play a dominant role in controlling the heterogeneity and dynamics of the simulated redox conditions. This modeling‐focused exploratory study enabled us to better understand the complex interactions among soil, water and microbes that govern the hydro‐biogeochemical processes at the TAIs, which is an important step toward representing coastal ecosystems in larger‐scale Earth system models.

Dynamic near-seafloor sediment transport in Kaikōura Canyon following a large canyon-flushing event

ABSTRACT Submarine canyons are important deep-sea environments and conduits for transferring and accumulating sediment and organic matter and pollutants. Recent advances in observing, sampling, and analyzing modern canyon sediment transport systems illustrate near-seafloor dynamics and highlight the potential roles of submarine canyons in transporting and storing organic carbon, nutrients, and contaminants in the deep sea, with implications for deep-sea ecosystems and global carbon budgets. Kaikōura Canyon, offshore northeastern Te Waipounamu South Island, Aotearoa New Zealand, is a benthic biomass hotspot that experienced an earthquake-triggered, canyon-flushing event in 2016. On return to the canyon in October 2020, benthic landers, with sediment traps at 2 m above the seafloor, were deployed along the canyon axis in ∼ 900–1500 m water depths for a period of three weeks. These instrumented platforms provide a detailed view of near-seafloor sediment and organic-carbon transport between canyon-flushing events, showing that the canyon environment hosts dynamic physical processes and short-term sediment fluxes and transport. Variations in sediment and organic carbon flux down-canyon and over time include small-scale sediment transport events, some of which are interpreted as turbidity currents, occurring on much shorter timescales than earthquake recurrence. We compare Kaikōura Canyon results with other longshore-fed, shelf-incised global submarine canyons and deep-ocean sites, revealing differences and likely multiple controlling factors for near-seafloor sediment flux. This Kaikōura Canyon high-resolution, benthic lander timeseries dataset highlights the complexity of submarine canyons and their role in organic carbon flux to the deep ocean, even under high present-day sea-level conditions. Evolving insights underscore the need for more observational data and samples to further quantify submarine canyon sediment and organic-carbon transport and contribute to global evaluations of deep-sea canyon distributary systems.

Variations in provenance and transport of terrestrial organic matter in the Changjiang River during the flood season

River is a crucial channel for the transport of terrestrial organic carbon (OCterr) into the sea, and has significant implications for the global carbon cycle. However, with the intensification of human activities within the watershed (such as dams and changes in land use), the sediment and OCterr output from rivers have significantly decreased. To study the influence of human activities on the provenance and transport of particulate organic carbon (POC) exported from the Changjiang River Basin (CRB), we collected suspended particulate matter samples during the rainy season of 2021. The POC content exhibited an increasing trend from the headwater zone to the estuary. Results of three-end-member mixing model indicated that both soil-derived and autochthonous OC (OCauto) contributed approximately more than 40.0 %. Notably, OCauto experienced a significant increase from the Three Gorges Dam (TGD) to estuary in the mainstem, attributed to the sediment interception effect of the TGD. The POC contents in the headwater zone and Jinshajiang River in 2021 were lower compared to those in 2007, which can be attributed to a decrease in cultivated land area and increase sediment trapping by cascade dams. Affected by TGD, the POC content in the middle and lower reaches as well as the delta zone first decreased in 2003 and then increased from 2007 to 2021. Additionally, the degradation of lignin phenols and n-alkanes was influenced by the TGD, which prolonged the retention time of terrestrial plants. Compared to previous studies, the decrease in soil-derived OC and increase in OCauto in CRB, influenced by dams and land use, could have long-lasting effect on carbon burial in the ECS.

Layer-specific mechanisms of perfluoroalkyl acid (PFAA) transport and partition in estuarine environments: Unveiling the depth-dependent differences

