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Evaluation of solid bitumen created from marine oil shale bituminite under hydrous and anhydrous pyrolysis conditions

To test the influence of environmental conditions on aromaticity of solid bitumen generated during petroleum generation, four organic-rich (26–36 wt% total organic carbon) oil shale samples collected from the Neoproterozoic–Lower Cambrian restricted marine Salt Range Formation in the upper Indus Basin, Pakistan, were pyrolyzed under hydrous and anhydrous conditions. Experiments used closed system batch reactors at subcritical water temperatures between 300 and 370°C for 72 h. Thermal conversion of bituminite in the Salt Range oil shales created a newly formed solid bitumen, similar to previous observations from experiments on the Eocene lacustrine Green River Formation Mahogany zone oil shale. Newly formed solid bitumen in the Salt Range Formation oil shales generally has higher reflectance (R o ) in hydrous residues compared to anhydrous experiments subjected to the same time-temperature conditions, also similar to prior observations. This finding supports the hypothesis that radical disproportionation is favored in the presence of hydrogen contributed by water, promoting aromatization in the solid bitumen residue with concomitant increased expulsion of saturated hydrocarbons. Indigenous solid bitumen (and vitrinite in a comparison sample) also shows higher reflectance values in hydrous versus anhydrous residues, indicating that additional aromatization in the presence of exogenous hydrogen occurs both in newly formed organic matter and in organic matter that is present throughout the experiment. Despite similarities in their bulk rock geochemical screening parameters, R o evolution shows different trajectories amongst the four Salt Range oil shales, suggesting as-yet undetermined differences in kinetic properties which are probably related to differences in a priori chemical composition. These results have implications for the use of solid bitumen reflectance (BR o ) as a thermal proxy, suggesting BR o values and appearance could vary as a function of the concentration of water. Variation in water concentration may be present at the reservoir or formation scale, but may also be present at a much finer scale in tight oil shales where permeability is several orders of magnitude lower than conventional reservoirs. Therefore, local variations in the presence of water potentially could explain substantial variation in BR o values and appearance in closely spaced source rock samples and even within an individual microscope field.

Journal of Analytical and Applied Pyrolysis

Simulation of groundwater flow in the Long Island, New York regional aquifer system for pumping and recharge conditions from 1900 to 2019

The U.S. Geological Survey has developed a transient, groundwater-flow model that simulates hydrologic conditions in the Long Island aquifer system as part of an ongoing (since 2016) multiyear, cooperative investigation with the New York State Department of Environmental Conservation. The goals of this investigation are to assist stakeholders and resource managers to evaluate the response of the hydrologic system to changes in future hydraulic stresses. Responses in the hydrologic system include changes in water levels in the hydrogeologic units; discharge to streams, coastal waters, and subsurface infrastructure; and the extent of saline groundwater in the aquifers. Hydraulic stresses include future water-supply management and changes in land use and infrastructure. The numerical model synthesizes a diverse set of physiographic, geologic, climatic, land-use, and historical population, water use, and infrastructure data to physically represent the Long Island aquifer system from land surface to bedrock and to simulate annual hydrologic conditions between 1900 and 2019. A three-dimensional hydrogeologic framework was developed from existing and recently collected borehole geologic and geophysical data collected as part of a companion drilling program. Water-transmitting properties of the principal aquifer sediments were defined in three dimensions from new and existing lithologic logs. The distribution of recharge from precipitation was estimated from landscape characteristics and climate data. Anthropogenic recharge from wastewater, leaky infrastructure, and storm runoff were estimated from population, infrastructure, and pumping data. Water-use data, including well locations, depths, and pumping rates, were obtained from historical sources and records and used to estimate pumping stresses continuously in time and space, at an annual average time scale. The data were incorporated into a three-dimensional numerical model using the U.S. Geological Survey finite difference modeling code MODFLOW 6; the model encompassed all of Long Island and surrounding surface waters and simulated historical hydrologic conditions from 1900 to 2019. The calibration process involved trial and error adjustments using prior knowledge to improve general fit to observations followed by an inverse calibration to update and optimize input parameters, using an iterative ensemble smoother algorithm implemented in PEST++ version 5.0. This resulted in a model that generally was in good agreement with observed, dynamically varying hydrologic conditions from 1900 to 2019. The calibrated model was used to develop two base-case models for scenario testing of future, hypothetical conditions where one represented average-annual conditions, and one represented average-seasonal conditions from 2010 to 2019. The model representing average-annual conditions was modified further to represent an alternate sea-level position of 6 feet above the North American Vertical Datum of 1988, and the model representing average-seasonal conditions was modified to represent the average seasonal effects of a 5-year drought imposed upon current hydrologic conditions. Recharge is the sole source of water to the aquifer system; groundwater discharges to coastal water and streams and is withdrawn by pumped wells. Model-estimated annual recharge ranged from about 11 inches in 1965 to 41 inches in 1983. On average, from 2010 to 2019, about 23 percent of water was pumped from wells, and about 47 and 27 percent discharged to coastal waters and streams, respectively; the remaining 4 percent was water that moved into storage in the aquifer matrix. Water levels on Long Island vary naturally during time in response to changes in recharge; the amount of variation is largest in the interior of the island, in areas with highest water table altitudes near groundwater divides and lowest near streams and the coastal waters. The total range of water table altitudes on Long Island between 1900 and 2019 ranged from near 0 to more than 70 feet in western parts of Long Island. The largest range in altitudes is in New York City and is associated with areas of large historical withdrawals between the 1920s and the late 1980s. Water table altitudes generally varied by less than 10 feet in eastern Suffolk County, where the aquifer is under more natural conditions. Saltwater intrusion is of great concern on Long Island, particularly in western Long Island where both the unconfined and confined parts of the aquifer system have been intruded in response to large-scale groundwater withdrawals; however, the volume of freshwater in the islandwide aquifer system only has changed by about 5 percent between 1900 and 2019. The decadal change in the freshwater volume was largest during the early and mid-20th century, corresponding to the largest historical pumping, but that volume change did not exceed 1 percent. The negligible change in freshwater volume suggests that saltwater intrusion as of 2019 was limited at an islandwide scale but continues to occur in local areas of Queens and Nassau Counties, adversely affecting current water supplies and limiting future water supplies for affected communities. The regional groundwater model developed for this investigation is a tool that can be used to help determine the viability of current and future water supplies at a regional scale and can be used to support development of additional models at finer scale to support more focused assessments of groundwater sustainability.

