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The balance between photosynthetic organic carbon production and respiration controls atmospheric composition and climate1,2. The majority of organic carbon is respired back to carbon dioxide in the biosphere, but a small fraction escapes remineralization and is preserved over geological timescales3. By removing reduced carbon from Earth’s surface, this sequestration process promotes atmospheric oxygen accumulation2and carbon dioxide removal1. Two major mechanisms have been proposed to explain organic carbon preservation: selective preservation of biochemically unreactive compounds4,5and protection resulting from interactions with a mineral matrix6,7. Although both mechanisms can operate across a range of environments and timescales, their global relative importance on 1,000-year to 100,000-year timescales remains uncertain4. Here we present a global dataset of the distributions of organic carbon activation energy and corresponding radiocarbon ages in soils, sediments and dissolved organic carbon. We find that activation energy distributions broaden over time in all mineral-containing samples. This result requires increasing bond-strength diversity, consistent with the formation of organo-mineral bonds8but inconsistent with selective preservation. Radiocarbon ages further reveal that high-energy, mineral-bound organic carbon persists for millennia relative to low-energy, unbound organic carbon. Our results provide globally coherent evidence for the proposed7importance of mineral protection in promoting organic carbon preservation. We suggest that similar studies of bond-strength diversity in ancient sediments may reveal how and why organic carbon preservation—and thus atmospheric composition and climate—has varied over geological time.

ABSTRACTIn practice, obtaining radiocarbon (14C) composition of organic matter (OM) in sediments requires first removing inorganic carbon (IC) by acid-treatment. Two common treatments are acid rinsing and fumigation. Resulting 14C content obtained by different methods can differ, but underlying causes of these differences remain elusive. To assess the influence of different acid-treatments on 14C content of sedimentary OM, we examine the variability in 14C content for a range of marine and river sediments. By comparing results for unacidified and acidified sediments [HCl rinsing (RinseHCl) and HCl fumigation (FumeHCl)], we demonstrate that the two acid-treatments can affect 14C content differentially. Our findings suggest that, for low-carbonate samples, RinseHClaffects the Fm values due to loss of young labile organic carbon (OC). FumeHClmakes the Fm values for labile OC decrease, leaving the residual OC older. High-carbonate samples can lose relatively old organic components during RinseHCl, causing the Fm values of remaining OC to increase. FumeHClcan remove thermally labile, usually young, OC and reduce the Fm values. We suggest three factors should be taken into account when using acid to remove carbonate from sediments: IC abundance, proportions of labile and refractory OC, and environmental matrix.

Arctic fluvial networks process, outgas, and transport significant quantities of terrestrial organic carbon (C), particularly dissolved organic carbon (DOC). The proportion of permafrost C in these fluxes, however, is poorly constrained. A primary obstacle to the quantification of permafrost‐derived DOC is that it is rapidly respired without leaving a unique tracer of its presence. In this study, we investigated the production of bacterial respiratory carbon dioxide (CO2; measured as dissolved inorganic carbon; DIC) during maximum late‐summer thaw in sites spanning a fluvial network (Kolyma Basin, Siberia) to assess whether the biodegradation of permafrost DOC could be detected by the presence of a persistent aged (14C‐depleted) signature on the DIC pool. Using Keeling plot interpretation of DIC produced in bioincubations of river water, we show that bacteria respire varying sources of DOC moving downstream through the fluvial network. Respiration of permafrost (production of aged CO2) was only detected in heavily permafrost thaw influenced sites. In nonpermafrost thaw impacted sites, ambient DIC was modern (14C‐enriched), but rather than precluding the respiration of permafrost OC upstream, we suggest that 14C‐depleted DIC is overwhelmed by modern DIC. Investigation of dissolved organic matter composition via Fourier transform ion cyclotron resonance mass spectrometry highlighted that elevated levels of aliphatic and nitrogen‐containing compounds were associated with the production of aged DIC, providing molecular‐level insight as to why permafrost‐derived dissolved organic matter is rapidly respired. Overall, results from this study demonstrate the difficulty of tracing inputs of a highly reactive substrate to systems with diverse organic matter sources. Bacterial respiratory isotopic signatures of carbon dioxide revealed a downstream gradient of dissolved organic carbon substratesIn streams with diverse organic carbon sources, the isotopic signature of respiratory carbon dioxide sourced from permafrost is maskedAliphatic and nitrogen‐containing dissolved organic matter was associated with the production of aged, permafrost‐derived carbon dioxide

As drinking‐water scarcity grows worldwide, we need to improve predictions of the quantity and quality of our water resources. An overarching problem for model improvement is that we do not know the geological structure of aquifers in sufficient detail. In this work, we demonstrate that mineral‐water reactions imprint structure in the subsurface that impacts the flow and transport of some chemical species. Specifically, pyrite, a ubiquitous mineral, commonly oxidizes and depletes in the upper layers of the weathering profile in most humid watersheds, only remaining at depths of meters. We hypothesize that variations in concentrations (C) of pyrite‐derived sulfate released into rivers as a function of discharge (q) reflect the rate‐limiting step and depth of pyrite‐oxidizing layers. We found that log C− log qbehaviors thus differ in small and large watersheds in the Susquehanna River Basin as well as in selected watersheds in the Western United States. Although coal mining changes pyrite oxidation from closed to open system with respect to O2, patterns in stream chemistry as a function of discharge are consistent with deep and shallow pyrite oxidation zones in small and large watersheds respectively. Therefore, understanding the subsurface patterns of mineral reactions and how they affect the architecture of aquifers will elucidate patterns of changing river chemistry and our ability to manage water resources in the future under accelerated land use and climate change. Blind‐source attribution of endmember sources of sulfate can elucidate open‐versus closed‐system pyrite oxidationConcentration‐discharge relationships reflect deep and shallow pyrite oxidation in small and large watersheds, respectivelyPyrite oxidation in watersheds with coal mining is kinetically limited, while oxidation in watersheds without mining is limited by oxygen transport Blind‐source attribution of endmember sources of sulfate can elucidate open‐versus closed‐system pyrite oxidation Concentration‐discharge relationships reflect deep and shallow pyrite oxidation in small and large watersheds, respectively Pyrite oxidation in watersheds with coal mining is kinetically limited, while oxidation in watersheds without mining is limited by oxygen transport

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 × 106m−2yr−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 CO2consumption yield of (3.55 ± 0.11) × 105mol CO2km−2yr−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. 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 CO2consumption yield was 3.55 × 105moles carbon dioxide per square kilometer Concentrations/fluxes of dissolved carbon, nitrogen, phosphorus, and major/trace ions were predominantly controlled by annual flood pulse Mean Amazon River dissolved organic carbon flux was 25.5 teragrams per year Annual carbonate + silicate weathering CO2consumption yield was 3.55 × 105moles carbon dioxide per square kilometer