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Holocene tephrochronology of the Cold Bay area, southwest Alaska Peninsula

The major-element glass geochemistry of 92 tephra samples from the southwest Alaska Peninsula provides the basis for establishing a Holocene tephrochronology for the region. Electron microprobe analysis has been combined with field descriptions of samples, stratigraphic relationships between tephra samples and sample localities, and glass shard micro-morphology to correlate these sampled distal tephra units throughout the area of Cold Bay and adjacent Morzhovoi Bay. Radiocarbon dating provides age constraints on correlated horizons. Previous research had clearly delineated only one horizon in the region, the so-called 'Funk/Fisher' ash, dating to between 8425 ± 350 and 9130 ± 140 14 C yr BP. In addition to constraining the bimodal andesitic and dacitic glass chemistry of that horizon, this study has recognized six additional tephra layers in the area. Two horizons pre-date the Funk/Fisher ash and four are younger than it. A tephra containing dacitic and andesitic components was identified in the vicinity of Morzhovoi Bay, with a minimum age of 9300 ± 80 14 C yr BP and a maximum age of 10,200 ± 75 14 C yr BP. A rhyolitic horizon composed of cm-sized, rounded pumice clasts was identified in the vicinity of Cold Bay; it has been correlated to the ca 9500 BP eruption of Roundtop volcano on Unimak Island. The four younger tephra beds date to between 6070 ± 340 and 3600 ± 140 14 C yr BP. The oldest of the four is rhyodacitic, followed by a mixed rhyodacitic-andesitic horizon, another rhyodacitic horizon, and finally an andesitic layer. Comparison of all the correlated horizons to proximal samples collected on Unimak Island provides conclusive geochemical evidence that the ca 9100 BP Caldera-forming eruption of Fisher volcano is the source of the Funk/Fisher ash. Correlation between the rhyodacitic tephra horizons and proximal samples from Fisher volcano suggests that Fisher Caldera is the source of one of the rhyodacitic tephra horizons that post-dates the Funk/Fisher ash. Additional tephra samples from the southwest Alaska Peninsula and Unimak Island that were collected prior to this study correlate to the tephra horizons identified in the Cold Bay area and identify one additional horizon.

Quaternary Science Reviews↗

Deformation of the Long Valley Caldera, California: Inferences from measurements from 1988 to 2001

Two periods of volcanic unrest occurred between 1989 and 1998 in the Long Valley Caldera, eastern California. Numerous earthquakes were recorded, and these periods of unrest were documented with high-precision geodetic measurements. The first round of unrest started rapidly in late 1989 and slowly decreased in rate through the early 1990s. For this interval there are both leveling and two-color electronic distance meter (EDM) measurements. The second round of unrest started slowly in mid-1997, climaxed in late 1997, and rapidly returned to quiescence by mid-1998. Deformation was recorded by both the two-color EDM and continuous GPS. Both episodes require inflation at 6-7 km beneath the resurgent dome, and both episodes had roughly 0.1 m extension across the resurgent dome. In addition, the data presented here suggest that there is a deeper, 10-20 km, inflation source beneath the south moat of the caldera. For both episodes, the better-resolved inflation beneath the resurgent dome is a near-vertical, prolate spheroid rather than an isotropic source, which suggests that magma came up through vertical cracks. However, the modeling suggests that the location changed with the depth from 6.0 to 6.7 km for the later episode. In contrast to the earlier episode, the 1997-1998 episode has additional deformation in the south moat, where the simplest model is that of a right-lateral slip on a steeply dipping plane that is defined by the location of earthquakes in the south moat. Models of the time-dependent behavior suggest that slip on this fault occurred from late November through December 1997, corresponding to the time of greatest moment release by the earthquake swarm in the south moat. Confounding the interpretation of these data is an active geothermal field near the center of the EDM network and adjacent to the south moat and resurgent dome. Additional modeling of leveling and EDM data within the geothermal field during a period of low rate of inflation of the dome suggests some methods of adjustments to the EDM data during the inflation episodes. ?? 2003 Elsevier B.V. All rights reserved.