New York

Evolution of arsenic speciation during thermal treatment simulating wildfire heating in arsenic-rich sediments

Understanding arsenic transformations during wildfires can help better constrain the environmental impacts of increased wildfire intensity, frequency, and burned area. Previous studies have monitored the evolution of metal(loid) speciation at specific time/temperature endpoints, hampering the comprehension of the dynamic transformations of metal(loid)s during wildfires. Here, a novel approach, namely in situ time-resolved X-ray absorption near edge structure (TR-XANES) spectroscopy, was used for the first time to monitor the heat-induced redox transformations of arsenic (As) in two As-rich sediments with different characteristics. No arsenic transformations were observed in either sediment at room temperature or when the sediments were heated to a maximum temperature of 400 ºC. When heated to a maximum temperature of 600 or 700 ºC, As underwent complex, dynamic, and partially reversible redox transformations, the extent of which varied with sediment properties, initial As speciation, and heating temperature and duration. In the case of sediments initially containing As(V) and a low sulfide/sulfate ratio, the As(V) was reduced to As(III) over a short period of time, followed by immediate reoxidation of As(III) to As(V). The extent of the transient As reduction increased with increasing maximum temperature. The final As speciation at the end of the heating experiment was not substantially different from that at the beginning of the experiment. In contrast, in sediments that were best described by a more complex combination of reference compounds (As(V) coprecipitated with or adsorbed on iron oxide, arseniosiderite, arsenopyrite) with a high sulfide/sulfate ratio, As(V) phases were reduced to As(III) and As(III) was further reduced to As(-I) (at 700 ºC, only), followed by delayed reoxidation of As(-I) to As(III) (at 700 ºC, only) and reoxidation of As(III) to As(V). Approximately 9% and 26% of all As remained as As(III) ( i.e., was not reoxidized to As(V)) at the end of the experiment when heated to a maximum temperature of 600 and 700 ºC, respectively, which is higher than the relative abundance of As(III) in the native sediment. These fire-induced As transformations can potentially enhance As mobilization to surface water and groundwater, posing risks to environmental and human health.

California

Confocal laser-scanning microscopy (CLSM)-based thermal maturity of Tasmanites and progress in standardization of fluorescence microspectrometry

Evaluation of thermal maturity in vitrinite-free or vitrinite-deficient sediments via fluorescence microspectrometry can provide relevant information related to petroleum exploration and thermal history assessment. However, variation in spectral fluorescence properties of alginite macerals with increasing thermal maturity is largely underexplored. Here, authors of this study have applied confocal laser-scanning microscopy (CLSM) in conjunction with fluorescence microspectrometry to a maturity series of marine Upper Devonian Tasmanites algae from the Ohio Shale (Huron Member) and a single sample from the Marcellus Formation of the Appalachian Basin. Spectral fluorescence properties of Tasmanites were evaluated in relation to orientation, measurement location, and the number of measurements per sample, and were compared to published literature. Emission spectra of Tasmanites from continuous wave laser excitation (405 nm) were acquired from sections perpendicular and parallel to bedding and at different positions within individual Tasmanites bodies. The results showed a progressive red-shift in emission maxima (λ max ) in a large sample sized maturity series ( N = 19), e.g., 493 to 578 nm for the perpendicular section at middle position. Further, blue-shifted apex and mineral-adjacent positions within sections perpendicular to bedding were observed, with the latter being reported here for the first time. While blue-shift at apex positions can be attributed to mechanical deformation-induced reorientation of photoselected fluorophores, the blue-shifted mineral-adjacent positions could result from strain loading and development of a plastic deformation region at the mineral contact zone with Tasmanites . A decrease in standard deviation with increasing number of measured emission maxima is well-observed, and 15 to 20 individual measurements per sample appears sufficient for low standard deviation and coefficient of variance. CLSM-derived thermal maturity parameters indicated that a moderate positive correlation of red/green quotient (Q 650/500 ; R 2 = 0.67) with solid bitumen reflectance (BR o in %) exists. For reproducible results, the determination of λ max and Q 650/500 should be conducted exclusively in the middle position at perpendicular and parallel sections of the polished whole-rock pellets, where the lowest standard deviation in measurement was observed. These results strengthen the suitability and relevance of the CLSM technique in thermal maturity studies of dispersed organic matter (DOM) and contribute to the standardization of fluorescence microspectrometry methods in organic petrology investigation.

