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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

Water-quality appraisal of NASQAN stations below impoundments, eastern Tennessee

The National Stream Quality Accounting Network (NASQAN) is a network of stations at which systematic and continuing water-quality data are collected. Major objectives of this U.S. Geological Survey program are (1) to depict areal variability of streamflow and water-quality conditions nationwide on a year-by-year basis and (2) to detect long-term changes in streamflow and stream quality. Several NASQAN stations in East Tennessee are downstream from impoundments which have a significant effect on water quality. NASQAN data obtained from the Tennessee River below Watts Bar Dam and the Clinch River below Melton Hill Dam were compared to water-quality data from the basins upstream. The comparison indicates that NASQAN data obtained below impoundment may not be adequate to describe a composite picture of water quality in the accounting unit. Detention time of storage in the impoundments is believed to moderate the range of constituent values observed at the NASQAN stations. Data obtained upstream and downstream from Watts Bar Dam indicate that the water sampled at the NASQAN station comes from stratified layers of the impoundment and is not representative of an integrated sample of water from the impoundment. Values of total recoverable iron suggest that, because of adsorption to sediments in impoundments, some constituents are not accurately described by sampling below impoundments. Relations between water-quality constituents and flow at stations on the Clinch River and Tennessee River are not well defined due to regulation. Direct load computations for many constituents were therefore not possible, which diminished the utility of data from these NASQAN stations to account for quantity versus quality of the water. Load computations were only possible for ionic constituents through use of a continuous specific-conductance record as an intermediary. Compensation for the effects of discharge prior to application of the Seasonal Kendall test for trends could not be done and identification of trends in water-quality constituents caused by some process (source) change was not possible. Some water-quality trends indicated by data from the Clinch and Tennessee Rivers might reflect the decreasing trend in discharge during the 1972-82 water years. Thus the stations below Watts Bar Dam and below Melton Hill Dam do not adequately meet the NASQAN objective to detect and assess long-term changes in stream quality.

Tennessee

Surficial geology and Quaternary tectonics of the Madison Valley and fault zone, Madison, Gallatin, and Beaverhead Counties, southwest Montana

The north-northwest-striking Madison fault is approximately 95 kilometers in length, lying at the confluence of the northeastern Basin and Range province and the Yellowstone tectonic parabola. The fault zone consists primarily of west-dipping normal faults that have east-dipping antithetic faults, which create the Madison Valley graben and several northeast-trending intrabasin faults. The Madison fault and associated sections discussed herein refer to the main west-dipping, range-bounding fault along the eastern side of the valley. Detailed geologic mapping (1:12,000 scale) of the entire fault zone and fault scarp profiling (total of 102 profiles) of the Madison fault reveal greater late Quaternary paleoseismic activity towards the south, including at least three paleoevents along the southern part of the fault that postdate Pinedale glaciation. Early to middle Holocene alluvial fans have vertical surface offsets that average between 2.0 and 3.0 meters and define the characteristic single-event surface offset. Pinedale lateral moraines have vertical surface offsets as great as 12.0 meters. Late Pleistocene to Holocene multiple-event fault scarps show little evidence of beveling, suggesting short seismic recurrence intervals and potential late Pleistocene and Holocene temporal clustering. Long-term average tectonic activity rates indicate slip rates ranging from 0.18–0.6 millimeters per year. Based on a comparison of fault-scarp height versus maximum slope angle of known regression lines developed from other paleoseismic investigations, the most recent event ranges from 5–1 ka. The northern section of the fault zone is defined by multiple normal faults, which detached the hanging walls of Laramide thrust faults within the Paleozoic and Mesozoic strata. This resulted in the partitioning of extension along multiple preexisting structures and less displacement along individual normal fault strands. Structural controls on lateral propagation of individual paleoevents involve the position of lateral ramps along preexisting Laramide contractional faults. This resulted in greater displacement within the larger basement-cored structures along the southern section of the fault zone, where extension is accommodated by one inferred principal basement-involved normal fault. Inferred east-northeast trending, intrabasin, normal faults within the southern half of the fault zone have no late Pleistocene displacement.

