Petrogenic Organic Carbon Research Articles

The Global Biogeochemical Cycle of Rhenium

AbstractThis paper is the first comprehensive synthesis of what is currently known about the different natural and anthropogenic fluxes of rhenium (Re) on Earth's surface. We highlight the significant role of anthropogenic mobilization of Re, which is an important consideration in utilizing Re in the context of a biogeochemical tracer or proxy. The largest natural flux of Re derives from chemical weathering and riverine transport to the ocean (dissolved = 62 × 106 g yr−1 and particulate = 5 × 106 g yr−1). This review reports a new global average [Re] of 16 ± 2 pmol L−1, or 10 ± 1 pmol L−1 for the inferred pre‐anthropogenic concentration without human impact, for rivers draining to the ocean. Human activity via mining (including secondary mobilization), coal combustion, and petroleum combustion mobilize approximately 560 × 106 g yr−1 Re, which is more than any natural flux of Re. There are several poorly constrained fluxes of Re that merit further research, including: submarine groundwater discharge, precipitation (terrestrial and oceanic), magma degassing, and hydrothermal activity. The mechanisms and the main host phases responsible for releasing (sources) or sequestrating (sinks) these fluxes remain poorly understood. This study also highlights the use of dissolved [Re] concentrations as a tracer of oxidation of petrogenic organic carbon, and stable Re isotopes as proxies for changes in global redox conditions.

Presence and implications of petrogenic organic carbon in High Himalayan Crystalline lake sediment

AbstractTwelve lacustrine sediment samples from a relict lake in the Kalla Glacier valley were co-dated using AMS radiocarbon (14C) and infrared stimulated luminescence (IRSL) dating methods. In general, the radiocarbon ages of bulk organic matter were older by a minimum of 1500 years compared to (age depth) modeled luminescence ages after fading corrections. This is observed for the first time in the lake sediments of High Himalayan Crystalline zone. A combination of lipid n-alkane data, Raman spectra and geochemical proxies suggested that this was due to ancient organic carbon (OCancient) that is a mixture of pre-aged (OCpre-aged) and petrogenic (OCpetro) organic carbon within older glacial moraine debris that served as sediment source to the lake. Raman spectra suggest the presence of moderate to highly graphitized OCpetro in all the profile samples. The OCpetro contributed 0.064 ± 0.032% to the sediment and the lake stored 2.5 ± 0.7 Gg OCpetro at variable rates during the last 16 kyr, with the mean burial flux 160 kg OCpetro yr−1. This study implies (1) employing another independent dating method in addition to radiocarbon method using bulk sediment organic matter, if the carbon content is low, to observe any discrepancy, and (2) a need to investigate on the fate of OCpetro as many such small lakes become relict in this region.

Organic Carbon Sources in Surface Sediments on the Northern South China Sea

AbstractThe burial of organic carbon (OC) in marine sediments regulates CO2 content in the atmosphere. However, the OC sources and their effect on the OC preservation in sediments of the continental marginal sea remain elusive. Here, we survey the abundance, stable carbon and radiocarbon isotopes of OC, as well as mineral surface area and grain size in surface sediments from the shelf to the abyssal plain of the South China Sea. We found that the marine OC comprises the 63 ± 9% and 78 ± 14% of sedimentary OC off South China and Luzon, respectively. The petrogenic OC contributing to sedimentary OC in these sites is generally higher than that of soil OC (22 ± 10% vs. 12 ± 6%). The sedimentary OC off Taiwan is predominantly derived from petrogenic OC, accounting for 57 ± 10%, with remaining consisting of marine OC (36 ± 10%) and soil OC (6 ± 1%). High soil OC contents are found in fine sediments on the inner shelf off South China, and high petrogenic OC contents occur in fine sediments off Taiwan. Marine OC contents are high in fine sediments on the middle shelf and upper slope off South China, but low in coarse sediments on the outer shelf and upper slope, and fine sediments on the lower slope and abyssal plain. The OC sources, mineral surface area, and oxygen exposure time of OC together control the preservation of OC in sediments with their relative importance differing on varying depositional settings of this sea.

