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The Amazon River mobilizes organic carbon across one of the world's largest terrestrial carbon reservoirs. Quantifying the sources of particulate organic carbon (POC) to this flux is typically challenging in large systems such as the Amazon River due to hydrodynamic sorting of sediments. Here, we analyze the composition of POC collected from multiple total suspended sediment (TSS) profiles in the mainstem at Óbidos, and surface samples from the Madeira, Solimões and Tapajós Rivers. As hypothesized, TSS and POC concentrations in the mainstem increased with depth and fit well to Rouse models for sediment sorting by grain size. Coupling these profiles with Acoustic Doppler Current Profiler discharge data, we estimate a large decrease in POC flux (from 540 to 370 kg per second) between the rising and falling stages of the Amazon River mainstem. The C/N ratio and stable and radiocarbon signatures of bulk POC are less variable within the cross‐section at Óbidos and suggest that riverine POC in the Amazon River is predominantly soil‐derived. However, smaller shifts in these compositional metrics with depth, including leaf wax n‐alkanes and fatty acids, are consistent with the perspective that deeper and larger particles carry fresher, less degraded organic matter sources (i.e., vegetation debris) through the mainstem. Overall, our cross‐sectional surveys at Óbidos highlight the importance of depth‐specific sampling for estimating riverine export fluxes. At the same time, they imply that this approach to sampling is perhaps less essential with respect to characterizing the composition of POC sources exported by the river. Plain Language Summary: The Amazon River transports one of the largest quantities of freshwater organic carbon into the Atlantic Ocean. In this study, we collected suspended particles at different depths within a cross‐section of the Amazon River mainstem during the rising and falling stages of the river's hydrological cycle. We analyzed the organic carbon, nitrogen, grain size, and leaf‐derived compounds in these particles, and integrated water velocity measurements to calculate the quantity of carbon in particle form moving through the river at these two stages. The analyses showed that large, dense particles concentrate with depth in the Amazon River mainstem. The composition of these particles is relatively homogenous, but slight variations in metrics like carbon‐to‐nitrogen ratio, age derived from carbon‐dating, and leaf waxes imply that less degraded sources of organic carbon are found in the deeper and coarser grained particles. Overall, the data suggest that the majority of Amazon River particulate organic carbon comes from a mixture of soil organic carbon washing in from different landscapes and soil depth horizons. A globally significant quantity of this carbon will get buried in the Atlantic Ocean, forming a long‐term carbon sink. Key Points: Amazon River suspended sediments show little variation in organic carbon composition with depth despite hydrodynamic sortingEstimated particulate organic carbon fluxes range from 370 to 540 kg per second during the falling and rising stages, respectivelyThe majority of Amazon River particulate organic carbon exported from the mainstem at Óbidos is soil‐derived [ABSTRACT FROM AUTHOR]

As major sites of carbon burial and remineralization, continental margins are key components of the global carbon cycle. However, heterogeneous sources of organic matter (OM) and depositional environments lead to complex spatial patterns in sedimentary organic carbon (OC) content and composition. To better constrain the processes that control OM cycling, we focus on the East Asian marginal seas as a model system, where we compiled extensive data on the OC content, bulk isotopic composition (δ13C and Δ14C), total nitrogen, and mineral surface area of surficial sediments from previous studies and new measurements. We developed a spatial machine learning modeling framework to predict the spatial distribution of these parameters and identify regions where sediments with similar geochemical signatures drape the seafloor (i.e., "isodrapes"). We demonstrate that both provenance (44%-77%) and hydrodynamic processes (22%-53%) govern the fate of OM in this margin. Hydrodynamic processes can either promote the degradation of OM in mobile mud-belts or preserve it in stable mud-deposits. The distinct isotopic composition of OC sources from marine productivity and individual rivers regulates the age and reactivity of OM deposited on the sea-floor. The East Asian marginal seas can be separated into three main isodrapes: hydrodynamically energetic shelves with coarser-grained sediment depleted in OC, OM-enriched mud deposits, and a deep basin with fine-grained sediments and aged OC affected by long oxygen exposure times and petrogenic input from rivers. This study confirms that both hydrodynamic processes and provenance should be accounted for to understand the fate of OC in continental margins. [ABSTRACT FROM AUTHOR]

The 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. [ABSTRACT FROM AUTHOR]