Journal of Volcanology and Geothermal Research↗

Water-level changes induced by local and distant earthquakes at Long Valley caldera, California

Distant as well as local earthquakes have induced groundwater-level changes persisting for days to weeks at Long Valley caldera, California. Four wells open to formations as deep as 300 m have responded to 16 earthquakes, and responses to two earthquakes in the 3-km-deep Long Valley Exploratory Well (LVEW) show that these changes are not limited to weathered or unconsolidated near-surface rocks. All five wells exhibit water-level variations in response to earth tides, indicating they can be used as low-resolution strainmeters. Earthquakes induce gradual water-level changes that increase in amplitude for as long as 30 days, then return more slowly to pre-earthquake levels. The gradual water-level changes are always drops at wells LKT, LVEW, and CH-10B, and always rises at well CW-3. At a dilatometer just outside the caldera, earthquake-induced strain responses consist of either a step followed by a contractional strain-rate increase, or a transient contractional signal that reaches a maximum in about seven days and then returns toward the pre-earthquake value. The sizes of the gradual water-level changes generally increase with earthquake magnitude and decrease with hypocentral distance. Local earthquakes in Long Valley produce coseismic water-level steps; otherwise the responses to local earthquakes and distant earthquakes are indistinguishable. In particular, water-level and strain changes in Long Valley following the 1992 M7.3 Landers earthquake, 450 km distant, closely resemble those initiated by a M4.9 local earthquake on November 22, 1997, during a seismic swarm with features indicative of fluid involvement. At the LKT well, many of the response time histories are identical for 20 days after each earthquake, and can be matched by a theoretical solution giving the pore pressure as a function of time due to diffusion of a nearby, instantaneous, pressure drop. Such pressure drops could be produced by accelerated inflation of the resurgent dome by amounts too small to be detected by the two-color electronic distance-measuring network. Opening-mode displacement in the south moat, inferred to have followed a M4.9 earthquake on November 22, 1997, could also create extensional strain on the dome and lead to water-level changes similar to those following dome inflation. Contractional strain that could account for earthquake-induced water-level rises at the CW-3 well is inconsistent with geodetic observations. We instead attribute these water-level rises to diffusion of elevated fluid pressure localized in the south moat thermal aquifer. For hydraulic diffusivities appropriate to the upper few hundred meters at Long Valley, an influx of material at temperatures of 300°C can thermally generate pressure of 6 m of water or more, an order of magnitude larger than needed to account for the CW-3 water-level rises. If magma or hot aqueous fluid rises to within 1 km of the surface in the eastern part of the south moat, then hydraulic diffusivities are high enough to allow fluid pressure to propagate to CW-3 on the time scale observed. The data indicate that seismic waves from large distant earthquakes can stimulate upward movement of fluid in the hydrothermal system at Long Valley.

California↗

Deformation near the Casa Diablo geothermal well field and related processes Long Valley caldera, Eastern California, 1993-2000

Regional first-order leveling lines, which extend from Lee Vining, CA, to Tom's Place, CA, have been surveyed periodically since 1957 by the U.S. Geological Survey (USGS), the National Geodetic Survey (NGS), and Caltrans. Two of the regional survey lines, or leveling networks, intersect at the Casa Diablo geothermal well field. These leveling networks, referenced to a distant bench mark (C916) near Lee Vining, provide time-series vertical control data of land-surface deformation that began around 1980. These data are also useful for delineating localized subsidence at Casa Diablo related to reservoir pressure and temperature changes owing to geothermal development that began in 1985. A comparison of differences in bench-mark elevations for five time periods between 1983 and 1997 shows the development and expansion of a subsidence bowl at Casa Diablo. The subsidence coincides spatially with the geothermal well field and temporally with the increased production rates and the deepening of injection wells in 1991, which resulted in an increase in the rate of pressure decline. The subsidence, superimposed on a broad area of uplift, totaled about 310 mm by 1997. The USGS established orthogonal tilt arrays in 1983 to better monitor deformation across the caldera. One tilt array (DBR) was established near what would later become the Casa Diablo geothermal well field. This array responded to magmatic intrusions prior to geothermal development, tilting away from the well field. With the start of geothermal fluid extraction in 1985, tilt at the DBR array reversed direction and began tilting into the well field. In 1991, geothermal power production was increased by a factor of four, and reservoir pressures began a period of steep decline. These changes caused a temporary three-fold increase in the tilt rate. The tilt rate became stable in 1993 and was about 40% lower than that measured in 1991-1992, but still greater than the rates measured during 1985-1990. Data from the local leveling networks spanning the well field and the bounding graben were analyzed for several 2-year periods (1993-1995, 1995-1997, and 1997-1999). Annual rates of change across the normal faults bounding the graben have steadily decreased for each 2-year period between 1993 and 1999, reflecting the slowing decline in geothermal reservoir pressure. Horizontal control data from a two-color electronic distance meter (EDM) defined the lateral extent of subsidence at Casa Diablo. The EDM and leveling data elucidate the localized effect of the shallow source of subsidence and the broader effect of the deeper magmatic inflation source. Data from bench marks common to both the vertical and the horizontal control networks were used to assess the effect of subsidence on the EDM base station (CASA). Modeling of geodetic data collected during periods of little or no magmatic inflation indicated that the CASA two-color EDM station is being drawn toward the well field at a rate of 3-5 mm/yr. ?? 2003 Elsevier B.V. All rights reserved.