Idaho, Montana, Wyoming

Seabed maps showing topography, ruggedness, backscatter intensity, sediment mobility, and the distribution of geologic substrates in quadrangle 2 of the Stellwagen Bank National Marine Sanctuary region offshore of Boston, Massachusetts

The U.S. Geological Survey, in cooperation with the National Marine Sanctuary Program of the National Oceanic and Atmospheric Administration, has conducted seabed mapping and related research in the Stellwagen Bank National Marine Sanctuary (SBNMS) region since 1993. The area being mapped using geophysical and geological data includes the SBNMS and the surrounding region, which totals approximately 3,700 square kilometers (km 2 ) and is subdivided into 18 quadrangles. The seabed is a glaciated terrain that is topographically and texturally diverse. Quadrangle 2, the subject of this scientific investigations map, has a mapped area of 209 km 2 and has water depths that range from about 19 meters (m) on the Stellwagen Bank crest to about 68 m in the Stellwagen Basin. Seven map types, each at a scale of 1:25,000, depict seabed topography, ruggedness, backscatter intensity, distribution of geologic substrates, sediment mobility, distribution of fine- and coarse-grained sand, and substrate mud content. These maps show the distribution of geologic substrates across the southwestern part of Stellwagen Bank, in Stellwagen Basin to the west and southwest of the bank, and in Little Stellwagen Basin and the western part of Race Point Channel to the south of the bank. Interpretations of multibeam sonar bathymetric and seabed backscatter imagery, photographs, video imagery, and grain-size analyses were used to create the geology-based maps. Data from 733 stations were analyzed, including 656 sediment samples. The geologic substrate maps of quadrangle 2 show the distribution of 19 geologic substrates that represent a wide range of textures, such as rippled and immobile sand, immobile muddy sand and sandy mud, sand that partially veneers gravel, and a boulder ridge. Mapped substrates are characterized by sediment grain-size composition, surface morphology, substrate layering, the mobility or immobility of substrate surfaces, and water depth range. This scientific investigations map portrays the major geological elements (substrates, topographic features, and processes) of environments in quadrangle 2. It is intended to provide a foundation for research into present and past sediment transport processes in a complex terrain, provide insights into the ecological requirements of invertebrate and vertebrate species that utilize the various substrates, and support seabed management in the region.

Massachusetts

Deep-ocean macrofaunal assemblages on ferromanganese and phosphorite-rich substrates in the Southern California Borderland

Mineral-rich hardgrounds, such as ferromanganese (FeMn) crusts and phosphorites, occur on seamounts and continental margins, gaining attention for their resource potential due to their enrichment in valuable metals in some regions. This study focuses on the Southern California Borderland (SCB), an area characterized by uneven and heterogeneous topography featuring FeMn crusts, phosphorites, basalt, and sedimentary rocks that occur at varying depths and are exposed to a range of oxygen concentrations. Due to its heterogeneity, this region serves as an optimal setting for investigating the relationship between mineral-rich hardgrounds and benthic fauna. This study characterizes the density, diversity, and community composition of macrofauna (>300 μm) on hardgrounds as a function of substrate type and environment (depth and oxygen ranges). Rocks and their macrofauna were sampled quantitatively using remotely operated vehicles (ROVs) during expeditions in 2020 and 2021 at depths above, within, and below the oxygen minimum zone (OMZ). A total of 3,555 macrofauna individuals were counted and 416 different morphospecies (excluding encrusting bryozoans and hydrozoans) were identified from 82 rocks at depths between 231 and 2,688 m. Average density for SCB macrofauna was 11.08 ± 0.87 ind. 200 cm −2 and mean Shannon-Wiener diversity per rock (H′ [loge] ) was 2.22 ± 0.07. A relationship was found between substrate type and macrofaunal communities. Phosphorite rocks had the highest H′ of the four substrates compared on a per-rock basis. However, when samples were pooled by substrate, FeMn crusts had the highest H′ and rarefaction diversity. Of all the environmental variables examined, water depth explained the largest variance in macrofaunal community composition. Macrofaunal density and diversity values were similar at sites within and outside the OMZ. This study is the first to analyze the macrofaunal communities of mineral-rich hardgrounds in the SCB, which support deep-ocean biodiversity by acting as specialized substrates for macrofaunal communities. Understanding the intricate relationships between macrofaunal assemblages and mineral-rich substrates may inform effects from environmental disruptions associated with deep-seabed mining or climate change. The findings contribute baseline information useful for effective conservation and management of the SCB and will support scientists in monitoring changes in these communities due to environmental disturbance or human impact in the future.

California

Geochemical geodatabase of sedimentary strata (coal, coal-adjacent rocks, tuffaceous oil shale, phosphate-rich rocks) and produced water in the Uinta region, Utah and Colorado