Kentucky, Ohio, Virginia, West Virginia

Identifying precursors and tracking pulses of magma ascent in multidisciplinary data during the 2018–2023 phreatomagmatic eruption at Semisopochnoi Island, Alaska

The 2018–2023 phreatomagmatic eruptions at Semisopochnoi Island, Alaska produced abundant long-period (LP) seismicity, harmonic and broadband tremor, and explosion signals over several well-monitored periods of eruption and quiescence. The corresponding dataset provides an excellent opportunity to investigate precursory and syn -eruptive geophysical signals of long-lived phreatomagmatic eruptions using multiparameter observations. We generated explosion and LP event catalogs through novel implementations of the REDPy ( Hotovec-Ellis, 2024 ) repeating event detector in mid-2021 following a network upgrade and the onset of a new phase of the eruption. The hundreds of detected explosions show a high degree of infrasound waveform similarity over more than a year, indicating a repeating source mechanism likely associated with explosive magma-water interaction. The seismic LP catalog shows that events began over a month prior to renewed explosive activity at the beginning of August 2021, and that lower frequency index (FI) LPs were generated in the week prior to the onset of explosions. We applied a recently developed machine learning tool (VOISS-Net, Tan et al., 2024 ) to catalog abundant broadband and harmonic seismic tremor recorded before and during the renewed explosive activity, along with LPs and explosions. The tremor catalogs complement the LP and explosion catalogs by filling out the seismic sequence with the dominant signal types. Together, these catalogs reveal a seismic sequence of renewed unrest that started with several weeks of LP events, followed by LPs with lower FI values and harmonic tremor in the days prior to explosive activity, and finally the onset of discrete explosions and broadband eruption tremor. We interpret this sequence as the ascent of a new pulse of magma that first interacted with the hydrothermal/groundwater system to produce LPs, followed by harmonic tremor, and that ultimately drove explosive magma-water interactions and periods of continuous ash emissions. The 2021 seismic sequence, in combination with long-term records of satellite SO 2 emissions, deformation from interferometric synthetic aperture radar (InSAR) analysis, ash sample analysis, infrasound, and volcano tectonic seismicity, allows us to interpret the entire 9-year period of unrest and eruption that began with an intrusion and earthquake swarm in 2014.

Alaska

Will there be water? Climate change, housing needs, and future water demand in California

Climate change in California is expected to alter future water availability, impacting water supplies needed to support future housing growth and agriculture demand. In groundwater-dependent regions like California's Central Coast, new land-use related water demand and decreasing recharge is already stressing depleted groundwater basins. We developed a spatially explicit state-and-transition simulation model that integrates climate, land-use change, water demand, and groundwater gain-loss to examine the impact of future climate and land use change on groundwater balance and water demand in five counties along the Central Coast from 2010 to 2060. The model incorporated downscaled groundwater recharge projections based on a Warm/Wet and a Hot/Dry climate future from a spatially explicit hydrological process-based model. Two urbanization projections from a parcel-based, regional urban growth model representing 1) recent historical and 2) state-mandated housing growth projections were used as alternative spatial targets for future urban growth. Agricultural projections were based on recent historical trends from remote sensing data. Annual projected changes in groundwater balance were calculated as the difference between land-use related water demand, based on historical estimates, and climate-driven recharge plus agriculture return flows. Results indicate that future changes in climate-driven groundwater recharge, coupled with cumulative increases in agricultural water demand, result in overall declines in future groundwater balance, with a Hot/Dry future resulting in cumulative groundwater decline in all but Santa Cruz County. Cumulative declines by 2060 are especially prominent in San Luis Obispo (−2.9 to −5.1 Bm 3 ) and Monterey counties (−6.5 to −8.7 Bm 3 ), despite limited changes in agricultural water demand over the model period. These two counties show declining groundwater reserves in a Warm/Wet future as well, while San Benito and Santa Barbara County barely reach equilibrium. These results suggest future groundwater supplies may not be able to keep pace with regional demand and declining climate-driven recharge, resulting in a potential reduction in water security in the region. However, our county-scale projections showed new housing and associated water demand does not conflict with California's groundwater sustainability goals. Rather, future climate coupled with increasing agricultural groundwater demand may reduce water security in some counties, potentially limiting available groundwater supplies for new housing.

