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Determining the sources of water provisioning streams, soils, and vegetation can provide important insights into the water that sustains critical ecosystem functions now and how those functions may be expected to respond given projected changes in the global hydrologic cycle. We developed multi-year time series of water isotope ratios (δ18O and δ2H) based on twice monthly collections of precipitation, lysimeter, and tree branch xylem waters from a seasonally dry tropical montane cloud forest in the southeastern Andes mountains of Peru. We then used this information to determine indices of the seasonal origins, the young water fractions (Fyw), and the new water fractions (Fnew) of soil, stream, and tree water. There was no evidence for intra-annual variation in the seasonal origins of lysimeter and stream waters, which were predominantly comprised of wet season precipitation, even during the dry seasons. However, branch xylem waters demonstrated an intra-annual shift in seasonal origin: xylem waters were comprised of wet season precipitation during the wet season, and dry season precipitation during the dry season. The young water fractions of lysimeter (< 15 %) and stream (5 %) waters were lower than the young water fraction (37 %) in branch xylem waters. The new water fraction (an indicator of water ≤ 2 weeks old) was estimated to be 12 % for branch xylem waters, while there was no significant evidence for new water in streams. Our results indicate that the source of water for trees in this system varied seasonally, such that recent precipitation may be more immediately taken up by shallow tree roots. In comparison, the source of water for soils and streams did not vary seasonally, such that precipitation may mix and reside in soils and take longer to transit into the stream. Our insights into the seasonal origins and ages of water in soils, streams, and vegetation in this tropical montane cloud forest adds to understanding of the mechanisms that govern the partitioning of water moving through different ecosystems.

Large, sediment-laden floods in mountainous terrain can have disastrous consequences and play important roles in landscape evolution. These events often unfold as a series of interconnected processes, but understanding of such “hazard cascades” has been hampered by lack of quantitative data on sediment movement. Here, we use a time series of high-resolution satellite imagery to quantify erosion and aggradation during the 2021 Melamchi Khola Floods in the Himalaya of central Nepal, providing a unique sediment budget for such an event. Our analysis reveals massive headwater erosion via remobilization of Gorkha landslides, gullying, debris-flows, and incision of glacial deposits. Unlike many other high mountain floods, the widely distributed erosion suggests this event was not primarily driven by a single source, e.g., glacial lake or landslide dam failure. High sediment supply caused aggradation in a high-elevation, low-relief glacial valley and triggered catastrophic incision into associated ancient fills. As this material was transported downstream, it caused further riverbed incision that in turn resulted in failures of surrounding hillslopes. Further downstream, as river steepness diminished, the main channel in the lower basin was widened by 3-5-fold and aggraded by ~ 5–20 m. However, deposition in the Melamchi Khola was not enough to accommodate the vast amount of flood material, and over 70% was delivered from the Melamchi Khola to the downstream Indrawati basin. Our sediment budget provides rare insight into the chain of events involved in a massive flood and helps shed light on how such floods can magnify hazard and reshape the fluvial landscape.

Background: Large-scale social and behavioral change communication (SBCC) approaches can be beneficial to achieve improvements in knowledge, attitudes, and practices (KAP). Addressing Stunting in Tanzania Early (ASTUTE) included a significant SBCC component and targeted precursors to stunting including KAP related to maternal and child health, antenatal care, WASH, childhood development, and male involvement. METHODS: Baseline, midline, and endline surveys were conducted for a total of 14,996 female caregivers and 6726 male heads of household in the Lake Zone region of Tanzania. Regression analyses were used to estimate differences in KAP from baseline to midline and endline. Results: Women’s knowledge of handwashing and infant/child feeding practices, and attitudes related to male involvement, consistently improved from baseline to midline and baseline to endline. Women’s practices related to antenatal care, breastfeeding, and early child development improved from baseline to midline and baseline to endline. Improvements in KAP among male heads of household were varied across indicators with consistent improvement in practices related to child feeding practices from baseline to midline and baseline to endline. Conclusion: Many changes in KAP were observed from baseline to midline and baseline to endline and corresponded with SBCC programming in the region. These results provide support for the value of large SBCC interventions. Public health efforts in settings such as Tanzania may benefit from adopting these approaches.

