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The triple oxygen isotope composition (Δ’ 17 O) of sulfate minerals is widely used to constrain ancient atmospheric p O 2 / p CO 2 and rates of gross primary production. The utility of this tool is based on a model that sulfate oxygen carries an isotope fingerprint of tropospheric O 2 incorporated through oxidative weathering of reduced sulfur minerals, particularly pyrite. Work to date has targeted Proterozoic environments (2.5 billion to 0.542 billion years ago) where large isotope anomalies persist; younger timescale records, which would ground ancient environmental interpretation in what we know from modern Earth, are lacking. Here we present a high-resolution record of the δ 18 O and Δ’ 17 O in marine sulfate for the last 130 million years of Earth history. This record carries a Δ’ 17 O close to 0o, suggesting that the marine sulfate reservoir is under strict control by biogeochemical cycling (namely, microbial sulfate reduction), as these reactions follow mass-dependent fractionation. We identify no discernible contribution from atmospheric oxygen on this timescale. We interpret a steady fractional contribution of microbial sulfur cycling (terrestrial and marine) over the last 100 million years, even as global weathering rates are thought to vary considerably. 

The biogeochemical fluxes that cycle oxygen (O2) play a critical role in regulating Earth’s climate and habitability. Triple-oxygen isotope (TOI) compositions of marine dissolved O2 are considered a robust tool for tracing oxygen cycling and quantifying gross photosynthetic O2 production. This method assumes that photosynthesis, microbial respiration, and gas exchange with the atmosphere are the primary influences on dissolved O2 content, and that they have predictable, fixed isotope effects. Despite its widespread use, there are major elements of this approach that remain uncharacterized, including the TOI dynamics of respiration by marine heterotrophic bacteria and abiotic O2 sinks such as the photochemical oxidation of dissolved organic carbon (DOC). Here, we report the TOI fractionation for O2 utilization by two model marine heterotrophs and by abiotic photo-oxidation of representative terrestrial and coastal marine DOC. We demonstrate that TOI slopes associated with these processes span a significant range of the mass-dependent domain (λ = 0.499 to 0.521). A sensitivity analysis reveals that even under moderate productivity and photo-oxidation scenarios, true gross oxygen production may deviate from previous estimates by more than 20% in either direction. By considering a broader suite of oxygen cycle reactions, our findings challenge current gross oxygen production estimates and highlight several paths forward to better understanding the marine oxygen and carbon cycles.

 

The response of the terrestrial biosphere to warming remains one of the most poorly understood and quantified aspects of the climate system. One way to test the behavior of the Earth system in warm climate states is to examine the geological record. The abundance, distribution, and/or isotopic composition of source-specific organic molecules (biomarkers) have been used to reconstruct terrestrial paleoenvironmental change over a range of geological timescales. Here, we review new or recently improved biomarker approaches for reconstructing ( a) physical climate variables (land temperature, rainfall), ( b) ecosystem state variables (vegetation, fire regime), and ( c) biogeochemical variables (soil residence time, methane cycling). This review encompasses a range of key compound classes (e.g., lipids, lignin, and carbohydrates). In each section, we explore the concept behind key biomarker approaches and discuss their successes as paleoenvironmental indicators. We emphasize that analyzing several biomarkers in tandem can provide unique insights into the Earth system. ▪ Biomarkers can be used to reconstruct terrestrial environmental change over a range of geological timescales. ▪ Analyzing several biomarkers in tandem can provide unique insights into the Earth system. Expected final online publication date for the Annual Review of Earth and Planetary Sciences, Volume 50 is May 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates. 

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 logC− logqbehaviors 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.

 

Bacterial hopanoid lipids are ubiquitous in the geologic record and serve as biomarkers for reconstructing Earth’s climatic and biogeochemical evolution. Specifically, the abundance of 2-methylhopanoids deposited during Mesozoic ocean anoxic events (OAEs) and other intervals has been interpreted to reflect proliferation of nitrogen-fixing marine cyanobacteria. However, there currently is no conclusive evidence for 2-methylhopanoid production by extant marine cyanobacteria. As an alternative explanation, here we report 2-methylhopanoid production by bacteria of the genusNitrobacter, cosmopolitan nitrite oxidizers that inhabit nutrient-rich freshwater, brackish, and marine environments. The model organismNitrobacter vulgarisproduced only trace amounts of 2-methylhopanoids when grown in minimal medium or with added methionine, the presumed biosynthetic methyl donor. Supplementation of cultures with cobalamin (vitamin B₁₂) increased nitrite oxidation rates and stimulated a 33-fold increase of 2-methylhopanoid abundance, indicating that the biosynthetic reaction mechanism is cobalamin dependent. BecauseNitrobacterspp. cannot synthesize cobalamin, we postulate that they acquire it from organisms inhabiting a shared ecological niche—for example, ammonia-oxidizing archaea. We propose that during nutrient-rich conditions, cobalamin-based mutualism intensifies upper water column nitrification, thus promoting 2-methylhopanoid deposition. In contrast, anoxia underlying oligotrophic surface ocean conditions in restricted basins would prompt shoaling of anaerobic ammonium oxidation, leading to low observed 2-methylhopanoid abundances. The first scenario is consistent with hypotheses of enhanced nutrient loading during OAEs, while the second is consistent with the sedimentary record of Pliocene–Pleistocene Mediterranean sapropel events. We thus hypothesize that nitrogen cycling in the Pliocene–Pleistocene Mediterranean resembled modern, highly stratified basins, whereas no modern analog exists for OAEs.

