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At least 271 records · Page 15Linked to original sources
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↗
USGS2006

Occurrence and fate of organic contaminants during onsite wastewater treatment

Onsite wastewater treatment systems serve approximately 25% of the U.S. population. However, little is known regarding the occurrence and fate of organic wastewater contaminants (OWCs), including endocrine disrupting compounds, during onsite treatment. A range of OWCs including surfactant metabolites, steroids, stimulants, metal-chelating agents, disinfectants, antimicrobial agents, and pharmaceutical compounds was quantified in wastewater from 30 onsite treatment systems in Summit and Jefferson Counties, CO. The onsite systems represent a range of residential and nonresidential sources. Eighty eight percent of the 24 target compounds were detected in one or more samples, and several compounds were detected in every wastewater sampled. The wastewater matrices were complex and showed unique differences between source types due to differences in water and consumer product use. Nonresidential sources generally had more OWCs at higher concentrations than residential sources. Additional aerobic biofilter-based treatment beyond the traditional anaerobic tank-based treatment enhanced removal for many OWCs. Removal mechanisms included volatilization, biotransformation, and sorption with efficiencies from <1% to >99% depending on treatment type and physico chemical properties of the compound. Even with high removal rates during confined unit onsite treatment, OWCs are discharged to soil dispersal units at loadings up to 20 mg/m 2 /d, emphasizing the importance of understanding removal mechanisms and efficiencies in onsite treatment systems that discharge to the soil and water environments.

Environmental Science & Technology↗
USGS2011

Effects of humic substances on precipitation and aggregation of zinc sulfide nanoparticles

Nanoparticulate metal sulfides such as ZnS can influence the transport and bioavailability of pollutant metals in anaerobic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences the stability of zinc sulfide nanoparticles as they nucleate and aggregate in water with dissolved NOM. We compared NOM fractions that were isolated from several surface waters and represented a range of characteristics including molecular weight, type of carbon, and ligand density. Dynamic light scattering was employed to monitor the growth and aggregation of Zn−S−NOM nanoparticles in supersaturated solutions containing dissolved aquatic humic substances. The NOM was observed to reduce particle growth rates, depending on solution variables such as type and concentration of NOM, monovalent electrolyte concentration, and pH. The rates of growth increased with increasing ionic strength, indicating that observed growth rates primarily represented aggregation of charged Zn−S−NOM particles. Furthermore, the observed rates decreased with increasing molecular weight and aromatic content of the NOM fractions, while carboxylate and reduced sulfur content had little effect. Differences between NOM were likely due to properties that increased electrosteric hindrances for aggregation. Overall, results of this study suggest that the composition and source of NOM are key factors that contribute to the stabilization and persistence of zinc sulfide nanoparticles in the aquatic environment.

Environmental Science & Technology↗
USGS2013

Association of toxin-producing Clostridium botulinum with the macroalga Cladophora in the Great Lakes

Avian botulism, a paralytic disease of birds, often occurs on a yearly cycle and is increasingly becoming more common in the Great Lakes. Outbreaks are caused by bird ingestion of neurotoxins produced by Clostridium botulinum, a spore-forming, gram-positive, anaerobe. The nuisance, macrophytic, green alga Cladophora (Chlorophyta; mostly Cladophora glomerata L.) is a potential habitat for the growth of C. botulinum. A high incidence of botulism in shoreline birds at Sleeping Bear Dunes National Lakeshore (SLBE) in Lake Michigan coincides with increasingly massive accumulations of Cladophora in nearshore waters. In this study, free-floating algal mats were collected from SLBE and other shorelines of the Great Lakes between June and October 2011. The abundance of C. botulinum in algal mats was quantified and the type of botulism neurotoxin (bont) genes associated with this organism were determined by using most-probable-number PCR (MPN-PCR) and five distinct bont gene-specific primers (A, B, C, E, and F). The MPN-PCR results showed that 16 of 22 (73%) algal mats from the SLBE and 23 of 31(74%) algal mats from other shorelines of the Great Lakes contained the bont type E (bont/E) gene. C. botulinum was present up to 15 000 MPN per gram dried algae based on gene copies of bont/E. In addition, genes for bont/A and bont/B, which are commonly associated with human diseases, were detected in a few algal samples. Moreover, C. botulinum was present as vegetative cells rather than as dormant spores in Cladophora mats. Mouse toxin assays done using supernatants from enrichment of Cladophora containing high densities of C. botulinum (>1000 MPN/g dried algae) showed that Cladophora-borne C. botulinum were toxin-producing species (BoNT/E). Our results indicate that Cladophora provides a habitat for C. botulinum, warranting additional studies to better understand the relationship between this bacterium and the alga, and how this interaction potentially contributes to botulism outbreaks in birds.