We test whether X-ray micro-computed tomography (microCT) imaging can be used as a tool for screening magnetite grains to improve the accuracy and precision of cosmogenic 3 He exposure dating. We extracted detrital magnetite from a soil developed on a fanglomerate at Whitewater, California, which was offset by the Banning strand of the San Andreas Fault. This study shows that microCT screening can distinguish between inclusion-free magnetite and magnetite with fluid or common solid inclusions. Such inclusions can produce bulk 3 He concentrations that are significantly in excess of the expected spallation production. We present Li concentrations, major and trace element analyses, and estimated magnetite (U–Th) / He cooling ages of samples in order to model the contribution from fissiogenic, nucleogenic, and cosmogenic thermal neutron production of 3 He. We show that mineral inclusions in magnetite can produce 3 He concentrations of up to 4 times that of the spallation component, leading to erroneous exposure ages. Therefore, grains with inclusions must be avoided in order to facilitate accurate and precise magnetite 3 He exposure dating. Around 30 % of all grains were found to be without inclusions, as detectable by microCT, with the largest proportion of suitable grains in the grain size range of 400–800 µ m. While grains with inclusions have 3 He concentrations far in excess of the values expected from existing 10 Be and 26 Al data in quartz at the Whitewater site, magnetite grains without inclusions have concentrations close to the predicted depth profile. We measured 3 He concentrations in aliquots without inclusions and corrected them for Li-produced components. By comparing these data to the known exposure age of 53.5 ± 2.2 ka, we calibrate a production rate for magnetite 3 He at sea level and high latitude (SLHL) of 116 ± 13 at g −1 a −1 . We suggest that this microCT screening approach can be used to improve the quality of cosmogenic 3 He measurements of magnetite and other opaque mineral phases for exposure age and detrital studies.

The evolution of the global carbon and silicon cycles is thought to have contributed to the long-term stability of Earth's climate1-3. Many questions remain, however, regarding the feedback mechanisms at play, and there are limited quantitative constraints on the sources and sinks of these elements in Earth's surface environments4-12. Here we argue that the lithium-isotope record can be used to track the processes controlling the long-term carbon and silicon cycles. By analysing more than 600 shallow-water marine carbonate samples from more than 100 stratigraphic units, we construct a new carbonate-based lithium-isotope record spanning the past 3 billion years. The data suggest an increase in the carbonate lithium-isotope values over time, which we propose was driven by long-term changes in the lithium-isotopic conditions of sea water, rather than by changes in the sedimentary alterations of older samples. Using a mass-balance modelling approach, we propose that the observed trend in lithium-isotope values reflects a transition from Precambrian carbon and silicon cycles to those characteristic of the modern. We speculate that this transition was linked to a gradual shift to a biologically controlled marine silicon cycle and the evolutionary radiation of land plants13,14.

In steep landscapes, river incision sets the pace of landscape evolution. Transport of coarse sediment controls incision by evacuating material delivered to river channels by landslides. However, large landslide-derived boulders that impede bedrock erosion are immobile even in major runoff-driven floods. Glacial lake outburst floods (GLOFs) mobilize these boulders and drive incision, yet their role in regional-scale erosion is poorly understood, largely because of their rarity. Here, we find a topographic signature consistent with widespread GLOF erosion in the Nepal Himalaya. Our interpretations emerge from the analysis of normalized channel steepness patterns, knickpoint distributions, and valley wideness. In rivers with glaciated headwaters that generate GLOFs, valleys stay narrow and relatively free of sediment, with bedrock often exposed to erosion. In turn, tributaries to these valleys are steep, allowing less efficient erosional regimes to keep pace with GLOF-driven incision. Where GLOFs are less frequent, valleys are more alluviated and incision stalls. Our results suggest that the extent of headwater glaciation may play an important role in the erosion of Himalayan river valleys and deserves more attention in future work.

Iron is a micronutrient critical to fundamental biological processes including respiration and photosynthesis, and it can therefore impact primary and heterotrophic productivity. Yet in oxic environments, iron is highly insoluble, rendering it, in principle, unavailable as a nutrient for biological growth. Life has "solved" this problem via the invention of iron chelates, known as siderophores, that keep iron available for microbial productivity. In this work, we examined the impact of siderophore synthesis on the speciation, mobility, and bioavailability of iron from rock-forming silicate minerals-shedding new light on the mechanisms by which microbes use mineral substrates to support primary productivity, as well as the consequent effects on silicate dissolution. Growth experiments were performed with Shewanella oneidensis MR-1 in an oxic, iron-depleted minimal medium, amended with olivine minerals as the sole source of iron. Experiments included the wild-type strain MR-1, and a siderophore synthesis gene deletion mutant strain (ΔMR-1). Relative to MR-1, ΔMR-1 exhibited a very pronounced growth penalty and an extended lag phase. However, substantial growth of ΔMR-1, comparable to MR-1 growth, was observed when the mutant strain was provided with siderophores in the form of either filtrate from a well-grown MR-1 culture, or commercially available deferoxamine. These observations suggest that siderophores are critical for S. oneidensis to acquire iron from olivine. Growth-limiting concentrations of deferoxamine amendments were observed to be ≤5-10 µM, concentrations significantly lower than previously recorded as necessary to impact mineral dissolution rates. X-ray photoelectric spectroscopy analyses of the incubated olivine surfaces suggest that siderophores deplete mineral surface layers of ferric iron. Combined, these results demonstrate that low micromolar concentrations of siderophores can effectively mobilize iron bound within silicate minerals, supporting very significant biological growth in limiting environments. The specific mechanism would involve siderophores removing a protective layer of nanometer-thick iron oxides, enhancing silicate dissolution and nutrient bioavailability.