California

A joint Gaussian process model of geochemistry, geophysics, and temperature for groundwater TDS in the San Ardo Oil Field, California, USA

Decline in availability of fresh groundwater has expanded interest in brackish groundwater resources; however, the distribution of brackish groundwater is poorly understood. Water resources in sedimentary basins across the United States often overlie oil and gas development. Mapping of groundwater total dissolved solids (TDS) using data from oil well geophysical logs has become an important technique for identifying fresh and brackish groundwater. Existing geophysical log analysis methods use porosity and temperature to relate formation resistivity to TDS. Typically, natural geothermal gradients are used to estimate temperature at the location of collected resistivity. However, in thermally enhanced oil fields, steam is injected into the subsurface to mobilize high viscosity oil, creating variable temperature distributions. Furthermore, TDS derived from resistivity also depends on the fractions of dominant ions. Typically, chloride and bicarbonate fractions must be determined. It is also necessary to model TDS across many geologic units with heterogenous porosity distributions. Collectively, each quantity used to estimate TDS (resistivity, porosity, temperature, bicarbonate fraction) varies in space and time, and available data points are rarely collocated. Here, we present a new method of mapping groundwater TDS that continuously models each quantity together with a joint Gaussian process. This method enables mapping fresh and brackish water with practically available data. We apply this method to the San Ardo Oil Field in Monterey County, California, where steam injection occurs. In some areas of the aquifer system overlying the oil zone, the temperature is ∼75 °C, roughly twice the natural background value. Groundwater TDS is typically <1,500 mg/L in the aquifer and increases with depth to ∼9,000 mg/L in the oil-producing zone. A low-permeability clay layer delineates the fresh and brackish water, likely by inhibiting surface recharge from penetrating the deeper zones, allowing higher-TDS connate water to remain in place. Weaker lateral TDS trends may be controlled by recharge patterns associated with the Salinas River. Our model reveals with high certainty that groundwater has freshened in one localized part of the oil-producing zone and suggests with less certainty that more widespread freshening has also occurred. The lowering of TDS was possibly from decades of low-TDS steam injection and the associated fluid production and disposal operations.

California

Tracing mercury from land to river: Global sources, retention, and implications for sustainability

Mercury (Hg) pollution in river systems is a global sustainability challenge. Yet the transport, transformation, and retention of Hg within global rivers remain poorly quantified, particularly in regions with sparse observations such as Southeast Asia and Africa, hindering effective pollution mitigation and reinforcing geographic inequities in scientific knowledge and environmental governance. Here, we present the first global, high-resolution simulation of riverine Hg dynamics using a process-based model that traces Hg from land-based sources through river networks to the ocean. Under a realistic scenario, we estimate that ~1,900 megagrams per year (Mg/yr) of Hg enters global rivers, including 1,500 Mg/yr from human-induced sources and 400 Mg/yr from soil erosion. Nearly half of this flux (~1,000 Mg/yr) is retained in reservoirs and dams, which act as major sinks. While such retention limits downstream delivery to the oceans, it also heightens in-reservoir Hg methylation risks. By bridging the gap between Hg releases and observed riverine exports, our framework offers a scalable tool for data-limited regions, promotes data access, and supports global freshwater and pollution-management strategies.

EarthArXiv

Tracing mercury from land to river: Global sources, retention, and implications for sustainability

Mercury (Hg) pollution in river systems is a global sustainability challenge. Yet the transport, transformation, and retention of Hg within global rivers remain poorly quantified, particularly in regions with sparse observations such as Southeast Asia and Africa, hindering effective pollution mitigation and reinforcing geographic inequities in scientific knowledge and environmental governance. Here, we present the first global, high-resolution simulation of riverine Hg dynamics using a process-based model that traces Hg from land-based sources through river networks to the ocean. Under a realistic scenario, we estimate that ∼1900 megagrams per year (Mg/yr) of Hg enters global rivers, including 1500 Mg/yr from human-induced sources and 400 Mg/yr from soil erosion. Nearly half of this flux (∼1000 Mg/yr) is retained in reservoirs and dams, which act as major sinks. While such retention limits downstream delivery to the oceans, it also heightens in-reservoir Hg methylation risks. By bridging the gap between Hg releases and observed riverine exports, our framework offers a scalable tool for data-limited regions, promotes data access, and supports global freshwater and pollution-management strategies.

Environmental Science & Technology

Hydrology and water and sediment quality at James Campbell National Wildlife Refuge near Kahuku, Island of Oahu, Hawaii

