Europium sorption to sediments in the presence of natural organic matter: A laboratory and modeling study

Cellulosic materials, such as wood, paper products and cardboard that have been co-disposed with low-level nuclear waste have been shown to produce leachate with natural organic matter (NOM) concentrations of hundreds of mg/L C and, as such, have the potential to influence the fate and transport of radionuclides in the subsurface environment. The objective of this study was to examine the influence of NOM on the sorption of Eu (an analogue for trivalent radionuclides) to two coastal plain sediments from the US Department of Energy’s Savannah River Site. Particular attention was directed at quantifying Eu interactions with NOM sorbed to sediments (NOM_sed) in laboratory experiments and developing conditional stability constants for that interaction using the thermodynamic equilibrium speciation model MINTEQA2. Europium sorption to the two sediments systematically increased as pH increased from 3.9 to 6.7. With increasing additions of NOM to the aqueous phase from 0 to 222 mg/L C, Eu sorption initially increased to a maximum at 10 mg/L C NOM_aq and then decreased with increasing NOM_aq concentrations. Increases in Eu sorption at low NOM additions was attributed to the sorption of NOM to the sediment surface increasing the number of sorption sites on the low cation-exchange capacity sediments and/or increasing the association constant (log K) for the Eu-sediment surface reaction. Decreases in Eu sorption at higher NOM levels was attributed to Eu_aq complexation to NOM_aq being more favored than Eu sorption to the solid phase. A component additivity model was developed to describe the Eu–NOM-sediment system by the additive effects of the three binary system models: Eu–NOM, Eu-sediment and NOM-sediment. The model generally captured the data trends in the ternary system. Conditional stability constants developed from the experimental data for the complexation of Eu to NOM_sed were as much as four orders of magnitude greater than Eu complexation with NOM_aq, presumably due to the NOM_sed deriving additional negative (attractive) charge from the sediment surface. At high initial NOM_aq levels, >99 mg/L C, the model captured the trend of reduced Eu sorption but tended to over-estimate Eu sorption. The additivity approach of combining binary models to form a ternary model was only successful when the unique complexation properties of the NOM_sed were properly calculated.     

Titan's diverse landscapes as evidenced by Cassini RADAR's third and fourth looks at Titan

Cassini's third and fourth radar flybys, T7 and T8, covered diverse terrains in the high southern and equatorial latitudes, respectively. The T7 synthetic aperture radar (SAR) swath is somewhat more straightforward to understand in terms of a progressive poleward descent from a high, dissected, and partly hilly terrain down to a low flat plain with embayments and deposits suggestive of the past or even current presence of hydrocarbon liquids. The T8 swath is dominated by dunes likely made of organic solids, but also contain somewhat enigmatic, probably tectonic, features that may be partly buried or degraded by erosion or relaxation in a thin crust. The dark areas in T7 show no dune morphology, unlike the dark areas in T8, but are radiometrically warm like the dunes. The Huygens landing site lies on the edge of the T8 swath; correlation of the radar and Huygens DISR images allows accurate determination of its coordinates, and indicates that to the north of the landing site sit two large longitudinal dunes. Indeed, had the Huygens probe trajectory been just 10 km north of where it actually was, images of large sand dunes would have been returned in place of the fluvially dissected terrain actually seen—illustrating the strong diversity of Titan's landscapes even at local scales.     

Identification and composition of secondary meniscus calcite in fossil coral and the effect on predicted sea surface temperature

This study uses electron backscatter diffraction (EBSD) and atomic force microscopy (AFM) to identify secondary calcite in coral skeletons. Secondary calcite appears to have nucleated on the original aragonite dissepiments, producing horizontal structures that mimic the morphology of the original coral aragonite, forming dissepiment-like meniscus structures. The Sr/Ca and δ¹⁸O of the pristine aragonite and secondary calcite were analysed by secondary ion mass spectrometry (SIMS). The effect of calcite inclusion on the mean geochemistry of the coral carbonate and subsequent sea surface temperature (SST) calculations were determined for both Sr/Ca and δ¹⁸O. Inclusion of as little as 1% secondary calcite within the primary coral aragonite elevates the Sr/Ca-derived SST by 1.2 °C and could markedly offset estimates of past tropical climate. Conversely, inclusion of 10% secondary calcite has little effect on the SST estimated from δ¹⁸O (+ 0.6 °C) indicating that this proxy is relatively robust to even large amounts of calcite. The different extents to which the two proxies would be influenced by inadvertent inclusion of such meniscus calcite demonstrate the importance of a multi-proxy approach.     