Mineral weathering plays a primary role in the geologic carbon cycle. Silicate weathering by carbonic acid consumes CO2 and stabilizes Earth's climate system. However, when sulfuric acid drives weathering, CO2 can be released to the atmosphere. Recent work has established that sulfuric acid weathering resulting from sulfide mineral oxidation is globally significant and particularly important in rapidly eroding environments. In contrast, if SO42− produced by sulfide oxidation is reduced during continental transit, then CO2 release may be negated. Yet, little is known about how much SO42− reduction takes place in terrestrial environments. We report oxygen and sulfur stable isotope ratios of SO42− in river waters and mass budget calculations, which together suggest that SO42− released from pyrite oxidation in the Peruvian Andes mountains is conservatively exported across ∼300 km of the Amazon floodplain. In this system, floodplain SO42− reduction does not counteract the large SO42− flux from Andean pyrite weathering or measurably affect the stable isotope composition of riverine SO42−. These findings support the hypothesis that uplift and erosion of sedimentary rocks drive release of CO2 from the rock reservoir to the atmosphere.

The role of topography on water transit times and pathways through catchments is unclear, especially in mountainous environments – yet these environments play central roles in global water, sediment, and biogeochemical fluxes. Moreover, the vast majority of intensively monitored catchments are located in northern latitudes. As a result, the interplay between water transit, topography and other landscape characteristics is particularly underexplored in tropical environments. Here we present the results of a multi-year hydrologic sampling campaign (twice-monthly and storm sampling) to quantify water transit in seven small catchments (< 3 km2) across the transition from the Andes mountains to Amazon floodplain in southern Peru. We use the stable isotope composition of water (δ18OH2O) to calculate the fraction of streamflow comprised of recent precipitation (“young water fraction”) for each of the seven small catchments. Mean unweighted young water fractions (Fyw) are 3–10 % in the Andes, 15–23 % at mid-elevation and 3–4 % in the foreland floodplain. Weighting the Fyw calculation by volume of streamflow and precipitation yield Fyw of 7–47 %. Across these catchments, topography does not exert a clear control on water transit; instead stream Fyw is controlled by a combination of hydroclimate and bedrock permeability. Mid-elevation sites are posited to have the highest Fyw due to less permeable bedrock, poorly developed soils and more frequent and intense rainfall. The data presented here allow us to explore relationships between topography, bedrock permeability, hydroclimate and stream baseflow Fyw – particularly highlighting the role of bedrock permeability and hydroclimate in determining water transit times in a tropical mountain setting.

Seawater lithium stable isotope ratios, represented by δ 7 Li sw (‰), hold key information about the evolution of global climate and the carbon cycle over geologic time. Reconstructions based on foraminifera suggest an ∼9‰ increase in δ 7 Li sw over the past 60 m.y., interpreted as reflecting changes in the silicate weathering regime that may have contributed to global cooling over this time. However, culture experiments suggest that vital effects in foraminifers might cause varied δ 7 Li fractionation that could have affected past records. Thus, other archives are needed to determine whether the observed rise in foraminifer δ 7 Li values over the Cenozoic indeed reflects secular changes in δ 7 Li sw . Such archives would also open possibilities for robust determination of δ 7 Li sw deeper in geologic time. We analyzed δ 7 Li compositions in modern brachiopods ( n = 34) and found a relatively narrow range of +24.2 ‰ to +28.8‰ (mean = +26.8‰; 1σ = 0.5‰), similar to the range reported for inorganic calcite precipitated from seawater. These results confirm that brachiopods are good candidates for providing a representative record of δ 7 Li sw . We present data from fossil specimens dating from 65 Ma to ca. 700 ka, finding that fossilized brachiopods record a similar magnitude of change in δ 7 Li sw as foraminifers. These results are the first to corroborate the ∼9‰ increase in Cenozoic δ 7 Li sw and open possibilities for generating robust records of δ 7 Li sw in deep time, prior to foraminifer evolution.

Mountain building results in high erosion rates and the interaction of rocks with the atmosphere, water and life. Carbon transfers that result from increased erosion could control the evolution of Earth’s long-term climate. For decades, attention has focused on the hypothesized role of mountain building in drawing down atmospheric carbon dioxide (CO2) via silicate weathering. However, it is now recognized that mountain building and erosion affect the carbon cycle in other important ways. For example, erosion mobilizes organic carbon (OC) from terrestrial vegetation, transferring it to rivers and sediments, and thereby acting to draw down atmospheric CO2 in tandem with silicate weathering. Meanwhile, exhumation of sedimentary rocks can release CO2 through the oxidation of rock OC and sulfide minerals. In this Review, we examine the mechanisms of carbon exchange between rocks and the atmosphere, and discuss the balance of CO2 sources and sinks. It is demonstrated that OC burial and oxidative weathering, not widely considered in most models, control the net CO2 budget associated with erosion. Lithology strongly influences the impact of mountain building on the global carbon cycle, with an orogeny dominated by sedimentary rocks, and thus abundant rock OC and sulfides, tending towards being a CO2 source. By increasing erosion, mountain building can steer the evolution of atmospheric carbon dioxide (CO2) and global climate. This Review expands from the canonical focus on silicate weathering to consider the net carbon budget of erosion, including both CO2 sinks (silicate weathering, organic-carbon burial) and CO2 sources (oxidative weathering).