The James Campbell National Wildlife Refuge occupies two lowland marsh and pond complexes on the northern coastal plain of Oahu: the mostly natural ponds and wetlands of the Punamano Unit and the constructed ponds of the Kii Unit. The U.S. Fish and Wildlife Service manages the Refuge primarily to protect and enhance habitat for four endangered species of Hawaiian waterbirds. Kii Unit is fed by artesian wells and rainfall, whereas Punamano Unit is fed naturally by rainfall, runoff, and ground-water seepage. Streams drain from the uplands into lowland ditches that pass through Kii Unit on their way to the ocean. A high-capacity pump transfers water from the inner ditch terminus at Kii to the ocean outlet channel. Stormwaters also exit the inner ditch system over flood-relief swales near the outlet pump and through a culvert with a one-way valve. A hydrologic investigation was done from November 1996 through February 1998 to identify and quantify principal inflows and outflows of water to and from the Refuge, identify hydraulic factors affecting flooding, document ground-water/surface-water interactions, determine the adequacy of the current freshwater supply, and determine water and sediment quality. These goals were accomplished by installing and operating a network of stream-gaging stations, meteorology stations, and shallow ground-water piezometers, by computing water budgets for the two Refuge units, and by sampling and analyzing water and pond-bottom sediments for major ions, trace metals, and organic compounds. Streamflow during the study was dominated by winter stormflows, followed by a gradual recession of flow into summer 1997, as water that had been stored in alluvial fans drained to lowland ditches. Outflow at the ditch terminus in 1997 was 125 million gallons greater than measured inflow to the coastal plain, mainly reflecting gains from ground water along the ditches between outlying gages and the ditch terminus. Of the measured 1997 outflow, 98 percent was through the Kii outlet pump, with the outlet culvert valve only opening for brief periods during storms. Large volumes of stormflow overflowed the flood-relief swales unmeasured. The largest storm of the study, in November 1996, was estimated to have a flood frequency of about 3 to 4 years. Streamflow exceeded culvert capacity and overtopped Kamehameha Highway at Kalaeokahipa Stream and Hospital ditch. Slight overbank flooding in Kii ditch resulted strictly from high discharge. Minor overbank flooding farther out on the coastal plain probably was caused mainly by the small hydraulic gradients available to convey stormflows along the lowland ditches. Stormwaters flooded Kii ponds and flowed back upstream along Punamano ditch into Punamano marsh, introducing suspended sediment and possibly other contaminants to the Refuge. Two smaller storms in January 1997 resulted in smaller flows and no overbank flooding. The Kii outlet pump ran continuously for 7 days during the November 1996 storm and for 1 to 2 days during the January 1997 storms. During all three storms, the outlet culvert valve opened and the inner ditches overtopped the flood-relief swales, allowing free outflow of water from the inner ditch. Backwater effects hindered drainage during the January 1997 storms at Hospital ditch at Kamehameha Highway, and at Punamano ditch at Nudist Camp Road (where the backflow into Punamano marsh in November 1996 constituted an extreme backwater effect). A probable marine backwater effect was imposed at the ocean outlet ditch during the November 1996 storm through a combination of high spring tides and wave setup from large surf. Whether this backwater effect propagated upstream in the ditches to affect inland sites could not be determined conclusively. A sand plug may have built up in the ocean outlet channel before the November 1996 storm, but if so, it probably washed out prior to, or early in the storm, and was not present at the time of peak stage at inland sites. A season-long buildup of the sand plug in late 1997 was inferred from rising water levels in the outlet ditch. Seawater flows up the outlet channel or over the sand berm and into the outer ditch system on most high tides, and particularly during spring high tides. Ponds and ditches of the Refuge and surrounding lowlands have mud- and clay-lined bottoms that form an effective confining unit and inhibit interaction with an underlying shallow limestone aquifer. At Kii Unit, pond levels are higher than adjacent ditch levels and underlying ground-water levels, establishing lateral and downward head gradients that could foster seepage losses from the ponds. Regional ground-water discharge from the Koolau aquifer to the coastal-plain sediments is mostly diffuse, but is concentrated where ridges of Koolau Basalt plunge beneath coastal-plain sediments near Punamano Unit and at the head of Hospital ditch. Kii ditch gains brackish ground water downstream of Kamehameha Highway. Wastewater disposal from the sewage treatment plant adjoining Kii Unit poses little or no threat to Refuge habitat. Disposal is at six injection wells located 0.45 mi away at Kahuku, and the wells inject into confined limestone aquifers that do not extend to Kii Unit. The natural freshwater supply to Punamano Unit is adequate for maintaining the wildlife habitat, judging from stable pond levels and low salinities there. A monthly water budget for Punamano showed an apparent annual deficit in measurable flows in 1997, requiring unmeasured ground-water gains equalling 51 inches of water. The freshwater supply to Kii Unit is inadequate according to Refuge managers, because there is not enough water to manipulate levels adequately in the ponds during most of the year, and particularly during the driest months. This is confirmed by monthly deficits in the water budget for the Kii ponds during summer months. However, the Kii budget showed an annual surplus in measurable flows for 1997 equalling 24 inches of water. Unmeasured losses are required to explain the apparent annual surplus, such as discharge to the ditches through pond water-control structures and downward and/or lateral ground-water seepage. The apparent surplus at Kii is strictly hydrologic and is not a surplus in a management sense; it cannot be stored or used to supply the Refuge, but instead reflects losses from the system that render this amount of water unavailable for use. The budget year, 1997, was drier than normal (24 percent below long-term mean rainfall) and so the measured potential evaporation for 1997 was probably higher than the long-term mean. Few metals or organic compounds of potential concern were detected in pond and ditch waters and in pond-bottom sediments. Detected pesticides were at trace levels or just above minimum reporting limits. Exceptions that exceeded quality guidelines for freshwater sediment were copper and zinc in sediment from Kii ponds C and D, and copper in sediment from Punamano north pond. Therefore, urban and agricultural runoff probably have contributed little in the way of harmful metals or organic compounds to the Refuge, although the potential for such contribution remains from periodic flooding of the ponds by ditch stormflows. Salinity was low throughout most Refuge waters, qualifying as fresh to slightly brackish and suitable for the environmental needs of Refuge fauna. Higher salinities have been observed in ditches during past periods of sugarcane cultivation and saltwater aquaculture, however. Resumption of saltwater aquaculture could raise ditch salinities if saltwater effluents are disposed directly into the ditches, as they were in the past.

