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USGS2019

Kinetics of elemental sulfur reduction by petroleum hydrocarbons and the implications for hydrocarbon thermal chemical alteration

Although sulfur-containing compounds are known to play a significant role in the diagenic and catagenic processes that generate oil and gas, relatively little is known about the kinetics of reactions between elemental S and petroleum hydrocarbons. To investigate this subject, a series of closed-system pyrolysis experiments using paraffin, a low-sulfur oil, and a high-sulfur oil with and without elemental S were conducted, and first-order chemical kinetics were fit to the experimental results. The average value for the activation energy required to reduce elemental S to H 2 S and to thermochemically alter higher molecular weight hydrocarbons to methane was calculated to be 193 kJ mol -1 (46 kcal mol -1 ). The results of this study demonstrate that under typical geologic conditions the rate of reduction of elemental S to H 2 S by petroleum hydrocarbons is quite rapid. The maximum time for substantial amounts of elemental S to persist in contact with petroleum hydrocarbons is estimated to be no more than a few million years in cool reservoirs (e.g., <80 °C), and in hotter reservoirs (e.g., >120 °C) the half-life of elemental S may be as short as hundreds of years. Additionally, the presence of elemental S substantially lowers the onset temperature of hydrocarbon thermal chemical alteration (TCA). The activation energy for TCA of a low-sulfur oil to generate methane is estimated to be lowered by 92 kJ mol -1 (22 kcal mol -1 ) due to the presence of elemental sulfur. Consequently, the presence of elemental S in petroleum reservoirs is expected to lower the thermal stability of oil and decrease the maximum depth at which oil occurs within a basin (thermal deadline). The observed acceleration of hydrocarbon TCA is possibly due to organic sulfur compounds (e.g., thiols and sulfides) that form through the reaction of H 2 S or polysulfides with hydrocarbons and subsequently thermally degrade leading to the formation of sulfur radicals that in turn enhance TCA reactions.

Geochimica et Cosmochimica Acta↗

USGS2019

Temperature-dependent variations in mineralogy, major element chemistry and the stable isotopes of boron, lithium and chlorine resulting from hydration of rhyolite glass: Constraints from hydrothermal experiments at 150 to 350°C and 25 MPa

Rhyolite-hosted hydrothermal systems in the continental crust contain valuable energy and mineral resources that make them of special interest across several scientific disciplines. Despite extensive research on these systems, the temperature-dependence of chemical reactions between host rocks and aqueous-rich fluids and the mineralogical transformations resulting from these reactions are not well quantified. To expand our understanding of the controlling processes operating in these systems, we carried out seven laboratory experiments in which rhyolite was reacted with deionized water at 150 °C to 350 °C and 25 MPa. An additional experiment at 200 °C was carried out to examine the effect of dissolved CO 2 on the reactions. The overarching goal of this experimental study was to provide new insights on the temperature-dependence of water-rock interaction in continental hydrothermal systems. We applied a wide range of chemical, isotopic and mineralogical methods to analyze the reacted rhyolite and waters, and the major observations are: (1) the rhyolite progressively hydrates with increasing temperature between 150 °C to a maximum of 8.2 wt% H 2 O at 275 °C; hydration then decreases until 350 °C in conjunction with the destruction of the rhyolite glass and crystallization of secondary mineral phases; (2) the ratio of molecular water (H 2 O m ) to hydroxyl (OH − ) of the water that is dissolved in the reacted rhyolite decreases from ∼7 at 150 °C to ∼4 at 250 °C; (3) the main secondary minerals formed are the zeolite ferrierite (T ≥ 275 °C); biotite, albite and cristobalite mainly form at higher experimental temperatures (T ≥ 300 °C); (4) the reacted waters are nearly saturated with respect to amorphous silica; (5) at temperatures ≥ 275 °C nearly all the chlorine is leached into solution; (6) fluorine leaching from the rhyolite gradually increases between 150 °C and 250 °C, but then gradually decreases at higher temperatures and is incorporated into a secondary mineral phase; (7) dissolved CO 2 in the water enhances alkali metal cation leaching from the rhyolite; and (8) calculated Na-K and silica geothermometer temperatures differ from the experimental temperatures by varying amounts. In addition, apart from some small lithium isotope fractionation at temperatures ≤ 250 °C, the stable isotopes of boron, lithium and chlorine do not fractionate during rhyolite-water reactions, and the stable isotope compositions of these species in the reacted water are similar to those in the reactant rhyolite. These results provide new insights for a broad range of applications, including quantifying processes involving rhyolite glass hydration (obsidian hydration dating, perlite formation and discriminating secondary from magmatic water in rhyolitic matrix-glass of volcanic pyroclasts), for geothermal energy and mineral deposit exploration and for monitoring volcanoes.