Spatial and Temporal Patterns in Petrogenic Organic Carbon Mobilization During the Paleocene‐Eocene Thermal Maximum

AbstractThe Paleocene‐Eocene Thermal Maximum (PETM) was a transient global warming event and is recognized in the geologic record by a prolonged negative carbon isotope excursion (CIE). The onset of the CIE was due to a rapid influx of 13C‐depleted carbon into the ocean‐atmosphere system. However, the mechanisms required to sustain the negative CIE remains unclear. Enhanced mobilization and oxidation of petrogenic organic carbon (OCpetro) has been invoked to explain elevated atmospheric carbon dioxide concentrations after the onset of the CIE. However, existing evidence is limited to the mid‐latitudes and subtropics. Here, we determine whether: (a) enhanced mobilization and subsequent burial of OCpetro in marine sediments was a global phenomenon; and (b) whether it occurred throughout the PETM. To achieve this, we utilize a lipid biomarker approach to trace and quantify OCpetro burial in a global compilation of PETM‐aged shallow marine sites (n = 7, including five new sites). Our results confirm that OCpetro mass accumulation rates (MARs) increased within the subtropics and mid‐latitudes during the PETM, consistent with evidence of higher physical erosion rates and intense episodic rainfall events. High‐latitude sites do not exhibit drastic changes in the source of organic carbon during the PETM and OCpetro MARs increase slightly or remain stable, perhaps due a more stable hydrological regime. Crucially, we also demonstrate that OCpetro MARs remained elevated during the recovery phase of the PETM. Although OCpetro oxidation was likely an important positive feedback mechanism throughout the PETM, we show that this feedback was both spatially and temporally variable.

Probing the exchange of CO2 and O2 in the shallow critical zone during weathering of marl and black shale

Abstract. Chemical weathering of sedimentary rocks can release carbon dioxide (CO2) and consume oxygen (O2) via the oxidation of petrogenic organic carbon and sulfide minerals. These pathways govern Earth's surface system and climate over geological timescales, but the present-day weathering fluxes and their environmental controls are only partly constrained due to a lack of in situ measurements. Here, we investigate the gaseous exchange of CO2 and O2 during the oxidative weathering of black shales and marls exposed in the French southern Alps. On six field trips over 1 year, we use drilled headspace chambers to measure the CO2 concentrations in the shallow critical zone and quantify CO2 fluxes in real time. Importantly, we develop a new approach to estimate the volume of rock that contributes CO2 to a chamber, and assess effective diffusive gas exchange, by first quantifying the mass of CO2 that is stored in a chamber and connected rock pores. Both rock types are characterized by similar contributing rock volumes and diffusive movement of CO2. However, CO2 emissions differed between the rock types, with yields over rock outcrop surfaces (inferred from the contributing rock volume and the local weathering depths) ranging on average between 73 and 1108 tCkm-2yr-1 for black shales and between 43 and 873 tCkm-2yr-1 for marls over the study period. Having quantified diffusive processes, chamber-based O2 concentration measurements are used to calculate O2 fluxes. The rate of O2 consumption increased with production of CO2, and with increased temperature, with an average O2:CO2 molar ratio of 10:1. If O2 consumption occurs by both rock organic carbon oxidation and carbonate dissolution coupled to sulfide oxidation, either an additional O2 sink needs to be identified or significant export of dissolved inorganic carbon occurs from the weathering zone. Together, our findings refine the tools we have to probe CO2 and O2 exchange in rocks at Earth's surface and shed new light on CO2 and O2 fluxes, their drivers, and the fate of rock-derived carbon.

Large contributions of petrogenic and aged soil-derived organic carbon to Arctic fjord sediments in Svalbard

Svalbard fjords are recognized as hotspots for organic carbon (OC) burial and storage due to their high sedimentation rates, which effectively trap terrestrial sediments and inhibit extensive OC remineralization. In this study, we investigated surface sediments (n = 48) from eight Svalbard fjords, along with bedrock (n = 17), soil (n = 28), and plant (n = 12) samples, to identify the sources of sedimentary OC in these fjords using geochemical parameters. All examined surface sediments from the fjords showed a depletion in 14Corg (− 666.9 ± 240.3‰), indicating that recently fixed terrestrial and marine biomass alone cannot account for the entire sedimentary OC pool. Conventional bulk indicators such as Norg/TOC ratio and δ13Corg were insufficient for fully determining the sources of sedimentary OC. Therefore, we employed a four-end-member approach, using Δ14Corg, δ13Corg, and lignin phenols to assess the relative contributions of petrogenic, soil-derived, plant-derived, and marine OC to the sedimentary OC pool. The analyzed fjord sediments consisted, on average, of 59.0 ± 28.1% petrogenic OC, 16.8 ± 12.1% soil-derived OC, 2.5 ± 2.2% plant-derived OC, and 21.8 ± 18.5% marine OC. This approach highlights the substantial contributions of petrogenic and aged soil-derived OC to present-day sedimentary OC in Svalbard fjords. Considering predicted global warming, accelerated inputs of petrogenic and soil-derived OC into fjords due to rapid glacier retreat may significantly impact the active carbon cycle and potentially contribute to CO2 emissions to the atmosphere, depending on burial efficiency.