The Geochemical Geodatabase of Sedimentary Strata (Coal, Coal-adjacent Rocks, Tuffaceous Oil Shale, Phosphate-rich Rocks) and Produced Water in the Uinta Region, Utah and Colorado, consists of compiled datasets acquired as part of the Carbon Ore, Rare Earth, and Critical Mineral (CORE-CM) Uinta Region assessment funded by the U.S. Department of Energy (DEFE0032046, 2021–2024; Birgenheier et al., 2024). The CORE-CM assessment focused on providing comprehensive geological and geochemical characterization of current and prospective sedimentary-hosted resources including coal, oil shale, phosphatic limestone, and produced water from oil and gas targets present in eastern Utah and northwestern Colorado (Figure 1). This Data Series includes a geodatabase that consists of analytical geochemical data collected September 2021 through December 2024 via portable X-ray fluorescence (pXRF), and laboratory measured analyses produced by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectroscopy (ICP-OES). The coal-related geochemical data are derived primarily from the Cretaceous Blackhawk Formation and Ferron Sandstone of Utah, and the Mesaverde Group of Colorado. Additional non-coal resources assessed include oil shale-bearing strata of the Eocene upper Green River Formation (Utah and Colorado), phosphate-rich limestone of the Permian Park City Formation (Utah) and produced water from oil and gas-bearing strata of the Eocene Green River and Wasatch Formations (Uinta Basin) and the Pennsylvanian Paradox Formation (Paradox Basin) (Table 1). The CORE-CM assessment included a wide range of lithologies present in the coal, oil shale, and phosphate geologic resource systems whether or not the specific lithology has current economic value. Geochemical analyses of produced water from oil and gas wells focused on current and emerging hydrocarbon targets in the central Uinta Basin and northern Paradox Basin. A total of 13,092 geochemical analyses from these geologic systems is provided in the included geodatabase. A series of coal quality data (e.g., composition and maceral analyses) is also included in the database and was digitized from archived coal samples from the Utah Geological Survey (Appendix A).

Colorado, Utah

Inset groundwater-flow models for the Cache and Grand Prairie Critical Groundwater Areas, northeastern Arkansas

The water resources in the Mississippi alluvial plain, located in parts of Missouri, Kentucky, Tennessee, Mississippi, Louisiana, and Arkansas, supports a multibillion-dollar agricultural industry that relies heavily on pumping of groundwater for irrigation of crops and aquaculture. The primary source of groundwater for agricultural-related pumping is the Mississippi River Valley alluvial aquifer, which has declined in storage for decades; secondary groundwater sources include the middle Claiborne aquifer and Wilcox aquifer system. Two areas in northeastern Arkansas that lie within the Mississippi alluvial plain, part of the Cache and Grand Prairie regions, have been designated as Critical Groundwater Areas owing to decades of groundwater declines that resulted from past and current water use. The multidisciplinary Mississippi Alluvial Plain project, led by the U.S. Geological Survey, and funded by their Water Availability and Use Science Program, included objectives to develop numerical groundwater models in focus regions, including the part of the Cache and Grand Prairie regions of northeastern Arkansas. Two inset models were developed using the child model capabilities of MODFLOW 6, the U.S. Geological Survey’s Modular Hydrologic Model simulation software. Both models, called the Cache model and Grand Prairie model, simulated the groundwater system and surface-water/groundwater interactions for the Mississippi River Valley alluvial aquifer and underlying Tertiary-age aquifers and confining units to the Midway confining unit. Each model was spatially discretized into 500-meter x 500-meter orthogonal cells on a grid with 5-meter constant-thickness vertical layers that represented the Mississippi River Valley alluvial aquifer and increasing thickness layers for the aquifers and confining units below the alluvial aquifer. The Cache and Grand Prairie models were calibrated with the PEST++ iterative ensemble smoother Version 5 and employed high dimensional parameterization schemes of 13,740 and 30,436 parameters, respectively. The Cache mean absolute residual for groundwater-level observations within each model domain for the priority well was 1.58 meters. Grand Prairie mean absolute residuals for the alluvial aquifer and middle Claiborne aquifer groundwater-level observations were 2.71 and 10.78 meters, respectively. The groundwater budgets for the Cache and Grand Prairie models were characterized by substantial outflows to irrigation wells, which constituted about 52 and 54 percent of all outflows, with the primary source of water to those wells being releases from unconfined aquifer storage.

Arkansas

Estimating habitat availability for Chinook salmon (Oncorhynchus tshawytscha) and steelhead (O. mykiss) to inform reintroduction planning in the middle Snake River basin, USA