Rationale: Compound-specific oxygen stable isotope analysis has been commercially available for about 20 years but the technique has been infrequently applied and practical operating knowledge is limited. Existing reactor designs and chemistry fail to fully exclude contaminating oxygen, are chromatographically flawed, and are generally fabricated from expensive platinum tubing. Methods: As a new interface between the gas chromatograph and isotope ratio mass spectrometer, we used a nickel tube reactor (containing no platinum wires) in a ceramic sheath with countercurrent helium flushing, operated at 1250°C. We analyzed suites of four long-chain alcohols (LCAs), defining the least and most 18Oenriched LCAs as internal standards. The other two LCAs, co-injected in varying amounts, were treated as unknowns and amplitude-corrected during data reduction. Results: With this design, signals from non-oxygenated compounds are minimized with a hydrogen trickle, while excessive graphitization is counterproductive. A balance of hydrogen and graphite is required to maintain a proper, stable redox state in the reactor. With low extraneous oxygen, the exact hydrogen flow has little effect on final δ18O data quality. Overall average δ18O values precisions and errors for the unknowns were better than 0.4 ‰ for injections between 2 and 7 nmol per component. Conclusions: Our actively flushed sheath reduces oxygen infiltration to negligible levels and results in a chromatographic flow devoid of dead or poorly swept volumes. The improved design allows measurement of LCAs with accuracy and precision sufficient to enable investigating real processes, and may also have wider applications to other isotopes. [ABSTRACT FROM AUTHOR]

Increasing Arctic temperatures are thawing permafrost soils and liberating ancient organic matter, but the fate of this material remains unclear. Thawing of permafrost releases dissolved organic matter (DOM) into fluvial networks. Unfortunately, tracking this material in Arctic rivers such as the Kolyma River in Siberia has proven challenging due to its high biodegradability. Here, we evaluate late summer abruptly thawed yedoma permafrost dissolved organic carbon (DOC) inputs from Duvannyi Yar. We implemented ultrahigh‐resolution mass spectrometry alongside ramped pyrolysis oxidation (RPO) and isotopic analyses. These approaches offer insight into DOM chemical composition and DOC radiocarbon values of thermochemical components for a permafrost thaw stream, the Kolyma River, and their biodegraded counterparts (n = 4). The highly aliphatic molecular formula found in undegraded permafrost DOM contrasted with the comparatively aliphatic‐poor formula of Kolyma River DOM, represented by an 8.9% and 2.6% relative abundance, respectively, suggesting minimal inputs of undegraded permafrost DOM in the river. RPO radiocarbon fractions of Kolyma River DOC exhibited no "hidden" aged component indicative of permafrost influence. Thermostability analyses suggested that there was limited biodegraded permafrost DOC in the Kolyma River, in part determined by the formation of high‐activation energy (thermally stable) biodegradation components in permafrost DOM that were lacking in the Kolyma River. A mixing model based on thermostability and radiocarbon allowed us to estimate a maximum input of between 0.8% and 7.7% of this Pleistocene‐aged permafrost to the Kolyma River DOC. Ultimately, our findings highlight that export of modern terrestrial DOC currently overwhelms any permafrost DOC inputs in the Kolyma River. Plain Language Summary: Climate change is warming the Arctic faster than anywhere on Earth. Permafrost, or frozen soil, contains a vast amount of carbon locked in an icy repository. With warming temperatures, permafrost is thawing, and this thawed organic material can be transformed by microbes into greenhouse gases, leading to further warming. The amount of permafrost thawing into rivers, however, has been difficult to determine. In this study, we examined material in both permafrost thaw water, and thaw water material degraded by microbes, then compared it to material in a major Arctic river to see if we can find a sign of permafrost inputs. Permafrost is also very old and this old carbon mixes with modern sources of carbon in the river. We used a new analytical technique to see if we could find old carbon derived from permafrost in the river during late summer when permafrost thaw inputs are greatest. Even with the novel approach, we found little evidence of old carbon, suggesting that major Arctic rivers are currently only exporting a limited amount of permafrost carbon to the Arctic Ocean. This research highlights that the exported carbon is predominantly from plants and other contemporary sources within the watershed. Key Points: Molecular composition indicated minimal inputs of microbially unaltered permafrost thaw dissolved organic carbon (DOC) into the Kolyma RiverThermochemical composition and radiocarbon ages indicated minimal inputs of 28‐days microbially degraded permafrost thaw DOCNo directly permafrost‐aged component was evident in underlying age structure of Kolyma River DOC [ABSTRACT FROM AUTHOR]