Journal of Volcanology and Geothermal Research↗

The fine structure of the sperm of the round goby (Neogobius melanostomus)

The fine structural details of the spermatozoon of the round goby are presented for the first time in this study. Scanning and transmission electron microscopic examination of testis reveals an anacrosomal spermatozoon with a slightly elongate head and uniformly compacted chromatin. The midpiece contains a single, spherical mitochondrion. Two perpendicularly oriented centrioles lie in a deep, eccentric nuclear fossa with no regularly observed connection to the nucleus. The flagellum develops bilateral fins soon after emerging from the fossa; each extends approximately 1 μm fro m the axoneme and persists nearly the length of the flagellum.

Journal of Great Lakes Research↗

Embryonic developmental progression in lake trout ( Salvelinus namaycush ) (Walbaum, 1792) and its relation to lake temperature

Developmental progression of lake trout ( Salvelinus namaycush ) embryos was examined with light and scanning electron microscopy. From this examination, key developmental stages were described in detail. The key developmental stages were then applied to individual lake trout egg lots incubated in constant temperatures of 2, 4, 6, 8, and 10°C. We used Belehradek's, Thermodynamic, and Power models, and also developed the Zero model to determine stage specific developmental rates of lake trout eggs for each background temperature. From the models, hatch dates and staging were predicted for temperature regimes from Lake Superior (1990–91) and Lake Huron (1996–97). Based on the existing lake temperature data and the observed spawning dates, the Zero and the Power models predict that post peak spawning may contribute significantly to overall recruitment success for these years.

Journal of Great Lakes Research↗

Concentrations of dissolved and particulate Polychlorinated Biphenyls in water from the Saginaw River, Michigan

The Saginaw River receives water from a major drainage basin in the east-central portion of the lower peninsula of Michigan. Historically the river has been contaminated with polychlorinated biphenyls (PCBs) from several sources. The present study was conducted to determine the concentrations of PCBs in both the dissolved and particulate phases of water in the lower Saginaw River, as well as the relative contribution of PCBs from the lower portion of the river relative to more upstream locations. Water samples were collected in 1990–1991, during a range of discharge conditions. Suspended particulates were collected from water onto glass-fiber filters by use of a “Penta-plate” filtration apparatus. Filtered water was subsequently passed through XAD-2 macroreticular resin to collect the “dissolved” PCBs. Concentrations of PCBs in both phases were determined by congener specific gas chromatography with electron capture detection. Total concentrations of PCBs ranged from 11 to 31 ng/L. The concentrations of PCBs in the dissolved phase ranged from 1.9 to 16 ng/L. The ratio of total PCBs bound to suspended particulates, relative to dissolved PCBs, was 2:1 and remained fairly constant for discharges less than approximately 400 M 3 /sec. The loading of total PCBs to Saginaw Bay was estimated to be 225 kg/yr, of which approximately 60% was found to be contributed by the lower 8 km of the Saginaw River.

Michigan↗

Iron reduction in the sediments of a hydrocarbon-contaminated aquifer

Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.

Applied Geochemistry↗

Copper localization, elemental content, and thallus colour in the copper hyperaccumulator lichen Lecanora sierrae from California

An unusual dark blue-green lichen, Lecanora sierrae , was discovered over 30 years ago by Czehura near copper mines in the Lights Creek District, Plumas County, Northern California. Using atomic absorption spectroscopy, Czehura found that dark green lichen samples from Warren Canyon contained 4% Cu in ash and suggested that its colour was due to copper accumulation in the cortex. The present study addressed the hypothesis that the green colour in similar material we sampled from Warren Canyon in 2008, is caused by copper localization in the thallus. Optical microscopy and electron microprobe analysis of specimens of L. sierrae confirmed that copper localization took place in the cortex. Elemental analyses of L. sierrae and three other species from the same localities showed high enrichments of copper and selenium, suggesting that copper selenates or selenites might occur in these lichens and be responsible for the unusual colour.