Anadromous fishes have been blocked from the middle Snake River basin since the construction of flood control, irrigation, and hydroelectric projects during the 19 th and 20 th centuries, culminating with the construction of Hells Canyon Dam (river kilometer [rkm] 398) in 1967. Seven large watersheds in the blocked area of the basin are under consideration for Pacific salmon reintroduction. The primary objective of this study was to identify and characterize potential reintroduction sites with high-quality rearing and spawning habitat for Chinook salmon ( Oncorhynchus tshawytscha ) and steelhead ( O. mykiss ) upstream of the Hells Canyon Complex in Idaho, Oregon, and Nevada, USA. We created and tested habitat models to predict rearing presence/absence, rearing abundance, and spawning presence/absence using channel morphology, hydrology, and stream temperature variables obtained from regional peer-reviewed datasets. Habitat models were trained with salmonid presence and abundance records collected in the lower Snake River basin (downstream of Hells Canyon Dam), where anadromous fish can currently access, from 1993 to 2011. Model performance was tested with set-aside data comprised of randomly selected reaches and independent environmental DNA data. An index model was created in the middle Snake River basin for each species by combining results from the habitat models. Modeling covariates differed by species and life stage and included different combinations of August stream temperature, summer flow, channel slope, and quadratic terms for temperature and slope. The habitat models predicted high versus low Chinook salmon and steelhead probability and abundance with 66% to 85% accuracy depending on species and life stage. The index models predicted a total of 2,887 km of Chinook salmon habitat and 2,434 km of steelhead habitat in the blocked area. The three basins in the blocked area with the greatest amount of predicted habitat were the Powder River, South Fork Payette River, and North Fork Payette River for Chinook salmon, and the Powder River, South Fork Boise River, and South Fork Payette River for steelhead. The modeling approach presented here is complementary to other planning efforts for Chinook salmon and steelhead reintroduction in the blocked area of the Snake River basin, and similar approaches may be useful for reintroduction planning in other systems.

Idaho, Nevada, Oregon, Utah, Washington, Wyoming

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

Temporal, spatial, and chemical evolution of Quaternary high-silica rhyolites in the Mineral Mountains, Utah

The Mineral Mountains in southwestern Utah are a structurally controlled core complex at the confluence of the Colorado Plateau and the Basin and Range physiographic provinces. Aside from hosting Utah’s largest batholith, the Mineral Mountains host some of the State’s youngest high-silica rhyolites, which have been linked to a magma source that is presently being utilized as an enhanced geothermal system. The high-silica rhyolites take the form of effusive lavas and domes, and explosive products are rare. Previous K-Ar dating of these Pleistocene rhyolites placed eruptions between about 790 and 500 kilo-annum (ka) with contemporaneous basalts erupting in the valley to the east of the Mineral Mountains. Large uncertainties on these ages obscured the tempo of eruptions and thus hindered attempts to constrain the timescales of the petrogenetic processes that produced the rhyolites. In this study, we build on previous studies conducted in the 1970s and 1980s by using new geochronologic and geochemical data to investigate the temporal and spatial evolution of the youngest phase of volcanism in the Mineral Mountains. We identify two major eruptive periods, from approximately 850 to 750 ka and from approximately 590 to 480 ka. The older phase is characterized by the eruption of several basaltic lavas, two obsidian flows, and a series of coalescing porphyritic rhyolite domes. The younger phase included the eruption of six evolved high-silica rhyolite domes and one pyroclastic deposit, followed by the eruption of trachyandesite in the adjacent valley to the east. Whole-rock geochemical data indicate that the rhyolites can be divided into three chemical groups, with more evolved compositions erupting through time. The youngest rhyolites along the range crest have the lowest total iron and TiO 2 concentrations and the highest incompatible element concentrations, indicative of increasing differentiation with time and elevation. Improved precision on the eruption ages indicates a recurrence interval of approximately 20 thousand years. The eruptive flux for both periods of rhyolitic volcanism is about 0.01 cubic kilometers per thousand years, which is less than the magma resurgence flux rates for syn-caldera and post-caldera eruptions of the Valles Caldera and Yellowstone Caldera volcanic systems. Collectively, these geochemical, geochronological, and volumetric data may facilitate a better understanding of heat flux and the longevity of magmatic sources related to geothermal resources in similar small-volume, silicic systems.

