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At least 847 records · Page 47Linked to original sources

USGS2022

Increasing the uptake of ecological model results in policy decisions to improve biodiversity outcomes

Models help decision-makers anticipate the consequences of policies for ecosystems and people; for instance, improving our ability to represent interactions between human activities and ecological systems is essential to identify pathways to meet the 2030 Sustainable Development Goals. However, use of modeling outputs in decision-making remains uncommon. We share insights from a multidisciplinary National Socio-Environmental Synthesis Center working group on technical, communication, and process-related factors that facilitate or hamper uptake of model results. We emphasize that it is not simply technical model improvements, but active and iterative stakeholder involvement that can lead to more impactful outcomes. In particular, trust- and relationship-building with decision-makers are key for knowledge-based decision making. In this respect, nurturing knowledge exchange on the interpersonal (e.g., through participatory processes), and institutional level (e.g., through science-policy interfaces across scales), represent promising approaches. To this end, we offer a generalized approach for linking modeling and decision-making.

Environmental Modelling & Software↗

USGS2024

An open-source workflow for scaling burn severity metrics from drone to satellite to support post-fire watershed management

Wildfires are increasing in size and severity across much of the western United States, exposing vulnerable wildland-urban interfaces to post-fire hazards. The Mediterranean chaparral region of Northern California contains many high sloping watersheds prone to hazardous post-fire flood events and identifying watersheds at high risk of soil loss and debris flows is a priority for post-fire response and management. Uncrewed Aerial Systems (UAS; aka drones) offer post-fire management teams the ability to quickly mobilize and survey burned areas with very high-resolution imagery (∼1 cm), facilitating emergency management and post-fire hazard assessment. However, adoption of this technology by hazard response teams may be hindered by complicated workflows for UAS data acquisition, image processing and analysis. We present an open-source workflow using mature Geographic Information Systems (GIS) software and Python packages in a Jupyter Notebook environment that guides users through classification of true-color UAS imagery to generate high resolution burn severity maps which can then be scaled across larger watersheds using Sentinel-2 normalized burn ratio (NBR) images. Soil burn severity classifications using a weighted brightness (WB) image and Char Index (CI) generated from UAS imagery were validated with in-situ data and random stratified points, resulting in the CI having the highest overall accuracy of 87.5%. CI also displayed a marginally stronger relationship over the WB with the post-fire Sentinel-2 NBR, R 2 = 0.79 and R 2 = 0.78 respectively. Our methods offer the unique opportunity to standardize GIS workflows, promoting replication through transparency, while improving the user's understanding of scientific GIS functionality.

California↗

USGS2024

The US COVID-19 and Influenza Scenario Modeling Hubs: Delivering long-term projections to guide policy

Between December 2020 and April 2023, the COVID-19 Scenario Modeling Hub (SMH) generated operational multi-month projections of COVID-19 burden in the US to guide pandemic planning and decision-making in the context of high uncertainty. This effort was born out of an attempt to coordinate, synthesize and effectively use the unprecedented amount of predictive modeling that emerged throughout the COVID-19 pandemic. Here we describe the history of this massive collective research effort, the process of convening and maintaining an open modeling hub active over multiple years, and attempt to provide a blueprint for future efforts. We detail the process of generating 17 rounds of scenarios and projections at different stages of the COVID-19 pandemic, and disseminating results to the public health community and lay public. We also highlight how SMH was expanded to generate influenza projections during the 2022–23 season. We identify key impacts of SMH results on public health and draw lessons to improve future collaborative modeling efforts, research on scenario projections, and the interface between models and policy.

Epidemics↗

USGS2016

Insights into methane dynamics from analysis of authigenic carbonates and chemosynthetic mussels at newly-discovered Atlantic Margin seeps

