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The oxidation of organic carbon contained within sedimentary rocks ("petrogenic" carbon, or hereafter OCpetro) emits nearly as much C2 as is released by volcanism, thereby playing a key role in the long-term global C budget. High erosion rates in mountains have been shown to increase OCpetro oxidation. However, these settings also export unweathered material that may continue to react in downstream floodplains. The relative importance of OCpetro oxidation in mountains versus floodplains remains difficult to assess as disparate methods have been used in the different environments. Here, we investigate the sources and fluxes of rhenium (Re) in the Rio Madre de Dios to quantify OCpetro oxidation from the Andes to the Amazon floodplain using a common approach. Dissolved rhenium concentrations (n = 131) range from 0.01 to 63 pmol L-1 and vary depending on lithology and geomorphic setting. We find that >75% of the dissolved Re derives from OCpetro oxidation and that this proportion increases downstream. We estimate that in the Andes, OCpetro oxidation releases 11.2+4.5/-2.8 tC km-2 y-1 of C2, which corresponds to ~41% of the total OCpetro denudation (sum of oxidized and solid OCpetro). A Re mass balance across the Rio Madre de Dios shows that 46% of OCpetro oxidation takes place in the Andes, 14% in the foreland-lowlands, and 40% in the Andean-fed floodplains. This doubling of OCpetro oxidation flux downstream of the Andes demonstrates that, when present, floodplains can greatly increase OCpetro oxidation and C2 release. [ABSTRACT FROM AUTHOR]

Oxidative weathering of sedimentary rocks can release carbon dioxide (CO2) to the atmosphere and is an important natural CO2 emission. Two mechanisms operate -- the oxidation of sedimentary organic matter and the dissolution of carbonate minerals by sulfuric acid. It has proved difficult to directly measure the rates at which CO2 is emitted in response to these weathering processes in the field, with previous work generally using methods which track the dissolved products of these reactions in rivers. Here we design a chamber method to measure CO2 production during the oxidative weathering of shale bedrock, which can be applied in erosive environments where rocks are exposed frequently to the atmosphere. The chamber is drilled directly into the rock face and has a high surface-area-to-volume ratio which benefits measurement of CO2 fluxes. It is a relatively low-cost method and provides a long-lived chamber (several months or more). To partition the measured CO2 fluxes and the source of CO2, we use zeolite molecular sieves to trap CO2 "actively" (over several hours) or "passively" (over a period of months). The approaches produce comparable results, with the trapped CO2 having a radiocarbon activity (fraction modern, Fm) ranging from FmD0.05 to FmD 0.06 and demonstrating relatively little contamination from local atmospheric CO2 (FmD1.01). We use stable carbon isotopes of the trapped CO2 to partition between an organic and inorganic carbon source. The measured fluxes of rockderived organic matter oxidation (171-5 mgCm river chemistry in rivers around the world. The high oxidative weathering fluxes are consistent with the high erosion rate of the study region. We propose that our in situ method has the potential to be more widely deployed to directly measure CO2 fluxes during the oxidative weathering of sedimentary rocks, allowing for the spatial and temporal variability in these fluxes to be determined. [ABSTRACT FROM AUTHOR]

Weathering of organic carbon contained in sedimentary rocks (petrogenic OC, OC petro) is an important control on the concentrations of carbon dioxide (CO 2) and oxygen in the atmosphere. Of particular significance are steep mountainous catchments, where high rates of physical erosion introduce OC petro to the surface, where oxygen in air and water can help drive oxidative weathering reactions, yet measurements of CO 2 emissions from OC petro oxidation are still scarce. Here, we use in situ gas accumulation chambers and show that CO 2 fluxes, and their environmental controls, can be determined during a stand-alone, short-term (8 days) field campaign, applied to a remote setting. In the rapidly eroding Waiapu River catchment, New Zealand, dominated by mudstones, we measured high rates of CO 2 release (222–1590 mgC m−2 d−1) in five accumulation chambers in the near-surface of naturally fractured and bedded rock outcrops. The corresponding CO 2 concentrations are very high (p CO 2 ~4700–27,100 ppmv), and such values could influence acid-hydrolysis reactions during chemical weathering of co-occurring silicate minerals. The CO 2 is radiocarbon depleted (fraction modern, F 14C = 0.0122–0.0547), confirming it is petrogenic in origin. Stable carbon isotopes suggest a source from OC petro , but δ13C values of the CO 2 are lower by ~3.5–3.7 ± 0.1 ‰ from those of OC petro (−25.9 ± 0.1 ‰), consistent with isotope fractionation associated with microbial respiration of OC petro. Over 6 days of measurement, we find that CO 2 fluxes respond quickly to changes in temperature and humidity, indicating an environmental regulation that is captured by our short-term installation. The approaches applied here mean that future research can now seek to constrain the climatic, lithological and biological controls on OC petro oxidation across regional to global scales. • CO 2 fluxes from oxidative weathering can be measured during short field campaigns. • Their size, regulated by temperature and humidity, reaches that of soil respiration. • Carbon isotopes reveal that measured CO 2 is sourced from petrogenic organic matter. • Microbial respiration is potentially associated with carbon isotope fractionation. • Partial pressures of CO 2 in rock can be high and induce silicate weathering. [ABSTRACT FROM AUTHOR]

Oxidation of rock-derived, petrogenic, organic carbon (OC petro ) during weathering of sedimentary rocks is a major source of carbon dioxide (CO 2 ) to the atmosphere. This geological respiration is thought to be enhanced by physical erosion, suggesting that mountain belts could release large amounts of CO 2 to counter the CO 2 sequestration achieved by the erosion, riverine transfer and oceanic burial of organic carbon from the terrestrial biosphere. However, OC petro oxidation rates in mountain belts have not been quantified. Here we use rhenium (Re) as a proxy to track OC petro oxidation in mountain river catchments of Taiwan, where existing measurements of physical erosion rate allow the controls on OC petro oxidation to be assessed. Re has been shown to be closely associated with OC petro in rocks and following oxidation during chemical weathering forms a soluble oxyanion ( ReO 4 − ) which contributes to the dissolved load of rivers. Soils on meta-sedimentary rocks in Taiwan show that Re loss is coupled to OC petro loss during weathering, confirming previous observations from soil profiles on sedimentary rocks elsewhere. In Taiwan rivers, dissolved Re flux increases with the catchment-average sediment yield, suggesting that physical erosion rate is a major control on OC petro oxidation. Based on our current understanding of Re mobility during weathering, the dissolved Re flux can be used to quantify an upper bound on the OC petro oxidation rate and the associated CO 2 transfer. The estimated CO 2 release from this mountain belt by OC petro oxidation does not negate estimates of CO 2 sequestration by burial of biospheric OC offshore. The findings are compared to OC transfers estimated for the Himalaya, where OC petro oxidation in the mountain belt remains unconstrained. Together, these cases suggest that mountain building in the tropics can result in a net sink of OC which sequesters atmospheric CO 2 . [ABSTRACT FROM AUTHOR]