Geochimica et Cosmochimica Acta↗

USGS2017

Projected atoll shoreline and run-up changes in response to sea-level rise and varying large wave conditions at Wake and Midway Atolls, Northwestern Hawaiian Islands

Atoll islands are dynamic features that respond to seasonal alterations in wave conditions and sea level. It is unclear how shoreline wave run-up and erosion patterns along these low elevation islands will respond to projected sea-level rise (SLR) and changes in wave climate over the next century, hindering communities' preparation for the future. To elucidate how these processes may respond to climate change, extreme boreal winter and summer wave conditions under future sea-level rise (SLR) and wave climate scenarios were simulated at two atolls, Wake and Midway, using a shallow-water hydrodynamic model. Nearshore wave conditions were used to compute the potential longshore sediment flux along island shorelines via the CERC empirical formula and wave-driven erosion was calculated as the divergence of the longshore drift; run-up and the locations where the run-up exceed the berm elevation were also determined. SLR is projected to predominantly drive future island morphological change and flooding. Seaward shorelines (i.e., ocean fronted shorelines directly facing incident wave energy) were projected to experience greater erosion and flooding with SLR and in hypothetical scenarios where changes to deep water wave directions were altered, as informed by previous climate change forced Pacific wave modeling efforts. These changes caused nearshore waves to become more shore-normal, increasing wave attack along previously protected shorelines. With SLR, leeward shorelines (i.e., an ocean facing shoreline but sheltered from incident wave energy) became more accretive on windward islands and marginally more erosive along leeward islands. These shorelines became more accretionary and subject to more flooding with nearshore waves becoming more shore-normal. Lagoon shorelines demonstrated the greatest SLR-driven increase in erosion and run-up. They exhibited the greatest relative change with increasing wave heights where both erosion and run-up magnitudes increased. Wider reef flat-fronted seaward shorelines became more accretive as all oceanographic forcing parameters increased in magnitude and exhibited large run-up increases following increasing wave heights. Island end shorelines became subject to increased flooding, erosion at Wake, and accretion at Midway with SLR. Under future conditions, windward and leeward islands are projected to become thinner as ocean facing and lagoonal shorelines erode, with leeward islands becoming more elongate. Island shorelines will change dramatically over the next century as SLR and altered wave climates drive new erosional regimes. It is vital to the sustainability of island communities that the relative magnitudes of these effects are addressed when planning for projected future climates.

Midway Atoll, Wake Atoll↗

USGS2021

The impacts of the 2015/2016 El Niño on California's sandy beaches

The El Niño Southern Oscillation is the most dominant mode of interannual climate variability in the Pacific. The 2015/2016 El Niño event was one of the strongest of the last 145 years, resulting in anomalously high wave energy across the U.S. West Coast, and record coastal erosion for many California beaches. To better manage coastal resources, it is critical to understand the impacts of both short-term climate variability and long-term climate impacts across the varied coastal settings of California. This study is the first to quantify the coastal response for one of the strongest El Niño events in the historical record across the coast of California through the analysis of nearshore wave conditions and seasonal beach changes for 8000 shore-normal transects. Through the analysis of pre- and post- El Niño LiDAR, we find that that central and northern California experienced the most sandy beach shoreline retreat/erosion during the El Niño winter, with a mean of 45.7 m of erosion (96% of beaches) in central California, a mean of 25.5 m of erosion (89% of beaches) in northern California, and a mean of 9.7 m of erosion (79% of beaches) in southern California. These patterns are compared to LiDAR and satellite-derived long-term shoreline change rates, in which southern California and central California beaches are moderately accreting, while northern California is eroding at an average of 79 cm per year. A significant correlation is found between cumulative wave energy flux and shoreline change during the El Niño winter across the state of California. Although local beach response during the El Niño winter was highly variable, heightened erosion was observed at river mouths and on the southern side of structures impeding littoral drift, with accretion observed on the northern side of these structures. These erosional patterns, driven by a northerly wave direction anomaly, contrast those of classic El Niño events such as the 1982–.83 and 1997–98 events, where more southerly storm tracks and southerly wave directions were key factors controlling shoreline behavior, and may indicate a shift in El Niño storm patterns driven by climate change.

