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USGS2008

Thermal stability of ladderane lipids as determined by hydrous pyrolysis

Anaerobic ammonium oxidation (anammox) has been recognized as a major process resulting in loss of fixed inorganic nitrogen in the marine environment. Ladderane lipids, membrane lipids unique to anammox bacteria, have been used as markers for the detection of anammox in marine settings. However, the fate of ladderane lipids after sediment burial and maturation is unknown. In this study, anammox bacterial cell material was artificially matured by hydrous pyrolysis at constant temperatures ranging from 120 to 365 ??C for 72 h to study the stability of ladderane lipids during progressive dia- and catagenesis. HPLC-MS/MS analysis revealed that structural alterations of ladderane lipids already occurred at 120 ??C. At temperatures >140 ??C, ladderane lipids were absent and only more thermally stable products could be detected, i.e., ladderane derivatives in which some of the cyclobutane rings were opened. These diagenetic products of ladderane lipids were still detectable up to temperatures of 260 ??C using GC-MS. Thus, ladderane lipids are unlikely to occur in ancient sediments and sedimentary rocks, but specific diagenetic products of ladderane lipids will likely be present in sediments and sedimentary rocks of relatively low maturity (i.e., C31 hopane 22S/(22S + 22R) ratio <0.2 or ????/(???? + ???? + ????) ratio of >0.5). ?? 2008 Elsevier Ltd.

Organic Geochemistry↗

USGS2015

Biogeochemical environments of streambed-sediment pore waters with and without arsenic enrichment in a sedimentary rock terrain, New Jersey Piedmont, USA

Release of arsenic (As) from sedimentary rocks has resulted in contamination of groundwater in aquifers of the New Jersey Piedmont Physiographic Province, USA; the contamination also may affect the quality of the region's streamwater to which groundwater discharges. Biogeochemical mechanisms involved in the release process were investigated in the streambeds of Six Mile Run and Pike Run, tributaries to the Millstone River in the Piedmont. At Six Mile Run, streambed pore water and shallow groundwater were low or depleted in oxygen, and contained As at concentrations greater than 20 μg/L. At Pike Run, oxidizing conditions were present in the streambed, and the As concentration in pore water was 2.1 μg/L. The 16S rRNA gene and the As(V) respiratory reductase gene, arrA , were amplified from DNA extracted from streambed pore water at both sites and analyzed, revealing that distinct bacterial communities that corresponded to the redox conditions were present at each site. Anaerobic enrichment cultures were inoculated with pore water from gaining reaches of the streams with acetate and As(V). As(V) was reduced by microbes to As(III) in enrichments with Six Mile Run pore water and groundwater, whereas no reduction occurred in enrichments with Pike Run pore water. Cloning and sequencing of the arrA gene indicated 8 unique operational taxonomic units (OTUs) at Six Mile Run and 11 unique OTUs at Pike Run, which may be representative of the arsenite oxidase gene arxA . Low-oxygen conditions at Six Mile Run have favored microbial As reduction and release, whereas release was inhibited by oxidizing conditions at Pike Run.

New Jersey↗

USGS2020

Degradation of RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine) in contrasting coastal marine habitats: Subtidal non-vegetated (sand), subtidal vegetated (silt/eel grass), and intertidal marsh