Hawaii

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

Widespread occurrence of former anhydrite phenocrysts in Laramide-age magmas related to porphyry-skarn Cu mineralization at Santa Rita and Hanover-Fierro, New Mexico, USA

Reports of magmatic anhydrite are relatively rare, with only ~30 occurrences documented worldwide so far. However, magmatic anhydrite saturation is difficult to recognize because anhydrite decomposes rapidly in near-surface environments. In most cases, only anhydrite inclusions shielded within other phenocryst phases were able to survive. Alternatively, since anhydrite phenocrysts preserved in fresh volcanic rocks are characteristically intergrown with apatite phenocrysts, the former presence of anhydrite phenocrysts can be recognized based on the occurrence of lath-shaped cavities that show a strong spatial association with apatite phenocrysts. These cavities can be either empty or filled with low-temperature, secondary minerals such as zeolites, carbonates, or microcrystalline silica. A systematic search for the occurrence of such cavities, combined with optical and Raman-spectroscopic identification of anhydrite inclusions preserved within apatite, hornblende and quartz phenocrysts, demonstrates that most of the Laramide-age magmas associated with the Santa Rita and Hanover-Fierro porphyry-skarn Cu (Zn, Mo, Au, Pb) deposits were saturated in magmatic anhydrite. The anhydrite typically coexisted with monosulfide solid solution (MSS), suggesting oxygen fugacities of ~2.0±0.5 log units above the fayalite-magnetite-quartz buffer. The magmas range from andesitic to rhyodacitic in composition, and from shortly pre-mineralization (~61 Ma) to shortly post-mineralization (~57 Ma) in age. In three samples with particularly well-recognizable former anhydrite phenocrysts, their modal abundance could be quantified based on high-resolution scans of polished hand specimens. The observed modal anhydrite abundances of 0.63–1.8 vol% translate into minimum magma sulfur contents of 0.20–0.56 wt% S. The highest sulfur content of 0.56 wt% S is difficult to reconcile with available anhydrite solubility models, but it could be reproduced in an anhydrite solubility experiment performed at 950 °C and 1.15 GPa on a natural latite containing 13.1 wt% dissolved H2O. The sample with the second-highest sulfur content of 0.26 wt% S requires ~10 wt% H2O in the silicate melt, and, consequently, a minimum pressure of ~0.5 GPa. Taken together, the results suggest that the magmas of the Central Mining District were extremely hydrous and thus originated from great depth. Indeed, their major element compositions and reconstructed H2O and S contents agree well with experimentally observed and numerically predicted compositions of residual silicate melts after 50–70 wt% crystallization of ordinary arc basalts at high pressure and high oxygen fugacities.

New Mexico

Mineral chemistry perspective on remobilization of stored magma at Kamakai'a Hills, Southwest Rift Zone of Kilauea, Island of Hawai'i, USA

Differentiated magmas stored in the rift zones of Kīlauea have received more attention in recent years following eruption of andesite during the early phase of 2018 lower East Rift Zone activity. Despite this growing interest, some of the most voluminous eruptions of differentiated rift zone magmas remain poorly studied. One such eruption, and the most voluminous exposed differentiated flow field at Kīlauea, is the Kamakaiʻa Hills. This eruption took place in the Southwest Rift Zone of Kīlauea, a region that is hypothesized to contain a long-lived rift zone reservoir. The Kamakaiʻa Hills flow field encompasses >250 × 10 6 m 3 of basaltic andesite and basalt compositions with a mineral assemblage of orthopyroxene + clinopyroxene + plagioclase during its early ʻaʻā phase and clinopyroxene + plagioclase + olivine during its late pāhoehoe phase. To better understand storage conditions and magma accumulation, this study focuses on major, minor, and trace elements from the mineral assemblage present within the early ʻaʻā and late pāhoehoe phases. The diversity of clinopyroxene and plagioclase compositions within the early ʻaʻā and late pāhoehoe phases, as well as diverse compositions of plagioclase and orthopyroxene within the early ʻaʻā phase, suggest multiple magma bodies and limited pre-eruption magma mixing within the broader Kamakaiʻa Hills reservoir. Oscillatory zoning patterns (particularly in clinopyroxene) imply processes such as recharge events, magma mixing or mingling, or convection within a differentially cooling, chemically stratified reservoir over protracted time intervals, whereas only limited resorbed mineral textures indicate incomplete mixing of heat and chemically distinct magmas during the dike intrusion that triggered the eruption. Mineral-mineral and mineral-melt thermobarometry indicate predominantly shallow (≤2.5 km depth) crustal storage conditions of the cooled, differentiated magma (∼1100 °C and cooler for the basaltic andesites) to hotter temperatures for the basalts (all >1100 °C). Despite the known large standard errors estimated for mineral-melt and mineral-mineral barometry (10s to >100 MPa), the calculated pressures and depths broadly correspond with earthquake swarm depths beneath the Kamakaiʻa Hills, and drill core and fluid inclusion barometry storage depths of differentiated magmas within the lower East Rift Zone. The Kamakaiʻa Hills differentiated magmas have H 2 O contents (∼0.5 wt%, using plagioclase-melt hygrometry) equivalent to typical Kīlauea basalts. Our data and interpretations demonstrate a complex, long-lived rift zone storage system that consisted of multiple magma bodies and was mobilized into eruption through intrusion of a hotter and more primitive summit-derived (uprift) magma.