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.

Fossil organic carbon utilization in marine Arctic fjord sediments by subsurface micro-organisms

Rock-derived or petrogenic organic carbon has traditionally been regarded as being non-bioavailable and bypassing the active carbon cycle when eroded. However, it has become apparent that this organic carbon might not be so inert, especially in fjord systems where petrogenic organic carbon influxes can be high, making its degradation another potential source of greenhouse gas emissions. The extent to which subsurface micro-organisms use this organic carbon is not well constrained, despite its potential impacts on global carbon cycling. Here, we performed compound-specific radiocarbon analyses on intact polar lipid–fatty acids of live micro-organisms from marine sediments in Hornsund Fjord, Svalbard. By this means, we estimate that local bacterial communities utilize between 5 ± 2% and 55 ± 6% (average of 25 ± 16%) of petrogenic organic carbon for their biosynthesis, providing evidence for the important role of petrogenic organic carbon as a substrate after sediment redeposition. We hypothesize that the lack of sufficient recently synthesized organic carbon from primary production forces micro-organisms into utilization of petrogenic organic carbon as an alternative energy source. The input of petrogenic organic carbon to marine sediments and subsequent utilization by subsurface micro-organisms represents a natural source of fossil greenhouse gas emissions over geological timescales.

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.

Deep root activity overprints weathering of petrogenic organic carbon in shale

The oxidation of organic carbon in sedimentary bedrock (petrogenic OC, OCpetro) is increasingly recognized as a potential source of CO2 to the atmosphere. Recent studies provide evidence for the mobilization and oxidation of OCpetro in sedimentary bedrock during rock weathering. However, the mechanisms and rates remain uncertain, particularly where overlying soils and vegetation drive contemporaneous oxidation of recently fixed organic carbon. Here, we quantify OCpetro weathering across a 16 m shale depth profile in a steep, rapidly eroding forested hillslope in the Northern California Coast Ranges. We report solid and gas phase radiocarbon and stable isotope analyses of samples extracted from specialized in-situ samplers, and a supporting laboratory incubation experiment of the shale regolith. OCpetro is removed from the weathered bedrock at a rate of approximately 0.12 gC/m3yr, which is orders of magnitude lower than the rate of OCpetro oxidation we achieved in the laboratory with crushed samples (557.1 gC/m3/yr). This disparity occurs despite high O2(g) content across the depth profile, indicating that physical accessibility of OCpetro can regulate oxidative weathering. There is no direct radiocarbon evidence of OCpetro oxidation in CO2(g) across the upper 13 m of the weathering profile during both wet and dry seasons. Instead, vadose zone CO2(g) production at the site is dominated by respiration of recently fixed carbon associated with deep rooting. OCpetro is clearly mobilized across the vadose zone during weathering in this rapidly eroding, oxygen-rich, biologically dynamic hillslope, but at rates far below what can be measured given the contribution of root-derived CO2(g).

Low rates of rock organic carbon oxidation and anthropogenic cycling of rhenium in a slowly denuding landscape