The rate of chemical weathering has been observed to increase with the rate of physical erosion in published comparisons of many catchments, but the mechanisms that couple these processes are not well understood. We investigated this question by examining the chemical weathering and porosity profiles from catchments developed on marine shale located in Pennsylvania, USA (Susquehanna Shale Hills Critical Zone Observatory, SSHCZO); California, USA (Eel River Critical Zone Observatory, ERCZO); and Taiwan (Fushan Experimental Forest). The protolith compositions, protolith porosities, and the depths of regolith at these sites are roughly similar while the catchments are characterized by large differences in erosion rate (1–3 mm yr−1 in Fushan ≫ 0.2–0.4 mm yr−1 in ERCZO ≫ 0.01–0.025 mm yr−1 in SSHCZO). The natural experiment did not totally isolate erosion as a variable: mean annual precipitation varied along the erosion gradient (4.2 m yr−1 in Fushan > 1.9 m yr−1 in ERCZO > 1.1 m yr−1 in SSHCZO), so the fastest eroding site experiences nearly twice the mean annual temperature of the other two. Even though erosion rates varied by about 100×, the depth of pyrite and carbonate depletion (defined here as regolith thickness) is roughly the same, consistent with chemical weathering of those minerals keeping up with erosion at the three sites. These minerals were always observed to be the deepest to react, and they reacted until 100% depletion. In two of three of the catchments where borehole observations were available for ridges, these minerals weathered across narrow reaction fronts. On the other hand, for the rock-forming clay mineral chlorite, the depth interval of weathering was wide and the extent of depletion observed at the land surface decreased with increasing erosion/precipitation. Thus, chemical weathering of the clay did not keep pace with erosion rate. But perhaps the biggest difference among the shales is that in the fast-eroding sites, microfractures account for 30–60% of the total porosity while in the slow-eroding shale, dissolution could be directly related to secondary porosity. We argue that the microfractures increase the influx of oxygen at depth and decrease the size of diffusion-limited internal domains of matrix, accelerating weathering of pyrite and carbonate under high erosion-rate conditions. Thus, microfracturing is a process that can couple physical erosion and chemical weathering in shales.

Arctic river systems erode permafrost in their banks and mobilize particulate organic carbon (OC). Meandering rivers can entrain particulate OC from permafrost many meters below the depth of annual thaw, potentially enabling OC oxidation and the production of greenhouse gases. However, the amount and fate of permafrost OC that is mobilized by river erosion is uncertain. To constrain OC fluxes due to riverbank erosion and deposition, we collected riverbank and floodplain sediment samples along the Koyukuk River, which meanders through discontinuous permafrost in central Alaska. We measured sediment total OC (TOC), radiocarbon content, water content, bulk density, grain size, and floodplain stratigraphy. Radiocarbon abundance and TOC were higher in samples dominated by silt as compared to sand, which we used to map OC content onto floodplain stratigraphy and estimate carbon fluxes due to river meandering. Results showed that sediment being eroded from cutbanks and deposited as point bars had similar OC stocks (mean ± 1SD of 125.3 ± 13.1 kgOC m−2 in cutbanks versus 114.0 ± 15.7 kgOC m−2 in point bars) whether or not the banks contained permafrost. We also observed radiocarbon-depleted biospheric OC in both cutbanks and permafrost-free point bars. These results indicate that a significant fraction of aged biospheric OC that is liberated from floodplains by bank erosion is subsequently re-deposited in point bars, rather than being oxidized. The process of aging, erosion, and re-deposition of floodplain organic material may be intrinsic to river-floodplain dynamics, regardless of permafrost content.

Description, Silicate weathering and physical erosion markedly increased during the rapid warming of the PETM, allowing climatic recovery., The Paleocene-Eocene Thermal Maximum (PETM; ~55.9 Ma) was a geologically rapid warming period associated with carbon release, which caused a marked increase in the hydrological cycle. Here, we use lithium (Li) isotopes to assess the global change in weathering regime, a critical carbon drawdown mechanism, across the PETM. We find a negative Li isotope excursion of ~3‰ in both global seawater (marine carbonates) and in local weathering inputs (detrital shales). This is consistent with a very large delivery of clays to the oceans or a shift in the weathering regime toward higher physical erosion rates and sediment fluxes. Our seawater records are best explained by increases in global erosion rates of ~2× to 3× over 100 ka, combined with model-derived weathering increases of 50 to 60% compared to prewarming values. Such increases in weathering and erosion would have supported enhanced carbon burial, as both carbonate and organic carbon, thereby stabilizing climate.