The recent discovery of active methane venting along the US northern and mid-Atlantic margin represents a new source of global methane not previously accounted for in carbon budgets from this region. However, uncertainty remains as to the origin and history of methane seepage along this tectonically inactive passive margin. Here we present the first isotopic analyses of authigenic carbonates and methanotrophic deep-sea mussels, Bathymodiolus sp., and the first direct constraints on the timing of past methane emission, based on samples collected at the upper slope Baltimore Canyon (&sim;385 m water depth) and deepwater Norfolk (&sim;1600 m) seep fields within the area of newly-discovered venting. The authigenic carbonates at both sites were dominated by aragonite, with an average signature of −47&permil; , a value consistent with microbially driven anaerobic oxidation of methane-rich fluids occurring at or near the sediment–water interface. Authigenic carbonate U and Sr isotope data further support the inference of carbonate precipitation from seawater-derived fluids rather than from formation fluids from deep aquifers. Carbonate stable and radiocarbon ( and ) isotope values from living Bathymodiolus sp. specimens are lighter than those of seawater dissolved inorganic carbon, highlighting the influence of fossil carbon from methane on carbonate precipitation. U–Th dates on authigenic carbonates suggest seepage at Baltimore Canyon between 14.7±0.6 ka to 15.7±1.6 ka , and at the Norfolk seep field between 1.0±0.7 ka to 3.3±1.3 ka , providing constraint on the longevity of methane efflux at these sites. The age of the brecciated authigenic carbonates and the occurrence of pockmarks at the Baltimore Canyon upper slope could suggest a link between sediment delivery during Pleistocene sea-level lowstand, accumulation of pore fluid overpressure from sediment compaction, and release of overpressure through subsequent venting. Calculations show that the Baltimore Canyon site probably has not been within the gas hydrate stability zone (GHSZ) in the past 20 ka, meaning that in-situ release of methane from dissociating gas hydrate cannot be sustaining the seep. We cannot rule out updip migration of methane from dissociation of gas hydrate that occurs farther down the slope as a source of the venting at Baltimore Canyon, but consider that the history of rapid sediment accumulation and overpressure may play a more important role in methane emissions at this site.

Baltimore Canyon seep fields, Norfolk seep fields↗

USGS2017

Evidence for strong lateral seismic velocity variation in the lower crust and upper mantle beneath the California margin

Regional seismograms from earthquakes in Northern California show a systematic difference in arrival times across Southern California where long period (30–50 seconds) SH waves arrive up to 15 seconds earlier at stations near the coast compared with sites towards the east at similar epicentral distances. We attribute this time difference to heterogeneity of the velocity structure at the crust-mantle interface beneath the California margin. To model these observations, we propose a fast seismic layer, with thickness growing westward from the San Andreas along with a thicker and slower continental crust to the east. Synthetics generated from such a model are able to match the observed timing of SH waveforms better than existing 3D models. The presence of a strong upper mantle buttressed against a weaker crust has a major influence in how the boundary between the Pacific plate and North American plate deforms and may explain the observed asymmetric strain rate across the boundary.

California↗

USGS2018

Stress rotation across the Cascadia megathrust requires a weak subduction plate boundary at seismogenic depths

The Mendocino Triple Junction region is the most seismically active part of the Cascadia Subduction Zone. The northward moving Pacific plate collides with the subducting Gorda plate causing intense internal deformation within it. Here we show that the stress field rotates rapidly with depth across the thrust interface from a strike-slip regime within the subducting plate, reflecting the Pacific plate collision, to a thrust regime in the overriding plate. We utilize a dense focal mechanism dataset, including observations from the Cascadia Initiative ocean bottom seismograph experiment, to constrain the stress orientations. To quantify the implications of this rotation for the strength of the plate boundary, we designed an inversion that solves for the absolute stress tensors in a three-layer model subject to assumptions about the strength of the subducting mantle. Our results indicate that the shear stress on the plate boundary fault is likely no more than about ∼50 MPa at ∼20 km depth. Regardless of the assumed mantle strength, we infer a relatively weak megathrust fault with an effective friction coefficient of ∼0 to 0.2 at seismogenic depths. Such a low value for the effective friction coefficient requires a combination of high fluid pressures and/or fault-zone minerals with low inherent friction in the region where a great earthquake is expected in Cascadia.