California↗

USGS2012

Differential melt scaling for oblique impacts on terrestrial planets

Analytical estimates of melt volumes produced by a given projectile and contained in a given impact crater are derived as a function of impact velocity, impact angle, planetary gravity, target and projectile densities, and specific internal energy of melting. Applications to impact events and impact craters on the Earth, Moon, and Mars are demonstrated and discussed. The most probable oblique impact (45°) produces &sim;1.6 times less melt volume than a vertical impact, and &sim;1.6 and 3.7 times more melt volume than impacts with 30° and 15° trajectories, respectively. The melt volume for a particular crater diameter increases with planetary gravity, so a crater on Earth should have more melt than similar-size craters on Mars and the Moon. The melt volume for a particular projectile diameter does not depend on gravity, but has a strong dependence on impact velocity, so the melt generated by a given projectile on the Moon is significantly larger than on Mars. Higher surface temperatures and geothermal gradients increase melt production, as do lower energies of melting. Collectively, the results imply thinner central melt sheets and a smaller proportion of melt particles in impact breccias on the Moon and Mars than on Earth. These effects are illustrated in a comparison of the Chicxulub crater on Earth, linked to the Cretaceous–Tertiary mass extinction, Gusev crater on Mars, where the Mars Exploration Rover Spirit landed, and Tsiolkovsky crater on the Moon. The results are comparable to those obtained from field and spacecraft observations, other analytical expressions, and hydrocode simulations.

Icarus↗

USGS2015

Enhanced understanding of ectoparasite: host trophic linkages on coral reefs through stable isotope analysis

Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids ( Gnathia marleyi ) and permanently parasitic cymothoids ( Anilocra ) . To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp ( Ancylomenes pedersoni ) for at least 1 month. Parasitic isopods had δ 13 C and δ 15 N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15 N and depleted in 13 C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ 13 C values consistent with their food source and enriched in 15 N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically.

Lameshur Bay, St. John, Virgin Islands↗

USGS2025

Reaction kinetics and accelerant effects of sulfides in early mature hydrocarbon generation using hydrous pyrolysis

Hydrocarbon generation in organic-rich sediments is influenced by the molecular organic composition and relative abundance of associated minerals. Certain mineral-derived elements act as catalysts and reaction intermediaries, facilitating early-stage hydrocarbon formation in potential source rocks. This study investigated the role of sulfur contributed from pyrite as an accelerant in thermal reaction, focusing on its effects on early maturation and consequent hydrocarbon generation from gilsonite (low-sulfur solid petroleum). Hydrous pyrolysis (HP) experiments were conducted on mixtures of gilsonite and pyrite in varying ratios (1:0.1, 1:0.5, 1:1, 1:2, and 1:10 w/w gilsonite:pyrite) at 320, 350, and 370 °C for 72 h. Untreated and thermally altered residues were analyzed using solid bitumen reflectance (BR o , %), total organic carbon (TOC) content, programmed temperature pyrolysis, scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) to evaluate the potential accelerant role of pyritic sulfur in hydrocarbon formation. The results show HP residues at 320 and 350 °C with greater pyrite concentrations had higher BR o , while reflectance values were similar in the 370 °C residues, regardless of pyrite concentration, suggesting enhanced reaction at lower thermal conditions. Increasing pyrite content systematically decreased hydrogen index (HI) values while increasing the transformation ratio (TR) and production index (PI), indicating enhanced conversion of organic matter to hydrocarbons with increasing pyrite concentrations. Gas yields increased with pyrite addition, particularly at 350 °C, confirming secondary cracking effects. However, gas production stabilized or declined at higher pyrite loadings (1:10), suggesting alternative reaction pathways such as coke formation. Our data indicate the presence of pyrite lowers the activation energy for thermal cracking, shifting peak experimental hydrocarbon generation temperatures downward by 20–30 °C, with the most pronounced accelerant effects observed at moderate pyrite concentrations (1:0.5 and 1:1). The thermodynamic framework reveals that pyrite stability is influenced by experimental conditions, with pyrrhotite formation favored in the presence of gilsonite due to reduced oxygen fugacity. Pyrite transformation to pyrrhotite, as observed through XRD, SEM-EDS, and predicted by thermodynamic data, further supports the accelerant role of S, as pyrrhotite exhibits a higher hydrogen transfer potential, promoting early oil generation. These findings highlight the importance of pyrite in modulating hydrocarbon generation pathways in organic-rich systems.