A man in his 20s presented with headache and acute deterioration in visual acuity. He was found to have panuveitis and raised intracranial pressure with papilloedema. MRI and F-fluorodeoxyglucose positron emission tomography confirmed a subclinical, but active, inflammatory mastoid process. Histology of the mastoid showed immunoglobulin G4 (IgG4) cells, plasma cells and storiform fibrosis.This presentation of IgG4 disease has not been previously described.Treatment with high-dose steroids was initiated, followed by long-term immunosuppressive therapy. The patient’s symptoms improved, although he remains dependent on azathioprine and low dose oral steroids for symptom control. To date, there has been no progression of the disease.

Permafrost soils store approximately twice the amount of carbon currently present in Earth’s atmosphere and are acutely impacted by climate change due to the polar amplification of increasing global temperature. Many organic-rich permafrost sediments are located on large river floodplains, where river channel migration periodically erodes and redeposits the upper tens of meters of sediment. Channel migration exerts a first-order control on the geographic distribution of permafrost and floodplain stratigraphy and thus may affect microbial habitats. To examine how river channel migration in discontinuous permafrost environments affects microbial community composition, we used amplicon sequencing of the 16S rRNA gene on sediment samples from floodplain cores and exposed riverbanks along the Koyukuk River, a large tributary of the Yukon River in west-central Alaska. Microbial communities are sensitive to permafrost thaw: communities found in deep samples thawed by the river closely resembled near-surface active-layer communities in nonmetric multidimensional scaling analyses but did not resemble floodplain permafrost communities at the same depth. Microbial communities also displayed lower diversity and evenness in permafrost than in both the active layer and permafrost-free point bars recently deposited by river channel migration. Taxonomic assignments based on 16S and quantitative PCR for the methyl coenzyme M reductase functional gene demonstrated that methanogens and methanotrophs are abundant in older permafrost-bearing deposits but not in younger, nonpermafrost point bar deposits. The results suggested that river migration, which regulates the distribution of permafrost, also modulates the distribution of microbes potentially capable of producing and consuming methane on the Koyukuk River floodplain. IMPORTANCE Arctic lowlands contain large quantities of soil organic carbon that is currently sequestered in permafrost. With rising temperatures, permafrost thaw may allow this carbon to be consumed by microbial communities and released to the atmosphere as carbon dioxide or methane. We used gene sequencing to determine the microbial communities present in the floodplain of a river running through discontinuous permafrost. We found that the river’s lateral movement across its floodplain influences the occurrence of certain microbial communities—in particular, methane-cycling microbes were present on the older, permafrost-bearing eroding riverbank but absent on the newly deposited river bars. Riverbank sediment had microbial communities more similar to those of the floodplain active-layer samples than permafrost samples from the same depth. Therefore, spatial patterns of river migration influence the distribution of microbial taxa relevant to the warming Arctic climate.

Lithium isotopes are a relatively novel tracer of present and past silicate weathering processes. Given that silicate weathering is the primary long-term method by which CO2 is removed from the atmosphere, Li isotope research is going through an exciting phase. We show the weathering processes that fractionate dissolved and sedimentary Li isotope ratios, focusing on weathering intensity and clay formation. We then discuss the carbonate and silicate archive potential of past seawater δ7Li. These archives have been used to examine Li isotope changes across both short and long timescales. The former can demonstrate the rates at which the climate is stabilised from perturbations via weathering, a fundamental piece of the puzzle of the long-term carbon cycle.

In steep landscapes, river incision sets the pace of landscape evolution. Transport of coarse sediment controls incision by evacuating material delivered to river channels by landslides. However, large landslide-derived boulders that impede bedrock erosion are immobile even in major runoff-driven floods. Glacial lake outburst floods (GLOFs) mobilize these boulders and drive incision, yet their role in regional-scale erosion is poorly understood, largely because of their rarity. Here, we find a topographic signature consistent with widespread GLOF erosion in the Nepal Himalaya. In rivers with glaciated headwaters that generate GLOFs, valleys stay narrow and relatively free of sediment, with bedrock often exposed to erosion. In turn, tributaries to these valleys are steep, allowing less efficient erosional regimes to keep pace with GLOF-driven incision. Where GLOFs are less frequent, valleys are more alluviated and incision stalls. Our results suggest the extent of headwater glaciation may play an important role in erosion of Himalayan river valleys and deserves more attention in future work.