Hawaii

Component identification of solid biomass fuels using reflected light microscopy: Interlaboratory study 2

As nations transition toward sustainable energy systems , biomass has become a vital component of global energy portfolios. Derived from organic materials such as wood, agricultural residues, forestry byproducts, and organic waste, biomass is a renewable energy source with significant environmental and economic benefits. Responsible biomass energy production can improve waste management, reduce emissions of greenhouse gases, and mitigate environmental pollution. However, as the diversity of biomass-derived fuels increases, robust quality assessment methods are essential to ensure their efficiency, safety, and minimal environmental impact. Reflected light microscopy (RLM) is one such technique with the potential to complement conventional physico-chemical analyses by enabling a rapid identification of material constituents and impurities. To refine this methodology and evaluate the reproducibility of solid biomass component identification using RLM, an interlaboratory study (ILS) was conducted. The study involved the recognition of 58 components across 45 photomicrographs, with the participation of 65 scientists and students from 25 countries. The participants faced high difficulty identifying some of the marked components, and as a result, the percentage of correct answers ranged from 19.0 % to 98.3 %, with an average correct identification rate of 62.7 %. The most challenging aspects of the identification process included distinguishing between woody and non-woody (agro) biomass, accurately identifying petroleum-derived materials, and differentiating agro biomass from inorganic matter. The results suggest that while RLM is an important tool for characterizing solid biomass, further development of methodology guidelines and training are necessary to enhance its effectiveness. Future research should prioritize preparing detailed, image-rich, microscopic morphological descriptions of biomass fuel components, which could improve the accuracy and reliability of using RLM in biomass fuel characterization.

International Journal of Coal Geology

Constraining landslide frequency across the United States to inform county-level risk reduction

Informative landslide hazard estimates are needed to support landslide mitigation strategies to reduce landslide risk across the United States. Whereas existing national-scale landslide susceptibility products assess where landslides are likely to occur, they do not address how often , which is a critical element of landslide hazard and risk assessments. In particular, the U.S. Federal Emergency Management Agency's National Risk Index (NRI) requires landslide frequency estimates to inform expected annual loss estimates. We present county-level landslide frequency (landslides per area per year) estimates for the 50 US states. We applied Bayesian negative binomial regression to estimate both the expected (average) reported landslide frequency and full distribution of annual landslide counts for each county. We compared a suite of models that used combinations of landslide-susceptible area, probability of potentially triggering earthquakes, frequency of potentially triggering precipitation, and ecological region as predictors. We trained our models with landslide inventory data from counties with the most comprehensive records available nationwide and used zero-inflated negative binomial distributions as an incompleteness model to correct for temporal reporting gaps. We selected a preferred frequency model to inform the NRI based on information criteria and physically plausible parameter estimates. The model showed that average annual reported landslide frequencies vary by 5 orders of magnitude across US counties, ranging from 0.002 (0.00015–0.05) landslides 1000 km −2 yr −1 in Kusilvak Census Area, Alaska, to 29 (19–46) landslides 1000 km −2 yr −1 in Lake County, California, reflecting the country's strong variations in landslide susceptibility, earthquake probability, and other factors for which ecological region serves as a proxy. Counties with estimated frequencies in the top 20 % of all counties are predominately along the West Coast of the continental United States, in mountainous regions of the Pacific Northwest and Intermountain West, in locally steep or earthquake-prone regions of the Midwest and Southeast, along the Appalachians, in southern and southeastern Alaska, and on some Hawaiian islands. By examining the number of landslides predicted in 99th percentile years for each county, we identified that 26 % of US counties likely have potential for widespread landsliding with more than 10 landslides 1000 km −2 yr −1 , even when such large events have not been reported in the training data for that county. Overall, our results better represent the range of possible landslide frequencies and spatial variations than previous national-scale estimates reported in the NRI, and our approach can inform other risk-reduction and loss-mitigation efforts across the United States and globally.

Natural Hazards and Earth System Sciences

Small-volume tephra deposits of the May 1924 explosions from Halemaʻumaʻu, Kīlauea volcano, and their origin

