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Structural and spectral features of selenium nanospheres produced by Se-respiring bacteria

Certain anaerobic bacteria respire toxic selenium oxyanions and in doing so produce extracellular accumulations of elemental selenium [Se(0)]. We examined three physiologically and phylogenetically diverse species of selenate- and selenite-respiring bacteria, Sulfurospirillum barnesii, Bacillus selenitireducens, and Selenihalanaerobacter shriftii, for the occurrence of this phenomenon. When grown with selenium oxyanions as the electron acceptor, all of these organisms formed extracellular granules consisting of stable, uniform nanospheres (diameter, ???300 nm) of Se(0) having monoclinic crystalline structures. Intracellular packets of Se(0) were also noted. The number of intracellular Se(0) packets could be reduced by first growing cells with nitrate as the electron acceptor and then adding selenite ions to washed suspensions of the nitrate-grown cells. This resulted in the formation of primarily extracellular Se nanospheres. After harvesting and cleansing of cellular debris, we observed large differences in the optical properties (UV-visible absorption and Raman spectra) of purified extracellular nanospheres produced in this manner by the three different bacterial species. The spectral properties in turn differed substantially from those of amorphous Se(0) formed by chemical oxidation of H2Se and of black, vitreous Se(0) formed chemically by reduction of selenite with ascorbate. The microbial synthesis of Se(0) nanospheres results in unique, complex, compacted nanostructural arrangements of Se atoms. These arrangements probably reflect a diversity of enzymes involved in the dissimilatory reduction that are subtly different in different microbes. Remarkably, these conditions cannot be achieved by current methods of chemical synthesis.

Applied and Environmental Microbiology

Organo-facies and mineral effects on sorption capacity of low-maturity Permian Barakar shales from the Auranga Basin, Jharkhand, India

Shales associated with the Lower Permian (Barakar Formation) sediments of the Auranga Coalfield, India, occur in the immature–early mature stage. The sorption capacity of Barakar shale samples has been studied through high-pressure methane (CH 4 ) adsorption and low-pressure N 2 gas adsorption (LPN 2 GA) methods, supported with proximate analyses, programmed pyrolysis, optical petrography, and with energy-dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma mass spectrometry. The sorption capacity is a function of the organic and inorganic constituents present in the shale samples. The methane sorption capacity (MSC) and Langmuir volume of the shale samples vary from 0.217 to 0.314 and 0.315 to 0.429 mmol/g rock, respectively. The BET-calculated surface area of the studied shales varies from 8.12 to 30.36 m 2 /g. The sorption capacities show the importance of the total organic content (TOC) through weak but positive correlations with MSC ( r 2 = 0.45) and S 1 values (mg hydrocarbons/g rock from programmed pyrolysis; r 2 = 0.40). Moreover, apparent inverse relationships were observed between MSC and clay mineral abundances, suggesting that individual clay mineral types may influence MSC, although more work is needed. The TOC-normalized MSC (MSC*) of shale samples shows a positive trend with quartz plus clay mineral content and ash yield of r 2 = 0.64 for both. In addition, MSC* shows a negative logarithmic relationship with S 1 + S 2 ( r 2 = 0.63) and a positive linear relationship with TOC-normalized total organic matter (TOM*) ( r 2 = 0.88, when 5 low TOM* samples are excluded) indicating complex relationships possibly including bitumen retention in the sample pore spaces. The micropore study of the samples through LPN 2 GA, applying Dubinin–Radushkevich, Dubinin–Astakhov, and density functional theory models, shows the dominance of micro-mesopore concentrations in the shale matrix of ∼2 nm pore diameter. However, these pores might be present as blind or closed pores. The presence of thorium and zirconium is reflective of terrigenous detrital matter, i.e., moderately to strongly recycled sediments. The fluviatile facies of deposited shales in the Auranga Coalfield are noted by the significant presence of kaolinite (32.5–78.3%), which suggests the importance of its effect on the sorption capacity of proximal terrigenous shales.