The Amazon River drains a diverse tropical landscape greater than 6 million km2, culminating in the world's largest export of freshwater and dissolved constituents to the ocean. Here, we present dissolved organic carbon (DOC), organic and inorganic nitrogen (DON, DIN), orthophosphate (PO43−), and major and trace ion concentrations and fluxes from the Amazon River using 26 samples collected over three annual hydrographs. Concentrations and fluxes were predominantly controlled by the annual wet season flood pulse. Average DOC, DON, DIN, and PO43− fluxes (±1 s.d.) were 25.5 (±1.0), 1.14 (±0.05), 0.82 (±0.03), and 0.063 (±0.003) Tg yr−1, respectively. Chromophoric dissolved organic matter absorption (at 350 nm) was strongly correlated with DOC concentrations, resulting in a flux of 74.8 × 106 m−2 yr−1. DOC and DON concentrations positively correlated with discharge while nitrate + nitrite concentrations negatively correlated, suggesting mobilization and dilution responses, respectively. Ammonium, PO43−, and silica concentrations displayed chemostatic responses to discharge. Major and trace ion concentrations displayed clockwise hysteresis (except for chloride, sodium, and rubidium) and exhibited either dilution or chemostatic responses. The sources of weathered cations also displayed seasonality, with the highest proportion of carbonate‐ and silicate‐derived cations occurring during peak and baseflow, respectively. Finally, our seasonally resolved weathering model resulted in an average CO2 consumption yield of (3.55 ± 0.11) × 105 mol CO2 km−2 yr−1. These results represent an updated and temporally refined quantification of dissolved fluxes that highlight the strong seasonality of export from the world's largest river and set a robust baseline against which to gauge future change. Key Points: Concentrations/fluxes of dissolved carbon, nitrogen, phosphorus, and major/trace ions were predominantly controlled by annual flood pulseMean Amazon River dissolved organic carbon flux was 25.5 teragrams per yearAnnual carbonate + silicate weathering CO2 consumption yield was 3.55 × 105 moles carbon dioxide per square kilometer [ABSTRACT FROM AUTHOR]

In the late Miocene, grasslands spread across the forested floodplains of the Himalayan foreland, but the causes of the ecological transition are still debated. Recent seafloor drilling by the International Ocean Discovery Program (IODP) provides an opportunity to study the transition across a larger region as archived in the Indus submarine fan. We present a multiproxy study of past vegetation change based on analyses of the carbon isotopic composition (δ13C) of bulk organic carbon, plant wax n‐alkanes and n‐alkanoic acids, and quantification of lignin phenols, charcoal, and pollen. We analyze the hydrogen isotopic composition (δD) of plant wax to reconstruct precipitation δD. We use the Branched and Isoprenoid Tetraether (BIT) index to diagnose shifts between terrestrial versus marine lipid inputs between turbidite and hemipelagic sediments. We reconstruct ocean temperatures using the TEX86 index only where marine lipids dominate. We find evidence for the late Miocene grassland expansion in both facies, confirming this was a regional ecosystem transformation. Turbidites contain dominantly terrestrial matter from the Indus catchment (D‐depleted plant wax), delivered via fluvial transport as shown by the presence of lignin. In contrast, hemipelagic sediments lack lignin and bear D‐enriched plant wax consistent with wind‐blown inputs from the Indian peninsula; these show a 7.4–7.2 Ma expansion of C4 grasslands on the Indian subcontinent. Within each facies, we find no clear change in δD values across the late Miocene C4 expansion, implying consistent distillation of rainfall by monsoon dynamics. Yet, a cooling in the Arabian Sea is coincident with the C4 expansion. Plain Language Summary: This project studied the mud and sand on the seafloor in the Indian Ocean, west of India and south of Pakistan. We drilled a core through the mud and focused on a section corresponding to 5.5 to 10 Ma. Much of the sand came from the Indus River, but when the river sediments went elsewhere, layers of chalky sediments formed from the shells of marine organisms. Those chalks contain the history of longer spans of time. In the sediments, we found molecular fossils from the waxy coating on plant leaves and the woody parts of plants as well as pollen and charcoal; these point to the types of plants that were growing on land whose remains were washed or blown out to sea. We also found molecular fossils of microbes that lived in the oceans, whose structures indicate ocean temperatures—although when soils washed out in large amounts, ocean temperature estimates are not available. The main finding is that grasses replaced forests across much of the Indian subcontinent and Indus catchment, accompanied by more grass fire and cooler ocean temperatures. Key Points: Multiproxy study of the Indus Fan organic matter reveals that terrestrial sources differ between turbidite and hemipelagic faciesCarbon isotopes, grass pollen, and charcoal indicate that C4 grasslands expanded between 7.4–7.2 Ma in hemipelagic faciesHydrogen isotopes in plant waxes differ between source regions but do not detect monsoon rainfall changes across the C4 grassland expansion [ABSTRACT FROM AUTHOR]