California↗

USGS2019

Seismic velocity structure across the 2013 Craig, Alaska rupture from aftershock tomography: Implications for seismogenic conditions

The 2013 Craig, Alaska M W 7.5 earthquake ruptured along ∼150 km of the Queen Charlotte Fault (QCF), a right-lateral strike-slip plate boundary fault separating the Pacific and North American plates. Regional shear wave analyses suggest that the Craig earthquake rupturepropagated in the northward direction faster than the S-wave (supershear). Theoretical studies suggest that a bimaterial interface, such as that along the QCF, which separates oceanic and continental crust with differing elastic properties, can promote supershear rupture propagation. We deployed short-period ocean-bottom seismometers (OBS) as a part of a rapid-response effort less than four months after the Craig earthquake mainshock. During a 21-day period, 1,133 aftershocks were recorded by 8 OBS instruments. Aftershock spatial distribution indicates that the base of the seismogenic zone along the QCF approaches ∼25 km depth, consistent with a thermally-controlled fault rheology expected for igneous rocks at oceanic transform faults. The spatial distribution also provides supporting evidence for a previously hypothesized active strand of the QCF system within the Pacific Plate. Tomographic traveltime inversion for velocity structure indicates a low-velocity (V P and V S ) zone on the Pacific side of the plate boundary at 5–20 km depths, where NeogenePacific crust and upper mantle seismic velocities average ∼3–11% slower than the North American side, where the Paleozoic North American crust is seismically faster. Our results suggest that elastic properties along the studied portion of the QCF are different than those of a simple oceanic–continental plate boundary fault. In our study region, velocity structure across the QCF, while bimaterial, does not support faster material on the west side of the fault, which has been proposed as one possible explanation for northward supershear propagation during the Craig earthquake. Instead, we image low-velocity material on the west side of the fault. Explanations could include that part of the rupture was subshear, or that fault damage zone properties or fault smoothness are more important controls on supershear rupture than a bimaterial contrast.

Alaska↗

USGS2026

In vitro assessment of human alveolar epithelial responses to acute combined exposure to volcanic ash and sulphur dioxide gas

Volcanic activity releases sulphur dioxide (SO₂) gas and fine particulate matter that may degrade air quality in populated areas, yet the effects of combined exposure remain insufficiently characterised. We examined the biological effects of acute combined exposure to volcanic ash and SO₂ in human alveolar epithelial cells (A549) maintained at the air-liquid interface. Cells were exposed to respirable ash from the 2021 Tajogaite eruption (La Palma; 100 µg/cm²) and SO₂ gas (nominal concentration 50 ppm; 1, 2, or 3 h), separately or sequentially. Cellular outcomes evaluated after exposure included cytotoxicity, pro-inflammatory and redox responses. Tajogaite ash alone had limited effects on cells, while exposure to SO 2 altered inflammatory responses (increasing gene transcription while reducing extracellular cytokine levels). Co-exposure responses were largely comparable to SO₂ alone, with no statistically significant evidence of synergistic effects under the conditions tested. These findings highlight the importance of considering gas-phase exposures in volcanic environments.

Canary Islands, La Palma, Tajogaite volcano↗

USGS2011

Comparing the role of fuel breaks across southern California national forests

Fuel treatment of wildland vegetation is the primary approach advocated for mitigating fire risk at the wildland–urban interface (WUI), but little systematic research has been conducted to understand what role fuel treatments play in controlling large fires, which factors influence this role, or how the role of fuel treatments may vary over space and time. We assembled a spatial database of fuel breaks and fires from the last 30 years in four southern California national forests to better understand which factors are consistently important for fuel breaks in the control of large fires. We also explored which landscape features influence where fires and fuel breaks are most likely to intersect. The relative importance of significant factors explaining fuel break outcome and number of fire and fuel break intersections varied among the forests, which reflects high levels of regional landscape diversity. Nevertheless, several factors were consistently important across all the forests. In general, fuel breaks played an important role in controlling large fires only when they facilitated fire management, primarily by providing access for firefighting activities. Fire weather and fuel break maintenance were also consistently important. Models and maps predicting where fuel breaks and fires are most likely to intersect performed well in the regions where the models were developed, but these models did not extend well to other regions, reflecting how the environmental controls of fire regimes vary even within a single ecoregion. Nevertheless, similar mapping methods could be adopted in different landscapes to help with strategic location of fuel breaks. Strategic location of fuel breaks should also account for access points near communities, where fire protection is most important.