Hundreds of explosive-contaminated marine sites exist globally, many of which contain the common munitions constituent hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Quantitative information about RDX transformation in coastal ecosystems is essential for management of many of these sites. Isotopically labelled RDX containing 15 N in all 3 nitro groups was used to track the fate of RDX in three coastal ecosystem types. Flow-through mesocosms representing subtidal vegetated (silt/eel grass), subtidal non-vegetated (sand) and intertidal marsh ecosystems were continuously loaded with isotopically labelled RDX for 16–17 days. Sediment, pore-water and overlying surface water were analyzed to determine the distribution of RDX, nitroso-triazine transformation products (NXs) and nitrogen containing complete mineralization products, including ammonium, nitrate+nitrite, nitrous oxide and nitrogen gas. The marsh, silt, and sand ecotypes transformed 94%, 90% and 76% of supplied RDX, respectively. Total dissolved NXs accounted for 2%–4% of the transformed 15 N-RDX. The majority of RDX transformation in the water column was by mineralization to inorganic N (dissolved and evaded; 64%–78% of transformed 15 N-RDX). RDX was mineralized primarily to N 2 O (62–74% of transformed 15 N-RDX) and secondarily to N 2 (1–2% of transformed 15 N-RDX) which exchanged with the atmosphere. Transformation of RDX was favored in carbon-rich lower redox potential sediments of the silt and marsh mesocosms where anaerobic processes of iron and sulfate reduction were most prevalent. RDX was most persistent in the carbon-poor sand mesocosm. Partitioning of 15 N derived from RDX onto sediment and suspended particulates was negligible in the overall mass balance of RDX transformation (2%–3% of transformed 15 N-RDX). The fraction of 15 N derived from RDX that was sorbed or assimilated in sediment was largest in the marsh mesocosm (most organic carbon), and smallest in the sand mesocosm (largest grain size and least organic carbon). Sediment redox conditions and available organic carbon stores affect the fate of RDX in different coastal marine habitats.

Connecticut, New York↗

USGS2021

Repeated large-scale mechanical treatment of invasive Typha under increasing water levels promotes floating mat formation and wetland methane emissions

Invasive species management typically aims to promote diversity and wildlife habitat, but little is known about how management techniques affect wetland carbon (C) dynamics. Since wetland C uptake is largely influenced by water levels and highly productive plants, the interplay of hydrologic extremes and invasive species is fundamental to understanding and managing these ecosystems. During a period of rapid water level rise in the Laurentian Great Lakes, we tested how mechanical treatment of invasive plant Typha × glauca shifts plant-mediated wetland C metrics. From 2015 to 2017, we implemented large-scale treatment plots (0.36-ha) of harvest (i.e., cut above water surface, removed biomass twice a season), crush (i.e., ran over biomass once mid-season with a tracked vehicle), and Typha -dominated controls. Treated Typha regrew with approximately half as much biomass as unmanipulated controls each year, and Typha production in control stands increased from 500 to 1500 g-dry mass m −2 yr −1 with rising water levels (~10 to 75 cm) across five years. Harvested stands had total in-situ methane (CH 4 ) flux rates twice as high as in controls, and this increase was likely via transport through cut stems because crushing did not change total CH 4 flux. In 2018, one year after final treatment implementation, crushed stands had greater surface water diffusive CH 4 flux rates than controls (measured using dissolved gas in water), likely due to anaerobic decomposition of flattened biomass. Legacy effects of treatments were evident in 2019; floating Typha mats were present only in harvested and crushed stands, with higher frequency in deeper water and a positive correlation with surface water diffusive CH 4 flux. Our study demonstrates that two mechanical treatments have differential effects on Typha structure and consequent wetland CH 4 emissions, suggesting that C-based responses and multi-year monitoring in variable water conditions are necessary to accurately assess how management impacts ecological function.

Michigan↗

USGS2012

Microbial transformations of arsenic: Mobilization from glauconitic sediments to water

In the Inner Coastal Plain of New Jersey, arsenic (As) is released from glauconitic sediment to carbon- and nutrient-rich shallow groundwater. This As-rich groundwater discharges to a major area stream. We hypothesize that microbes play an active role in the mobilization of As from glauconitic subsurface sediments into groundwater in the Inner Coastal Plain of New Jersey. We have examined the potential impact of microbial activity on the mobilization of arsenic from subsurface sediments into the groundwater at a site on Crosswicks Creek in southern New Jersey. The As contents of sediments 33–90 cm below the streambed were found to range from 15 to 26.4 mg/kg, with siderite forming at depth. Groundwater beneath the streambed contains As at concentrations up to 89 μg/L. Microcosms developed from site sediments released 23 μg/L of As, and active microbial reduction of As(V) was observed in microcosms developed from site groundwater. DNA extracted from site sediments was amplified with primers for the 16S rRNA gene and the arsenate respiratory reductase gene, arrA , and indicated the presence of a diverse anaerobic microbial community, as well as the presence of potential arsenic-reducing bacteria. In addition, high iron (Fe) concentrations in groundwater and the presence of iron-reducing microbial genera suggests that Fe reduction in minerals may provide an additional mechanism for release of associated As, while arsenic-reducing microorganisms may serve to enhance the mobility of As in groundwater at this site.

