Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

Seasonal δS variations in two high elevation snow pits measured by S-S double spike thermal ionization mass spectrometry

δ³⁴S and sulfate concentrations were determined in snow pit samples using a thermal ionization mass spectrometric technique capable of 0.2‰ accuracy and requires ≈5 μg (0.16 μmol) natural S. The technique utilizes a ³³S-³⁶S double spike for instrumental mass fractionation correction, and has been applied to snow pit samples collected from the Inilchek Glacier, Kyrgyzstan and from Summit, Greenland. These δ³⁴S determinations provide the first high-resolution seasonal data for these sites, and are used to estimate seasonal sulfate sources. Deuterium (δD) and oxygen (δ¹⁸O) isotope data show that the Inilchek and Summit snow pit samples represent precipitation over ≈20 months.The δ³⁴S values for the Inilchek ranged from +2.6 ± 0.4‰ to +7.6 ± 0.4‰ on sample sizes ranging from 0.3 to 1.8 μmol S. δ³⁴S values for Greenland ranged from +3.6 ± 0.7‰ to +13.3 ± 5‰ for sample sizes ranging from 0.05 to 0.29 μmol S. The concentration ranged from 92.6 ± 0.4 to 1049 ± 4 ng/g for the Inilchek and 18 ± 9 to 93 ± 6 ng/g for the Greenland snow pit. Anthropogenic sulfate dominates throughout the sampled time interval for both sites based on mass balance considerations. Additionally, both sites exhibit a seasonal signature in both δ³⁴S and concentration. The thermal ionization mass spectrometric technique has three advantages compared to gas source isotopic methods: (1) sample size requirements of this technique are 10-fold less permitting access to the higher resolution S isotope record of low concentration snow and ice, (2) the double spike technique permits δ³⁴S and S concentration to be determined simultaneously, and (3) the double spike is an internal standard.     

Acid mine drainage contaminates groundwater of a Tennessee watershed

Water samples were collected from 18 natural springs within the West Fork of the Obey River watershed. Overton County, Tennessee, to determine if groundwater was adversely affected by runoff from abandoned surface coal mines Six springs were found to be affected severely and deemed unfit as a source of potable water Water quality of the remaining springs was essentially unaffected it appeared that proximity to surface mines, elevation at the outflow, and geology of the surrounding strata determined the quality of the groundwater The unit is jointly supported by Tennessee Technological University, the Tennessee Wildlife Resource Agency, and the US. Fish and Wildlife Service     

Buried trees,water table fluctuations,and 3000 years of changing climate in west-central Oklahoma

A sequence of radiocarbon-dated buried trees, buried soils, a carbonate zone, and a molluscan fauna from Carnegie Canyon indicate that between 3200 and 2600 yr B.P. the climate of west-central Oklahoma was drier than today. A high water table accompanied a period of moister climate 2000 to 1000 yr B.P. The water table dropped after 1000 yr B.P. due to a change toward dry conditions.     

Experimental thermal discoloration and heat conductivity studies of caliche from eastern new mexico

Thermal experiments under laboratory conditions examined caliche discoloration and thermal conductivity/shock. the results provide information about caliche behavior under thermal conditions, which in some environmental settings will assist archaeologists in identifying discolored caliche from cultural activities as opposed to that from natural range fires. Generally, temperature intensity affects discoloration more than heat exposure duration. Sample colors change markedly towards darker values with carbon reduction between 300° and 700° C caliche glows during heating as the carbon oxidizes; the samples tend towards paler colors, lighter weight, and increased fissures. the thermal conductivity experiment compared heat transference of caliche with other lithic resources of the Llano Estacado, while the thermal shock measured caliche resilience. Metaquartzites and cherts from the Llano Estacado are better heat conductors than caliche, but caliche is far more resilient to repeated thermal shock.     