Journal of Analytical and Applied Pyrolysis↗

USGS2004

Mechanisms of electron acceptor utilization: Implications for simulating anaerobic biodegradation

Simulation of biodegradation reactions within a reactive transport framework requires information on mechanisms of terminal electron acceptor processes (TEAPs). In initial modeling efforts, TEAPs were approximated as occurring sequentially, with the highest energy-yielding electron acceptors (e.g. oxygen) consumed before those that yield less energy (e.g., sulfate). Within this framework in a steady state plume, sequential electron acceptor utilization would theoretically produce methane at an organic-rich source and Fe(II) further downgradient, resulting in a limited zone of Fe(II) and methane overlap. However, contaminant plumes often display much more extensive zones of overlapping Fe(II) and methane. The extensive overlap could be caused by several abiotic and biotic processes including vertical mixing of byproducts in long-screened monitoring wells, adsorption of Fe(II) onto aquifer solids, or microscale heterogeneity in Fe(III) concentrations. Alternatively, the overlap could be due to simultaneous utilization of terminal electron acceptors. Because biodegradation rates are controlled by TEAPs, evaluating the mechanisms of electron acceptor utilization is critical for improving prediction of contaminant mass losses due to biodegradation. Using BioRedox-MT3DMS, a three-dimensional, multi-species reactive transport code, we simulated the current configurations of a BTEX plume and TEAP zones at a petroleum- contaminated field site in Wisconsin. Simulation results suggest that BTEX mass loss due to biodegradation is greatest under oxygen-reducing conditions, with smaller but similar contributions to mass loss from biodegradation under Fe(III)-reducing, sulfate-reducing, and methanogenic conditions. Results of sensitivity calculations document that BTEX losses due to biodegradation are most sensitive to the age of the plume, while the shape of the BTEX plume is most sensitive to effective porosity and rate constants for biodegradation under Fe(III)-reducing and methanogenic conditions. Using this transport model, we had limited success in simulating overlap of redox products using reasonable ranges of parameters within a strictly sequential electron acceptor utilization framework. Simulation results indicate that overlap of redox products cannot be accurately simulated using the constructed model, suggesting either that Fe(III) reduction and methanogenesis are occurring simultaneously in the source area, or that heterogeneities in Fe(III) concentration and/or mineral type cause the observed overlap. Additional field, experimental, and modeling studies will be needed to address these questions. ?? 2004 Elsevier B.V. All rights reserved.

Journal of Contaminant Hydrology↗

USGS2024

Does the extent of glacial cover across watersheds and discharge periods affect dietary resource use of nearshore fishes in the Northern Gulf of Alaska?