New Jersey↗

USGS2026

Aging of biosolids in fields prolongs the release of biosolid-borne PFAS and promotes the release of select PFCA in water

Land application of biosolids can introduce PFAS into croplands. Biosolids transported to surface waters through runoff may subsequently release PFAS into aquatic environments. The objective was to evaluate the effects of the aging of biosolids and the presence of sediment on the release of biosolid-borne PFAS to water at the water-sediment interface under anaerobic conditions. Through two independent rounds of microcosm experiments, we demonstrate that by day 136, most of the PFAS compounds (e.g., perfluorocarboxylic acids, or PFCAs) released <10 ng per g biosolids dry weight, except for 5:3 FTCA. Kinetically, the aging process substantially delayed the release of some long-chain PFAS (i.e., PFNA, PFDA, and PFOS) to water, due to the collapse of the porous structure of biosolids during aging. After day 136, the amount of long-chain PFAS released from aged biosolids reached levels similar to those released from the fresh biosolids due to the recovery of the pore structure during the release experiment. Mass balance analysis showed considerably higher, final masses of PFPeA, PFHxA, and PFOA than their initial masses, suggesting that precursors were biotransformed into these compounds during the release experiment, and biosolid aging led to elevated biotransformation and release of these three PFCAs. Sediment had little effect on the kinetics or extent of PFAS release from biosolids, except that the extent of FTCA release was reduced in the presence of sediment potentially due to adsorption. Overall, biosolid aging can delay the release of long-chain PFAS and promote the biotransformation to and release of PFCAs.

Water Research↗

USGS2000

Fractionation of selenium isotopes during bacterial respiratory reduction of selenium oxyanions

Reduction of selenium oxyanions by microorganisms is an important process in the biogeochemical cycling of selenium. Numerous bacteria can reduce Se oxyanions, which are used as electron acceptors during the oxidation of organic matter in anoxic environments. In this study, we used a double spike ( 82 Se and 74 Se) thermal ionization mass spectrometry technique to quantify the isotopic fractionation achieved by three different species of anaerobic bacteria capable of accomplishing growth by respiratory reduction of selenate [SeO 4 2− or Se(VI)] or selenite [SeO 3 2− or Se(IV)] to Se(IV) or elemental selenium [Se(0)] coupled with the oxidation of lactate. Isotopic discrimination in these closed system experiments was evaluated by Rayleigh fractionation equations and numerical models. Growing cultures of Bacillus selenitireducens , a haloalkaliphile capable of growth using Se(IV) as an electron acceptor, induced a 80 Se/ 76 Se fractionation of −8.0 ± 0.4‰ (instantaneous ϵ value) during reduction of Se(IV) to Se(0). With Bacillus arsenicoselenatis , a haloalkaliphile capable of growth using Se(VI) as an electron acceptor, fractionations of −5.0 ± 0.5‰ and −6.0 ± 1.0‰ were observed for reduction of Se(VI) to Se(IV) and reduction of Se(IV) to Se(0), respectively. In growing cultures of Sulfurospirillum barnesii , a freshwater species capable of growth using Se(VI), fractionation was small initially, but near the end of the log growth phase, it increased to −4.0 ± 1.0‰ and −8.4 ± 0.4‰ for reduction of Se(VI) to Se(IV) and reduction of Se(IV) to Se(0), respectively. Washed cell suspensions of S. barnesii induced fractionations of −1.1 ± 0.4‰ during Se(VI) reduction, and −9.1 ± 0.5% for Se(IV) reduction, with some evidence for smaller values (e.g., −1.7‰) in the earliest-formed Se(0) results. These results demonstrate that dissimilatory reduction of selenate or selenite induces significant isotopic fractionation, and suggest that significant Se isotope ratio variation will be found in nature.