Using winter flounder growth rates to assess habitat quality across an anthropogenic gradient in Narragansett Bay, Rhode Island

We used growth rates of juvenile winter flounderPseudopleuronectes americanus to assess anthropogenic influence on habitat quality at three sites in Narragansett Bay, Rhode Island. The upper bay site, Gaspee Point, had the highest population density and concentration of total nitrogen; human inputs decreased down bay. Growth rates of individually marked fish were measured in three 15-d experiments from June 8 to July 6, 1998 in 1-m² cages placed at upper, middle, and lower bay sites. Water temperature, salinity, dissolved oxygen (DO), and benthic food were also measured. Stable isotopes of nitrogen and carbon were measured in experimental fish as possible indicators of nutrient enrichment and to identify organic carbon sources. Growth rates were 0.22–0.60 mm d⁻¹, with the highest average at the mid-bay site. Growth was initially fastest at Gaspee Point, but dropped off as DO concentrations fell. Step-wise multiple regression indicated that location (upper, middle, or lower bay) explained most of the variability in fish growth (40%). Coefficients of other significant variables indicated that fish grew faster at lower salinities, smaller sizes, and with decreased time that DO was below 2.3 mg l⁻¹. Benthic prey varied among sites and there was significantly less food and fewer species at Gaspee Point.Polydora cornuta was a favored food at all sites and was found in over half the stomachs. Values of δ¹⁵N in fish and sediments did not reflect differences in total nitrogen concentrations recorded near the sites. We suggest that anthropogenic influences, such as nutrients and sewage, affected habitat quality by reducing DO, which lowered fish growth rates.     

Viruses as potential regulators of regional brown tide blooms caused by the alga,Aureococcus anophagefferens

Blooms of the brown tide organismAureccoccus anophagefferens have recurred in the coastal bays in New Jersey since 1995 and in the coastal bays of Long Island since 1985. Intracellular viral-like particles (VLPs) were documented during 1999–2000 brown tide blooms in Little Egg Harbor, New Jersey, but it was not determined whether cells were infected during the termination of the bloom. The objective of this study was to determine if VLPs infected and lysed natural populations ofA. anophagefferens in coastal bays of New Jersey and New York in 2002 with the same frequency as in 1999–2000 and especially at the termination of the bloom. Our results confirmed that the highest percentage (37.5%) of VLP-infected cells occurred at the termination of the brown tide bloom in New Jersey in 2002. Intracellular VLPs were present throughout the bloom event. The percentage of visibly infected cells was higher at the beginning of the bloom than during the peak of the bloom. The intracellular VLPs in natural populations ofA. anophagefferens were consistent in size and shape (approximately 140 nm in diameter) and comparable to those in previous studies. Concentrated viral isolates, prepared from waters during brown tide blooms in New York and New Jersey in 2002, infected healthy laboratoryA. anophagefferens cultures in vitro. The viral isolates associated with the highest laboratory viral activity (lysis positive) were concentrated from water samples having the highest viral and bacteria concentrations. The intracellular viruses in these virally infected laboratory cultures ofA. anophagefferens were similar in size and shape to those found in natural populations. The successful isolation of a virus specific toA. anophagefferens from a brown tide bloom in the field, the similarity of ultrastructure of VLPs infecting both natural populations and laboratory infected cultures, and the pattern of VLP infection during bloom activity in combination with the observed high percentage of VLP-infected cells during bloom termination, supports, the hypothesis that viruses may be a major source of mortality for brown tide blooms in regional coastal bays of New Jersey and New York.     

A Rhaetian microvertebrate fauna from Stowey Quarry,Somerset, U.K.

Rhaetian bone beds have been described from many locations in south-west England, around Bristol. One site that has never been reported is Stowey Quarry, some 13?km south of Bristol. This quarry yielded Lias, and revealed thin Rhaetian units in the quarry floor, including two bone beds, the basal Rhaetian bone bed, and a second, higher bone bed, also within the Westbury Formation. The fossil fauna of both includes elements typical of Rhaetian bone beds elsewhere, but showing differences in faunal composition between the two. The basal bone bed yielded more specimens and more species, with three taxa (Sargodon tomicus, Rhomphaiodon minor and Hybodus cloacinus) exclusive to this bed and eleven identified in total. Severnichthys acuminatus accounts for more than 50% of the countable teeth from the basal bone bed, followed by Gyrolepis albertii with 20%, Lissodus minimus with 14% and Rhomphaiodon minor with 9%. The basal bone bed, as ever, is dominated by chondrichthyans, whereas the upper bone bed is dominated by osteichthyans, which form 90% of the non-dental remains. The only unique taxon is Dapedium, and Gyrolepis albertii is the most abundant species with 45% of countable teeth, followed by Severnichthys acuminatus with 38% and Duffinselache holwellensis with 11%. These faunal differences, and the equally good condition of specimens between both samples confirms that the upper bone bed is independent of the basal bone bed, and is not a reworked subsample.     