AbstractThe oxidation of petrogenic organic carbon (OCpetro) is a source of carbon dioxide to the atmosphere over geological timescales. The rates of OCpetro oxidation in locations that experience low rates of denudation remain poorly constrained, despite these landscapes dominating Earth's continental surface area. Here, we track OCpetro oxidation using radiocarbon and the trace element rhenium (Re) in the deep weathering profiles, soils and stream waters of the Susquehanna Shale Hills Critical Zone Observatory (PA, USA). In a ridge‐top borehole, radiocarbon measurements reveal the presence of a broad OCpetro weathering front, with a first‐order assessment of ~40% loss occurring over ~6 m. However, the low OCpetro concentration (< 0.05 wt%) and inputs of radiocarbon throughout the deepest parts of the profile complicate the assessment of OCpetro loss. The OCpetro weathering front coincides with a zone of Re depletion (~90% loss), and we estimate that > 80% of Re in the rock is associated with OCpetro, based on Re/Na and Re/S ratios. Using estimates of long‐term denudation rates, the observed OCpetro loss and the Re proxy are equivalent to a low OCpetro oxidation yield of < 1.7 × 10−2 tC km−2 yr−1. This is consistent with the low OCpetro concentrations and low denudation rates at this location. In addition, we find the surface cycle of Re is decoupled from that of deep weathering, with an enrichment of Re in surface soils and elevated Re concentrations in stream water, precipitation, and shallow groundwater. A mass balance model shows that this can be explained by a historical anthropogenic contribution of Re through atmospheric deposition. We estimate that the topsoil Re pool could take decades to centuries to deplete and call for a renewed focus on anthropogenic perturbation of the surface Re cycle in low denudation rate settings.

Environmental and hydrologic controls on sediment and organic carbon export from a subalpine catchment: insights from a time series

Abstract. Studies engaging in tracking headwater carbon signatures downstream remain sparse, despite their importance for constraining transfer and transformation pathways of organic carbon (OC) and developing regional-scale perspectives on mechanisms influencing the balance between remineralization and carbon export. Based on a 40-month time series, we investigate the dependence of hydrology and seasonality on the discharge of sediment and OC in a small (350 km2) Swiss subalpine watershed (Sihl River basin). We analyze concentrations and isotopic compositions (δ13C, F14C) of particulate OC and use dual-isotope mixing and machine learning frameworks to characterize and estimate source contributions, transport pathways, and export fluxes. The majority of transferred OC is sourced from plant biomass and soil material. The relative amount of bedrock-derived (petrogenic) OC, abundant in headwater streams, progressively decreases downstream in response to a lack of source material and efficient overprinting with biospheric OC, illustrating rapid organic matter alteration over short distances. Large variations in OC isotopic compositions observed during baseflow conditions converge and form a homogenous mixture enriched in OC and characterized by higher POC-F14C values following precipitation-driven events. Particulate OC isotopic data and model results suggest that storms facilitate surface runoff and the inundation of riparian zones, resulting in the entrainment of loose plant-derived debris and surficial soil material. Although particle transport in the Sihl River basin is mainly driven by hydrology, subtle changes in bedrock erosivity, slope angle, and floodplain extent likely have profound effects on the POC composition, age, and export yields.

Deglacial release of petrogenic and permafrost carbon from the Canadian Arctic impacting the carbon cycle

The changes in atmospheric pCO2 provide evidence for the release of large amounts of ancient carbon during the last deglaciation. However, the sources and mechanisms that contributed to this process remain unresolved. Here, we present evidence for substantial ancient terrestrial carbon remobilization in the Canadian Arctic following the Laurentide Ice Sheet retreat. Glacial-retreat-induced physical erosion of bedrock has mobilized petrogenic carbon, as revealed by sedimentary records of radiocarbon dates and thermal maturity of organic carbon from the Canadian Beaufort Sea. Additionally, coastal erosion during the meltwater pulses 1a and 1b has remobilized pre-aged carbon from permafrost. Assuming extensive petrogenic organic carbon oxidation during the glacial retreat, a model-based assessment suggests that the combined processes have contributed 12 ppm to the deglacial CO2 rise. Our findings suggest potentially positive climate feedback of ice-sheet retreat by accelerating terrestrial organic carbon remobilization and subsequent oxidation during the glacial-interglacial transition.