Geochimica et Cosmochimica Acta↗

USGS1999

Bacterial respiration of arsenic and selenium

Oxyanions of arsenic and selenium can be used in microbial anaerobic respiration as terminal electron acceptors. The detection of arsenate and selenate respiring bacteria in numerous pristine and contaminated environments and their rapid appearance in enrichment culture suggest that they are widespread and metabolically active in nature. Although the bacterial species that have been isolated and characterized are still few in number, they are scattered throughout the bacterial domain and include Gram- positive bacteria, beta, gamma and epsilon Proteobacteria and the sole member of a deeply branching lineage of the bacteria, Chrysiogenes arsenatus. The oxidation of a number of organic substrates (i.e. acetate, lactate, pyruvate, glycerol, ethanol) or hydrogen can be coupled to the reduction of arsenate and selenate, but the actual donor used varies from species to species. Both periplasmic and membrane-associated arsenate and selenate reductases have been characterized. Although the number of subunits and molecular masses differs, they all contain molybdenum. The extent of the environmental impact on the transformation and mobilization of arsenic and selenium by microbial dissimilatory processes is only now being fully appreciated.

FEMS Microbiology Reviews↗

USGS2001

Progression of natural attenuation processes at a crude oil spill site: II. Controls on spatial distribution of microbial populations

A multidisciplinary study of a crude-oil contaminated aquifer shows that the distribution of microbial physiologic types is strongly controlled by the aquifer properties and crude oil location. The microbial populations of four physiologic types were analyzed together with permeability, pore-water chemistry, nonaqueous oil content, and extractable sediment iron. Microbial data from three vertical profiles through the anaerobic portion of the contaminated aquifer clearly show areas that have progressed from iron-reduction to methanogenesis. These locations contain lower numbers of iron reducers, and increased numbers of fermenters with detectable methanogens. Methanogenic conditions exist both in the area contaminated by nonaqueous oil and also below the oil where high hydrocarbon concentrations correspond to local increases in aquifer permeability. The results indicate that high contaminant flux either from local dissolution or by advective transport plays a key role in determining which areas first become methanogenic. Other factors besides flux that are important include the sediment Fe(II) content and proximity to the water table. In locations near a seasonally oscillating water table, methanogenic conditions exist only below the lowest typical water table elevation. During 20 years since the oil spill occurred, a laterally continuous methanogenic zone has developed along a narrow horizon extending from the source area to 50–60 m downgradient. A companion paper [J. Contam. Hydrol. 53, 369–386] documents how the growth of the methanogenic zone results in expansion of the aquifer volume contaminated with the highest concentrations of benzene, toluene, ethylbenzene, and xylenes.

Journal of Contaminant Hydrology↗

USGS1999

Geochemical heterogeneity of a gasoline-contaminated aquifer

The scale of biogeochemical reactions was studied in a physically and chemically heterogeneous surficial Coastal Plain aquifer contaminated by a gasoline spill. The physical heterogeneity of the aquifer is manifested in two hydrologic units, a shallow local aquifer of perched water and a regional sandy aquifer. Over the studied vertical interval of 21.3 ft (6.5 m), concentrations of reactive species varied by orders of magnitude, and the impact of biodegradation was expressed to widely varying degrees. A thin (3 ft thick) section of the perched-water zone was the most contaminated; total aromatic hydrocarbons were as high as 19.4 mg/l. Hydrocarbons were degraded by microbially mediated reactions that varied over short vertical distances and time. Anaerobic processes dominated within the low-permeability clay unit, whereas in the more permeable sandy layers nitrate reduction and aerobic degradation occurred. Hydrocarbons were more persistent over time in the low-permeability layer due to the limited availability of electron acceptors for degradation. The microbial degradation of hydrocarbons was linked to sulfate and iron reduction in the clay unit and led to alterations in the aquifer solids; electron microscopy revealed the presence of FeS minerals encrusting primary aquifer grains. High concentrations of Fe 2+ in groundwater, up to 34.5 mg/l, persist in kinetic disequilibrium in the presence of elevated H 2 S levels of 1.0 mg/l. Assessment of aquifer heterogeneities and groundwater contamination was possible due to sample discrimination at a scale of approximately 2 ft (∼0.6 m), a much finer resolution than is attempted in many remedial investigations of polluted aquifers. The information obtained in this type of study is essential to the development of models capable of estimating the fate of hydrocarbons at a site scale.