Understanding of characteristics and transport of perfluoroalkyl acids (PFAAs) in heterogeneous estuarine environments is limited. Furthermore, the role of suspended particles (SPS) in different layers remains unclear. This study explores the multiphase distribution process and mechanism of PFAAs controlled by SPS across surface and bottom layers in five small estuaries. Peaks in PFAA concentrations are consistently observed at strongly stratified sites. Concentrations of the PFAAs in both surface and bottom SPS decreased as the degree of mixing increased from strongly stratified levels to well-mixed levels. The water-SPS partitioning of some short-chain PFAAs (PFBS, PFHxA, and PFHpA) is influenced by environmental factors (pH, depth, temperature, and salinity) due to electrostatic interactions, while the sorption of some long-chain PFAAs (PFOA, PFOS, and PFNA) is controlled by SPS and dissolved organic carbon (OC), driven by hydrophobic interactions. Additionally, SPS dominates OC transport in estuarine systems, except in sandy sediment environments. SPS plays a dominant role in PFAA partitioning in both surface and bottom water-SPS systems (p < 0.05), and salinity only significantly affects PFBS in bottom layer (p < 0.01). These findings are critical for understanding the drivers of PFAA partitioning and the roles of SPS in different layers, underscoring the necessity of considering particle-associated PFAA fractions in future coastal environmental management.

Predicting Future Trends of Terrestrial Dissolved Organic Carbon Transport to Global River Systems

AbstractA fraction of CO2 uptake by terrestrial ecosystems is exported as organic carbon (C) through the terrestrial‐aquatic continuum. This translocated C plays a significant role in the terrestrial C balance; however, obtaining global assessments remains challenging due to the predominant reliance on empirical approaches. Leaching of dissolved organic C (DOC) from soils to rivers represents an important fraction of this C export and is assumed to drive a large proportion of the net‐heterotrophy of river systems and the related CO2 emissions. Using the model JULES‐DOCM, we projected DOC leaching trends over the 21st century based on three scenarios with high (RCP 2.6), intermediate (RCP 4.5), and low (RCP 8.5) climate mitigation efforts. The RCP 8.5 scenario led to the largest DOC leaching increase of +42% to 395 Tg C yr−1 by 2100. In comparison, RCP 2.6 and RCP 4.5 led to increases of 10% and 21%, respectively. Under RCP 8.5, the sub‐tropical zone showed the highest relative increase of 50% above current levels. In the boreal and tropical zones, the simulations revealed similar increases of 48% and 41%, respectively. However, given the pre‐eminence of the tropics in DOC leaching, the absolute increment is markedly substantial from this region (+59 Tg C yr−1). The temperate zone displayed the lowest relative increase with 35%. Our analysis identified the rising atmospheric CO2 concentration and its fertilizing effect on terrestrial NPP as the main reason for the future increase in DOC leaching.

The impacts of profile concavity on turbidite deposits: Insights from the submarine canyons on global continental margins

Submarine canyons are primary conduits for turbidity currents transporting terrestrial sediments, nutrients, pollutants and organic carbon to the deep sea. The concavity in the longitudinal profile of these canyons (i.e. the downstream flattening rate along the profiles) influences the transport processes and results in variations in turbidite thickness, impacting the transfer and burial of particles. To better understand the controlling mechanisms of canyon concavity on the distribution of turbidite deposits, here we investigate the variation in sediment accumulation as a function of canyon concavity of 20 different modern submarine canyons, distributed on global continental margins. In order to effectively assess the isolated impact of the concavity of 20 different canyons, a series of two-dimensional, depth-resolved numerical simulations are conducted. Simulation results show that the highly concave profile (e.g. Surveyor and Horizon) tends to concentrate the turbidite deposits mainly at the slope break, while nearly straight profiles (e.g. Amazon and Congo) result in deposition focused at the canyon head. Moderately concave profiles with a smoother canyon floor (e.g. Norfolk-Washington and Mukluk) effectively facilitate the downstream transport of suspended sediments in turbidity currents. Furthermore, smooth and steep upper reaches of canyons commonly contribute to sediment bypass (i.e. Mukluk and Chirikof), while low slope angles lead to deposition at upper reaches (i.e. Bounty and Valencia). At lower reaches, the distribution of turbidite deposits is consistent with the occurrence of hydraulic jumps. Under the influence of different canyon concavities, three types of deposition patterns are inferred in this study, and verified by comparison with observed turbidite deposits on the modern or paleo-canyon floor. This study demonstrates a potential difference in sediment transport efficiency of submarine canyons with different concavities, which has potential consequences for sediment and organic carbon transport through submarine canyons.