Great Lakes↗
USGS2013

Mercury speciation and mobilization in a wastewater-contaminated groundwater plume

We measured the concentration and speciation of mercury (Hg) in groundwater down-gradient from the site of wastewater infiltration beds operated by the Massachusetts Military Reservation, western Cape Cod, Massachusetts. Total mercury concentrations in oxic, mildly acidic, uncontaminated groundwater are 0.5–1 pM, and aquifer sediments have 0.5–1 ppb mercury. The plume of impacted groundwater created by the wastewater disposal is still evident, although inputs ceased in 1995, as indicated by anoxia extending at least 3 km down-gradient from the disposal site. Solutes indicative of a progression of anaerobic metabolisms are observed vertically and horizontally within the plume, with elevated nitrate concentrations and nitrate reduction surrounding a region with elevated iron concentrations indicating iron reduction. Mercury concentrations up to 800 pM were observed in shallow groundwater directly under the former infiltration beds, but concentrations decreased with depth and with distance down-gradient. Mercury speciation showed significant connections to the redox and metabolic state of the groundwater, with relatively little methylated Hg within the iron reducing sector of the plume, and dominance of this form within the higher nitrate/ammonium zone. Furthermore, substantial reduction of Hg(II) to Hg0 within the core of the anoxic zone was observed when iron reduction was evident. These trends not only provide insight into the biogeochemical factors controlling the interplay of Hg species in natural waters, but also support hypotheses that anoxia and eutrophication in groundwater facilitate the mobilization of natural and anthropogenic Hg from watersheds/aquifers, which can be transported down-gradient to freshwaters and the coastal zone.

Massachusetts↗
USGS2013

Microbiological reduction of Sb(V) in anoxic freshwater sediments

Microbiological reduction of millimolar concentrations of Sb(V) to Sb(III) was observed in anoxic sediments from two freshwater settings: (1) a Sb- and As-contaminated mine site (Stibnite Mine) in central Idaho and 2) an uncontaminated suburban lake (Searsville Lake) in the San Francisco Bay Area. Rates of Sb(V) reduction in anoxic sediment microcosms and enrichment cultures were enhanced by amendment with lactate or acetate as electron donors but not by H2, and no reduction occurred in sterilized controls. Addition of 2- 14 C-acetate to Stibnite Mine microcosms resulted in the production of 14 CO 2 coupled to Sb(V) reduction, suggesting that this process proceeds by a dissimilatory respiratory pathway in those sediments. Antimony(V) reduction in Searsville Lake sediments was not coupled to acetate mineralization and may be associated with Sb-resistance. The microcosms and enrichment cultures also reduced sulfate, and the precipitation of insoluble Sb(III)-sulfide complexes was a major sink for reduced Sb. The reduction of Sb(V) by Stibnite Mine sediments was inhibited by As(V), suggesting that As(V) is a preferred electron acceptor for the indigenous community. These findings indicate a novel pathway for anaerobic microbiological respiration and suggest that communities capable of reducing high concentrations of Sb(V) commonly occur naturally in the environment.