Evidence for multiple modes of uranium immobilization by an anaerobic bacterium

Microbial reduction of hexavalent uranium has been studied widely for its potential role in bioremediation and immobilization of soluble U(VI) in contaminated groundwater. More recently, some microorganisms have been examined for their role in immobilization of U(VI) via precipitation of uranyl phosphate minerals mediated by microbial phosphate release, alleviating the requirement for long-term redox control. Here, we investigated the mechanism of U(VI) removal mediated by an environmental isolate, strain UFO1, that is indigenous to the Field Research Center (FRC) in Oak Ridge, TN and has been detected in U(VI)-contaminated sediments. Changes in U(VI) speciation were examined in the presence and absence of the electron-shuttling moiety, anthraquinone-2,6-disulfonate (AQDS). Cell suspensions were capable of nearly complete removal of 100 μM U(VI) from solution within 48 h; U(VI) removal was not dependent on the presence of an exogenous electron donor or AQDS, although AQDS increased the rate of U(VI) removal. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopic measurements indicated that U(IV) was the predominant oxidation state of uranium in cell suspensions in both the absence and presence of 100 μM AQDS. Interestingly, 17% of the cell-associated precipitates in a U(VI)-treated suspension that lacked AQDS had spectral characteristics consistent with a uranyl phosphate solid phase. The potential involvement of phosphate was consistent with observed increases in soluble phosphate concentrations over time in UFO1 cell suspensions, which suggested phosphate liberation from the cells. TEM-EDS confirmed the presence of uranyl phosphate with a U:P ratio consistent with autunite (1:1). EXAFS analyses further suggested that U(IV) was bound to low-Z neighbors such as C or P, inferred to be present as functional groups on biomass. These results suggest that strain UFO1 has the ability to facilitate U(VI) removal from solution via reductive and phosphate precipitation mechanisms. Both mechanisms offer potential for the remediation of U-contaminated sediments at the FRC or elsewhere.     

Large-Scale Differences in Community Structure and Ecosystem Services of Eelgrass (<Emphasis Type="Italic">Zostera marina</Emphasis>) Beds Across Three Regions in Eastern Canada

Eelgrass (Zostera marina) forms extensive beds in temperate coastal and estuarine environments worldwide and provides important ecosystem services, including habitat for a wide range of species as well as nutrient cycling and carbon storage. However, little is known about how eelgrass ecosystem structure and services differ naturally among regions. Using large-scale field surveys, we examined differences in eelgrass bed structure, carbon and nitrogen storage, community composition, and habitat services across three distinct regions in Eastern Canada. We focused on eelgrass beds with low anthropogenic impacts to compare natural differences. In addition, we analyzed the relationships of eelgrass bed structure with environmental conditions, and species composition with bed structure and environmental conditions, to elucidate potential drivers of observed differences. Our results indicate that regional differences in eelgrass bed structure were weakly correlated with water column properties, whereas differences in carbon and nitrogen storage were mainly driven by differences in eelgrass biomass. There were distinct regional differences in species composition and diversity, which were particularly linked to temperature, as well as eelgrass bed structure indicating differences in habitat provision. Our results highlight natural regional differences in ecosystem structure and services which could inform spatial management and conservation strategies for eelgrass beds.     

Observing lingering hyporheic storage using electrical resistivity: variations around stream restoration structures,Crabby Creek,PA

Time‐lapse geophysical surveys can map lingering hyporheic storage by detecting changes in response to saline tracer. Tracer tests were conducted in Crabby Creek, an urban stream outside Philadelphia, to examine the influence of stream restoration structures and variable sediment thickness. We compared electrical resistivity surveys with extensive well sampling (57 wells) in two 13.5‐m‐long reaches, each with a step drop created by a J‐hook. The two step drops varied in tracer behaviour, based on both the well data and the geophysical data. The well data showed more variation in arrival time where the streambed sediment was thick and was more uniform where sediment was thin. The resistivity in the reach with thin sediment showed lingering tracer in the hyporheic zone both upstream and downstream from the J‐hook. In the second reach where the sediment was thicker, the lingering tracer in the hyporheic zone was more extensive downstream from the J‐hook. The contrasting results between the two reaches from both methods suggested that sediments influenced hyporheic exchange more than the step at this location. Resistivity inversion differed from well data in both reaches in that it showed evidence for tracer after well samples had returned to background, mapping lingering tracer either upstream or downstream of a step. We conclude that resistivity surveys may become an important tool for hyporheic zone characterization because they provide information on the extent of slow moving fluids in the hyporheic zone, which have the potential to enhance chemical reactions. Copyright © 2012 John Wiley & Sons, Ltd.     

Progress in defining the solar wind sputter rate on protoplanets and interplanetary matter

Solar wind sputtering of exposed surfaces in heliocentric orbits is considered for bodies ranging in size from planets down to micrometeoroids. Erosion rates derived from APOLLO sample lunar regolith studies are presented together with the results of computer modelling of surface topographical alteration in order to characterize the sputter erosion process on Solar System bodies bombarded by the solar wind. The consensus of recent measurements leads to a rate of between 0.025 to 0.045 Å yr^?1 near the lunar equator.