Oxidation of petrogenic organic carbon in a large river-dominated estuary

Riverine export of petrogenic organic carbon (OCpetro) from continents to coastal oceans is a dynamic component of the global carbon budget and affects the long-term atmospheric carbon reservoir. In large fluvial systems, oxidation of OCpetro during transit releases a large flux of carbon dioxide to the atmosphere, influencing climate changes; however, the transport and fate of OCpetro and their controls along the fluvial–marine transition remain poorly constrained. Here, we combined Raman spectral, radiocarbon activity (F14C), mineralogical, and sedimentological techniques with multiple geochemical analyses to characterize the dynamics of OCpetro in the water column and sediment particles from the Yangtze River channel–estuary–shelf continuum systems.Our data show that much of the OCpetro present in suspended sediment (POCpetro) exported by the Yangtze River is “labile” fractions (mostly disordered materials) that can be degraded or lost during transport across the estuarine continuum, whereas the OCpetro deposited in seabed sediment are characterized by highly recalcitrant, unreactive, and graphitic carbon phases. As discrete “free” particles, coarse plant debris (>63 μm) with ages of several thousand years observed in the proximal delta of the Yangtze River exhibit nearly identical characteristics of disordered materials, and the presence of aged vascular plant detritus (carbon-rich and 14C-depleted materials) may lead to an overestimate of OCpetro in marine sediments. Using a Bayesian endmember mixing approach, a binary mixing model, and the ratio of fraction modern carbon (F14C) to Al/OC, we found a large decrease in POCpetro concentration and loading from the suspended sediments to seabed sediments, suggesting a loss of mineral-bound OCpetro fraction during sediment transport through the estuary and deposition on the shelf. We estimated that, on average, 46 ± 35 % of the POCpetro initially present in suspended sediments delivered to the Yangtze River Estuary during a flood event was primarily oxidized at the sediment–water interface, leaving the most graphitic carbon components transported laterally and efficiently reburied in shelf sediments. We found that during estuarine mixing, flocculation process-induced microaggregates may provide transient physical protection for POCpetro in the form of inclusions/aggregates with carbonate minerals; however, when POCpetro is physically and chemically separated from its mineral matrix via disaggregation and dissolution, it may be easily oxidized by microbial activity. In contrast, OC-phyllosilicates interactions exert a first-order control on the preservation of OCpetro in marine sediments. Our findings suggest that the importance of POCpetro oxidation and loss in carbon cycling and budget assessments of estuaries may be underestimated.

Impacts of Climate Change and Human Perturbations on Organic Carbon Burial in the Pearl River Estuary Over the Last Century

Estuaries have experienced significant changes due to global climate change and human perturbations since the last century. However, the climate and anthropogenic influence on the burial of sedimentary organic carbon (OC) in estuaries is still not understood well yet. Here, a 3-meter sediment core was taken from the Pearl River Estuary (PRE) in China. Depth profiles of both bulk OC and lignin biomarker data indicated three stages with different features of buried OC during the 130-year sediment deposition. The 1893-1957 stage showed 20% more burial of marine derived OC, which was mostly adsorbed on finer minerals compared to the years after 1957. The 1957-1980 period witnessed 4.6 times higher burial rate of petrogenic OC, which made the radiocarbon age of total organic carbon 42% older than before due to soil erosion and carbonate rock weathering. The 7-year running average variation of terrestrial OC input based on endmember mixing model was correlated with the Pacific Decadal Oscillation index before 1957, but correlated with the Atlantic Multidecadal Oscillation between 1957 and 1980 in the region. The reduction of land derived OC content after 1980s was mostly affected by human perturbations such as deforestation and dam construction which corresponded to the beginning of Economic Reform and Open Up in China. The overall increase of lignin content from bottom to surface sediment indicated increased vascular plant derived OC due to deforestation activities during the urbanization process. The study suggested different time periods when climate or human disturbance dominantly affected the OC burial in the PRE, which have significant indications for local and global carbon cycling and environmental ecology.

Terrestrial organic carbon age and reactivity in the Yellow River fueling efficient preservation in marine sediments