Northern high-latitude glaciers impact nearshore marine ecosystems through the discharge of cold and fresh waters, including nutrients and organic matter. Fishes are important integrators of ecosystem processes and hold key positions in the transfer of energy to higher trophic positions in such systems. This study used a natural gradient in space and time, including watershed glacial cover (0–60%) of five adjacent estuaries and three sequential discharge periods (pre-peak, peak, post-peak) in the northern Gulf of Alaska (Kachemak Bay) to test whether differences in glacial cover of watersheds upstream of estuaries affect dietary resource use of nearshore fishes. Dietary resource use was assessed using stomach content and stable carbon and nitrogen isotope analyses to determine fish diet composition and trophic niche width. Crescent gunnel ( Pholis laeta ), a mostly sedentary species, was our focal species for comparisons across estuaries and discharge periods. Discharge period had a greater influence on diet composition and trophic niche width of crescent gunnels than watershed glacial coverage. Niche width of crescent gunnel was larger during the post-peak discharge period compared to pre-peak and peak periods, coincident with a shift in prey spectrum. However, watershed glacial cover was not a suitable predictor of niche width of crescent gunnel. Trophic resource use was also considered along this glacial cover gradient for two other fish species, Pacific staghorn sculpin ( Leptocottus armatus ) and starry flounder ( Platichthys stellatus ), but within the post-peak discharge period only. These species exploited a larger prey base compared to crescent gunnel, likely due to their greater mobility. Similar to crescent gunnel, there were no relationships in trophic niche width associated with watershed glacial coverage for these other species during the post-peak discharge period. Instead, trophic resource use of these three nearshore fish species was influenced by a more complex set of dynamic environmental variables (salinity, temperature, turbidity, and discharge), as well as static watershed characteristics, especially vegetation cover. Such drivers can act through changes in metabolic rates, modulating foraging strategies and trophic connectivity, as well as terrestrial nutrient delivery to support estuarine production. The environmental conditions associated with the glacially influenced estuaries during our study period (2020−2021) seemed within a range that allowed nearshore fishes to maintain energy pathways and prey bases across these estuaries, but it is unknown how these estuarine food webs may be influenced in years of extreme conditions such as during heat waves, droughts, or floods.

Alaska↗

USGS2015

Monitoring and modeling wetland chloride concentrations in relationship to oil and gas development

Extraction of oil and gas via unconventional methods is becoming an important aspect of energy production worldwide. Studying the effects of this development in countries where these technologies are being widely used may provide other countries, where development may be proposed, with some insight in terms of concerns associated with development. A fairly recent expansion of unconventional oil and gas development in North America provides such an opportunity. Rapid increases in energy development in North America have caught the attention of managers and scientists as a potential stressor for wildlife and their habitats. Of particular concern in the Northern Great Plains of the U.S. is the potential for chloride-rich produced water associated with unconventional oil and gas development to alter the water chemistry of wetlands. We describe a landscape scale modeling approach designed to examine the relationship between potential chloride contamination in wetlands and patterns of oil and gas development. We used a spatial Bayesian hierarchical modeling approach to assess multiple models explaining chloride concentrations in wetlands. These models included effects related to oil and gas wells (e.g. age of wells, number of wells) and surficial geology (e.g. glacial till, outwash). We found that the model containing the number of wells and the surficial geology surrounding a wetland best explained variation in chloride concentrations. Our spatial predictions showed regions of localized high chloride concentrations. Given the spatiotemporal variability of regional wetland water chemistry, we do not regard our results as predictions of contamination, but rather as a way to identify locations that may require more intensive sampling or further investigation. We suggest that an approach like the one outlined here could easily be extended to more of an adaptive monitoring approach to answer questions about chloride contamination risk that are of interest to managers.

Montana, North Dakota↗

USGS2015

PCB concentrations of lake whitefish ( Coregonus clupeaformis ) vary by sex

We determined whole-fish polychlorinated biphenyl (PCB) concentrations in 26 female lake whitefish ( Coregonus clupeaformis ) and 34 male lake whitefish from northern Lake Huron. In 5 of the 26 female lake whitefish, we also determined PCB concentrations in the somatic tissue and ovaries. In addition, bioenergetics modeling was used to determine the contribution of the growth dilution effect to the observed difference in PCB concentrations between the sexes. Whole-fish PCB concentrations for females and males averaged 60 ng/g and 80 ng/g, respectively; thus males were 34% higher in PCB concentration compared with females. Based on the PCB determinations in the somatic tissue and ovaries, we predicted that PCB concentration of females would increase by 2.5%, on average, immediately after spawning due to release of eggs. Thus, the change in PCB concentration due to release of eggs did not explain, to any degree, the higher PCB concentrations observed in males compared with females. Bioenergetics modeling results indicated that the growth dilution effect could account for males being only 0.7% higher in PCB concentration compared with females. Thus, the growth dilution effect contributed very little to the observed difference in PCB concentrations between the sexes. We conclude that males were higher than females in PCB concentration most likely due to a higher rate of energy expenditure, stemming from greater activity and a greater resting metabolic rate. A higher rate of energy expenditure leads to a higher rate of food consumption, which, in turn, leads to a higher PCB accumulation rate.