Seasonal and interannual dissolved organic carbon transport process dynamics in a subarctic headwater catchment revealed by high-resolution measurements

Abstract. Dissolved organic carbon (DOC) dynamics are evolving in the rapidly changing Arctic and a comprehensive understanding of the controlling processes is urgently required. For example, the transport processes governing DOC dynamics are prone to climate-driven alteration given their strong seasonal nature. Hence, high-resolution and long-term studies are required to assess potential seasonal and interannual changes in DOC transport processes. In this study, we monitored DOC at a 30 min resolution from September 2018 to December 2022 in a headwater peatland-influenced stream in northern Finland (Pallas catchment, 68° N). Temporal variability in transport processes was assessed using multiple methods: concentration–discharge (C–Q) slope for seasonal analysis, a modified hysteresis index for event analysis, yield analysis, and random forest regression models to determine the hydroclimatic controls on transport. The findings revealed the following distinct patterns: (a) the slope of the C–Q relationship displayed a strong seasonal trend, indicating increasing transport limitation each month after snowmelt began; (b) the hysteresis index decreased post-snowmelt, signifying the influence of distal sources and DOC mobilization through slower pathways; and (c) interannual variations in these metrics were generally low, often smaller than month-to-month fluctuations. These results highlight the importance of long-term and detailed monitoring to enable separation of inter- and intra-annual variability to better understand the complexities of DOC transport. This study contributes to a broader comprehension of DOC transport dynamics in the Arctic, specifically quantifying seasonal variability and associated mechanistic drivers, which is vital for predicting how the carbon cycle is likely to change in Arctic ecosystems.

Autogenic evolution of valley‐confined deltas during sea‐level rise: Insights from numerical and physical modelling

AbstractNearshore incised valleys are important conduits for the transport of sediment, nutrients, pollutants and organic carbon from the continents to the sea. Therefore, it is essential to understand the autogenic evolution of deltas confined within incised valleys and how such evolution is affected by relative sea‐level rise. To date, limited research has focused on how deltas constrained by incised valleys or other forms of antecedent topography respond to rising sea level. An existing theory of autostratigraphy envisages scenarios in which two‐dimensional or unconfined three‐dimensional fan deltas can experience three evolutionary stages under constant rates of relative sea‐level rise and sediment supply: progradation, autoretreat and post‐autobreak transgression. In this work, an integrated study of geometric numerical models and physical experiments is undertaken to investigate autostratigraphic delta evolution for a variety of incised‐valley geometries, under conditions of constant rates of relative sea‐level rise and sediment supply. Results indicate that interplays of antecedent topography (valley geometries) and sediment mass balance expressed in resultant deltaic geometries can result in autogenic changes in shoreline dynamics and river avulsion frequency on deltas. The following primary findings arise. (i) Compared to valleys with rectangular and trapezoidal cross‐sectional profiles, valleys with triangular cross‐sections tend to contain deltas that experience faster rates of progradation, autoretreat and post‐autobreak transgression under rising sea level, and exhibit a more prominent convex‐seaward shoreline trajectory. (ii) The shoreline trajectory is also related to delta topset geometry, becoming more convex‐seaward under decreasing topset slopes. (iii) River avulsion frequency on deltas with rising sea level varies markedly across valleys with different geometries, even under the same rate of relative sea‐level rise; this is attributed to the difference in temporal evolution of shoreline migration for different valley geometries and the resultant difference in the delta topset aggradation. This study highlights complexities in responses of sedimentary systems under the confinement of different topographic configurations that have hitherto largely been overlooked in sequence‐stratigraphic models. The findings provide insight into future shoreline behaviour and river avulsion hazard on confined deltas, and for decoding the stratigraphic record.

Channel cross-section heterogeneity of particulate organic carbon transport in the Huanghe

Abstract. The Huanghe (Yellow River), one of the largest turbid river systems in the world, has long been recognized as a major contributor of suspended particulate matter (SPM) to the ocean. However, over the last few decades, the SPM export flux of the Huanghe has decreased over 90 % due to the high management, impacting the global export of particulate organic carbon (POC). To better constrain sources and modes of transport of POC beyond the previously investigated transportation of POC near the channel surface, SPM samples were for the first time collected over a whole channel cross-section in the lower Huanghe. Riverine SPM samples were analyzed for particle size and major element contents, as well as for POC content and dual carbon isotopes (13C and 14C). Clear vertical and lateral heterogeneities of the physical and chemical properties of SPM are observed within the river cross-section. For instance, finer SPM carry more POC in general with higher 14C activity near the surface of the right bank. Notably, we discuss how bank erosion in the alluvial plain is likely to generate lateral heterogeneity in POC composition. The Huanghe POC is millennial-aged (4020 ± 500 radiocarbon years) and dominated by organic carbon (OC) from the biosphere, while the lithospheric fraction is ca. 12 %. The mobilization of aged and refractory OC, including radiocarbon-dead biospheric OC, from deeper soil horizons of the loess–paleosol sequence through erosion in the Chinese Loess Plateau is an important mechanism contributing to fluvial POC in the Huanghe drainage basin. Altogether, anthropogenic activities can drastically change the compositions and transport dynamics of fluvial POC, consequentially altering the feedback of the source-to-sink trajectory of a river system to regional and global carbon cycles.