We investigate the implications of upstream processes and hydrological seasonality on the transfer of soil organic carbon (OC) from the Andes mountains to the Amazon lowlands by the Madre de Dios River (Peru), using branched glycerol dialkyl glycerol tetraether (brGDGT) lipids. The brGDGT signal in Andean soils (0.5 to 3.5 km elevation) reflects air temperature, with a lapse rate of -6.0 °C/km elevation (r2 = 0.89, p < 0.001) and -5.6 °C/km elevation (r2 = 0.89, p < 0.001) for organic and mineral horizons, respectively. The same compounds are present in river suspended particulate matter (SPM) with a lapse rate of -4.1 °C/km elevation (r2 = 0.82, p < 0.001) during the wet season, where the offset in intercept between the temperature lapse rates for soils and SPM indicates upstream sourcing of brGDGTs. The lapse rate for SPM appears insensitive to an increasing relative contribution of 6-methyl isomer brGDGTs produced within the river. River depth profiles show that brGDGTs are well mixed in the river and are not affected by hydrodynamic sorting. The brGDGTs accumulate relative to OC downstream, likely due to the transition of particulate OC to the dissolved phase and input of weathered soils toward the lowlands. The temperature-altitude correlation of brGDGTs in Madre de Dios SPM contrasts with the Lower Amazon River, where the initial soil signature is altered by changes in seasonal in-river production and variable provenance of brGDGTs. Our study indicates that brGDGTs in the Madre de Dios River system are initially soil derived and highlights their use to study OC sourcing in mountainous river systems. [ABSTRACT FROM AUTHOR]

Abstract: Compositional changes in marine particulate organic carbon (POC) throughout the water column trace important processes that underlie the biological pump's efficiency. While labor‐intensive, particle sampling efforts offer potential to expand the empirical POC archive at different stages in the water column, provided that organic composition is sufficiently preserved between sampling and analysis. The standard procedure for preserving organic matter composition in marine samples is to immediately store particles at −80°C to −20°C until they can be freeze‐dried for analysis. This report investigates the effect of warmer drying and storage temperatures on POC composition, which applies to the majority of POC samples collected in the field without intention for organic analysis. Particle samples collected off Woods Hole, Massachusetts were immediately dried at 56°C, at room temperature, or stored in a freezer until freeze‐drying. Results show that oven‐ and air‐drying did not shift the bulk composition (i.e., carbon and nitrogen content and stable isotope composition) of POC in the samples relative to freeze‐drying. Similarly, warmer drying temperatures did not affect POC thermal stability, as inferred by ramped pyrolysis/oxidation, a growing technique that uses a continuous temperature ramp to differentiate components of organic carbon by their decomposition temperature. Oven‐ and air‐drying did depress lipid abundances relative to freeze‐drying, the extent of which depended on compound size and structure. The data suggest that field samples dried at room temperatures and 56°C are appropriate for assessing bulk POC composition and thermal stability, but physical mechanisms such as molecular volatilization bias their lipid composition. [ABSTRACT FROM AUTHOR]

The determination of total organic carbon content and composition in detrital sediments requires careful removal of their carbonate minerals. In detrital sediments containing large amounts of carbonates, including dolomite, this can only be achieved by liquid acid leaching that may solubilise a significant proportion of the organic carbon. For a set of detrital sediments from the Himalayan system and the Amazon River as well as five geological reference materials, we determined the proportion of organic carbon (Corg) solubilised during acid leaching. This proportion is significant for all analysed sediments and generally tends to increase with the organic carbon content. Compared to other types of sediments analysed, clay fractions extracted from river sediments and bed sediments with very low organic carbon content have high and low proportions of acid soluble Corg respectively. In Himalayan and Amazon river sediments, the proportion of Corg solubilised during acid leaching was relatively constant with average values of 14 and 19 % respectively. Thus, it is possible to correct the Corg content for the dissolved organic carbon content measured after decarbonation. Data presented here show that Corg dissolved during liquid acid leaching must be taken into account. After careful calibration, the method presented here should, therefore, be applied to any carbonate-rich detrital sediment. [ABSTRACT FROM AUTHOR]