Journal of Contaminant Hydrology↗

USGS1998

Flow of river water into a karstic limestone aquifer: 2. Dating the young fraction in groundwater mixtures in the Upper Floridan aquifer near Valdosta, Georgia

Tritium/helium-3 ( 3 H/ 3 He) and chlorofluorocarbon (CFCs, CFC–11, CFC–12, CFC–113) data are used to date the young fraction in groundwater mixtures from a karstic limestone aquifer near Valdosta, Georgia, where regional paleowater in the Upper Floridan aquifer receives recharge from two young sources—the flow of Withlacoochee River water through sinkholes in the river bed, and leakage of infiltration water through post-Eocene semi-confining beds above the Upper Floridan aquifer. In dating the young fraction of mixtures using CFCs, it is necessary to reconstruct the CFC concentration that was in the young fraction prior to mixing. The 3 H/ 3 He age is independent of the extent of dilution with older ( 3 H-free and 3 He trit -free) water. The groundwater mixtures are designated as Type-1 for mixtures of regional paleowater and regional infiltration water and Type-2 for mixtures containing more than approximately 4% of river water. The fractions of regional paleowater, regional infiltration water, and Withlacoochee River water in the groundwater mixtures were determined from Cl − and δ 18 O data for water from the Upper Floridan aquifer at Valdosta, Georgia. The chlorofluorocarbons CFC–11 and CFC–113 are removed by microbial degradation and/or sorption processes in most anaerobic (Type-2) groundwater at Valdosta, but are present in some aerobic Type-1 water. CFC–12 persists in both SO 4 -reducing and methanogenic water. The very low detection limits for CFCs (approximately 0.3 pg kg −1 ) permitted CFC–11 and CFC–12 dating of the fraction of regional infiltration water in Type-1 mixtures, and CFC-12 dating of the river-water fraction in Type-2 mixtures. Overall, approximately 50% of the 85 water samples obtained from the Upper Floridan aquifer have CFC–12-based ages of the young fraction that are consistent with the 3 H concentration of the groundwater. Because of uncertainties associated with very low 3 H and 3 He content in dilute mixtures, 3 H/ 3 He dating is limited to the river-water fraction in Type-2 mixtures containing more than about 10% river water. Of the 41 water samples measured for 3 H/ 3 He dating, dilution of 3 H and low 3 He concentration limited 3 H/ 3 He dating to 16 mixtures in which 3 H/ 3 He ages are defined with errors ranging from ±2 to ±7.5 a (1 σ). After correction for dilution with (assumed) CFC-free regional infiltration water and regional paleowater in the Upper Floridan aquifer, adjusted CFC–12 ages agree with 3 H/ 3 He ages within 5 a or less in 7 of the 9 co-dated Type-2 mixtures. Tritium data and dating based on both CFC–11 and CFC–12 in Type-1 mixtures indicate that travel times of infiltration water through the overlying Post-Eocene semi-confining beds exceed 35 a. The CFC and 3 H/ 3 He dating indicate that the river fraction in most groundwater entered the groundwater reservoir in the past 20 to 30 a. Few domestic and municipal supply wells sampled intercept water younger than 5 a. Calculated velocities of river water in the Upper Floridan aquifer downgradient of the sinkhole area range from 0.4 to 8.2 m/d. Radiocarbon data indicate that ages of the regional paleowater are on the 10 000-a time scale. An average lag time of approximately 10 to 25 a is determined for discharge of groundwater from the surficial and intermediate aquifers above the Upper Floridan aquifer to the Withlacoochee River.