Utah

Igneous differentiation in arcs

This chapter assesses crystallization-differentiation of convergent-margin magmas both from the standpoints of natural rock suites and from laboratory phase-equilibrium experiments. Crystallization-differentiation of dry subalkaline and alkaline basalts are summarized at the beginning for reference and context. Experiments crystallizing arc basalts through andesites at middle to upper crustal pressures (100–400 MPa), saturated either with H 2 O or mixed H 2 O-CO 2 , produce liquid lines of descent similar to arc igneous suites, with higher f O 2 s giving results closer to calc-alkaline magma series. Early enrichment of melts in SiO 2 with little or no enrichment in FeO* (total Fe as FeO) comes about by the combined effects of H 2 O suppressing crystallization of plagioclase relative to olivine, shifting plagioclase to more calcic – therefore lower SiO 2 – compositions, and suppressing silicate minerals to greater extents than Fe-rich spinel. Also contributing to SiO 2 enrichment is crystallization near the liquidus of higher proportions of olivine relative to calcic clinopyroxene, compared with MORB, but it is unclear if this is brought about by H 2 O or elevated pressure. Exhumed arc terranes, however, generally fail to expose evidence for primitive liquids having reached and differentiated at middle to upper crustal depths, at least in any abundance. Instead, most differentiation in arcs appears to take place in the lower crust or near the crust-mantle transition, and although hydrous experiments at such pressures produce liquids broadly similar to arc suites in their SiO 2 enrichment, the experimental liquids differ in becoming peraluminous at early stages of differentiation while melts have basaltic, basaltic andesitic, or andesitic SiO 2 concentrations. Crystallization of abundant calcic clinopyroxene close to the liquidus causes the high-pressure experimental liquids to become peraluminous with only small increases in SiO 2 concentration. In contrast, natural arc volcanic and plutonic suites become gradually less metaluminous with increasing SiO 2 , crossing to peraluminous at dacitic to rhyolitic SiO 2 concentrations. Hybridism, encompassing magma-mixing, assimilation of old crust, and incorporation of near-solidus melts from only shortly older deep, antecedent arc intrusions may accompany natural crystallization-differentiation, preventing melts from attaining peraluminous compositions at low-SiO 2 concentrations. If so, then nearly all arc suites are to substantial extents composites, rather than preserving simple, progressive liquid lines of descent. Some comments and assessments are also made on the participation of garnet in arc differentiation and on the production of arc batholiths.

Book chapter

Seabed maps showing topography, ruggedness, backscatter intensity, sediment mobility, and the distribution of geologic substrates in quadrangle 3 of the Stellwagen Bank National Marine Sanctuary region offshore of Boston, Massachusetts

The U.S. Geological Survey, in cooperation with the National Marine Sanctuary Program of the National Oceanic and Atmospheric Administration, has conducted seabed mapping and related research in the Stellwagen Bank National Marine Sanctuary (SBNMS) region since 1993. The area being mapped using geophysical and geological data includes the SBNMS and the surrounding region, which totals approximately 3,700 square kilometers (km 2 ) and is subdivided into 18 quadrangles. The seabed is a glaciated terrain that is topographically and texturally diverse. Quadrangle 3, the subject of this scientific investigations map, has a mapped area of 185 km 2 and has water depths that range from about 30 meters (m) on the Stellwagen Bank crest to about 135 m in a basin east of South Ninety Bank, which lies off the eastern margin of Stellwagen Bank. Seven map types, each at a scale of 1:25,000, depict seabed topography, ruggedness, backscatter intensity, distribution of geologic substrates, sediment mobility, distribution of fine- and coarse-grained sand, and substrate mud content. These maps show the distribution of geologic substrates on the southeastern part of Stellwagen Bank, on adjacent banks and basins in deeper water to the east, in the eastern part of Race Point Channel to the south of the bank, and on the northern slope of Cape Cod. Interpretations of multibeam sonar bathymetric and seabed backscatter imagery, photographs, video imagery, and grain-size analyses were used to create the geology-based maps. Data from 309 stations were analyzed, including 279 sediment samples. The geologic substrate maps of quadrangle 3 show the distribution of 21 geologic substrates that represent a wide range of textures, such as rippled sand, immobile sand, immobile muddy sand, sand that partially veneers gravel, and boulder ridges. Mapped substrates are characterized by sediment grain-size composition, surface morphology, substrate layering, the mobility or immobility of substrate surfaces, and water depth range. This scientific investigations map portrays the major geological elements (substrates, topographic features, and processes) of environments in quadrangle 3. It is intended to provide a foundation for research into present and past sediment transport processes in a complex terrain, provide insights into the ecological requirements of invertebrate and vertebrate species that use the various substrates, and support seabed management in the region.

Quadrangle 3 of the Stellwagen Bank National Marin

Wangyanite, PdNi8S8, a new Pd end-member mineral of the pentlandite group from the J-M reef, Stillwater Complex, Montana, USA