Michigan↗

USGS2019

Seasonal trophic variation of yellow perch exceeds spatial variation in a large lake basin

Trophic structuring of complex food webs may vary at multiple spatial and temporal scales, both in terms of direct trophic connections and underlying energy pathways that support production. In large freshwater systems, the prey and primary producers that support individual higher-order consumers may vary across seasons and habitats due to differences in food availability, predator consumption patterns, seasonal succession of organisms at lower trophic levels, and heterogeneous nutrient inputs. We examined spatial and temporal variation in stomach contents, fatty acids, and stable isotopes of yellow perch ( Perca flavescens ) across seasons and across sites spanning approximately 200 km in Lake Erie's Central Basin (LECB). Stomach contents provided a short-term index of trophic patterns, while biochemical markers (fatty acids and stable isotopes) provided a more temporally integrated description of underlying energy pathways and trophic links. We found limited spatial variation of biochemical indicators and documented seasonal variation for all three trophic indicators, especially fatty acid profiles. Differences in stomach contents were driven by relative chironomid consumption, the most abundant prey resource, while fatty acid profiles were predominantly influenced by seasonal fluctuations in C22:6n-3 (DHA). Seasonal trends were evident in δ 13 C and δ 15 N; however, they varied within a narrow range of values. Our findings suggest that adult yellow perch in LECB showed little differentiation in resource use across space in 2014, but their diets and biochemical compositions varied seasonally.

Ohio↗

USGS2026

The Great Lakes aquatic tissue analysis repository (GLATAR)

Empiricists and modellers use information on energy density, proximate composition, stable isotopes, fatty acids, thiamine, and bioaccumulative tracers (e.g., PCBs and mercury) to understand the state and inter-relationships of aquatic food webs. Data exist in many published and unpublished sources, but are not consolidated in an easily accessible database that would serve as a vital resource to i) provide basic estimates of these diet-derived measures of body composition, ii) understand sources of variation in the underlying data, iii) facilitate exploration and development of data proxies, and iv) assist in study design. We designed GLATAR (Great Lakes Aquatic Tissue Analysis Repository, glatar.org ) to address this need. GLATAR is an open-access, searchable database linked to a web-based toolbox to visualise and generate user-defined summaries on diet-derived ecological metrics, with a focus on taxa of importance to the Great Lakes. GLATAR currently contains over 50,000 records on energy density, chemical tracers, and proximate body composition from 67 species of fish and 72 invertebrate taxa. We hope this user-friendly interface will entice others to upload their published and unpublished data to the repository, enriching the breadth of data accessible to researchers. In this way, GLATAR will become a ‘living’ and interactive resource for empiricists and modellers working in freshwater ecosystems as they make critical decisions related to growth, production, and consumption across a diverse group of economically and ecologically important aquatic species.

Journal of Great Lakes Research↗

USGS2026

Spatio-temporal modeling for assessing geoenergy resources: A workflow applied to gas in place variation in coal beds

The ability to estimate spatio-temporal changes in hydrocarbon reservoir properties and energy resources within pore volumes is essential for optimizing production, reservoir management, geologic energy storage, and safety in underground mining operations. In coal seams, predicting remaining methane gas-in-place (GIP) is critical for quantifying producible gas and improving mine safety and productivity through effective ventilation planning. Although such changes are commonly evaluated using physics-based numerical simulation models, these approaches often require extensive data, calibration effort, and time. This study presents a spatio-temporal geostatistical modeling approach that bridges the gap between purely spatial models and full numerical simulations. The method is applied to a case study of coal seam degasification in the Mary Lee coal group, Black Warrior Basin, Alabama, USA, to estimate GIP evolution over time within a selected mining district. The analysis uses published data from prior natural gas production history-matching of degasification using vertical wells. Empirical spatial and temporal statistics were calculated for reservoir pressure and water saturation, and spatio-temporal variogram models were fitted to experimental variograms. These models provided the structural basis for spatio-temporal kriging, integrated with spatial estimates of time-invariant parameters (porosity, density, and thickness) to estimate GIP. This approach enabled estimation of GIP changes over time, including periods without data. Boxplots of GIP estimates indicated systematic depletion and decreasing spatial variability, reflecting the impacts of degasification. Comparison with cumulative gas production from empirical well records showed approximately 85% agreement based on a relative similarity metric. Spatio-temporal GIP estimates were also used to estimate methane emissions to longwall ventilation systems and compared with reported emissions from the U.S. EPA Greenhouse Gas Reporting Program, showing similar distributions (≈80%) given data limitations. Overall, this integrated modeling approach provides time-dependent GIP estimates with broader implications for resource assessment applications.