The Yellow River is one of the largest suppliers of sediments and organic carbon (OC) to the ocean. Previous studies have revealed that OC transported by the Yellow River largely derives from the erosion of the Chinese Loess Plateau, which is dominated by pre-aged soil carbon and could be efficiently preserved in marine sediments. Here, we used ramped oxidation radiocarbon analysis (RPO-14C) to characterize the age and reactivity distribution of OC in two Yellow River suspended sediment samples and six Bohai Sea and Yellow Sea (BS–YS) surface sediments from a transect along the sediment transport pathway. RPO-14C independently characterizes the full spectrum of OC thermal stability and isotope compositions to reveal the source, age and reactivity structure of OC transported by the Yellow River and preserved in Chinese marginal sea sediments. We calculated the activation energy (E) distribution—a proxy for bonding environment and by extension reactivity—which, combined with 14C and stable carbon isotope (δ13C) compositions, reveals OC origin and stability. Our data suggest that 96% of OC in Yellow River suspended sediments is biospheric and weathered petrogenic, while unweathered petrogenic OC only accounts for 4% which is almost an order of magnitude lower than the fossil OC estimates (32%) based on compound specific 14C analysis. RPO data reveal the prevalence of aged biospheric loess OC in the Yellow River. We use δ13C, 14C and RPO-derived activation energy data to quantify the contribution of terrestrial OC to surface sediments in the BS–YS. The resulting estimates of terrestrial OC proto-burial efficiencies yield an average value of 89 ± 30%, revealing overall very high terrestrial OC preservation in the BS–YS. Additionally, and somewhat counter intuitively, we find that the preservation of terrestrial OC decreases with increasing E. This pattern may arise from an enhanced preservation of a pre-aged C4 plants derived fraction of the loess-derived OC associated with secondary clays characterized by smaller grain size and higher surface area. Alternatively, the high E component of the Yellow River OC might comprise partially weathered petrogenic carbon, undergoing further mineralization during transport from rivers to marginal sea sediments via marine organic matter priming.

Increased petrogenic and biospheric organic carbon burial in sub‐Antarctic fjord sediments in response to recent glacier retreat

AbstractFjords are recognized as hotspots of organic carbon (OC) burial in the coastal ocean. In fjords with glaciated catchments, glacier discharge carries large amounts of suspended matter. This sedimentary load includes OC from bedrock and terrigenous sources (modern vegetation, peat, soil deposits), which is either buried in the fjord or remineralized during export, acting as a potential source of CO2 to the atmosphere. In sub‐Antarctic South Georgia, fjord‐terminating glaciers have been retreating during the past decades, likely as a response to changing climate conditions. We determine sources of OC in surface sediments of Cumberland Bay, South Georgia, using lipid biomarkers and the bulk 14C isotopic composition, and quantify OC burial at present and for the time period of documented glacier retreat (between 1958 and 2017). Petrogenic OC is the dominant type of OC in proximity to the present‐day calving fronts (60.4 ± 1.4% to 73.8 ± 2.6%) and decreases to 14.0 ± 2.7% outside the fjord, indicating that petrogenic OC is effectively buried in the fjord. Beside of marine OC, terrigenous OC comprises 2.7 ± 0.5% to 7.9 ± 5.9% and is mostly derived from modern plants and Holocene peat and soil deposits that are eroded along the flanks of the fjord, rather than released by the retreating fjord glaciers. We estimate that the retreat of tidewater glaciers between 1958 and 2017 led to an increase in petrogenic carbon accumulation of 22% in Cumberland West Bay and 6.5% in Cumberland East Bay, suggesting that successive glacier retreat does not only release petrogenic OC into the fjord, but also increases the capacity of OC burial.

Source, transport and fate of terrestrial organic carbon from Yangtze River during a large flood event: Insights from multiple-isotopes (δ13C, δ15N, Δ14C) and geochemical tracers

Climate change-triggered episodic and intensive flood events are increasing in frequency globally; these events play a disproportionate role in the carbon cycle at land-ocean interfaces by influencing the delivery of terrestrial organic matter to the sea. However, the transport and burial of flood-driven terrestrial organic carbon (Corg) in river-dominated marginal seas remains poorly understood. Here, water column particles (surface, intermediate, and bottom layers) and surface sediments from the Yangtze River estuary system were collected during a large flooding event (>60,000 m3 s−1) for a multiproxy geochemical study. We analyzed N/C, δ13Corg, δ15N, F14C, grain size, and elemental (Al and Si) to characterize the sources, ages, and alterations of particulate organic carbon (POC) and sedimentary Corg from the river channel to the estuarine mixing zone to the continental shelf and fingerprint the fate of Corg burial in marine sediments.We found that terrestrial POC delivered by the Yangtze flood is characterized by low F14C (0.625 ± 0.002; Δ14C = −379.8 ± 2.3‰, 14C age = 4,135 yr before present (BP)) and δ13Corg (−27.1 ± 0.5‰) values and high δ15N (3.9 ± 0.6‰), and N/C (0.15 ± 0.01) values, and was adsorbed on fine-grained particles. Using a Bayesian-Monte Carlo simulation approach, we estimated that terrestrial POC is dominated by C3 plant detritus (42 ± 16% on average), followed by petrogenic organic carbon (33 ± 7%), and soil (26 ± 22%). Moving offshore, hydrodynamic sorting of lithogenic particles exerts first-order control on POC by selecting particles with unique signatures. Petrogenic organic carbon and aged plant debris associated with coarse-sized particles preferentially accumulated within the proximal delta, whereas POC derived from catchment soil and adsorbed on fine-grained particles was transported offshore along the sediment dispersion system. We estimated that, on average, 76 ± 18% of POC initially present in the water column is oxidized at the water column-seabed interface during seaward transport and constitutes a source of atmospheric carbon dioxide. In contrast, the stable form of the organic matter-aluminosilicate mineral association controls the preservation of the sedimentary Corg. Our results suggest that frequent flooding events in the near future will likely increase lithospheric Corg delivery to marine sediments and have the potential to promote petrogenic Corg burial efficiency in the river-dominated marginal seas and accelerate biospheric POC oxidation and CO2 release, thus generating a positive feedback to global warming.