Lichenologist↗

Assessing open-system behavior of 14C in terrestrial gastropod shells

In order to assess open-system behavior of radiocarbon in fossil gastropod shells, we measured the 14 C activity on 10 aliquots of shell material recovered from Illinoian (~190–130 ka) and pre-Illinoian (~800 ka) loess and lacustrine deposits in the Midwestern USA. Eight of the 10 aliquots yielded measurable 14 C activities that ranged from 0.25 to 0.53 percent modern carbon (pMC), corresponding to apparent 14 C ages between 48.2 and 42.1 ka. This small level of open-system behavior is common in many materials that are used for 14 C dating (e.g. charcoal), and typically sets the upper practical limit of the technique. Two aliquots of gastropod shells from the Illinoian-aged Petersburg Silt (Petersburg Section) in central Illinois, USA, however, yielded elevated 14 C activities of 1.26 and 1.71 pMC, which correspond to apparent 14 C ages of 35.1 and 32.7 ka. Together, these results suggest that while many fossil gastropods shells may not suffer from major (>1%) open-system problems, this is not always the case. We then examined the mineralogy, trace element chemistry, and physical characteristics of a suite of fossil and modern gastropod shells to identify the source of contamination in the Petersburg shells and assess the effectiveness of these screening techniques at identifying samples suitable for 14 C dating. Mineralogical (XRD) and trace element analyses were inconclusive, which suggests that these techniques are not suitable for assessing open-system behavior in terrestrial gastropod shells. Analysis with scanning electron microscopy (SEM), however, identified secondary mineralization (calcium carbonate) primarily within the inner whorls of the Petersburg shells. This indicates that SEM examination, or possibly standard microscope examination, of the interior of gastropod shells should be used when selecting fossil gastropod shells for 14 C dating.

Radiocarbon↗

Hanawaltite, Hg1+6Hg2+[Cl,(OH)]2O3 - A new mineral from the Clear Creek claim, San Benito County, California: Description and crystal structure

Hanawaltite, ideally Hg 1+ 6 Hg 2+ O 3 Cl 2 , is orthorhombic, Pbma (57), with unit-cell parameters refined from powder data: a =11.790(3), b =13.881(4), c =6.450(2) Å, V =1055.7(6) Å 3 , a : b : c =0.8494:1:0.4647, Z =4. The strongest six lines of the X-ray powder-diffraction pattern [ d in Å ( I )( hkl )] are: 5.25 (80)(111), 3.164 (60)(231), 3.053 (100)(041), 2.954 (70)(141), 2.681 (50)(401), and 2.411 (50)(232,341). The mineral is an extremely rare constituent in a small prospect pit near the long-abandoned Clear Creek mercury mine, New Idria district, San Benito County, California. It was found on a single-fracture surface where it is intimately associated with calomel, native mercury, cinnabar, montroydite, and quartz. Individual crystals are subhedral to anhedral, platy to somewhat bladed, and average about 50 μm in longest dimension. The largest known crystal is approximately 0.3×0.3 mm in size and is striated parallel [001]. Hanawaltite is opaque to translucent (on very thin edges), black to very dark brown–black in color, with a black to dark red–brown streak. Other physical properties include: metallic luster; cleavage {001} good; uneven fracture; brittle; nonfluorescent; H <5; calculated density (for the empirical formula) 9.51 g/cm 3 . In polished section, hanawaltite is moderately to strongly bireflectant and is pleochroic white ( R I ) to blue–white ( R 2 ). In reflected plane-polarized light, it is white with orange–red internal reflections in very thin grains and at grain margins. The anisotropy is strong with bright metallic blue rotation tints. Measured reflectance values, in air and in oil, are tabulated. Electron-microprobe analysis yielded Hg 2 O 82.46, HgO 14.27, Cl 3.33, H 2 O [0.34], sum [100.40], less O=Cl 0.75, total [99.65] wt. %, corresponding to Hg 1+ 6.00 Hg 2+ 1.00 [Cl 1.43 (OH) 0.57 ] Σ2.00 O 3.00 , based on O+Cl=5. After the crystal structure was determined, the original microprobe value for Hg 2 O, 96.2, was partitioned in a ratio of 6Hg 2 O:HgO and (OH) was calculated, such that Cl+(OH)=2. The hanawaltite structure consists of undulatory [Hg–Hg] 2+ ribbons which roughly parallel (100). The diatomic [Hg–Hg] 2+ groups have anion tails which, in turn, serve as cross linkages between dimer ribbons through [Hg 2+ O 2 Cl 2 ] planar rhombs. The structure is compared to that of other mercury oxychlorides and each is found to have its own unique structural features. This structural diversity is attributed to the inherent ability of mercury to adopt either metallic or ionic types of bonds. The mineral name honors the late Dr. J. D. (Don) Hanawalt (1903–1987), who was a pioneer in the field of X-ray powder diffraction.