Jharkhand

High-Resolution mapping of biomass and distribution of marsh and forested wetlands in southeastern coastal Louisiana

This study estimates herbaceous and forested wetland coverage and aboveground biomass (AGB) within the Atchafalaya and Terrebonne coastal basins representing sediment rich and sediment poor coastal regions of southern Louisiana. Louisiana coastal wetlands account for approximately one third (37%) of the estuarine wetland area in the conterminous United States, yet the spatial distribution of their extent and aboveground biomass estimates are not well defined. Despite the importance of Louisiana’s coastal wetlands, existing maps on their extent are often outdated yet repeatedly used in national greenhouse gas (GHG) inventories and within regional aboveground biomass and carbon content estimates. Sentinel-2 optical satellite data was used within an object-oriented machine learning approach to classify wetland extent, mapping the spatial distribution of the coastal wetlands at high-resolution. A total wetland extent of 2950 km2 was mapped during a period of peak biomass in September 2017, comprised of forested and herbaceous wetlands (accuracy >90%) and demonstrated considerable differences (793.7 km2) from currently available estimates of wetland area. The distribution of aboveground biomass (AGB) was mapped using class averaged values derived from field data collected during May and September 2015. Total herbaceous biomass at the study site increased by 108.9% from May (668,684.5 Mg) to September (1,396,969.2 Mg) whilst the total woody vegetation biomass (27,667,232.1 Mg) was sampled in May only. This method provides a tractable means of mapping wetland extent and biomass, in a region threatened with wetland loss under projections of increasing sea-level rise and local subsidence.

Louisiana

First stereoscopic radar images of Titan

Saturn's giant, cloud-covered satellite Titan, larger than the planet Mercury, is the last major piece of unexplored real estate in the Solar system. The NASA/ESA Cassini spacecraft carries a variety of instruments that are being used to map the surface of Titan, including optical instruments that provide a global synoptic view and spectroscopic information, and microwave imager (Cassini Titan RADAR) that can produce a 5000-km long 300- 1400 m resolution image that covers ~1% of Titan during a flyby encounter with the satellite. The first 7 such images, obtained between October 2004 and July 2006, covered nonoverlapping areas and revealed a diverse (and surprisingly Earth-like, despite the very cold temperature and different chemistry of the surface) set of geologic features, including volcanos, dune fields, channels, mountains, and impact craters. Beginning with the T18 encounter in September 2006, all but one of the dozen RADAR images obtained during the remainder of Cassini's prime mission will overlap with previous coverage. The repeat coverage has numerous cartographic and scientific applications, including serving as the basis for the most accurate geodetic control network of Titan, providing information about the surface materials as revealed by their angle-dependent microwave-scattering properties, allowing comparisons to look for temporal changes, and providing information about surface relief that can be exploited by radar-stereogrammetric mapping. We report the initial results of automated and manual stereo elevation measrurements at the USGS and JPL. These reveal local relief of several hundred to a thousand meters, associated with a canyon system and probable lakes in the northern hemisphere, a result that is consistent with the available topographic information about other parts of Titan from altimetry and radar shape-from-shading. Work is underway to develop more rigorous and efficient stereomapping tools at both institutions, based on those originally designed for the Magellan radar imagery of Venus, and to apply these to the extended stereo coverage that will become available over the next few years.

Conference Paper

Technological advances in suspended‐sediment surrogate monitoring

Surrogate technologies to continuously monitor suspended sediment show promise toward supplanting traditional data collection methods requiring routine collection and analysis of water samples. Commercially available instruments operating on bulk optic (turbidity), laser optic, pressure difference, and acoustic backscatter principles are evaluated based on cost, reliability, robustness, accuracy, sample volume, susceptibility to biological fouling, and suitable range of mass concentration and particle size distribution. In situ turbidimeters are widely used. They provide reliable data where the point measurements can be reliably correlated to the river's mean cross section concentration value, effects of biological fouling can be minimized, and concentrations remain below the sensor's upper measurement limit. In situ laser diffraction instruments have similar limitations and can cost 6 times the approximate $5000 purchase price of a turbidimeter. However, laser diffraction instruments provide volumetric‐concentration data in 32 size classes. Pressure differential instruments measure mass density in a water column, thus integrating substantially more streamflow than a point measurement. They are designed for monitoring medium‐to‐large concentrations, are generally unaffected by biological fouling, and cost about the same as a turbidimeter. However, their performance has been marginal in field applications. Acoustic Doppler profilers use acoustic backscatter to measure suspended sediment concentrations in orders of magnitude more streamflow than do instruments that rely on point measurements. The technology is relatively robust and generally immune to effects of biological fouling. Cost of a single‐frequency device is about double that of a turbidimeter. Multifrequency arrays also provide the potential to resolve concentrations by clay silt versus sand size fractions. Multifrequency hydroacoustics shows the most promise for revolutionizing collection of continuous suspended sediment data by instruments that require only periodic calibration for correlation to mean concentrations in river cross sections. Broad application of proven suspended sediment surrogate technologies has the potential to revolutionize fluvial sediment monitoring. Once applied, benefits could be enormous, providing for safer, more frequent and consistent, arguably more accurate, and ultimately less expensive sediment data for managing the world's sedimentary resources.