Post-injection spreading and trapping of CO2 in saline aquifers: impact of the plume shape at the end of injection

We use an analytical model for the post-injection spreading of a plume of CO₂ in a saline aquifer under the action of buoyancy and capillary trapping to show that the spreading behavior is at all times strongly influenced by the shape of the plume at the end of the injection period. We solve the spreading equation numerically and confirm that, at late times, the volume of mobile CO₂ is given by existing asymptotic analytical solutions. The key parameters governing plume spreading are the mobility ratio, M, and the capillary trapping number, Γ—the former sets the shape of the plume at the end of the injection period, and the latter sets the amount of trapping. As a quantitative measure of the dependence of the spreading behavior on the initial shape, we use a volume ratio. That is, we evolve the plume from a true end-of-injection initial shape and also from an idealized “step” initial shape, and we take the ratio of these mobile plume volumes in the asymptotic regime. We find that this volume ratio is a power-law in M, where the exponent is governed exclusively by Γ. For conditions that are representative of geologic CO₂ sequestration, the ratio of mobile volumes between “true” and “step” initial plume shapes can be 50% or higher.     

Scales and causes of heterogeneity in bars in a large multi‐channel river: Río Paraná, Argentina

To date, published studies of alluvial bar architecture in large rivers have been restricted mostly to case studies of individual bars and single locations. Relatively little is known about how the depositional processes and sedimentary architecture of kilometre‐scale bars vary within a multi‐kilometre reach or over several hundreds of kilometres downstream. This study presents Ground Penetrating Radar and core data from 11, kilometre‐scale bars from the Río Paraná, Argentina. The investigated bars are located between 30 km upstream and 540 km downstream of the Río Paraná – Río Paraguay confluence, where a significant volume of fine‐grained suspended sediment is introduced into the network. Bar‐scale cross‐stratified sets, with lengths and widths up to 600 m and thicknesses up to 12 m, enable the distinction of large river deposits from stacked deposits of smaller rivers, but are only present in half the surface area of the bars. Up to 90% of bar‐scale sets are found on top of finer‐grained ripple‐laminated bar‐trough deposits. Bar‐scale sets make up as much as 58% of the volume of the deposits in small, incipient mid‐channel bars, but this proportion decreases significantly with increasing age and size of the bars. Contrary to what might be expected, a significant proportion of the sedimentary structures found in the Río Paraná is similar in scale to those found in much smaller rivers. In other words, large river deposits are not always characterized by big structures that allow a simple interpretation of river scale. However, the large scale of the depositional units in big rivers causes small‐scale structures, such as ripple sets, to be grouped into thicker cosets, which indicate river scale even when no obvious large‐scale sets are present. The results also show that the composition of bars differs between the studied reaches upstream and downstream of the confluence with the Río Paraguay. Relative to other controls on downstream fining, the tributary input of fine‐grained suspended material from the Río Paraguay causes a marked change in the composition of the bar deposits. Compared to the upstream reaches, the sedimentary architecture of the downstream reaches in the top ca 5 m of mid‐channel bars shows: (i) an increase in the abundance and thickness (up to metre‐scale) of laterally extensive (hundreds of metres) fine‐grained layers; (ii) an increase in the percentage of deposits comprised of ripple sets (to >40% in the upper bar deposits); and (iii) an increase in bar‐trough deposits and a corresponding decrease in bar‐scale cross‐strata (<10%). The thalweg deposits of the Río Paraná are composed of dune sets, even directly downstream from the Río Paraguay where the upper channel deposits are dominantly fine‐grained. Thus, the change in sedimentary facies due to a tributary point‐source of fine‐grained sediment is primarily expressed in the composition of the upper bar deposits.