Humid tropical forests play a dominant role in the functioning of Earth but are under increasing threat from changes in land use and climate. How forest vulnerability varies across space and time and what level of stress forests can tolerate before facing a tipping point are poorly understood. Here, we develop a tropical forest vulnerability index (TFVI) to detect and evaluate the vulnerability of global tropical forests to threats across space and time. We show that climate change together with land-use change have slowed the recovery rate of forest carbon cycling. Temporal autocorrelation, as an indicator of this slow recovery, increases substantially for above-ground biomass, gross primary production, and evapotranspiration when climate stress reaches a critical level. Forests in the Americas exhibit extensive vulnerability to these stressors, while in Africa, forests show relative resilience to climate, and in Asia reveal more vulnerability to land use and fragmentation. TFVI can systematically track the response of tropical forests to multiple stressors and provide early-warning signals for regions undergoing critical transitions.

We test whether X-ray micro-computed tomography (microCT) imaging can be used as a tool for screening magnetite grains to improve the accuracy and precision of cosmogenic 3He exposure dating. We extracted detrital magnetite from a soil developed on a fanglomerate at Whitewater, California, which was offset by the Banning strand of the San Andreas Fault. This study shows that microCT screening can distinguish between inclusion-free magnetite and magnetite with fluid or common solid inclusions. Such inclusions can produce bulk 3He concentrations that are significantly in excess of the expected spallation production. We present Li concentrations, major and trace element analyses, and estimated magnetite (U–Th) / He cooling ages of samples in order to model the contribution from fissiogenic, nucleogenic, and cosmogenic thermal neutron production of 3He. We show that mineral inclusions in magnetite can produce 3He concentrations of up to 4 times that of the spallation component, leading to erroneous exposure ages. Therefore, grains with inclusions must be avoided in order to facilitate accurate and precise magnetite 3He exposure dating. Around 30 % of all grains were found to be without inclusions, as detectable by microCT, with the largest proportion of suitable grains in the grain size range of 400–800 µm. While grains with inclusions have 3He concentrations far in excess of the values expected from existing 10Be and 26Al data in quartz at the Whitewater site, magnetite grains without inclusions have concentrations close to the predicted depth profile. We measured 3He concentrations in aliquots without inclusions and corrected them for Li-produced components. By comparing these data to the known exposure age of 53.5 ± 2.2 ka, we calibrate a production rate for magnetite 3He at sea level and high latitude (SLHL) of 116 ± 13 at g−1 a−1. We suggest that this microCT screening approach can be used to improve the quality of cosmogenic 3He measurements of magnetite and other opaque mineral phases for exposure age and detrital studies.

Silicate minerals represent an important reservoir of nutrients at Earth's surface and a source of alkalinity that modulates long-term geochemical cycles. Due to the slow kinetics of primary silicate mineral dissolution and the potential for nutrient immobilization by secondary mineral precipitation, the bioavailability of many silicate-bound nutrients may be limited by the ability of micro-organisms to actively scavenge these nutrients via redox alteration and/or organic ligand production. In this study, we use targeted laboratory experiments with olivine and the siderophore deferoxamine B to explore how microbial ligands affect nutrient (Fe) release and the overall rate of mineral dissolution. Our results show that olivine dissolution rates are accelerated in the presence of micromolar concentrations of deferoxamine B. Based on the non-linear decrease in rates with time and formation of a Fe3+ -ligand complex, we attribute this acceleration in dissolution rates to the removal of an oxidized surface coating that forms during the dissolution of olivine at circum-neutral pH in the presence of O2 and the absence of organic ligands. While increases in dissolution rates are observed with micromolar concentrations of siderophores, it remains unclear whether such conditions could be realized in natural environments due to the strong physiological control on microbial siderophore production. So, to contextualize our experimental results, we also developed a feedback model, which considers how microbial physiology and ligand-promoted mineral dissolution kinetics interact to control the extent of biotic enhancement of dissolution rates expected for different environments. The model predicts that physiological feedbacks severely limit the extent to which dissolution rates may be enhanced by microbial activity, though the rate of physical transport modulates this limitation.

Fly ash—the residuum of coal burning—contains a considerable amount of fossilized particulate organic carbon (FOC_(ash)) that remains after high-temperature combustion. Fly ash leaks into natural environments and participates in the contemporary carbon cycle, but its reactivity and flux remained poorly understood. We characterized FOC_(ash) in the Chang Jiang (Yangtze River) basin, China, and quantified the riverine FOC_(ash) fluxes. Using Raman spectral analysis, ramped pyrolysis oxidation, and chemical oxidation, we found that FOC_(ash) is highly recalcitrant and unreactive, whereas shale-derived FOC (FOC_(rock)) was much more labile and easily oxidized. By combining mass balance calculations and other estimates of fly ash input to rivers, we estimated that the flux of FOCash carried by the Chang Jiang was 0.21 to 0.42 Mt C⋅y⁻¹ in 2007 to 2008—an amount equivalent to 37 to 72% of the total riverine FOC export. We attributed such high flux to the combination of increasing coal combustion that enhances FOCash production and the massive construction of dams in the basin that reduces the flux of FOC_(rock) eroded from upstream mountainous areas. Using global ash data, a first-order estimate suggests that FOC_(ash) makes up to 16% of the present-day global riverine FOC flux to the oceans. This reflects a substantial impact of anthropogenic activities on the fluxes and burial of fossil organic carbon that has been made less reactive than the rocks from which it was derived.