Georgia↗

USGS1999

Effects of dynamic redox zonation on the potential for natural attenuation of trichloroethylene at a fire-training-impacted aquifer

Hydrogeochemical and microbiological methods were used to characterize temporal changes along a transect of an aquifer contaminated by mixed hydrocarbon and solvent wastes from fire training activities at Wurtsmith Air Force Base (Oscoda, MI). Predominant terminal electron accepting processes (TEAPs) as measured by dissolved hydrogen indicated reoxygenation along the transect between October 1995 and October 1996, possibly because of recharge, fluctuations in water table elevation, or microbial activity. Microbiological analyses using universal and archaeal probes revealed a relationship between groundwater hydrogen concentration, TEAP, and predominant bacterial phylogeny. Specifically, a raised water table level and evidence of methanogenesis corresponded to an order of magnitude increase in archaeal 16S rRNA relative to when this zone was unsaturated. Spatial microbial and geochemical dynamics did not result in measurable differences in trichloroethylene (TCE) mineralization potential in vadose, capillary fringe, and saturated zone soils during a 500-day microcosm experiment using unprocessed contaminated soil and groundwater. Aerobic systems indicated that methane, but not toluene, may serve as cosubstrate for TCE cometabolism. Anaerobic microcosms demonstrated evidence for methanogenesis, CO2 production and hydrogen consumption, yet dechlorination activity was only observed in a microcosm with sulfate-reduction as the dominant TEAP. Mass balance calculations indicated less than 5% mineralization, regardless of redox zone or degree of saturation, at maximum rates of 0.01-0.03 ??mol/g soil??d. The general lack of dechlorination activity under laboratory conditions corroborates the limited evidence for natural dechlorination at this site, despite abundant electron donor material and accumulated organic acids from microbial degradation of alkylbenzenes. Thus, the short-term temporal dynamics in redox conditions is unlikely to have measurable effects on the long-term natural remediation potential of the aquifer.

Physics and Chemistry of the Earth, Part B: Hydrol↗

USGS2016

Hydrologic controls on nitrogen cycling processes and functional gene abundance in sediments of a groundwater flow-through lake

The fate and transport of inorganic nitrogen (N) is a critically important issue for human and aquatic ecosystem health because discharging N-contaminated groundwater can foul drinking water and cause algal blooms. Factors controlling N-processing were examined in sediments at three sites with contrasting hydrologic regimes at a lake on Cape Cod, MA. These factors included water chemistry, seepage rates and direction of groundwater flow, and the abundance and potential rates of activity of N-cycling microbial communities. Genes coding for denitrification, anaerobic ammonium oxidation (anammox), and nitrification were identified at all sites regardless of flow direction or groundwater dissolved oxygen concentrations. Flow direction was, however, a controlling factor in the potential for N-attenuation via denitrification in the sediments. Potential rates of denitrification varied from 6 to 4500 pmol N/g/h from the inflow to the outflow side of the lake, owing to fundamental differences in the supply of labile organic matter. The results of laboratory incubations suggested that when anoxia and limiting labile organic matter prevailed, the potential existed for concomitant anammox and denitrification. Where oxic lake water was downwelling, potential rates of nitrification at shallow depths were substantial (1640 pmol N/g/h). Rates of anammox, denitrification, and nitrification may be linked to rates of organic N-mineralization, serving to increase N-mobility and transport downgradient.