Alabama↗

USGS2009

Ground and surface temperature variability for remote sensing of soil moisture in a heterogeneous landscape

At the Little River Watershed (LRW) heterogeneous landscape near Tifton Georgia US an in situ network of stations operated by the US Department of Agriculture-Agriculture Research Service-Southeast Watershed Research Lab (USDA-ARS-SEWRL) was established in 2003 for the long term study of climatic and soil biophysical processes. To develop an accurate interpolation of the in situ readings that can be used to produce distributed representations of soil moisture (SM) and energy balances at the landscape scale for remote sensing studies, we studied (1) the temporal and spatial variations of ground temperature (GT) and infra red temperature (IRT) within 30 by 30 m plots around selected network stations; (2) the relationship between the readings from the eight 30 by 30 m plots and the point reading of the network stations for the variables SM, GT and IRT; and (3) the spatial and temporal variation of GT and IRT within agriculture landuses: grass, orchard, peanuts, cotton and bare soil in the surrounding landscape. The results showed high correlations between the station readings and the adjacent 30 by 30 m plot average value for SM; high seasonal independent variation in the GT and IRT behavior among the eight 30 by 30 m plots; and site specific, in-field homogeneity in each 30 by 30 m plot. We found statistical differences in the GT and IRT between the different landuses as well as high correlations between GT and IRT regardless of the landuse. Greater standard deviations for IRT than for GT (in the range of 2-4) were found within the 30 by 30 m, suggesting that when a single point reading for this variable is selected for the validation of either remote sensing data or water-energy models, errors may occur. The results confirmed that in this landscape homogeneous 30 by 30 m plots can be used as landscape spatial units for soil moisture and ground temperature studies. Under this landscape conditions small plots can account for local expressions of environmental processes, decreasing the errors and uncertainties in remote sensing estimates caused by landscape heterogeneity.

Journal of Hydrology↗

USGS2016

The chemistry and isotopic composition of waters in the low-enthalpy geothermal system of Cimino-Vico Volcanic District, Italy

Geothermal energy exploration is based in part on interpretation of the chemistry, temperature, and discharge rate of thermal springs. Here we present the major element chemistry and the δD, δ 18 O, 87 Sr/ 86 Sr and δ 11 B isotopic ratio of groundwater from the low-enthalpy geothermal system near the city of Viterbo in the Cimino-Vico volcanic district of west-Central Italy. The geothermal system hosts many thermal springs and gas vents, but the resource is still unexploited. Water chemistry is controlled by mixing between low salinity,HCO 3 -rich fresh waters (<24.2°C) flowing in shallow volcanic rocks and SO 4 -rich thermal waters (25.3°C to 62.2°C) ascending from deep, high permeability Mesozoic limestones. The (equivalent) SO 4 /Cl (0.01–0.02), Na/Cl (2.82–5.83) and B/Cl ratios (0.02–0.38) of thermal waters differs from the ratios in other geothermal systems from Central Italy, probably implying a lack of hydraulic continuity across the region. The δ 18 O (−6.6‰ to −5.9‰) and δD (−40.60‰ to −36.30‰) isotopic composition of spring water suggest that the recharge area for the geothermal system is the summit region of Mount Cimino. The strontium isotope ratios ( 87 Sr/ 86 Sr) of thermal waters (0.70797–0.70805) are consistent with dissolution of the Mesozoic evaporite-carbonate units that constitute the reservoir, and the ratios of cold fresh waters mainly reflect shallow circulation through the volcanic cover and some minor admixture (<10%) of thermal water as well. The boron isotopic composition (δ 11 B) of fresh waters (−5.00 and 6.12‰) is similar to that of the volcanic cover, but the δ 11 B of thermal waters (−8.37‰ to −4.12‰) is a mismatch for the Mesozoic reservoir rocks and instead reflects dissolution of secondary boron minerals during fluid ascent through flysch units that overlie the reservoir. A slow and tortuous ascent enhances extraction of boron but also promotes conductive cooling, partially masking the heat present in the reservoir. Overall data from this study is consistent with previous studies that concluded that the geothermal system has a large energy potential.