Environmental Science & Technology↗
USGS2008

Dating groundwater with trifluoromethyl sulfurpentafluoride (SF 5CF3), sulfur hexafluoride (SF6), CF 3Cl (CFC-13), and CF2Cl2 (CFC-12)

[1] A new groundwater dating procedure using the transient atmospheric signal of the environmental tracers SF5CF3, CFC-13, SF6, and CFC-12 was developed. The analytical procedure determines concentrations of the four tracers in air and water samples. SF 5CF3 and CFC-13 can be used to date groundwaters in some environments where the CFCs and SF6 have previously failed because these new tracers have increasing atmospheric input functions, no known terrigenic source, and are believed to be stable under reducing conditions. SF5CF3 has a dating range from 1970 to modern; the mixing ratio (mole fraction) in North American air has increased from the detection limit of 0.005 parts per trillion (ppt) to the 2006 mole fraction of about 0.16 ppt. No evidence was found for degradation of SF5CF3 in laboratory anaerobic systems. The solubility of SF5CF3 was measured in water from 1 to 35??C. Groundwater samples that contained large amounts of terrigenic SF6 did not contain terrigenic SF 5CF3. CFC-13 is a trace atmospheric gas with a dating range in groundwater of about 1965 to modem. CFC-13 has been used primarily in very low-temperature refrigeration; thus groundwater environments are less likely to be contaminated with nonatmospheric sources as compared to other widely used CFCs. Because of the low solubility of SF5CF3 and CFC-13 in water, an excess air correction must be applied to the apparent ages. The new dating procedure was tested in water samples from wells and springs from Maryland, Virginia, and West Virginia.

Water Resources Research↗
USGS2018

Direct observations of hydrologic exchange occurring with less‐mobile porosity and the development of anoxic microzones in sandy lakebed sediments

Quantifying coupled mobile/less‐mobile porosity dynamics is critical to the prediction of biogeochemical storage, release, and transformation processes in the zone where groundwater and surface water exchange. The recent development of fine‐scale geoelectrical monitoring paired with pore‐water sampling in groundwater systems enables direct characterization of hydrologic exchange between more‐ and less‐mobile porosity during tracer tests. We adapt this technique to sandy interface sediments at a groundwater flow‐through kettle lake. Tracer experiments were conducted within controlled‐head permeameters over a range of specified downward flow conditions over several days. Although the bed was predominantly composed of highly permeable sands and gravels, cobble inclusions created less‐mobile flow zones at the centimeter scale. Less‐mobile porosity fractions, residence times, and rates of exchange were inferred from paired bulk and fluid electrical conductivity data, without the need for inverse model calibration. The conservative solute experiments were paired with 15 NO 3 − and other reactive amendments, revealing anaerobic processes occurring at shallow sediment depths where pore‐water sampling indicated bulk‐oxic conditions. The average less‐mobile porosity residence times as evaluated with the geoelectrical method were on 1‐hr timescales, which appear to be biogeochemically important in the context of creating anoxic microzones within less‐mobile porosity of sandy interface sediments.

Water Resources Research↗
USGS2020

Formation criteria for hyporheic anoxic microzones: Assessing interactions of hydraulics, nutrients and biofilms

Recent experimental studies have detected the presence of anoxic microzones in hyporheic sediments. These microzones are small‐scale anoxic pores, embedded within oxygen‐rich porous media and can act as anaerobic reaction sites producing reduction compounds such as nitrous oxide, a potent greenhouse gas. Microbes are a key control on nutrient transformation in hyporheic sediment, but their associated biomass growth is also capable of altering hydraulic flux, leading to potential bioclogging. Here, we developed one of the first computational modeling approaches that combined hydraulics and microbial conditions to explore the continuous evolution of microzones in stream sediments. The model assessed stream and sediment conditions with different hydraulic flux (0.1–1.0 m/day Darcy flux), nutrient concentrations (O 2 = 8 mg/L, OrgC = 20 mg/L, NO − 3 = 1.5–3 mg/L, and NH 3 = 0.5–1 mg/L), and biomass scenarios (with and without). The model domain is a pore network model with random sized pore‐throat radii creating heterogeneous and anisotropic flow that is representative of a natural streambed composed of medium sand with a hydraulic conductivity of 0.8 m/day. Results from 30 day simulations indicate that hyporheic microzone formation will occur and microzone distributions are not simply controlled by residence time alone, rather by the complex interactions of hydraulic flux, nutrient concentrations, and biomass, with bioclogging having strong feedbacks on both hydraulics and nutrients. Under all conditions with biomass growth, anoxic microzones were unstable, perishing a few days after formation, because bioclogging primarily occurs near the influent (downwelling) area of the hyporheic zone. In turn, this bioclogging shifts transport conditions from advection‐dominated to diffusion‐dominated transport, removing all oxic regions in the hyporheic zone. Overall, results from the modeling show that anoxic microzones are likely to form under many hyporheic zone conditions, and be dynamic through space and time as they are dependent on both hydraulic flux and nutrient transport.