Massachusetts↗

USGS2020

Tracing the uptake of Hg(II) in an iron-reducing bacterium using mercury stable isotopes

Anaerobic microorganisms play a key role in the biological mercury (Hg) cycle due to their ability to produce bioaccumulative neurotoxic methylmercury (MeHg). However, despite recent advances, how bacteria accumulate inorganic Hg [Hg(II)] prior to methylation is largely unknown. In this study, we applied Hg stable isotopes to measure changes in cellular compartments of Geobacter sulfurreducens and a nonmethylating mutant strain to investigate intracellular transport of Hg(II). Both strains accumulated intracellular Hg(II) that was lower in δ 202 Hg relative to dissolved extracellular Hg(II), demonstrating mass-dependent fractionation during uptake. Hg reduction by the mutant strain (50% Hg concentration loss in 24 h) resulted in higher δ 202 Hg values of cellular Hg than in wild-type cells. Further observations showed increasing δ 202 Hg values in dissolved extracellular MeHg and Hg(II) but decreasing δ 202 Hg values of intracellular Hg(II) in wild-type G. sulfurreducens suggesting that external Hg pools may be the proximate source of Hg for methylation in this bacterium. This investigation demonstrates that cellular uptake is comprised of multiple processes and transformations that influence Hg(II) prior to methylation, which can impart distinct isotopic signatures to Hg(II) and MeHg pools in the environment.

Environmental Science and Technology Letters↗

USGS2024

Methane clumped isotopologue variability from ebullition in a mid-latitude lake

Methane is a greenhouse gas and is an important component of carbon cycling in freshwater environments. Isotope ratios of methane ( 13 C/ 12 C and D/H) are used extensively as tracers to identify methane sources. Recent advances in the measurement of clumped methane isotopologues ( 13 CH 3 D, 12 CH 2 D 2 ) offer new opportunities to constrain sources and sinks of atmospheric methane. Previous measurements of clumped methane isotopologues from freshwater environments have been spatially and temporally limited. The abundance of 13 CH 3 D and methane flux from ebullition in the deep basin of Upper Mystic Lake were measured from May to November 2021 to characterize the source isotopologue signatures and methane fluxes for mid-latitude lakes. The trends in δ 13 C and δD values support decreased methane oxidation in the early summer compared to fall. The Δ 13 CH 3 D values from this study range from 2.0 to 4.2‰, reflecting methane oxidation occurring anaerobically in lake sediments and euxinic bottom waters at sample sites. The relatively large variation in the Δ 13 CH 3 D values observed within this lake basin aligns with previous observations of bubbles from arctic lakes. The values of Δ 13 CH 3 D do not correlate with methane flux, suggesting that Δ 13 CH 3 D measurements from background ebullition are not sensitive as a proxy for ebullition rates. This study presents a uniquely large ( n = 40) set of freshwater Δ 13 CH 3 D values from a single lake basin, which we use to recommend a sampling strategy of ≥9 samples to constrain the Δ 13 CH 3 D source signal within ∼0.5‰ from similar environments. This data demonstrates the utility of clumped methane isotopologues to gain insights into local biogeochemical processes from field studies and points to the challenge of using clumped isotopologue measurements to constrain global freshwater–methane sources to the atmosphere.

ACS Earth and Space Chemistry↗

USGS2017

How could a freshwater swamp produce a chemical signature characteristic of a saltmarsh?

Reduction–oxidation (redox) reaction conditions, which are of great importance for the soil chemistry of coastal marshes, can be temporally dynamic. We present a transect of cores from northwest Florida wherein radical postdepositional changes in the redox regime has created atypical geochemical profiles at the bottom of the sedimentary column. The stratigraphy is consistent along the transect, consisting of, from the bottom upward, carbonate bedrock, a gray clay, an organic mud section, a dense clay layer, and an upper organic mud unit representing the current saltwater marsh. However, the geochemical signature of the lower organic mud unit suggests pervasive redox reactions, although the interval has been identified as representing a freshwater marsh, an unlikely environment for such conditions. Analyses indicate that this discrepancy results from postdepositional diagenesis driven by millennial-scale environmental parameters. Rising sea level that led to the deposition of the capping clay layer, created anaerobic conditions in the freshwater swamp interval, and isolated it hydrologically from the rest of the sediment column. The subsequent infiltration of marine water into this organic material led to sulfate reduction, the buildup of H 2 S and FeS, and anoxic conditions. Continued sulfidation eventually resulted in euxinic conditions, as evidenced by elevated levels of Fe, S, and especially Mo, the diagnostic marker of euxinia. Because this chemical transformation occurred long after the original deposition the geochemical signature does not reflect soil chemistry at the time of deposition and cannot be used to infer syn-depositional environmental conditions, emphasizing the importance of recognizing diagenetic processes in paleoenvironmental studies.

