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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 q behaviors 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. Key Points: 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 [ABSTRACT FROM AUTHOR]

Hopanoid lipids, bacteriohopanols and bacteriohopanepolyols, are membrane components exclusive to bacteria. Together with their diagenetic derivatives, they are commonly used as biomarkers for specific bacterial groups or biogeochemical processes in the geologic record. However, the sources of hopanoids to marine and freshwater environments remain inadequately constrained. Recent marker gene studies suggest a widespread potential for hopanoid biosynthesis in marine bacterioplankton, including nitrifying (i.e., ammonia‐ and nitrite‐oxidizing) bacteria. To explore their hopanoid biosynthetic capacities, we studied the distribution of hopanoid biosynthetic genes in the genomes of cultivated and uncultivated ammonia‐oxidizing (AOB), nitrite‐oxidizing (NOB), and complete ammonia‐oxidizing (comammox) bacteria, finding that biosynthesis of diverse hopanoids is common among seven of the nine presently cultivated clades of nitrifying bacteria. Hopanoid biosynthesis genes are also conserved among the diverse lineages of bacterial nitrifiers detected in environmental metagenomes. We selected seven representative NOB isolated from marine, freshwater, and engineered environments for phenotypic characterization. All tested NOB produced diverse types of hopanoids, with some NOB producing primarily diploptene and others producing primarily bacteriohopanepolyols. Relative and absolute abundances of hopanoids were distinct among the cultures and dependent on growth conditions, such as oxygen and nitrite limitation. Several novel nitrogen‐containing bacteriohopanepolyols were tentatively identified, of which the so called BHP‐743.6 was present in all NOB. Distinct carbon isotopic signatures of biomass, hopanoids, and fatty acids in four tested NOB suggest operation of the reverse tricarboxylic acid cycle in Nitrospira spp. and Nitrospina gracilis and of the Calvin–Benson–Bassham cycle for carbon fixation in Nitrobacter vulgaris and Nitrococcus mobilis. We suggest that the contribution of hopanoids by NOB to environmental samples could be estimated by their carbon isotopic compositions. The ubiquity of nitrifying bacteria in the ocean today and the antiquity of this metabolic process suggest the potential for significant contributions to the geologic record of hopanoids. [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]

Abstract: 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. [ABSTRACT FROM AUTHOR]

Black carbons, including soots, chars, activated carbons, and engineered nanocarbons, have different surface properties, but the extent to which these affect their sorbent properties is not known. To evaluate this for an environmentally ubiquitous form of black carbon, biomass char, the surface of a well-studied wood char was probed using 14 sorbates exhibiting diverse functional groups, and the data were fit with a polyparameter linear free energy relationship to assess the importance of the various possible sorbate-char surface interactions. Sorption from water to water-wet char evolved with the sorbate's degree of surface saturation and depended on only a few sorbate parameters: log Kd(L/kg) = [(4.03 ± 0.14) + (-0.15 ± 0.04) log ai] V + [(-0.28 ± 0.04) log ai] S + (-5.20 ± 0.21) B, where ai is the aqueous saturation of the sorbate i, V is McGowan's characteristic volume, S reflects polarity, and B represents the electron-donation basicity. As is generally observed for activated carbon, the sorbate's size encouraged sorption from water to the char, whereas its electron donation and proton acceptance discouraged sorption from water. The magnitude and saturation dependence differed significantly from what has been seen for activated carbons, presumably reflecting the unique surface chemistries of these 2 black carbon materials and suggesting that black carbon-specific sorption coefficients will yield more accurate assessments of contaminant mobility and bioavailability, as well as evaluation of a site's response to remediation. Environ Toxicol Chem 2015;34:1464-1471. © 2015 SETAC [ABSTRACT FROM AUTHOR]