Hydrostatic pressure impedes the degradation of sinking copepod carcasses and fecal pellets.

Fast-sinking zooplankton carcasses and fecal pellets appear to contribute significantly to the vertical transport of particulate organic carbon (POC), partly because of low temperature that decreases microbial degradation during the descent into the deep ocean. Increasing hydrostatic pressure could further reduce the degradation efficiency of sinking POC, but this effect remains unexplored. Here, the degradation of carcasses and fecal pellets of the abundant marine copepod Calanus finmarchicus was experimentally studied as a function of pressure (0.1-100MPa). Samples were either exposed to elevated pressure in short 1-day incubations or a gradual pressure increase, simulating continuous particle sinking during a 20-day incubation. Both experiments revealed gradual inhibition of microbial respiration in the pressure range of 20-100MPa, corresponding to 2-10-km depth. This suggests that hydrostatic pressure impedes carbon mineralization of fast-sinking carcasses and fecal pellets and enhances the deep-sea deposition rate of zooplankton-derived organic material.

Modeling the Vertical Flux of Organic Carbon in the Global Ocean.

The oceans play a fundamental role in the global carbon cycle, providing a sink for atmospheric carbon. Key to this role is the vertical transport of organic carbon from the surface to the deep ocean. This transport is a product of a diverse range of physical and biogeochemical processes that determine the formation and fate of this material, and in particular how much carbon is sequestered in the deep ocean. Models can be used to both diagnose biogeochemical processes and predict how the various processes will change in the future. Global biogeochemical models use simplified representations of food webs and processes but are converging on values for the export of organic carbon from the surface ocean. Other models concentrate on understanding specific processes and can be used to develop parameterizations for global models. Model development is continuing by adding representations and parameterizations of higher trophic levels and mesopelagic processes, and these are expected to improve model performance.

Long-term carbon sequestration in the Eocene of the Levant Basin through transport of organic carbon from nearshore to deep marine environments

This study addresses a specific component associated with mass transport complexes in marine systems: the role of hyperpycnal flows, dense shelf water cascading, submarine canyons, distributary channels, and other transport mechanisms in transferring organic matter from continental and shallow marine settings into deep-marine environments. We speculate that during the Eocene, allowing for only 0.1‰ of shelf carbon to be preserved through transport mechanisms would account for up to 13.7% of all organic carbon burial. As such, the potential to mobilize through this mechanism large quantities of organic carbon is significant.Our case study focuses on a 150 m Eocene sequence composed of organic-rich chalks interleaved with displaced neritic limestones. TOC values range between 1.5 and 14%, averaging 4.5%. Displaced limestones are composed of a variety of poorly cemented mud- and wackestones, with low-diversity assemblages of large benthic foraminifera associated with planktonic foraminifera, suggesting deposition under low-energy conditions within the oligophotic zone on the outer ramp. Transport overprints include soft-sediment deformation, partially lithified rip-ups, folds, small diapirs, bed-scale imbrication, brecciation and syn-sedimentary shear. These features indicate detachment, movement and emplacement following initial sedimentation, in some cases more than once. Emplacement occurs into a chalk facies that can vary in appearance from darker (higher TOC) and lighter (lower TOC) lithofacies.Combination between the sedimentological, petrophysical, and elemental analyses indicates shifts between autochthonous and allochthonous sedimentation, whereas the organic geochemical analysis reveals a correlation between modes of sedimentation and preservation/composition of organic matter. Organic richness seems to increase within intervals of allochthonous sedimentation, with lower TOC values within intervals of autochthonous sedimentation. Organic matter preservation is enhanced due to poor oxygenation of the sea floor, further depleted by rapid burial beneath mass-transport deposits, increasing sedimentation rates and thus organic matter preservation. Horizons rich in organic matter may be derived from three different sources: organic matter with a fingerprint of terrestrial sources (e.g., enhanced contribution of plant leaf waxes) transported from nearshore environments; an allochthonous marine fingerprint with sulfurized hopanoids, which seem to be reworked from pre-existing Cretaceous organic-rich carbonates entrained within fined-grained micro-turbidites in the para-autochthonous facies; and productivity-derived organic matter deposited on the seafloor of the deep marine environment.This study demonstrates how transport mechanisms allow for the long-term burial of organic carbon in marine systems. When taking into consideration similar processes reported to occur in the world oceans today, it is clear that sediment transport and long-term burial of organic carbon is a fundamental part of the global carbon cycle.