Water Resources Research↗
USGS2021

Isolating detrital and diagenetic signals in magnetic susceptibility records from methane-bearing marine sediments

Volume-dependent magnetic susceptibility (κ) is commonly used for paleoenvironmental reconstructions in both terrestrial and marine sedimentary environments where it reflects a mixed signal between primary deposition and secondary diagenesis. In the marine environment, κ is strongly influenced by the abundance of ferrimagnetic minerals regulated by sediment transport processes. Post-depositional alteration by H 2 S, however, can dissolve titanomagnetite, releasing reactive Fe that promotes pyritization and subsequently decreases κ. Here, we provide a new approach for isolating the detrital signal in κ and identifying intervals of diagenetic alteration of κ driven by organoclastic sulfate reduction (OSR) and the anaerobic oxidation of methane (AOM) in methane-bearing marine sediments offshore India. Using the correlation of a heavy mineral proxy from X-ray fluorescence data (Zr/Rb) and κ in unaltered sediments, we predict the primary detrital κ signal and identify intervals of decreased κ, which correspond to increased total sulfur content. Our approach is a rapid, high-resolution method that can identify overprinted κ resulting from pyritization of titanomagnetite due to H 2 S production in marine sediments. In addition, total organic carbon, total sulfur, and authigenic carbonate δ 13 C measurements indicate that both OSR and AOM can drive the observed κ loss, but AOM drives the greatest decreases in κ. Overall, our approach can enhance paleoenvironmental reconstructions and provide insight into paleo-positions of the sulfate-methane transition zone, past enhancements of OSR or paleo-methane seepage, and the role of detrital iron oxide minerals on the marine sediment sulfur sink, with consequences influencing the development of chemosynthetic biological communities at methane seeps.

Geochemistry, Geophysics, Geosystems↗
USGS2023

Comparing sediment microbial communities of Arctic beaver ponds to tundra lakes and streams

In recent decades the habitat of North American beaver ( Castor canadensis ) has expanded from boreal forests into Arctic tundra ecosystems. Beaver ponds in Arctic watersheds are known to alter stream biogeochemistry, which is likely coupled with changes in the activity and composition of microbial communities inhabiting beaver pond sediments. We investigated bacterial, archaeal, and fungal communities in beaver pond sediments along tundra streams in northwestern Alaska (AK), USA and compared them to those of tundra lakes and streams in north-central Alaska that are unimpacted by beavers. β -glucosidase activity assays indicated higher cellulose degradation potential in beaver ponds than in unimpacted streams and lakes within a watershed absent of beavers. Beta diversity analyses showed that dominant lineages of bacteria and archaea in beaver ponds differed from those in tundra lakes and streams, but dominant fungal lineages did not differ between these sample types. Beaver pond sediments displayed lower relative abundances of Crenarchaeota and Euryarchaeota archaea and of bacteria from typically anaerobic taxonomic groups, suggesting differences in rates of fermentative organic matter (OM) breakdown, syntrophy, and methane generation. Beaver ponds also displayed low relative abundances of Chytridiomycota (putative non-symbiotic) fungi and high relative abundances of ectomycorrhizal (plant symbionts) Basidiomycota fungi, suggesting differences in the occurrence of plant and fungi mutualistic interactions. Beaver ponds also featured microbes with taxonomic identities typically associated with the cycling of nitrogen and sulfur compounds in higher relative abundances than tundra lakes and streams. These findings help clarify the microbiological implications of beavers expanding into high latitude regions.