This study presents lithium and magnesium isotope ratios of soils and their drainage waters from a well-characterised weathering experiment with two soil cores, one with olivine added to the surface layer, and the other a control core. The experimental design mimics olivine addition to soils for CO2 sequestration and/or crop fertilisation, as well as natural surface addition of reactive minerals such as during volcanic deposition. More generally, this study presents an opportunity to better understand how isotopic fractionation records weathering processes. At the start of the experiment, waters draining both cores have similar Mg isotope composition to the soil exchangeable pool. The composition in the two cores evolve in different directions as olivine dissolution progresses. Mass balance calculations show that the water δ26Mg value is controlled by congruent dissolution of carbonate and silicates (the latter in the olivine core only), plus an isotopically fractionated exchangeable pool. For Li, waters exiting the base of the cores initially have the same isotope composition, but then diverge as olivine dissolution progresses. For both Mg and Li, the transport down-core is significantly retarded and fractionated by exchange with the exchangeable pool. This observation has implications for the monitoring of enhanced weathering using trace elements or isotopes, because dissolution rates and fluxes will be underestimated during the time when the exchangeable pool evolves towards a new equilibrium.

Chemical weathering of volcanic rocks in warm and humid climates contributes disproportionately to global solute fluxes. Geochemical signatures of solutes and solids formed during this process can help quantify and reconstruct weathering intensity in the past. Here, we measured silicon (Si) and germanium (Ge) isotope ratios of the soils, clays, and fluids from a tropical lowland rainforest in Costa Rica. The bulk topsoil is intensely weathered and isotopically light (mean±1σ: δ 30Si = –2.1 ± 0.3‰, δ 74Ge = –0.13 ± 0.12‰) compared to the parent rock (δ 30Si = –0.11 ± 0.05‰, δ 74Ge = 0.59 ± 0.07‰). Neoforming clays have even lower values (δ 30Si = –2.5 ± 0.2‰, δ 74Ge = –0.16 ± 0.09‰), demonstrating a whole-system isotopic shift in extremely weathered systems. The lowland streams represent mixing of dilute local fluids (δ 30Si = 0.2 – 0.6‰, δ 74Ge = 2.2 – 2.6‰) with solute-rich interbasin groundwater (δ 30Si = 1.0±0.2‰, δ 74Ge = 4.0‰). Using a Ge-Si isotope mass balance model, we calculate that 91 ± 9% of Ge released via weathering of lowland soils is sequestered by neoforming clays, 9 ± 9% by vegetation, and only 0.2 ± 0.2% remains dissolved. Vegetation plays an important role in the Si cycle, directly sequestering 39 ± 14% of released Si and enhancing clay neoformation in surface soils via the addition of amorphous phytolith silica. Globally, volcanic soil δ 74Ge closely tracks the depletion of Ge by chemical weathering (τGe), whereas δ 30Si and Ge/Si both reflect the loss of Si (τSi). Because of the different chemical mobilities of Ge and Si, a δ 74Ge-δ 30Si multi-proxy system is sensitive to a wider range of weathering intensities than each isotopic system in isolation.

In this study, we present new data on the δ7Li values and Li/(Ca+Mg) ratios of carbonate cores from the Great Bahama Bank (Clino, Unda), a deep water core off of the bank top (ODP Leg 166 Site 1007), and the coralline Key Largo Limestone. We use these samples to evaluate the influence of meteoric diagenesis, marine burial diagenesis, and dolomitization on the Li isotope system in carbonates. We find that recrystallization of aragonite to low-Mg calcite in the presence of meteoric fluids results in a systematic decrease of the Li/(Ca+Mg) ratio in Clino, Unda and Key Largo samples, due to the lower Li/(Ca+Mg) ratio in meteoric fluids compared to seawater. For Li isotopes, we observe that the δ7Li of meteorically altered low-Mg calcite is +22.0±3.8‰ (n=28, 1σ), which is coincidentally similar to the original aragonite-rich sediments (+22±1‰ in the Bahamas, +18±1‰ in Key Largo), but with a larger variability (from +15 to +27‰). We interpret these features as reflecting the overprinting of primary Li during meteoric alteration with a highly variable isotope signature that may be controlled by a combination of local porewater and/or global climatic conditions; in either case, meteoric diagenesis produces isotopic signatures that are unrelated to seawater composition. In contrast, marine burial diagenesis and dolomitization of Clino and Unda sediments under “fluid-buffered” conditions result in Li isotope composition that is similar (+30.2±1.5‰, n=36, 1σ) to modern seawater (+31‰). For Site 1007, the δ7Li values range between +23 permil and +31 permil. We interpret this range as reflecting a combination of varying diagenesis style (fluid to sediment-buffered) and varying contribution of calcite derived from pelagic sediments, with distinct isotopic composition due to primary mineralogy. Altogether, our results show that diagenesis does not invalidate the use of bulk carbonates for deriving Li isotope paleo-records, but the reliability of past carbonates as recorders of seawater δ7Li values will depend on carefully characterizing their diagenetic history.