California↗

Approach for quantifying rare Earth elements at low keV

The challenges of analyzing bastnaesite (REECO3F) and hydroxylbastnaesite (REECO3OH) include beam sensitivity, quantification of light elements in a heavy element matrix, the presence of elements that cannot be analyzed with EPMA (H), and the use of x-ray lines whose physical constants are not well known. To overcome some of these challenges, Ca, La, Ce, Pr, Nd, and Sm were analyzed at 15 keV accelerating voltage and the light elements (C, O, F) were analyzed at 7 keV accelerating voltage. This approach is ideal for samples that are homogeneous within the volume analyzed. However, for the bastnaesite of interest, this solution is unsatisfactory as backscattered electron imaging reveals chemical variations at scales of less than 1 m (fig. 1). Monte Carlo simulations and wavescans of the REE M family of x-rays were evaluated to determine the best analytical approach. Monte Carlo simulations using Casino v2.42 were ran on a substrate of CeCO3F with a density of 5.00 g/cm3 at 15 keV and 7 kCV accelerating voltage. Depth distribution curves, φ(ρz), reveal x-ray generation at 15 keV for the Ce L shell x-rays approaches 1.0 m whereas the depth of Ce M shell x-ray generation at 7 keV is less than 0.4 m. Similarly, the K shell x-ray generation depth for C, O, and F at 7 keV is also less than 0.4 m. These simulations demonstrate an accelerating voltage of 7 keV or less and use of the REE M x-rays is necessary to acquire chemical information from the same volume of material for the light and heavy elements. Bastnaesite contains all REE and therefore one must consider the energy of the highest x-ray line of interest, namely the Lu M at 1.83 kV, to achieve an overvoltage (Eo/Ec) of over 2. Bastnaesite is also an insulator and requires a conductive coating, therefore 7 keV was used to avoid contributions of the coating material to the analysis given the above constraints. The USNM REE phosphate standards, Edinburgh REE glasses, CeO2, LaB6, and the metals of Sm, Dy, Gd, Er, and Yb were selected to evaluate the peak overlaps of the M family x-ray lines. The materials were coated with ~ 5nm iridium with a Leica ACE600 prior to analysis. Full spectrometer wavescans were collected at 7 keV accelerating voltage, 50 nA beam current, and 20 um beam diameter on a JEOL 8530F Plus using TAP and TAPL crystals. The step size was 0.109 mm along the length of the spectrometer with a dwell of 3 seconds at each step. M and M lines are broad and not individually resolved for the light REE but become more separated and sharper with increasing atomic number. M and M lines for each REE are also present across the spectrometer range further complicating peak interference corrections. The peak positions and overall shape for the Ce M and M lines vary with the coordination of the element. Significant shifts in position and shape were not observed when comparing the Ce M peaks of CeO2 and CePO4. Similar results were seen when comparing the available REE metal to the phosphate (Sm, Dy, Gd, Er, Yb). These wavescans suggest the use of the M or M lines if matrix matched standards are not available.

Microscopy and Microanalysis↗

Sources and magnitude of bias associated with determination of polychlorinated biphenyls in environmental samples