 

The mass-independent minor oxygen isotope compositions (Δ′¹⁷O) of atmospheric O₂and${\mathrm{C}\mathrm{O}}_2$are primarily regulated by their relative partial pressures,${\mathrm{p}\mathrm{O}}_2$/${\mathrm{p}\mathrm{C}\mathrm{O}}_2$. Pyrite oxidation during chemical weathering on land consumes${\mathrm{O}}_2$and generates sulfate that is carried to the ocean by rivers. The Δ′¹⁷O values of marine sulfate deposits have thus been proposed to quantitatively track ancient atmospheric conditions. This proxy assumes direct${\mathrm{O}}_2$incorporation into terrestrial pyrite oxidation-derived sulfate, but a mechanistic understanding of pyrite oxidation—including oxygen sources—in weathering environments remains elusive. To address this issue, we present sulfate source estimates and Δ′¹⁷O measurements from modern rivers transecting the Annapurna Himalaya, Nepal. Sulfate in high-elevation headwaters is quantitatively sourced by pyrite oxidation, but resulting Δ′¹⁷O values imply no direct tropospheric${\mathrm{O}}_2$incorporation. Rather, our results necessitate incorporation of oxygen atoms from alternative,¹⁷O-enriched sources such as reactive oxygen species. Sulfate Δ′¹⁷O decreases significantly when moving into warm, low-elevation tributaries draining the same bedrock lithology. We interpret this to reflect overprinting of the pyrite oxidation-derived Δ′¹⁷O anomaly by microbial sulfate reduction and reoxidation, consistent with previously described major sulfur and oxygen isotope relationships. The geologic application of sulfate Δ′¹⁷O as a proxy for past${\mathrm{p}\mathrm{O}}_2$/${\mathrm{p}\mathrm{C}\mathrm{O}}_2$should consider both 1) alternative oxygen sources during pyrite oxidation and 2) secondary overprinting by microbial recycling.

 

Terrestrial vegetation and soils hold three times more carbon than the atmosphere. Much debate concerns how anthropogenic activity will perturb these surface reservoirs, potentially exacerbating ongoing changes to the climate system. Uncertainties specifically persist in extrapolating point-source observations to ecosystem-scale budgets and fluxes, which require consideration of vertical and lateral processes on multiple temporal and spatial scales. To explore controls on organic carbon (OC) turnover at the river basin scale, we present radiocarbon ( 14 C) ages on two groups of molecular tracers of plant-derived carbon—leaf-wax lipids and lignin phenols—from a globally distributed suite of rivers. We find significant negative relationships between the 14 C age of these biomarkers and mean annual temperature and precipitation. Moreover, riverine biospheric-carbon ages scale proportionally with basin-wide soil carbon turnover times and soil 14 C ages, implicating OC cycling within soils as a primary control on exported biomarker ages and revealing a broad distribution of soil OC reactivities. The ubiquitous occurrence of a long-lived soil OC pool suggests soil OC is globally vulnerable to perturbations by future temperature and precipitation increase. Scaling of riverine biospheric-carbon ages with soil OC turnover shows the former can constrain the sensitivity of carbon dynamics to environmental controls on broad spatial scales. Extracting this information from fluvially dominated sedimentary sequences may inform past variations in soil OC turnover in response to anthropogenic and/or climate perturbations. In turn, monitoring riverine OC composition may help detect future climate-change–induced perturbations of soil OC turnover and stocks. 

ABSTRACT In practice, obtaining radiocarbon ( 14 C) 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 14 C content obtained by different methods can differ, but underlying causes of these differences remain elusive. To assess the influence of different acid-treatments on 14 C content of sedimentary OM, we examine the variability in 14 C content for a range of marine and river sediments. By comparing results for unacidified and acidified sediments [HCl rinsing (Rinse HCl ) and HCl fumigation (Fume HCl )], we demonstrate that the two acid-treatments can affect 14 C content differentially. Our findings suggest that, for low-carbonate samples, Rinse HCl affects the Fm values due to loss of young labile organic carbon (OC). Fume HCl makes the Fm values for labile OC decrease, leaving the residual OC older. High-carbonate samples can lose relatively old organic components during Rinse HCl , causing the Fm values of remaining OC to increase. Fume HCl can 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.