Tropical montane regions tend to have high rates of precipitation, biological production, erosion, and sediment export, which together move material off the landscape and toward sedimentary deposits downstream. Plant wax biomarkers can be used to investigate sourcing of organic matter and are often used as proxies to reconstruct past climate and environment in sedimentary deposits. To understand how plant waxes are sourced within a wet, tropical montane catchment, we measure the stable C and H isotope composition (δ13C and δD) of n-alkanes and n-alkanoic acids in soils along an elevation transect and from sediments within the Madre de Dios River network along the eastern flank of the Peruvian Andes, draining an area of 75,400 km2 and 6 km of elevation. Soils yield systematic trends in plant wax δ13C (+1.75 and +1.31‰ km−1, for the C29 n-alkanes and C30 n-alkanoic acids respectively in the mineral horizon) and δD values (−10 and −12‰ km−1, respectively) across a 3.5 km elevation transect, which approximates trends previously reported from canopy leaves, though we find offsets between δ13C values in plants and soils. River suspended sediments generally follow soil isotopic gradients defined by catchment elevations (δ13C: +1.03 and +0.99‰ km−1 and δD: −10 to −7‰ km−1, for the C29 n-alkanes and C30 n-alkanoic acids respectively) in the wet season, with a lowering in the dry season that is less well-constrained. In a few river suspended sediments, petrogenic contributions and depth-sorting influence the n-alkane δ13C signal. Our dual isotope, dual compound class and seasonal sampling approach reveals no Andean-dominance in plant wax export, and instead that the sourcing of plant waxes in this very wet, forested catchment approximates that expected for spatial integration of the upstream catchment, thus with a lowland dominance on areal basis, guiding paleoenvironmental reconstructions in tropical montane regions. The dual isotope approach provides a cross-check on the altitudinal signals and can resolve ambiguity such as might be associated with vegetation change or aridity in paleoclimate records. Further, the altitude effect encoded within plant waxes presents a novel dual-isotope biomarker approach to paleoaltimetry.

The ratio between the activity of dissolved 234U and 238U in river water, (234U/238U)Riv, shows promise for tracing weathering processes. It has been suggested that preferential 234U release generates a high (234U/238U)Riv under low weathering intensity while congruent weathering, as expected for high weathering intensity, would release uranium with a secular equilibrium (234U/238U)Riv of 1. However, weathering intensity depends on the combination of exposure age of weathering interfaces and dissolution rate, complicating the use of (234U/238U)Riv as a tool in weathering studies. This work attempts to resolve the weathering dynamics reflected by (234U/238U)Riv using catchment scale denudation rate (D) as a first order approximation for the age of weathering interfaces. A global dataset (n=653), including 132 new measurements from Chinese catchments, indicates changing responses of (234U/238U)Riv to D. Higher values (>1.5) and larger variability of (234U/238U)Riv are observed in catchments both with high (>3 mm/yr) and low D (234U/238U)Riv are associated with catchments of medium to high D (0.3–2 mm/yr). The observed pattern can be explained by a model that involves competing uranium release from active- and inactive-weathering interfaces in response to a shifting weathering regime, from kinetically-limited to supply-limited. (234U/238U)Riv decreases with decreasing D under a kinetically-limited weathering regime due to the increasing contribution of congruent weathering relative to the preferential dissolution of 234U from radioactively damaged sites as D decreases. In contrast, (234U/238U)Riv increases with decreasing D under a supply-limited weathering regime because the minerals that remain under these conditions continue to release 234U to solution by recoil, while contributing little to the dissolved 238U because of their slow dissolution rate. A much deeper depth of the weathering interface is suggested for catchments with high D due to higher weathering contribution from deep fractures relative to the poorly developed surface regolith. A young age of ∼10 kyrs is constrained by the model for complete dissolution of exposed weathering-active minerals, which implies a rapid shifting from kinetically-limited to supply-limited weathering regime and limited influence of weathering on the calculation of comminution age based on (234U/238U) in sediments. A site-specific dissolution rate that is consistent with those estimated from weathering profiles is also constrained, which suggests that the discrepancy between field and laboratory weathering rate may largely be controlled by the difference in chemical affinity associated with stagnant micro-pores, low permeability, and high rock/fluid ratios rather than the passivation of weathering interfaces.