Water Resources Research

Welded tuff porosity characterization using mercury intrusion, nitrogen and ethylene glycol monoethyl ether sorption and epifluorescence microscopy

Porosity of welded tuff from Snowshoe Mountain, Colorado, was characterized by mercury intrusion porosimetry (MIP), nitrogen sorption porosimetry, ethylene glycol monoethyl ether (EGME) gas phase sorption and epifluorescence optical microscopy. Crushed tuff of two particle-size fractions (1-0.3 mm and less than 0.212 mm), sawed sections of whole rock and crushed tuff that had been reacted with 0.1 N hydrochloric acid were examined. Average MIP pore diameter values were in the range of 0.01–0.02μm. Intrusion volume was greatest for tuff reacted with 0.1 N hydrochloric acid and least for sawed tuff. Cut rock had the smallest porosity (4.72%) and crushed tuff reacted in hydrochloric acid had the largest porosity (6.56%). Mean pore diameters from nitrogen sorption measurements were 0.0075–0.0187 μm. Nitrogen adsorption pore volumes (from 0.005 to 0.013 cm 3 /g) and porosity values (from 1.34 to 3.21%) were less than the corresponding values obtained by MIP. More than half of the total tuff pore volume was associated with pore diameters < 0.05μm. Vapor sorption of EGME demonstrated that tuff pores contain a clay-like material. Epifluorescence microscopy indicated that connected porosity is heterogeneously distributed within the tuff matix; mineral grains had little porosity. Tuff porosity may have important consequences for contaminant disposal in this host rock.

Applied Geochemistry

Properties of solid bitumen formed during hydrous, anhydrous, and brine pyrolysis of oil shale: Implications for solid bitumen reflectance in source-rock reservoirs

Solid bitumen reflectance (BR o in %) is widely used as a thermal maturity proxy in source-rock reservoirs, yet solid bitumen texture and physical attributes may be affected by varying environmental constraints during its formation, e.g., water saturation, mineral catalysis, or salinity. Herein we investigated the development of solid bitumen properties during artificial maturation using three diverse (lacustrine to marine) oil shale samples containing abundant amorphous H-rich sedimentary organic matter (bituminite). The oil shales were treated via pyrolysis (320 °C, 72 h) using hydrous, anhydrous, and brine conditions, causing the development of a newly formed solid bitumen in the experiment residues from the thermal conversion of bituminite. The properties of the newly formed solid bitumen then were evaluated via geochemical screening tests, optical and electron microscopy, and infrared spectroscopy. Experimental residues also were treated via solvent extraction, allowing characterization of the effects of extraction on solid bitumen. Results showed that bituminite with higher resin and asphaltene components evolved to a solid bitumen with higher reflectance (as a percentage of the original value) when exposed to the same heat treatment, relative to bituminite with higher saturate and aromatic components. Aromatization of solid bitumen also was generally more pronounced in the presence of deionized water relative to anhydrous conditions, supporting prior observations. These results suggest the compositions of primary sedimentary organic matter, and the local concentration of water, affect the development of solid bitumen during thermal advance, potentially explaining the origin of multiple solid bitumen populations with varying reflectance in source-rock reservoir samples or in a single microscope field. Experiments using brine were inconclusive regarding enhanced/decreased aromatization, which could be attributed to the salinities of the brines used in the tests. Extraction of residues caused a consistent increase in BR o values, suggesting that migrating or expelled oils could cause an increase in BR o via natural solvation and absent an increase in temperature. This work provides insights into the development and evolution of BR o in source-rock reservoirs as a function of the composition of the original bituminite and changing environmental conditions, with potentially broad application for petroleum prospecting and resource estimation.