More than 50 explosive eruptions occurred from Halemaʻumaʻu at Kīlauea volcano over 17 days from May 11 to 27, 1924. Ballistics weighing as much as 14,000 kg were ejected and most landed within 2 km of the vent. Fine ash made up a major component of the tephra and was dispersed tens of kilometers downwind. Draining of the Halemaʻumaʻu lava lake occurred in late February 1924, with the crater floor eventually subsiding by a further ∼70 m (to ∼180 m below the crater rim) by the time the first explosions took place during the night of May 10–11. The largest explosions occurred on May 17–18 and smaller explosions continued until May 27, at which point Halemaʻumaʻu had more than doubled in width and depth. The explosions generated plumes reaching up to ∼10 km high with ballistics ejected up to 2 km from the crater. Almost 100 years later, we investigate and characterize the preserved tephra deposits within ∼3 km of the 1924 crater rim. Grain size and shape analyses were performed on 202 samples collected from 34 tephra profiles using dynamic image analysis, with a subset of layers from nine tephra profiles used for componentry (200 grains per layer in the 0.5–1 mm size fraction). Additionally, we characterize the average diameters (using the five largest clasts) at 216 locations and measure the average diameters of 2291 ballistics (largest per ∼100 m 2 area). Physical descriptions from fieldwork and grain size distributions were used to subdivide the tephra layers into five lithofacies: coarse homogeneous, fine homogenous, red ash, accretionary lapilli-bearing, and finely laminated. Grain size versus shape data show a range of values that demonstrate most grains are dense, smooth, and equant, in alignment with lithic clasts dominating the tephra componentry. The fine grained and accretionary lapilli-bearing nature of some of these lithofacies confirms that water influenced the style of the explosions. However, we also note juvenile clasts within many of the tephra layers, indicating that many of the layers were formed during phreatomagmatic explosions (sensu stricto), despite the eruptive mechanism being dominantly phreatic. Juvenile clasts are more abundant higher in the tephra profiles, suggesting that juvenile magma was more involved later in the explosive sequence. Thermal and hydrologic modeling indicate that groundwater inflow into a short-lived, small-diameter volcanic conduit (10-m to 120-m-diameter used for modeling) during the 78–85 days preceding the first explosion provides a physically plausible mechanism for this eruptive sequence.

Hawaii

Effects of a low-lipid diet on the gut microbiome and head kidney transcriptome of juvenile Chinook Salmon

Objective Pacific salmon Oncorhynchus spp. reared in production hatcheries are typically fed high-lipid, energy-dense diets to achieve large size and high body condition prior to release. In contrast, juveniles in natural environments tend to consume low-lipid, high-protein diets, and fish reared for research or conservation purposes are sometimes fed diets that are formulated to mimic natural diets and promote wild-like phenotypes. Understanding how these alternative diets affect fish health beyond growth and body condition could ultimately contribute to improving hatchery fish fitness. Methods In this work, we evaluated changes in the fecal microbiome and gene expression of juvenile Chinook Salmon O. tshawytscha on a standard high-lipid hatchery diet versus a low-lipid diet formulated to mimic the nutrition profile of natural-origin fish. To evaluate the time scale at which diet alters the fecal microbiome, we collected longitudinal samples over a 12-week period and switched the diets of a subset of fish twice during the experiment. We used 16S ribosomal RNA gene amplicon sequencing to characterize fecal microbiome differences between fish on the two diets as well as hatchery-reared fish at a production hatchery, hatchery fish that had been captured after release into a stream, and natural-origin, stream-reared fish of similar ages. Additionally, we conducted RNA sequencing on head kidney samples from laboratory-reared fish to evaluate changes in gene expression in this important immune organ. Results We found that the low-lipid diet and the hatchery diet resulted in microbiomes that differed from the microbiome of natural-origin fish and from each other and that diet-driven changes to the microbiome could occur in under 14 d. The low-lipid diet did not result in a microbiome that resembled the microbiome of naturally produced fish. Instead, the low-lipid diet resulted in a microbiome community that was distinct from those of fish reared on the hatchery diet and fish sampled from the wild. The RNA sequencing results indicated differential enrichment of pathways related to immunity, metabolism, and hormone synthesis between fish that were fed the two experimental diets. Conclusions The results suggest that additional environmental factors influence the microbiome more strongly than diet formulation or that the low-lipid diet has a smaller effect on the microbiome than a natural, ­invertebrate-based diet. Given that the gut microbiome and systemic immune function contribute significantly to disease resistance, our findings highlight the importance of understanding how diets fed to fish in captivity may affect fish health beyond growth and body condition metrics.

Journal of Aquatic Animal Health

Per- and polyfluoroalkyl substances in waters associated with oil and gas development in the Denver Basin

Use of per- and polyfluoroalkyl substances (PFAS) in the petroleum industry could be a cause for concern due to the large volumes of produced water (PW) generated during oil and gas extraction, the reuse of these wastes in water-stressed regions, and adverse health outcomes related to PFAS exposures. However, PW PFAS characterization is nearly absent in the literature, and hydraulic fracturing (HF) chemical disclosures often omit the identities of additives as proprietary. Here we evaluate PFAS in PW samples from three petroleum wells in the Denver Basin during their first year of production. Total concentrations of targeted PFAS (Σ 40 PFAS) were < 35 ng/L in PW samples, with short-chain PFAS like perfluorobutanoic acid persisting throughout the sampled duration. Analysis of freshwater inputs for hydraulic fracturing (Σ 40 PFAS ~ 113 ng/L) and mixed fracture fluid (Σ 40 PFAS ~ 69 ng/L) indicated much of the targeted PFAS content was derived from the input water, and not from HF additives, however samples subjected to oxidation indicated the presence of PFAS precursors that would not be detected by targeted analysis. This study highlights that while PFAS content is low in the studied PWs, the potential for redistribution of PFAS in the environment may be a consideration for reuse applications.

Colorado, Nebraska, Wyoming