Florida↗

USGS2000

Bioavailability of particle-associated Se to the bivalve Potamocorbula amurensis

Elemental selenium, Se(0), is a prevalent chemical form in sediments, but little is known about its bioavailability. We evaluated the bioavailability of two forms of Se(0) by generating radioisotopic 75 Se(0) through bacterial dissimilatory reduction of 75 SeO 3 2 - by pure bacterial cultures (SES) and by an anaerobic sediment microbial consortium (SED). A third form was generated by reducing 75 SeO 3 2 - with ascorbic acid (AA). Speciation determinations showed that AA and SES were >90% Se(0), but SED showed a mixture of Se(0), selenoanions, and a residual fraction. Pulse-chase techniques were used to measure assimilation efficiencies (AE) of these particulate Se forms by the bivalve Potamocorbula amurensis . Mean AE values were 3 ± 2% for AA, 7 ± 1% for SES, and 28 ± 15% for SED, showing that the bioavailability of reduced, particle-associated Se is dependent upon its origin. To determine if oxidative microbial processes increased Se transfer, SES 75 Se(0) was incubated with an aerobic sediment microbial consortium. After 113 d of incubation, 36% of SES Se(0) was oxidized to SeO 3 2 - . Assimilation of total particulate Se was unaffected however (mean AE = 5.5%). The mean AE from the diatom Phaeodactylum tricornutum was 58 ± 8%, verifying the importance of Se associated with biogenic particles. Speciation and AE results from SED suggest that selenoanion reduction in wetlands and estuaries produces biologically available reduced selenium.

Environmental Science & Technology↗

USGS2002

In-situ evidence for uranium immobilization and remobilization

The in-situ microbial reduction and immobilization of uranium was assessed as a means of preventing the migration of this element in the terrestrial subsurface. Uranium immobilization (putatively identified as reduction) and microbial respiratory activities were evaluated in the presence of exogenous electron donors and acceptors with field push−pull tests using wells installed in an anoxic aquifer contaminated with landfill leachate. Uranium(VI) amended at 1.5 μM was reduced to less than 1 nM in groundwater in less than 8 d during all field experiments. Amendments of 0.5 mM sulfate or 5 mM nitrate slowed U(VI) immobilization and allowed for the recovery of 10% and 54% of the injected element, respectively, as compared to 4% in the unamended treatment. Laboratory incubations confirmed the field tests and showed that the majority of the U(VI) immobilized was due to microbial reduction. In these tests, nitrate treatment (7.5 mM) inhibited U(VI) reduction, and nitrite was transiently produced. Further push−pull tests were performed in which either 1 or 5 mM nitrate was added with 1.0 μM U(VI) to sediments that already contained immobilized uranium. After an initial loss of the amendments, the concentration of soluble U(VI) increased and eventually exceeded the injected concentration, indicating that previously immobilized uranium was remobilized as nitrate was reduced. Laboratory experiments using heat-inactivated sediment slurries suggested that the intermediates of dissimilatory nitrate reduction (denitrification or dissimilatory nitrate reduction to ammonia), nitrite, nitrous oxide, and nitric oxide were all capable of oxidizing and mobilizing U(IV). These findings indicate that in-situ subsurface U(VI) immobilization can be expected to take place under anaerobic conditions, but the permanence of the approach can be impaired by disimilatory nitrate reduction intermediates that can mobilize previously reduced uranium.

Environmental Science & Technology↗