Comparative dissolution kinetics of biogenic and chemogenic uraninite under oxidizing conditions in the presence of carbonate

The long-term stability of biogenic uraninite with respect to oxidative dissolution is pivotal to the success of in situ bioreduction strategies for the subsurface remediation of uranium legacies. Batch and flow-through dissolution experiments were conducted along with spectroscopic analyses to compare biogenic uraninite nanoparticles obtained from Shewanella oneidensis MR-1 and chemogenic UO_2.00 with respect to their equilibrium solubility, dissolution mechanisms, and dissolution kinetics in water of varied oxygen and carbonate concentrations. Both materials exhibited a similar intrinsic solubility of ∼10⁻⁸ M under reducing conditions. The two materials had comparable dissolution rates under anoxic as well as oxidizing conditions, consistent with structural bulk homology of biogenic and stoichiometric uraninite. Carbonate reversibly promoted uraninite dissolution under both moderately oxidizing and reducing conditions, and the biogenic material yielded higher surface area-normalized dissolution rates than the chemogenic. This difference is in accordance with the higher proportion of U(V) detected on the biogenic uraninite surface by means of X-ray photoelectron spectroscopy. Reasonable sources of a stable U(V)-bearing intermediate phase are discussed. The observed increase of the dissolution rates can be explained by carbonate complexation of U(V) facilitating the detachment of U(V) from the uraninite surface. The fraction of surface-associated U(VI) increased with dissolved oxygen concentration. Simultaneously, X-ray absorption spectra showed conversion of the bulk from UO_2.0 to UO_2+x. In equilibrium with air, combined spectroscopic results support the formation of a near-surface layer of approximate composition UO_2.25 (U₄O₉) coated by an outer layer of U(VI). This result is in accordance with flow-through dissolution experiments that indicate control of the dissolution rate of surface-oxidized uraninite by the solubility of metaschoepite under the tested conditions. Although U(V) has been observed in electrochemical studies on the dissolution of spent nuclear fuel, this is the first investigation that demonstrates the formation of a stable U(V) intermediate phase on the surface of submicron-sized uraninite particles suspended in aqueous solutions.     

A chlorine isotope study of DSDP/ODP serpentinized ultramafic rocks: Insights into the serpentinization process

Eight DSDP/ODP cores were analyzed for major ion concentrations and δ³⁷Cl values of water-soluble chloride (δ³⁷Cl_WSC) and structurally bound chloride (δ³⁷Cl_SBC) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition.The average total Cl content of all 86 samples is 0.26 ± 0.16 wt.% (0.19 ± 0.10 wt.% as water-soluble Cl (X_WSC) and 0.09 ± 0.09 wt.% as structurally bound Cl (X_SBC)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl⁻ site and the water-soluble Cl⁻ site varies from − 1.08‰ to + 1.16‰, averaging to + 0.21‰. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk δ³⁷Cl values (+ 0.05‰ to + 0.36‰); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk δ³⁷Cl values (− 1.26‰ and − 0.54‰). The cores with negative δ³⁷Cl values also have variable Cl⁻ / SO₄² ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ∼1‰ with depth for both the water-soluble and structurally bound Cl fractions.Non-zero bulk δ³⁷Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive δ³⁷Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of ³⁷Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low δ³⁷Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative δ³⁷Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.     

The behavior of total lightning activity in severe Florida thunderstorms

The development of a new observational system called LISDAD (Lightning Imaging Sensor Demonstration and Display) has enabled a study of severe weather in central Florida. The total flash rates for storms verified to be severe are found to exceed 60 fpm, with some values reaching 500 fpm. Similar to earlier results for thunderstorm microbursts, the peak flash rate precedes the severe weather at the ground by 5–20 min. A distinguishing feature of severe storms is the presence of lightning ‘jumps' — abrupt increases in flash rate in advance of the maximum rate for the storm. The systematic total lightning precursor to severe weather of all kinds — wind, hail, tornadoes — is interpreted in terms of the updraft that sows the seeds aloft for severe weather at the surface and simultaneously stimulates the ice microphysics that drives the intracloud lightning activity.     

Diagenetic evolution of Aptian evaporites in the Namibe Basin (south‐west Angola)

The widespread and dissected nature of the Angolan gypsiferous salt residuals offers a uniquely detailed view of the lateral and vertical relations inherent to secondary evaporite textures, which typify exhumed salt masses worldwide. Such secondary textures are sometimes misinterpreted as primary evaporite textures. Thin, metre‐scale and patchy, dome‐like gypsum accumulations are well‐exposed within strongly incised present‐day river valleys along the eastern margin of the Namibe and Benguela basins (south‐west Angola). These sections are time equivalent to the main basinward subsurface evaporites (Aptian Loeme Formation) which mostly consist of halite. The gypsum (here called the Bambata Formation) is interpreted to represent the final residual product of fractional dissolution and recrystallization of the halite mass that occurred during Late Cretaceous margin uplift and continues today. This halite underwent multiple episodes of diagenetic alteration between its deposition and its final exhumation, leading to the formation of various secondary gypsum fabrics and solution‐related karst and breccia textures that typify the current evaporite outcrop. Four different diagenetic gypsum fabrics are defined: thinly bedded alabastrine, nodular alabastrine, displacive selenite rosettes and fibrous satin‐spar gypsum. Current arid conditions are responsible for a thin weathered crust developed at the top of the outcropping gypsum, but the fabrics in the main core of the current at‐surface evaporite unit mostly formed during the telogenetic stage of uplift prior to complete subaerial exposure. Alteration occurred as various dissolving and rehydrating saline minerals encountered shallow aquifers in the active phreatic and vadose zones. Geomorphological and petrographic analyses, mostly based on the cross‐cutting relations and crystallographic patterns in the outcrop, are used to propose a sequence of formation of these different fabrics.     