Recently compiled data on the composition of commercial Aroclor mixtures and ECD (electron capture detector) response factors for all 209 PCB congeners are used to develop estimates of the bias associated with determination of polychlorinated blphenyis. During quantitation of multlcomponent peaks by congener-specific procedures error is introduced because of variable ECD response to isomeric PCBs. Under worst case conditions, the magnitude of this bias can range from less than 2% to as much as 600%. Multicomponent peaks containing the more highly and the lower chlorinated congeners experience the most bias. For this reason, quantitation of Σ PCB in Aroclor mixtures dominated by these species (e.g. 1016) are potentially subject to the greatest error. Comparison of response factor data for ECDs from two laboratories shows that the sign and magnitude of calibration bias for a given multicomponent peak is variable and depends, in part, on the response characteristics of individual detectors. By using the most abundant congener (of each multicomponent peak) for purposes of calibration, one can reduce the maximum bias to less than 55%. Moreover, due to cancellation of errors, the bias resulting from summation of all peak concentrations (i.e. Σ PCB) becomes vanishingly small (<1.2%). In contrast, bias associated with determination of Σ PCB as Aroclor equivalents by the traditional Aroclor method is potentially large (>200%) and highly variable in sign and magnitude. In this case, bias originates not only from the incomplete chromatographic resolution of PCB congeners but also the overlapping patterns of the Aroclor mixtures. Together these results illustrate the advantages of the congener-specific method of PCB quantitation over the traditional Aroclor Method and the extreme difficulty of estimating bias incurred by the latter procedure on a post hoc basis.

Analytical Chemistry↗

Oil in the Alaska North Slope gas hydrate reservoir: Micro-CT and flow simulation insights into permeability

Gas hydrate-bearing sands on the Alaska North Slope (ANS) host minor volumes of crude oil whose impact on formation permeability has never been quantified relative to a gas hydrate reservoir system. Here, we combine in situ pressure-core microcomputed-tomography (μ-CT), thermogravimetric analysis (TGA), gas-chromatography–mass-spectrometry (GC–MS), scanning-electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), and Stokes-flow simulation to (i) quantify oil saturation, (ii) infer its source, and (iii) evaluate its influence on permeability after gas-hydrate dissociation. μ-CT and SEM-EDS imaging identify the host sediment as silty, with some grain-coating clay present. Eight representative 300 3 -voxel subvolumes extracted from a preserved pressure core (Core 15P-3c, from the B1 sand (unit B), HYDRATE 02 Geo Data Well (GDW), 886.96–887.29 m measured depth, MD) exhibit porosities of 0.34–0.37 and an average oil saturation of 0.09 ± 0.03, in comparison to an independent TGA-based estimate of 0.16. GC-MS fingerprints obtained from an adjacent depressurized core (Core 17P-1, 891.37–891.44 m MD), together with oil pore habit revealed by μ-CT, suggest that the oil is partly native but also includes contributions from mineral oil-based drilling fluid contamination. Further analysis of oil–porewater interactions and flushing tests confirms that native oil saturation in the analyzed samples ranges from 0.04 to 0.08 with an average of approximately 0.06, and the oil is highly immobile. Flow simulations demonstrate that the native oil saturation of ≈0.06 reduces permeability by approximately 50% due to both pore blockage and increased flow-path tortuosity. These findings reveal the potential presence of native oil within the ANS gas hydrate reservoir and suggest that future simulation models may need to account for its impact on permeability to improve long-term performance predictions of gas and water production.

Alaska↗

Brief oil exposure reduces fitness in wild Gulf of Mexico mahi-mahi (Coryphaena hippurus)

The Deepwater Horizon (DWH) disaster released 3.19 million barrels of crude oil into the Gulf of Mexico (GOM) in 2010, overlapping the habitat of pelagic fish populations. Using mahi-mahi ( Coryphaena hippurus )─a highly migratory marine teleost present in the GOM during the spill─as a model species, laboratory experiments demonstrate injuries to physiology and behavior following oil exposure. However, more than a decade postspill, impacts on wild populations remain unknown. To address this gap, we exposed wild mahi-mahi to crude oil or control conditions onboard a research vessel, collected fin clip samples, and tagged them with electronic tags prior to release into the GOM. We demonstrate profound effects on survival and reproduction in the wild. In addition to significant changes in gene expression profiles and predation mortality, we documented altered acceleration and habitat use in the first 8 days oil-exposed individuals were at liberty as well as a cessation of apparent spawning activity for at least 37 days. These data reveal that even a brief and low-dose exposure to crude oil impairs fitness in wild mahi-mahi. These findings offer new perspectives on the lasting impacts of the DWH blowout and provide insight about the impacts of future deep-sea oil spills.