California↗

USGS2025

Wildfire risk information sources and the acceptability of fuels treatments near select WUI communities in the Western United States

Fuels treatments intended to reduce fuel loads and improve forest health on public lands offer one way to reduce wildfire hazards in the wildland-urban interface (WUI), where the natural and built environments meet. However, for fuels treatment implementation to be successful, it must comply with regulatory and scientific standards and be supported by local communities, as lack of acceptance can lead to alterations, delays, or abandonment. To foster support, public land managers can engage directly with residents in communities near treatment areas through various communication channels or engage indirectly through trusted local partners. This research uses paired household survey and observed parcel-level wildfire risk assessment data to investigate wildfire risk information sources' role in the acceptability of fuels treatment approaches on public lands near select WUI communities in the Western United States. We find that information deemed useful from sources is often positively correlated with acceptability, while information deemed not useful is sometimes negatively correlated. Local sources of information tend to be widely received, perceived as useful, and have positive correlations with acceptability, while nonlocal sources vary in their receipt, perceived usefulness, and correlations with acceptability. Public land managers, particularly those from national organizations, may benefit from leveraging and aligning messaging with trusted local partners. Developing fuels treatment plans that consider existing local sentiments may facilitate public trust in managers and acceptability of treatments.

Colorado, New Mexico, Oregon, Washington, Wyoming↗

USGS2004

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10 −8 to 1 · 10 −5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999–2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca 2+ , Mg 2+ , HCO 3 − , SO 4 2− , H 4 SiO 4 , and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.

Geochimica et Cosmochimica Acta↗

USGS2005

ATR-FTIR spectroscopic characterization of coexisting carbonate surface complexes on hematite

The speciation of carbonate adsorbed to hematite in air-equilibrated aqueous solutions has been studied using ATR-FTIR spectroscopy. Samples were measured over a range of pH conditions, at 0.1 M NaCl and at low ionic strength, and in H2O and D2O solutions to permit a multispecies analysis of the data. Second-derivative analyses and fits to the spectra indicate the presence of two major and two minor surface-bound carbonate species. The two major complexes coexist at near-neutral pH and low ionic strength. One of these two complexes is relatively sensitive to ionic strength, being displaced at 0.1 M NaCl, whereas the other is not. Comparison of experimental to DFT/MO-calculated frequencies suggest these two major species to be (a) a monodentate binuclear inner-sphere carbonate surface complex, and (b) a fully or partially solvated carbonate (CO32-) species that is symmetry broken and appears to reside in the structured vicinal water layers at the hematite-water interface, retained by hydrogen bonding and/or other forces. Minor carbonate complexes include diffuse layer CO32- and an unidentified inner-sphere species. Both of the dominant species observed here are likely to be significant controls of the surface charge and sorptive properties of Fe-oxides. Copyright ?? 2005 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

USGS2007

Insights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA

This study examined the removal of U, Mo, and Re from seawater by sedimentary processes at a shallow-water site with near-saturation bottom water O 2 levels (240–380 μmol O 2 /L), very high organic matter oxidation rates (annually averaged rate is 880 μmol C/cm 2 /y), and shallow oxygen penetration depths (4 mm or less throughout the year). Under these conditions, U, Mo, and Re were removed rapidly to asymptotic pore water concentrations of 2.2–3.3 nmol/kg (U), 7–13 nmol/kg (Mo), and 11–14 pmol/kg (Re). The depth order in which the three metals were removed, determined by fitting a diffusion-reaction model to measured profiles, was Re < U < Mo. Model fits also suggest that the Mo profiles clearly showed the presence of a near-interface layer in which Mo was added to pore waters by remineralization of a solid phase. The importance of this solid phase source of pore water Mo increased from January to October as the organic matter oxidation rate increased, bottom water O 2 decreased, and the O 2 penetration depth decreased. Experiments with in situ benthic flux chambers generally showed fluxes of U and Mo into the sediments. However, when the overlying water O 2 concentration in the chambers was allowed to drop to very low levels, Mn and Fe were released to the overlying water along with the simultaneous release of Mo and U. These experiments suggest that remineralization of Mn and/or Fe oxides may be a source of Mo and perhaps U to pore waters, and may complicate the accumulation of U and Mo in bioturbated sediments with high organic matter oxidation rates and shallow O 2 penetration depths. Benthic chamber experiments including the nonreactive solute tracer, Br − , indicated that sediment irrigation was very important to solute exchange at the study site. The enhancement of sediment–seawater exchange due to irrigation was determined for the nonreactive tracer (Br − ), TCO 2 , NH 4 + "> NH 4 + , U and Mo. The comparisons between these solutes showed that reactions within and around the burrows were very important for modulating the Mo flux, but less important for U. The effect of these reactions on Mo exchange was highly variable, enhancing Mo (and, to a lesser extent, U) uptake at times of relatively modest irrigation, but inhibiting exchange when irrigation rates were faster. These results reinforce the observation that Mo can be released to and removed from pore waters via sedimentary reactions. The removal rate of U and Mo from seawater by sedimentary reactions was found to agree with the rate of accumulation of authigenic U and Mo in the solid phase. The fluxes of U and Mo determined by in situ benthic flux chamber measurements were the largest that have been measured to date. These results confirm that removal of redox-sensitive metals from continental margin sediments underlying oxic bottom water is important, and suggest that continental margin sediments play a key role in the marine budgets of these metals.