Colorado

Local variations in broadband sensor installations: Orientations, sensitivities, and noise levels

As seismologists continue to place more stringent demands on data quality, accurately described metadata are becoming increasingly important. In order to better constrain the orientation and sensitivities of seismometers deployed in U.S. Geological Survey networks, the Albuquerque Seismological Laboratory (ASL) has recently begun identifying true north with a fiber optic gyroscope (FOG) and has developed methodologies to constrain mid-band, vertical component sensitivity levels to less than 1% in a controlled environment. However, questions remain regarding the accuracy of this new alignment technique as well as if instrument sensitivities and background noise levels are stable when the seismometers are installed in different environmental settings. In this study, we examine the stability and repeatability of these parameters by reinstalling two high-quality broadband seismometers (Streckeisen STS-2.5 and Nanometrics T-360 Global Seismographic Network (GSN) version) at different locations around the ASL and comparing them to each other and a reference STS-6 seismometer that stayed stationary for the duration of the experiment. We find that even in different environmental conditions, the sensitivities of the two broadband seismometers stayed stable to within 0.1% and that orientations attained using the FOG are generally accurate to within a degree. However, one install was off by 5° due to a mistake made by the installation team. These results indicate that while technology and methodologies are now in place to calibrate and orient a seismometer to within 1°, human error both during the installation and while producing the metadata is often a limiting factor. Finally, we find that background noise levels at short periods (0.1–1 s) become noisier when the sensors are emplaced in unconsolidated materials, whereas the noise levels at long periods (30–100 s) are not sensitive to local geological structure on the vertical components.

Pure and Applied Geophysics

Interaction of a legacy groundwater contaminant plume with the Little Wind River from 2015 through 2017, Riverton Processing site, Wyoming

The Riverton Processing site was a uranium mill 4 kilometers southwest of Riverton, Wyoming, that prepared uranium ore for nuclear reactors and weapons from 1958 to 1963. The U.S. Department of Energy completed surface remediation of the uranium tailings in 1989; however, groundwater below and downgradient from the tailings site and nearby Little Wind River was not remediated. Beginning in 2010, a series of floods along the Little Wind River began to mobilize contaminants in the unsaturated zone, resulting in substantial increases of uranium and other contaminants of concern in monitoring wells completed inside the contaminant plume. In 2011, the U.S. Department of Energy started a series of university and Government agency retrospective and field investigations to understand the processes controlling contaminant increases in the groundwater plume. The goals of the field investigations described in this report were to (1) identify and quantify the contaminant flux and potential associated biological effects from groundwater associated with the legacy plume as it enters a perennial stream reach, and (2) assess chemical exposure and potential effects to biological receptors from the interaction of the contaminant plume and the river. Field investigations along the Little Wind River were completed by the U.S. Geological Survey during 2015–17 in cooperation with the U.S. Department of Energy Office of Legacy Management to characterize: (1) seepage areas and seepage rates; (2) pore-water and bed sediment chemistry and hyporheic exchange and reactive loss; and (3) exposure pathways and biological receptors. All data collected during the study are contained in two U.S. Geological Survey data releases, available at https://doi.org/10.5066/F7BR8QX4 and https://doi.org/10.5066/P9J9VJBR . A variety of tools and methods were used during the field characterizations. Streambed temperature mapping, electrical resistivity tomography, electromagnetic induction, fiber-optic distributed temperature sensing, tube seepage meters, vertical thermal sensor arrays, and an environmental tracer (radon) were used to identify areas of groundwater seepage and associated seepage rates along specific sections of the study reach of the river. Drive points, minipiezometers, diffusive equilibrium in thin-film/diffusive gradients in thin-film probes, bed-sediment samples, and equal discharge increment sampling methods were used to characterize pore-water chemistry, estimate hyporheic exchange and reactive loss of selected chemical constituents, and quantify contaminant loadings entering the study reach. Sampling and analysis of surface sediments, filamentous algae, periphytic algae, and macroinvertebrates were used to characterize biological exposure pathways, metal uptake, and receptors. Areas of focused groundwater discharge identified by the fiber-optic distributed temperature sensing surveys corresponded closely with areas of elevated electrical conductivity identified by the electromagnetic induction survey results in the top 5 meters of sediment. During three monitoring periods in 2016, the mean vertical seepage rate measured with tube seepage meters was 0.45 meter per day, ranging from −0.02 to 1.55 meters per day. Five of the 11 locations where vertical thermal profile data were collected along the study reach during August 2017 indicated mean upwelling values ranging from 0.11 to 0.23 meter per day. Radon data collected from the Little Wind River during June, July, and August 2016 indicated a consistent inflow of groundwater to the central part of the study reach, in the area congruous with the center of the previously mapped groundwater plume discharge zone. During August 2017, the greatest attenuation of uranium from reactive loss in pore-water samples was observed at three locations along the study reach, at depths between 6 and 15 centimeters, and similar trends in molybdenum attenuation were also observed. Bed-sediment concentration profiles collected during 2017 also indicated attenuation of uranium and molybdenum from groundwater during hyporheic mixing of surface water with the legacy plume during groundwater upwelling into the river. Streamflow measurements combined with equal discharge increment water sampling along the study reach indicated an increase in dissolved uranium concentrations in the downstream direction during 2016 and 2017. Net uranium load entering the Little Wind River study reach was about 290 and 435 grams per day during 2016 and 2017, respectively. Biological samples indicated that low levels of uranium and molybdenum exposure were confined to the benthos in the Little Wind River within and immediately downstream from the perimeter of the groundwater plume. Concentrations of molybdenum and uranium in filamentous algae were consistently low at all sites in the study reach with no indication of increased exposure of dissolved bioavailable molybdenum or uranium at sites next to or downstream from the groundwater plume. Comparison of the August 2017 results from electromagnetic induction, tube seepage meters, vertical thermal profiling, and pore-water chemistry surveys were in general agreement in identifying areas with upwelling groundwater conditions along the study reach. However, the electroconductivity values measured with electromagnetic induction in the top 100 centimeters of sediment did not agree with sodium concentrations measured in pore-water samples collected at similar streambed depths. Differences and similarities between multiple methods can result in additional insights into hydrologic and biogeochemical processes that may be occurring along a reach of a river system interacting with shallow groundwater inputs. It may be advantageous to apply a variety of geophysical, geochemical, hydrologic, and biological tools at other Uranium Mill Tailings Remedial Action ( https://www.energy.gov/sites/prod/files/2014/10/f19/UMTRCA.pdf ) sites during the investigation of legacy contaminant plume interactions with surface-water systems.