Environmental Science and Technology↗

Predicting redox conditions in groundwater at a national scale using random forest classification

Redox conditions in groundwater may markedly affect the fate and transport of nutrients, volatile organic compounds, and trace metals, with significant implications for human health. While many local assessments of redox conditions have been made, the spatial variability of redox reaction rates makes the determination of redox conditions at regional or national scales problematic. In this study, redox conditions in groundwater were predicted for the contiguous United States using random forest classification by relating measured water quality data from over 30,000 wells to natural and anthropogenic factors. The model correctly predicted the oxic/suboxic classification for 78 and 79% of the samples in the out-of-bag and hold-out data sets, respectively. Variables describing geology, hydrology, soil properties, and hydrologic position were among the most important factors affecting the likelihood of oxic conditions in groundwater. Important model variables tended to relate to aquifer recharge, groundwater travel time, or prevalence of electron donors, which are key drivers of redox conditions in groundwater. Partial dependence plots suggested that the likelihood of oxic conditions in groundwater decreased sharply as streams were approached and gradually as the depth below the water table increased. The probability of oxic groundwater increased as base flow index values increased, likely due to the prevalence of well-drained soils and geologic materials in high base flow index areas. The likelihood of oxic conditions increased as topographic wetness index (TWI) values decreased. High topographic wetness index values occur in areas with a propensity for standing water and overland flow, conditions that limit the delivery of dissolved oxygen to groundwater by recharge; higher TWI values also tend to occur in discharge areas, which may contain groundwater with long travel times. A second model was developed to predict the probability of elevated manganese (Mn) concentrations in groundwater (i.e., ≥50 μg/L). The Mn model relied on many of the same variables as the oxic/suboxic model and may be used to identify areas where Mn-reducing conditions occur and where there is an increased risk to domestic water supplies due to high Mn concentrations. Model predictions of redox conditions in groundwater produced in this study may help identify regions of the country with elevated groundwater vulnerability and stream vulnerability to groundwater-derived contaminants.

contiguous United States↗

Predicting redox conditions in groundwater at a regional scale

Defining the oxic-suboxic interface is often critical for determining pathways for nitrate transport in groundwater and to streams at the local scale. Defining this interface on a regional scale is complicated by the spatial variability of reaction rates. The probability of oxic groundwater in the Chesapeake Bay watershed was predicted by relating dissolved O 2 concentrations in groundwater samples to indicators of residence time and/or electron donor availability using logistic regression. Variables that describe surficial geology, position in the flow system, and soil drainage were important predictors of oxic water. The probability of encountering oxic groundwater at a 30 m depth and the depth to the bottom of the oxic layer were predicted for the Chesapeake Bay watershed. The influence of depth to the bottom of the oxic layer on stream nitrate concentrations and time lags (i.e., time period between land application of nitrogen and its effect on streams) are illustrated using model simulations for hypothetical basins. Regional maps of the probability of oxic groundwater should prove useful as indicators of groundwater susceptibility and stream susceptibility to contaminant sources derived from groundwater.

Maryland, New York, Pennsylvania, Virginia↗

Role of anaerobic ammonium oxidation (anammox) in nitrogen removal from a freshwater aquifer

Anaerobic ammonium oxidation (anammox) couples the oxidation of ammonium with the reduction of nitrite, producing N 2 . The presence and activity of anammox bacteria in groundwater were investigated at multiple locations in an aquifer variably affected by a large, wastewater-derived contaminant plume. Anammox bacteria were detected at all locations tested using 16S rRNA gene sequencing and quantification of hydrazine oxidoreductase ( hzo ) gene transcripts. Anammox and denitrification activities were quantified by in situ 15 NO 2 &ndash; tracer tests along anoxic flow paths in areas of varying ammonium, nitrate, and organic carbon abundances. Rates of denitrification and anammox were determined by quantifying changes in 28 N 2 , 29 N 2 , 30 N 2 , 15 NO 3 &ndash; , 15 NO 2 &ndash; , and 15 NH 4 + with groundwater travel time. Anammox was present and active in all areas tested, including where ammonium and dissolved organic carbon concentrations were low, but decreased in proportion to denitrification when acetate was added to increase available electron supply. Anammox contributed 39&ndash;90% of potential N 2 production in this aquifer, with rates on the order of 10 nmol N 2 &ndash;N L &ndash;1 day &ndash;1 . Although rates of both anammox and denitrification during the tracer tests were low, they were sufficient to reduce inorganic nitrogen concentrations substantially during the overall groundwater residence times in the aquifer. These results demonstrate that anammox activity in groundwater can rival that of denitrification and may need to be considered when assessing nitrogen mass transport and permanent loss of fixed nitrogen in aquifers.

Environmental Science & Technology↗