Journal of Volcanology and Geothermal Research↗

USGS2019

Globally detected volcanic lightning and umbrella dynamics during the 2014 eruption of Kelud, Indonesia

Volcanic lightning shows considerable promise as a monitoring and research tool to characterize explosive eruptions. Its key strengths are rapid and remote detection, because the radio signals produced by lightning can propagate thousands of km at the speed of light. Despite these tantalizing properties, the scientific work on volcanic lightning has only recently started gaining momentum. Much more is needed to understand what lightning reveals about the evolution of an eruption in near-real time. Here we examine the timing and energy release of lightning generated by the eruption of Kelud volcano in Indonesia on 13 February 2014, as detected by the World Wide Lightning Location Network (WWLLN). The eruption column reached at least 26 km above sea level, representing the highest plume since the advent of global lightning networks in the last decade. Therefore, it provides valuable constraints on the electrification of end-member, sustained Plinian columns. We investigate the lightning in context with satellite images, photographs, and other published studies. Results show that the earliest satellite-detected activity was a thermal anomaly at ~15:46 UTC, corresponding to a directed blast at the onset of eruption (and only a few lightning strokes). Following a brief pause, the eruption produced a sustained column and umbrella cloud that spread outward into the tropical stratosphere. Rates of umbrella expansion provide an average mass eruption rate (MER) in the range of 8 × 10 7 –1 × 10 8 kg s −1 . A more nuanced picture emerges from the time-varying MERs (determined between each satellite pass), which show rapid intensification during the first hour of eruption, followed by constant MER for about an hour, and waning toward the end (after ~17:50 UTC). At this stage, decreasing flux into the umbrella cloud coincides with column instability and formation of pyroclastic density currents, as recorded by photos from the ground ~17:45 UTC. We infer that some of the erupted mass partitioned into ground-hugging currents, leading to a lower apparent MER. Interestingly, there is not a 1:1 correlation between lightning intensity and MER over the course of eruption. Stroke rates increase sharply within the first 30–40 min (during rapid intensification of the plume), and then drop below 2 strokes per min once the MER remains constant. This suggests that electrification was controlled by the rate of increase in MER—in other words, the acceleration of particles out of the vent. We also show that lightning stroke-rates and energies are greatest within 50 km of the vent, even when the ash cloud extends >200 km downwind, indicating that lightning was focused in the regions of highest particle concentration and turbulence. Overall, we conclude that abrupt changes in lightning rates are clearly linked to changes in eruption behavior, and that rapid detection could aid monitoring efforts to characterize eruption rates or styles.

Journal of Volcanology and Geothermal Research↗

USGS2020

Geophysical characterization of the Northwest Geysers geothermal field, California

The Clear Lake Volcanic Field in northern California is the youngest and northern-most part of a long-lived volcanic system that has produced recent (~10 ka) eruptions. Adjacent to the Clear Lake Volcanic Field is the worlds largest energy producing geothermal field, The Geysers. The hottest part of The Geysers geothermal field is in the northwest where temperatures reach ~400 C at 3 km depth. Low permeability, high thermal gradients, and low steam saturation prescribed development of an enhanced geothermal system (EGS) in the Northwest Geysers to increase energy producing capacity. Though the Northwest Geysers is known to be the hottest part of the field, geophysical methods have failed to adequately image any inferred heat source. This project aims to image the heat source of the Northwest Geysers using newly collected gravity and magnetotelluric (MT) measurements. Gravity data were jointly modeled with existing magnetic data along a two-dimensional profile aligned with an existing geologic cross-section. The key feature of the potential field model is a low-density, low-susceptibility body at 5 km depth (bmsl) under the EGS. MT data were modeled in three-dimensions to characterize subsurface resistivity structure, where the upper 3 km of the resistivity model agrees well with existing data. Lithologic and steam saturation are estimated from modeled resistivity values using existing geophysical data. Below 3 km depth (bmsl), the resistivity model images a possible young intrusion under the EGS. A possible zone of partial melt (<5%) below 7 km depth (bmsl) in the northwestern part of the field is also imaged which extends northeast towards the main part of the Clear Lake Volcanic Field.

California↗