Field test of the superconducting gravimeter as a hydrologic sensor

We report on a field test of a transportable version of a superconducting gravimeter (SG) intended for groundwater storage monitoring. The test was conducted over a 6-month period at a site adjacent to a well in the recharge zone of the karstic Edwards Aquifer, a major groundwater resource in central Texas. The purpose of the study was to assess requirements for unattended operation of the SG in a field setting and to obtain a gravimetric estimate of aquifer specific yield. The experiment confirmed successful operation of the SG, but water level changes were small (<0.3 m) leading to uncertainty in the estimate of specific yield. Barometric pressure changes were the dominant cause of both water level variations and non-tidal gravity changes. The specific yield estimate (0.26) is larger than most published values and dependent mainly on low frequency variations in residual gravity and water level time series.     

A large shock vein in L chondrite Roosevelt County 106: Evidence for a long‐duration shock pulse on the L chondrite parent body

A large shock‐induced melt vein in L6 ordinary chondrite Roosevelt County 106 contains abundant high‐pressure minerals, including olivine, enstatite, and plagioclase fragments that have been transformed to polycrystalline ringwoodite, majorite, lingunite, and jadeite. The host chondrite at the melt‐vein margins contains olivines that are partially transformed to ringwoodite. The quenched silicate melt in the shock veins consists of majoritic garnets, up to 25 μm in size, magnetite, maghemite, and phyllosilicates. The magnetite, maghemite, and phyllosilicates are the terrestrial alteration products of magnesiowüstite and quenched glass. This assemblage indicates crystallization of the silicate melt at approximately 20–25 GPa and 2000 °C. Coarse majorite garnets in the centers of shock veins grade into increasingly finer grained dendritic garnets toward the vein margins, indicating increasing quench rates toward the margins as a result of thermal conduction to the surrounding chondrite host. Nanocrystalline boundary zones, that contain wadsleyite, ringwoodite, majorite, and magnesiowüstite, occur along shock‐vein margins. These zones represent rapid quench of a boundary melt that contains less metal‐sulfide than the bulk shock vein. One‐dimensional finite element heat‐flow calculations were performed to estimate a quench time of 750–1900 ms for a 1.6‐mm thick shock vein. Because the vein crystallized as a single high‐pressure assemblage, the shock pulse duration was at least as long as the quench time and therefore the sample remained at 20–25 GPa for at least 750 ms. This relatively long shock pulse, combined with a modest shock pressure, implies that this sample came from deep in the L chondrite parent body during a collision with a large impacting body, such as the impact event that disrupted the L chondrite parent body 470 Myr ago.     

Fresnel modeling of hematite crystal surfaces and application to martian hematite spherules

The gray crystalline hematite at Meridiani Planum first discovered by the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) instrument occurs as spherules that have been interpreted as concretions. Analysis of the TES and mini-TES spectra shows that no 390 cm⁻¹ feature is present in the characteristic martian hematite spectrum. Here, we incorporate the mid-IR optical constants of hematite into a simple Fresnel reflectance model to understand the effect of emission angle and crystal morphology on the presence or absence of the 390 cm⁻¹ feature in an IR hematite spectrum. Based on the results we offer two models for the internal structure of the martian hematite spherules.     

Estuarine and coastal connectivity of an estuarine-dependent fishery species,Pomadasys commersonnii (Haemulidae)

Understanding the level of connectivity between estuarine and coastal waters is essential for appropriate management of estuarine-associated taxa. Most studies have focused on the role of a single estuary, while limited research exists on the importance of multiple estuaries to individuals of estuarine-associated species. This study used acoustic telemetry to assess the usage of multiple estuaries and coastal waters by the estuarine-dependent spotted grunter Pomadasys commersonnii. Twenty-six adult fish were tagged with acoustic transmitters in the Kariega and Bushmans estuaries, South Africa, and their movements along a 300-km stretch of Indian Ocean coastline were monitored for up to 17 months. Tagged individuals spent most of their time in the estuary where they were tagged (55% and 85% for fish tagged in the two estuaries, respectively), followed by time in the sea (30% and 15%) and in other estuaries (15% and <1%). The mean durations of sea trips for fish tagged in the Kariega Estuary or Bushmans Estuary, respectively, were 25 days (range 3–55) and 12 days (range 2–22). Of the fish that went to sea, 93% from the Kariega Estuary and 60% from the Bushmans Estuary visited other estuaries. Most visits were undertaken to the Swartkops, Bushmans and Kowie estuaries, although the longest durations were spent in the Sundays Estuary. Individuals moved to estuaries up to 130 km away. The total distance travelled between estuaries by an individual during the study was ～529 km, with means of 201 and 184 km, respectively, for fish tagged in the Kariega and Bushmans estuaries. Despite covering large distances between estuaries, individuals often returned to their tagging estuary. Residency in their tagging estuary, combined with frequent visits to a neighbouring estuary, highlights the importance of estuarine habitats for this popular fish species, even after reaching maturity.