Wangyanite (IMA2024-008a), ideally PdNi 8 S 8 , is a Pd end-member mineral of the pentlandite group that was discovered in the J-M reef of the Stillwater Complex, Montana, USA. Wangyanite occurs as anhedral-subhedral granular crystals 200–400 µm in size, associated with isoferroplatinum, braggite, pentlandite, and chalcopyrite interstitial to plagioclase grains within anorthosite. Wangyanite exhibits a yellowish brown color with a black streak and a metallic luster. It is brittle with uneven fractures, and has a calculated density of 5.14 g/cm 3 . The mineral does not show discernible pleochroism, bireflectance, or anisotropy. It has an average composition of 9.95 wt.% Pd, 31.95 wt.% Ni, 25.02 wt.% Fe, 0.57 wt.% Co, 31.74 wt.% S, totaling 99.23 wt.%. The empirical formula, based on eight sulfur atoms per formula unit, is (Pd 0.76 Co 0.08 ) Σ0.84 (Ni 4.39 Fe 3.60 ) Σ7.99 S 8 . Wangyanite has a cubic cell with a space group of Fm -3 m (#225), having lattice parameters of a = 10.1167(12) Å, V = 1035.4(4) Å 3 , and Z = 4. Its crystal structure has been solved by single-crystal three-dimensional electron diffraction study. The strongest X-ray diffraction lines of wangyanite are claculated at [ d in Å ( I %)( hkl )]: 5.841(14.03)(111), 3.050(100)(311), 1.947(29.16)(115,333), 1.264(11.66)(800), 3.577(8.79)(220), 2.920(20.82)(222), and 2.321(9.34)(331). Wangyanite shares the same crystal structure as pentlandite, but the octahedrally coordinated site is mainly occupied by Pd in wangyanite. Based on the textural features and previous experimental Pd-Fe-Ni-S phase system, wangyanite could form by peritectic reaction between braggite, pentlandite and sulfide liquid. These mineral associations are stable in a Ni-Pd-rich sulfide melt system at about 550 °C or even lower temperature. Therefore, wangyanite can potentially serve as an indicator of the presence of Pd-rich residual melts. The mineral is named in honor of Prof. Christina Yan Wang, a well-known researcher on platinum-group element (PGE) occurrences and enrichment mechanisms in mafic-ultramafic intrusions, notably those deposits related to the Emeishan large igneous province in China.

Montana

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

Evaluation of best management practices at an edge-of-field site in the Eagle Creek watershed, Ohio, 2012–20

In 2010, the U.S. Geological Survey worked in partnership with the Great Lakes Restoration Initiative and the Natural Resources Conservation Service to identify farm fields in priority watersheds—watersheds critically important to Great Lake health. Intensive best management practices were implemented in five States to test the efficacy of best management practices, also referred to as agricultural conservation practices, to reduce sediment and nutrient runoff on agricultural fields. These fields were chosen as representatives of the priority watersheds because their farming practices and geographical conditions were common among farms in those watersheds. A farm site located near Findlay, Ohio, in the Eagle Creek watershed used two conservation practices, cover crop (Natural Resources Conservation Service practice standard 340) and variable rate technology (VRT; Natural Resources Conservation Service practice standard 590), which represent common practices in the Maumee priority watershed. This study monitored surface runoff and subsurface tile runoff at the Eagle Creek watershed site. The effects of cover crop and VRT nutrient application on sediment and nutrient runoff were assessed from October 2012 to September 2020. Cover crops were applied in fall of 2016, 2017, and 2018, coinciding with VRT applications. The following parameters were analyzed as part of the study: runoff discharge; peak discharge; and concentrations and loads of total phosphorus, particulate phosphorus, dissolved reactive phosphorus, and suspended sediment. High peak runoff events disproportionally affected nutrient concentrations and loads in runoff. A threshold of the 85th percentile of the peak discharge was chosen to assess the effect of cover crop and VRT nutrient application on nutrient mitigation at each gage. Runoff events below the 85th percentile were considered small, and runoff events over the 85th percentile were considered large. Concentrations from collected water-quality samples were used for the analysis; estimated concentrations were excluded from the statistical evaluation. All surface runoff parameters during small runoff events, except surface runoff volume, were significantly lower in the period with cover crops and VRT implementation. Contrarily, subsurface runoff parameters during small events were not statistically different between the periods with and without cover crops and VRT implementation. Surface and subsurface parameters during large events were also not statistically different between the periods with and without cover crops and VRT implementation. These results indicate cover crops and VRT may improve water quality during small runoff events, but additional best management practices that mitigate large runoff events may lead to greater water-quality improvement given the contribution of large events to overall losses.

Ohio

Groundwater response to managed aquifer recharge at the Southeast Houghton Artificial Recharge Project in Tucson, Arizona