Geochimica et Cosmochimica Acta↗

USGS2009

Copper isotope fractionation in acid mine drainage

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ 65 Cu values (based on 65 Cu/ 63 Cu) of enargite (δ 65 Cu = −0.01 ± 0.10‰; 2 σ ) and chalcopyrite (δ 65 Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ 65 Cu < 1‰). These mineral samples show lower δ 65 Cu values than stream waters (1.38‰ ⩽ δ 65 Cu ⩽ 1.69‰). The average isotopic fractionation (Δ aq-min = δ 65 Cu aq − δ 65 Cu min , where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in 65 Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite ( Δ aq-min o = - 0.57 ± 0.14 ‰ ">‰ Δaq-mino=-0.57±0.14‰ , where min o refers to the starting mineral) and no apparent fractionation for enargite ( Δ aq-min o = 0.14 ± 0.14 ‰ ">‰ Δaq-mino=0.14±0.14‰ ). Abiotic fractionation is attributed to preferential oxidation of 65 Cu + at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of 65 Cu aq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ 65 Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.

Geochimica et Cosmochimica Acta↗

USGS2010

Influence of sea level rise on iron diagenesis in an east Florida subterranean estuary

Subterranean estuary occupies the transition zone between hypoxic fresh groundwater and oxic seawater, and between terrestrial and marine sediment deposits. Consequently, we hypothesize, in a subterranean estuary, biogeochemical reactions of Fe respond to submarine groundwater discharge (SGD) and sea level rise. Porewater and sediment samples were collected across a 30-m wide freshwater discharge zone of the Indian River Lagoon (Florida, USA) subterranean estuary, and at a site 250 m offshore. Porewater Fe concentrations range from 0.5 μM at the shoreline and 250 m offshore to about 286 μM at the freshwater–saltwater boundary. Sediment sulfur and porewater sulfide maxima occur in near-surface OC-rich black sediments of marine origin, and dissolved Fe maxima occur in underlying OC-poor orange sediments of terrestrial origin. Freshwater SGD flow rates decrease offshore from around 1 to 0.1 cm/day, while bioirrigation exchange deepens with distance from about 10 cm at the shoreline to about 40 cm at the freshwater–saltwater boundary. DOC concentrations increase from around 75 μM at the shoreline to as much as 700 μM at the freshwater–saltwater boundary as a result of labile marine carbon inputs from marine SGD. This labile DOC reduces Fe-oxides, which in conjunction with slow discharge of SGD at the boundary, allows dissolved Fe to accumulate. Upward advection of fresh SGD carries dissolved Fe from the Fe-oxide reduction zone to the sulfate reduction zone, where dissolved Fe precipitates as Fe-sulfides. Saturation models of Fe-sulfides indicate some fractions of these Fe-sulfides get dissolved near the sediment–water interface, where bioirrigation exchanges oxic surface water. The estimated dissolved Fe flux is approximately 0.84 μM Fe/day per meter of shoreline to lagoon surface waters. Accelerated sea level rise predictions are thus likely to increase the Fe flux to surface waters and local primary productivity, particularly along coastlines where groundwater discharges through sediments.