Using a novel approach to characterize the surface reactivities of silica-rich ferrihydrite and biogenic cyanobacteria-ferrihydrite aggregates and the implications for Archean ocean geochemistry

Precambrian banded iron formations (BIF) are iron- and silica-rich chemical sedimentary rocks that are commonly used as paleo-redox proxies for Archean and Paleoproterozoic seawater geochemistry. At the onset of the Great Oxidation Event (herein GOE) around 2.4 Ga, cyanobacteria flourished with increasing nutrient fluxes due to oxidative weathering on land. In turn, this led to increased primary productivity that facilitated the permanent shift from a reducing Earth atmosphere to an oxidizing one. Interestingly, the duration of GOE also overlapped with one of the most prolific periods of BIF deposition.It is widely accepted that cyanobacteria were likely responsible for BIF formation during the GOE. Oxidation of dissolved Fe(II) by oxygen produced from cyanobacteria forms a metastable and amorphous mineral phase ferrihydrite, Fe(OH)3. As an essential component in both ancient BIF deposits and various modern ecosystems, the surface reactivity of ferrihydrite has been extensively studied under different conditions (i.e., pH and ionic strengths). Not only are the highly reactive surfaces of ferrihydrite particles important shuttles for trace element transport from the water column to the sediment pile, but previous studies have also demonstrated that cyanobacterial cells and ferrihydrite tend to aggregate at seawater pH. This means that ferrihydrite was also a vector for the transport of organic carbon to the seafloor. However, a complicating issue is how co-ions affect the surface reactivity of ferrihydrite, specifically dissolved silica which was abundant in ancient seawater. Although previous studies have demonstrated that silica can passivate the surface reactivity of ferrihydrite, what remains unclear is how silica impacts ferrihydrite-biomass aggregation. To fill this knowledge gap, we formed both silica-spiked ferrihydrite and cyanobacteria-ferrihydrite aggregates in situ and subsequently conducted empirical potentiometric acid-base titrations and Cd adsorption experiments on the fresh aggregate samples at three different ionic strengths (0.56 M, 0.1 M and 0.01 M). We minimized sample processing (i.e., drying and powdering) to a simple washing step, in which the aggregate pellets remained hydrated to avoid any mineral transformation thus altering their true surface reactivity in seawater. Experimental results were then fitted with non-electrostatic model to predict both surface charges and metal-adsorption behavior of ferrihydrite aggregates. Different from previous surface-complexation modelling studies, here we used a novel and more powerful modelling program called Phreefit. It utilizes the global optimization algorithms instead of more commonly used Newton-Raphson method in FITEQL program, which is often too limited for precisely modelling complex systems such as the two samples in this study. Furthermore, we also measured the surface charges of both samples over the pH range from 3 to 9 on a Malvern Zetasizer and characterized the surface functional groups through Fourier-Transform Infrared Spectroscopy to help with our interpretation of the experimental data.Preliminary results show that cyanobacteria-ferrihydrite aggregates formed primarily due to ionic bridging. Cyanobacterial cells likely facilitated the precipitation of dissolved silica. Findings from titration and Cd adsorption experiments indicate that the surface reactivity and capacity of both silica-rich ferrihydrite cyanobacteria-ferrihydrite aggregates to adsorb trace elements differ from their individual components, likely due to site blockage. This distinction is particularly prominent when considering the expected Archean seawater pH from 6 to 8. This disparity implies that the biogenic ferrihydrite aggregates do not exhibit an additive surface reactivity, which is in agreement with similar previous studies. Our combined results are crucial to accurately predict the adsorption of trace elements onto the aggregate surface and, ultimately, comprehend the archive of trace elements in sedimentary rocks used to reconstruct Precambrian ocean chemistry.