Managed aquifer recharge is a widespread practice for storing water in the subsurface as groundwater. At a managed aquifer recharge facility in southern Arizona, groundwater-level and repeat microgravity data were collected to monitor aquifer response. These data were used to inform parameter identification for an unsaturated-zone flow model used to simulate the recharge process. The facility, the Southeast Houghton Artificial Recharge Project (SHARP), consists of 3 surface basins (about 27,600 square meters [6.8 acres] total surface area) where recycled water is distributed in recharge cycles lasting several months, with dry periods in between. During the study period, December 2020–December 2022, Tucson Water (the City of Tucson’s water utility) reported 6.56×10 6 cubic meters of water (5,320 acre-feet) recharged. Monitoring included groundwater-level observations at 3 monitoring wells and repeat microgravity measurements at as many as 22 locations (some stations were destroyed between surveys). Six gravity surveys were carried out using absolute- and relative-gravity meters. Large gravity increases, more than 250 microgals, were observed during the first repeat survey, 3.5 months after the start of recharge, but only in the immediate vicinity of the recharge basins. Data show that water moved downward to the water table, and storage changes in the unsaturated zone away from the facility were likely minimal. Gravity decreased at stations more than 1 kilometer from the facility, consistent with regional groundwater-level changes. Groundwater-level increases in wells adjacent to the recharge basins began 2 months after the second repeat gravity survey, and 5.5 months after recharge began. Unsaturated-zone flow modeling was carried out using software that simulates water movement and parameter estimation. Model calibration was carried out by minimizing an objective function calculated from the differences between simulated and observed groundwater levels, and between simulated and observed repeat microgravity data. Including repeat microgravity data in the objective function reduced the uncertainty in estimated parameter values for saturated hydraulic conductivity and saturated water content. Modeling indicated that the unsaturated zone between the recharge basins and the water table does not become saturated even after 685 days of simulated infiltration. This gradual wetting may account for increasing infiltration rates over time, as hydraulic conductivity increases with increasing water content. Unsaturated-zone water content decreased rapidly between recharge cycles. Model-simulated groundwater mounding extended about 1 kilometer from the center of SHARP after the 685-day period following the onset of recharge.

Arizona

Water-quality characteristics of the Red River of the North and tributaries in the Fargo-Moorhead metropolitan area, North Dakota, 2019–22

The Flood Risk Management Project was initiated in 2008 in the Fargo-Moorhead metropolitan area to reduce flood risk, flood damages, and flood protection costs in the Fargo-Moorhead metropolitan area. In cooperation with the U.S. Army Corps of Engineers, the U.S. Geological Survey initiated a water-quality monitoring study to describe the water-quality characteristics of the Red River of the North and its tributaries in the Fargo-Moorhead metropolitan area during the preconstruction period of the Flood Risk Management Project from October 1, 2019, to October 1, 2022. The monitoring study included the collection of discrete and continuous water-quality data and streamflow monitoring at selected sites that integrated and enhanced existing monitoring programs within the study area. Discrete samples collected at 10 sites in the Fargo-Moorhead metropolitan area were analyzed for major ions, trace elements, nutrients, suspended sediment, pesticides, and fecal indicator bacteria. In general, major ion concentrations were higher at sites on the tributaries (Wild Rice, Sheyenne, and Maple Rivers) compared to sites on the Red River of the North. In general, bicarbonate, calcium, magnesium, and sulfate represented most of the dissolved ions measured in samples collected at the 10 sites. Calcium, chloride, fluoride, potassium, silica, and sodium were also measured in samples, but they represented a smaller portion of the total dissolved ions. Sulfate was the most dominant dissolved ion that had the highest concentrations among the major ions measured in samples. A total of 18 trace elements were analyzed in discrete samples. Several of the trace elements had concentrations below the laboratory reporting level in all of the samples, including antimony, beryllium, cadmium, chromium, silver, and thallium. Sites on the Wild Rice River generally had the highest concentrations of arsenic, barium, boron, manganese, and nickel compared to the other sites. Nutrients analyzed in discrete samples included filtered and unfiltered concentrations of ammonia, nitrate plus nitrite, phosphorus, and organic carbon. The median filtered ammonia concentration at most sites was less than the laboratory reporting level of 0.03 milligram per liter as nitrogen except for the Sheyenne River at Harwood, North Dakota (U.S. Geological Survey [USGS] station 05060400), and Red River of the North near Georgetown, Minnesota (USGS station 05062130). The lowest median unfiltered nitrate plus nitrite concentration was measured at sites on the Red River of the North upstream from the Fargo-Moorhead metropolitan area and the highest median was at sites on the Red River of the North downstream from the Fargo-Moorhead metropolitan area compared to all other sites. The increase in nitrate plus nitrite concentrations could reflect the effect of the wastewater-treatment plant discharge that enters the Red River of the North upstream from the site located downstream from the Fargo-Moorhead metropolitan area and from urban runoff. Phosphorus (unfiltered) concentrations were generally higher at sites on the Maple and Sheyenne Rivers compared to the other sites and were higher at sites on the Red River of the North downstream from the Fargo-Moorhead metropolitan area compared to sites upstream on the Red River of the North. Suspended-sediment concentrations were generally highest at sites in the Sheyenne River and lowest in the upstream Red River of the North sites. Suspended-sediment concentration was highly variable in samples collected at the 10 sites, mostly influenced by the occurrence of snowmelt and rainfall-runoff events. The Sheyenne River near Kindred, N. Dak. (USGS station 05059000) had the largest range in sediment concentrations in samples collected at the 10 sites. For all sites other than the Sheyenne River near Kindred, N. Dak., 95 percent or more of the suspended sediment had particle diameter sizes less than 0.0625 millimeter in 50 percent of the samples (median). Of the 102 pesticides and pesticide degradates analyzed, 45 constituents had no detectable concentrations in any of the 17 samples collected at five sites. The remaining 57 pesticides had at least one detection in the samples collected at the five sites. The sites on the Wild Rice River (near Abercrombie, N. Dak., USGS station 05053000, and near St. Benedict, N. Dak., USGS station 05053500) and Sheyenne River near Kindred, N. Dak., had fewer pesticide detections compared to the Maple River below Mapleton, N.Dak. (USGS station 05060100) and the Red River of the North at Fargo, N. Dak (USGS station 05054000) and near Georgetown, Minn. Patterns in annual loads generally followed the same pattern as streamflow at the 10 sites for water years 2020–22. A water year is the 12-month period from October 1 to September 30 and is designated by the calendar year in which it ends. The greatest loads for all constituents were delivered at the two downstream sites on the Red River of the North; sites that also had the highest annual streamflows among the sites and the greatest loads were delivered in water year 2020 when the highest streamflows occurred at the sites. Likewise, the least loads for most constituents were at the Maple River and were least in 2021 compared to the other years because of low-streamflow conditions. Water-quality measurements continuously recorded at the Red River of the North at Hickson, N. Dak. (USGS station 05051522); Red River of the North at Fargo, N. Dak.; and Red River of the North near Georgetown, Minn. included water temperature, specific conductance, dissolved oxygen, pH, and turbidity. Specific conductance values were similar for the Red River of the North near Hickson, N. Dak., and Red River of the North at Fargo, N. Dak., when compared to the Red River of the North near Georgetown, Minn. that had higher values than the other two sites. Dissolved oxygen concentrations and pH were similar among the three sites on the Red River. The patterns in turbidity were mostly related to streamflow conditions and were similar among the three sites on the Red River of the North.