Alaska↗
USGS2024

Subsurface redox interactions regulate ebullitive methane flux in heterogeneous Mississippi River deltaic wetland

As interfaces connecting terrestrial and ocean ecosystems, coastal wetlands develop temporally and spatially complex redox conditions, which drive uncertainties in greenhouse gas emission as well as the total carbon budget of the coastal ecosystem. To evaluate the role of complex redox reactions in methane emission from coastal wetlands, a coupled reactive-transport model was configured to represent subsurface biogeochemical cycles of carbon, nitrogen, and sulfur, along with production and transport of multiple gas species through diffusion and ebullition. This model study was conducted at multiple sites along a salinity gradient in the Barataria Basin at the Mississippi River Deltaic Plain. Over a freshwater to saline gradient, simulated total flux of methane was primarily controlled by its subsurface production and consumption, which were determined by redox reactions directly (e.g., methanogenesis, methanotrophy) and indirectly (e.g., competition with sulfate reduction) under aerobic and/or anaerobic conditions. At fine spatiotemporal scales, surface methane fluxes were also strongly dependent on transport processes, with episodic ebullitive fluxes leading to higher spatial and temporal variability compared to the gradient-driven diffusion flux. Ebullitive methane fluxes were determined by methane fraction in total ebullitive gas and the frequency of ebullitive events, both of which varied with subsurface methane concentrations and other gas species. Although ebullition thresholds are constrained by local physical factors, this study indicates that redox interactions not only determine gas composition in ebullitive fluxes but can also regulate ebullition frequency through gas production.

Journal of Advances in Modeling Earth Systems↗
USGS2025

Organic matter availability and the production of methane-derived dissolved organic carbon at methane seeps

Methane seeps located along continental margins and slopes export sedimentary methane and dissolved organic carbon (DOC) into the ocean. The flux of these reduced carbon molecules from the seafloor into the ocean impacts ocean chemistry and supports deep-sea life. While significant effort has been made to understand how the anaerobic oxidation of methane (AOM) regulates the release of methane from the seafloor, little is known about the production of DOC in association with AOM or its flux and fate in the ocean. We hypothesize a mechanism for methane incorporation into DOC at seeps and investigate the relationship between sediment total organic carbon (TOC) availability and the incorporation of methane-derived carbon into DOC at four methane seep regions along the Cascadia margin, with a range of microbial and thermogenic methane sources. At sites with <2.0 wt.% TOC (Hydrate Ridge and Bullseye Vent), up to 60%–80% of carbon in DOC is methane-carbon, much more than sites with >2.0 wt.% TOC (Astoria Canyon and Barkley Canyon). We attribute the greater methane contribution at the more TOC-limited sites to a greater role of AOM in the carbon cycle, whereas at the organic matter-rich sites, microbial competition for sulfate as an electron acceptor for organic matter decomposition limits AOM and hence the transfer of carbon from methane to DOC. We estimate that the global diffusive flux of methane-derived DOC from the seafloor is 0.07–10.1 Tg C/yr, contributing to the stock of DOC present in the deep ocean and/or fueling the deep-sea microbial loop.

California, Oregon, Washington↗
USGS2010

Long-term frozen storage of stream water samples for dissolved orthophosphate, nitrate plus nitrite, and ammonia analysis

Many researchers have used freezing as an effective, short-term, water sample preservation method for subsequent nutrient analysis. In this study, filtered samples held at −16±2°C for 4–8 years were reanalyzed for orthophosphate, nitrate plus nitrite, and ammonia. Orthophosphate and ammonia concentrations decreased by 0.2 μg P/L and 5 μg N/L, respectively, at mean concentrations of 69.4 μg P/L and 246 μg N/L. Nitrate plus nitrite increased by 1.1 μg N/L at a mean concentration of 139.1 μg N/L. An anaerobic well sample proved to be unsuitable for freezing because it lost significant amounts of orthophosphate during the freezing process. None of the differences observed over long periods of frozen storage were more than twice the estimated standard deviation of the analytical methods used in the study. The small changes observed demonstrate the effectiveness of frozen storage as a means of nutrient preservation in water samples that are unaffected by the freezing process itself.

Water Resources Research↗
USGS2010

Chemical evolution of groundwater near a sinkhole lake, northern Florida: 2. Chemical patterns, mass-transfer modeling, and rates of chemical reactions

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO 2 ), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13 C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO 2 reduction pathway based on the isotopic composition of hydrogen (δ 2 H(CH 4 ) = −186 to −234‰) and carbon (δ 13 C(CH 4 ) = −65.7 to −72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L −1 yr −1 for groundwater downgradient from the lake.

Water Resources Research↗