Organo-mineral associations and size-fractionated colloidal organic carbon dynamics in a redox-controlled wetland

The formation of organo-mineral associations serves as a crucial mechanism for stabilizing soil organic matter, particularly for determining the fate of soil organic carbon (OC) in redox dynamic wetlands characterized by high C content. Despite its importance, few studies have assessed the retention, transformation, and transport of colloids (1–1000 nm) and colloidal OC (COC) in those environments. This leaves a crucial knowledge gap concerning the quantities of colloids and COC and their molecular compositions, especially considering the significant role of metabolically active depressional wetlands that may play as biogeochemical hotspots for C cycling. To address this gap, we conducted a study in a Delmarva Bay depressional wetland located in Blackbird State Forest, Delaware, USA. We established a transect encompassing upland (U), transition (T), and wetland (W) zones based on seasonal hydrologic conditions. We installed piezometers at 50 cm, 100 cm, and 200 cm depths within each zone and collected pore-water samples from 11/2017 to 05/2019. We then fractionated these samples into dissolved (<2.3 nm), natural nanoparticle (NNP, 2.3–100 nm), fine colloid (100–450 nm), and particulate (450–1000 nm) fractions via sequential centrifugation and ultrafiltration, and quantified their concentration and molecular composition. We observed variations in the concentration and molecular composition of soil COC both vertically at different soil depths and horizontally along a redox gradient from the U-T-W transect. The sum of the NNP and fine colloid fractions accounted for 47±20% of the operationally defined “dissolved” (<450 nm) fraction. Isotope ratio mass spectrometry and X-ray photoelectron spectroscopy analyses further revealed that the NNP fraction is more enriched in heavier δ13C isotope and oxidized carbonyl/carboxyl C functional groups (C=O, p<0.05) with significantly higher surficial atomic percentages of C (p<0.01), N (p<0.01), and Mg:Al ratios (p<0.05), and lower atomic percentages of Al (p<0.01) and Si (p<0.01) compared to the larger particles. The formation of cation bridges and/or hydrogen bonds between carboxylic OC and phyllosilicate minerals likely dominated the mineral-OC association in the NNP fraction. The higher surface C enrichment in the particulate fraction compared to the NNP fraction suggests a patchy distribution of more plant-derived OC through organo-organic interactions in the larger fractions. Along the transect, Zone U exhibited significant enrichment of heavier δ13C isotope and lower SUVA values than the Zones T and W indicating inefficient decomposition and dissociation of SOM from minerals due to the reductive dissolution of Fe and Al oxides under anoxic conditions. Furthermore, an increase in low molecular weight microbial metabolites with reduced aromatic OC content was observed at deeper depths in Zones U and T. Our study provides new insights into the concentration and molecular composition of size-fractionated COC, highlighting the need to separately consider the NNP and fine colloid fractions from the operationally defined “dissolved” phase. This is crucial for assessing the biogeochemical cycling of OC in redox-active wetlands, a pressing need amidst the growing concerns about the impacts of climate change.

Sources and Fate of Sedimentary Organic Matter in the Western Mediterranean Sea

AbstractMarine sediments comprise the primary long‐term sink of organic matter (OM) in marine systems. Disentangling the diverse origins of OM and the influence of the main processes that determine organic carbon (OC) fate at a global scale has proven difficult due to limited spatial data coverage. Thus, comprehensive studies of the spatial distribution of the content and geochemical characteristics of sedimentary OM at basin scales provide fundamental knowledge on the role of marine sediments in the global carbon cycle. Here, we shed light on the origin of OM and the underlying mechanisms that determine its fate in a semi‐enclosed basin by examining the spatial patterns in the isotopic and elemental composition of OM in 149 core‐top samples from the Western Mediterranean Sea and the adjacent Atlantic Ocean sector. Our results reveal an apparent SW‐NE gradient that reverses in the Gulf of Lions in most geochemical and sedimentological features. Changes in the OC content and ẟ13C and Δ14C signatures are ascribed to spatial variations in marine primary productivity and the influence of varying discharge of rivers and well‐developed canyons that favor the cross‐shelf transport of terrestrial (and petrogenic) OC. Our results also suggest the potential influence of two other mechanisms on the geochemical signatures of OM: (a) lateral transport of allochthonous OC and selective degradation of labile OM, which potentially occurs across the studied area having a greater impact toward the north‐eastern region, and (b) OM protection via association with mineral surfaces, potentially having a greater influence toward the south‐western basins.