Minnesota, North Dakota

Estimated groundwater recharge for mid-century and end-of-century climate projections, Kaua‘i, O‘ahu, Moloka‘i, Lāna‘i, Maui, and the Island of Hawai‘i

Demand for freshwater in the State of Hawaiʻi is expected to increase by roughly 13 percent from 2020 to 2035. Groundwater availability in Hawaiʻi is affected by a number of factors, including land cover, rainfall, runoff, evapotranspiration, and climate change. To evaluate the availability of fresh groundwater under projected future-climate conditions, estimates of groundwater recharge are needed. A water-budget model with a daily computation interval was used to estimate the spatial distribution of groundwater recharge for Kauaʻi, Oʻahu, Molokaʻi, Lānaʻi, Maui, and the Island of Hawaiʻi for recent climate conditions and three future-climate scenarios. Climate conditions from 1978 to 2007 were used as the reference period for recent climate conditions on each island. The three future-climate scenarios were developed using available high-resolution downscaled climate projections that include (1) a mid-century scenario using projected rainfall conditions for the Representative Concentration Pathway (RCP) scenario during 2041–71 with a total radiative forcing of 8.5 watts per square meter by the year 2100 (RCP8.5 2041–71 scenario), (2) a dry-climate scenario using projected rainfall conditions for the RCP8.5 scenario during 2071–99, and (3) a wet-climate scenario using projected rainfall conditions for the “Special Report on Emissions Scenarios” A1B scenario during 2080–99 for Maui, the RCP4.5 scenario during 2080–99 for Kauaʻi, Lānaʻi, and the Island of Hawaiʻi, and the RCP8.5 scenario during 2080–99 for Oʻahu and Molokaʻi. An additional drought scenario was added for Lānaʻi to assess the effect of extreme drought conditions during 2008–12 on groundwater recharge. All scenarios used 2020 land cover. Mean annual groundwater recharge is estimated to decrease between 5 and 55 percent on all six islands in this study for the mid-century and dry-climate scenarios relative to the reference-period recharge. Recharge is estimated to increase for Kauaʻi, Oʻahu, Molokaʻi, Lānaʻi, and Maui between 2 and 43 percent and decrease for the Island of Hawaiʻi by about 4 percent for the wet-climate scenario. Comparing the mid-century and dry-climate scenarios, all 110 aquifer systems (management areas defined by the State of Hawaiʻi Commission on Water Resource Management) from all six islands show similar direction in drying (104 aquifer systems) or wetting (6 aquifer systems) changes for recharge. However, among the three future scenarios, only 35 of 110 aquifer systems show similar direction in drying (30 aquifer systems) or wetting (5 aquifer systems) changes for recharge.

Hawaii