Presentation and applications of mixing elements and dissolved isotopes in rivers (MEANDIR), a customizable MATLAB model for Monte Carlo inversion of dissolved river chemistry

The dissolved chemistry of rivers has been extensively studied to elucidate physical and climatic controls of chemical weathering at local to global spatial scales, as well as the impacts of chemical weathering on climate over short to geologic temporal scales. Within this effort, mixing models with Monte Carlo uncertainty propagation are a common tool for inverting measurements of dissolved river chemistry to distinguish among contributions from end-members with distinct elemental and/or isotopic compositions. However, the methods underlying prior river inversion models have typically been opaque. Here we present Mixing Elements ANd Dissolved Isotopes in Rivers (MEANDIR), a set of MATLAB scripts that enable highly customizable inversion of dissolved river chemistry with Monte Carlo propagation of uncertainty. First, we present an overview of the mathematics underlying MEANDIR. This overview includes, among other topics, derivation of equations for mass balance, implementation of chlorine critical values, construction of cost functions, normalization to the sum of dissolved variables, quantification of river sulfate sourced from pyrite oxidation, resolution of petrogenic organic carbon oxidation, representation of secondary phase formation with isotopic fractionation, and calculation of the impact of weathering on atmospheric carbon dioxide. Second, we apply MEANDIR to five previously published datasets to demonstrate the sensitivity of results to parameter choices. We invert data from two global compilations of river chemistry (Gaillardet and others, 1999; Burke and others, 2018), the major element chemistry and sulfate sulfur isotope ratios of rivers in the Peruvian Amazon (Torres and others, 2016), the major element chemistry of Icelandic rivers (Gíslason and others, 1996), and the major and trace element chemistry of water samples from the Mackenzie River (Horan and others, 2019). MEANDIR and its user guide are freely available online.

Controls on Organic Carbon Burial in the Eastern China Marginal Seas: A Regional Synthesis

AbstractA regional synthesis of organic carbon (OC) burial was conducted using a comprehensive data set to reveal some of the key drivers and human multi‐stressors controlling OC burial and transport in the Eastern China Marginal Seas (ECMS). Both OC and Δ14C values of suspended particulate matter (SPM) in the Changjiang River, were significantly higher than estuarine mobile‐muds, suggesting selective decay of more labile younger OC from both marine and terrestrial sources and the accumulation of more recalcitrant older OC. Some of this decay is likely to be associated with iron‐redox cycling in mobile‐muds. In contrast, OC, δ13C, and Δ14C values increased along the Yellow River sediment dispersal pathway, indicating adding of young marine OC and less decay of terrestrial OC. OC burial efficiency in mud areas in the Bohai Sea (∼43%) was significantly higher than those in the Yellow (∼11%) and East China Seas (∼16%), owing to rapid deposition. Burial flux of biospheric OC in mud areas of the ECMS is 7.00 ± 0.79 Mt yr−1, corresponding to atmospheric CO2 drawdown by silicate weathering in major river drainage basins of mainland China. The burial flux of petrogenic OC was estimated to be 0.81 ± 0.25 Mt yr−1, accounting for >1.9% of total burial in the global ocean. While the ECMS is an important OC sink, river damming has greatly reduced OC burial. Thus, the overall impact on anthropogenically altered river‐dominated marginal seas remains an important and rapidly changing component of the coastal ocean carbon budget.