Geochimica et Cosmochimica Acta↗

USGS2013

Anaerobic methane oxidation in low-organic content methane seep sediments

Sulfate-dependent anaerobic oxidation of methane (AOM) is the key sedimentary microbial process limiting methane emissions from marine sediments and methane seeps. In this study, we investigate how the presence of low-organic content sediment influences the capacity and efficiency of AOM at Bullseye vent, a gas hydrate-bearing cold seep offshore of Vancouver Island, Canada. The upper 8 m of sediment contains < 0.4 wt% total organic carbon (OC) and primarily consists of glacially-derived material that was deposited 14,900 to 15,900 yrs BP during the retreat of the late Quaternary Cordilleran Ice Sheet. We hypothesize this aged and exceptionally low-OC content sedimentary OM is biologically refractory, thereby limiting degradation of non-methane OM by sulfate reduction and maximizing methane consumption by sulfate-dependent AOM. A radiocarbon-based dissolved inorganic carbon (DIC) isotope mass balance model demonstrates that respired DIC in sediment pore fluids is derived from a fossil carbon source that is devoid of 14 C. A fossil origin for the DIC precludes remineralization of non-fossil OM present within the sulfate zone as a significant contributor to pore water DIC, suggesting that nearly all sulfate is available for anaerobic oxidation of fossil seep methane. Methane flux from the SMT to the sediment water interface in a diffusion-dominated flux region of Bullseye vent was, on average, 96% less than at an OM-rich seep in the Gulf of Mexico with a similar methane flux regime. Evidence for enhanced methane oxidation capacity within OM-poor sediments has implications for assessing how climate-sensitive reservoirs of sedimentary methane (e.g., gas hydrate) will respond to ocean warming, particularly along glacially-influenced mid and high latitude continental margins.

Geochimica et Cosmochimica Acta↗

USGS2015

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13 C and 18 O isotopes bound to each other within carbonate minerals in 13 C 18 O 16 O 2 2- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13 C- 18 O bond ordering (Δ 47 ) and δ 18 O of CO 3 2- and HCO 3 - molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13 C- 18 O bond abundances and δ 18 O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ 47 and δ 18 O compositions of CO 3 2- and HCO 3- ions are significantly different from each other. Experiments constrain the Δ 47- δ 18 O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ 47- δ 18 O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ 47 and δ 18 O are intermediate between HCO 3 − and CO 3 2− . We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ 47 and δ 18 O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ 18 O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO 3 − ) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO 3 - dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Geochimica et Cosmochimica Acta↗

USGS2020

Sulfur isotope composition of individual compounds in immature organic-rich rocks and possible geochemical implications

We applied compound-specific sulfur isotope analysis (CSSIA) to organic matter (OM) extracted from ancient and immature organic-rich rocks from the Cretaceous Ghareb (Shefela Basin locality, Israel) and Miocene Monterey (Naples Beach locality, California, USA) Formations. Large variations in the δ 34 S values of different organosulfur compounds (OSCs), that reach up to 28‰ and 36‰, were observed in the Ghareb and Monterey samples, respectively. Additionally, some common OSCs in both locations showed consistent 34 S trends relative to each other. The consistent enrichment in 34 S of C 35 hopane thiophene relative to iC 20 thiophene in the studied sections probably resulted from differences in the timing of OM sulfurization. Reactive organic precursors quickly consume the most 34 S-depleted reduced S, while less reactive species incorporate the heavier residual S at a later time. Despite the differences in the depositional environments, ages, and the initial δ 34 S values of the reduced S (represented by the δ 34 S of pyrite) between the Ghareb and the Monterey Formations, the sulfurization order of common organic compounds seems to be similar. All of the δ 34 S values of OSCs are 34 S enriched relative to that of the coexisting pyrite with the exception of the C 25 highly branched isoprenoid (HBI) thiophene in several samples from the Monterey Formation. The existence of 34 S-depleted sulfurized HBI may point to OM sulfurization that occurred at or near the sediment-water interface during the deposition of the Monterey. Moreover, the δ 34 S of steroid sulfides shows an inverse trend with the pristane/phytane ratio, which may indicate that the sulfurization mechanism of these OSCs are affected by redox conditions. Further investigation of CSSI values in immature rocks from other basins may help constrain the OM sulfurization process, timescale, and depositional conditions and their possible use as paleoenvironmental proxies.

California↗