Wyoming

Application of ground-penetrating radar, digital optical borehole images, and cores for characterization of porosity hydraulic conductivity and paleokarst in the Biscayne aquifer, southeastern Florida, USA

This paper presents examples of ground-penetrating radar (GPR) data from two study sites in southeastern Florida where karstic Pleistocene platform carbonates that comprise the unconfined Biscayne aquifer were imaged. Important features shown on resultant GPR profiles include: (1) upward and lateral qualitative interpretative distribution of porosity and hydraulic conductivity; (2) paleotopographic relief on karstic subaerial exposure surfaces; and (3) vertical stacking of chronostratigraphic high-frequency cycles (HFCs). These characteristics were verified by comparison to rock properties observed and measured in core samples, and identified in digital optical borehole images. Results demonstrate that an empirical relation exists between measured whole-core porosity and hydraulic conductivity, observed porosity on digital optical borehole images, formation conductivity, and GPR reflection amplitudes-as porosity and hydraulic conductivity determined from core and borehole images increases, formation conductivity increases, and GPR reflection amplitude decreases. This relation allows for qualitative interpretation of the vertical and lateral distribution of porosity and hydraulic conductivity within HFCs. Two subtidal HFCs in the uppermost Biscayne aquifer have significantly unique populations of whole-core porosity values and vertical hydraulic conductivity values. Porosity measurements from one cycle has a median value about two to three times greater than the values from the other HFC, and median values of vertical hydraulic-conductivity about three orders of magnitude higher than the other HFC. The HFC with the higher porosity and hydraulic conductivity values is shown as a discrete package of relatively low-amplitude reflections, whereas the HFC characterized by lower porosity and hydraulic-conductivity measurements is expressed by higher amplitude reflections. Porosity and hydraulic-conductivity values measured from whole-core samples, and vuggy porosity identified on digital borehole images from shallowing-upward, peritidal HFCs show that the highest porosity occurs at the base of the cycles, moderate porosity at the middle of the cycles, and lowest porosity occurs at the top of cycles. Hydraulic conductivity is also highest at the base of the peritidal cycles and lowest in the middle to upper parts of cycles. This change in porosity and hydraulic conductivity from bottom to top is visible as an upward variation in reflection amplitude on GPR profiles-lowest amplitudes at the base and highest at the cycle tops. This study demonstrates that GPR can be used to show the qualitative distribution of porosity and hydraulic conductivity within a cycle-stratigraphic framework composed of carbonate HFCs. The distribution of porosity and hydraulic conductivity within HFCs is related to depositional textures. The upward and lateral patterns of the rock facies within the HFCs can be translated to geophysical-log properties and radar facies configurations that could aid in interpretation and prediction of ground-water flow through a carbonate aquifer. ?? 2003 Elsevier B.V. All rights reserved.

Journal of Applied Geophysics