Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Sublittoral seaweed communities on natural and artificial substrata in a high-latitude coral community in South Africa

Coral mortality may result in macroalgal proliferation or a phase shift into an alga-dominated state. Subtidal, high-latitude western Indian Ocean coral communities at Sodwana Bay on the KwaZulu-Natal coast, South Africa, have experienced some mortality because of warm-water anomalies, storms and other causes, but the response of the macroalgae is unknown. We investigated the abundance and diversity of benthic algae on different hard natural substrata (dead digitate, brain and plate corals and beach rock) on Two-Mile Reef, Sodwana Bay. We also compared algal communities colonising ceramic, marble and pretreated ceramic tiles placed on the reef for six months. We identified 95 algae (14 Chlorophyta, 11 Phaeophyceae, 69 Rhodophyta and one cyanobacterium). Assemblages on natural and artificial substrata were dominated by the brown alga Lobophora variegata (Lamouroux) Womersley ex Oliveira and non-geniculate corallines (Rhodophyta, Corallinaceae). Cluster and ordination analyses revealed that the algae showed no affinity for particular substrata, whether natural or artificial. Algal cover was occasionally higher on rougher tiles and crustose corallines were significantly more abundant on marble than ceramic tiles. Two-Mile Reef had 23.1% dead and 48.4% live scleractinian coral cover, where dead corals were colonised indiscriminately by many small algal species, but there was no evidence of algal proliferation. The results provide a baseline for monitoring this high-latitude reef system.     

Nutrient flux into an intense deep chlorophyll layer in a mode-water eddy

An intense deep chlorophyll layer in the Sargasso Sea was reported near the center of an anticyclonic mode-water eddy by McGillicuddy et al. [2007. Eddy–wind interactions stimulate extraordinary mid-ocean plankton blooms, Science, accepted]. The high chlorophyll was associated with anomalously high concentrations of diatoms and with a maximum in the vertical profile of ¹⁴C primary productivity. Here we report tracer measurements of the vertical advection and turbulent diffusion of deep-water nutrients into this chlorophyll layer. Tracer released in the chlorophyll layer revealed upward motion relative to isopycnal surfaces of about 0.4 m/d, due to solar heating and mixing. The density surfaces themselves shoaled by about 0.1 m/d. The upward flux of dissolved inorganic nitrogen, averaged over 36 days, was approximately 0.6 mmol/m²/d due to both upwelling and mixing. This flux is about 40% of the basin wide, annually averaged, nitrogen flux required to drive the annual new production in the Sargasso Sea, estimated from the oxygen cycle in the euphotic zone, the oxygen demand below the euphotic zone, and from the ³He excess in the mixed layer. The observed upwelling of the fluid was consistent with theoretical models [Dewar, W.K., Flierl, G.R., 1987. Some effects of wind on rings. Journal of Physical Oceanography 17, 1653–1667; Martin, A.P., Richards, K.J., 2001. Mechanisms for vertical nutrient transport within a North Atlantic mesoscale eddy. Deep-Sea Research II 48, 757–773] in which eddy surface currents cause spatial variations in surface stress. The diapycnal diffusivity at the base of the euphotic zone was 3.5±0.5×10⁻⁵ m²/s. Diapycnal mixing was probably enhanced over more typical values by the series of storms passing over the eddy during the experiment and may have been enhanced further by the trapping of near-inertial waves generated within the eddy.     

Carbonaceous chondrites as analogs for the composition and alteration of Ceres

The mineralogy and geochemistry of Ceres, as constrained by Dawn's instruments, are broadly consistent with a carbonaceous chondrite (CM/CI) bulk composition. Differences explainable by Ceres’s more advanced alteration include the formation of Mg‐rich serpentine and ammoniated clay; a greater proportion of carbonate and lesser organic matter; amounts of magnetite, sulfide, and carbon that could act as spectral darkening agents; and partial fractionation of water ice and silicates in the interior and regolith. Ceres is not spectrally unique, but is similar to a few other C‐class asteroids, which may also have suffered extensive alteration. All these bodies are among the largest carbonaceous chondrite asteroids, and they orbit in the same part of the Main Belt. Thus, the degree of alteration is apparently related to the size of the body. Although the ammonia now incorporated into clay likely condensed in the outer nebula, we cannot presently determine whether Ceres itself formed in the outer solar system and migrated inward or was assembled within the Main Belt, along with other carbonaceous chondrite bodies.     

Evaluating the effects of catch-and-release angling on Cape stumpnose Rhabdosargus holubi in a South African estuary

Fisheries managers are increasingly promoting catch-and-release (C&R) to manage recreationally angled fish stocks. Despite this, there is a scarcity of information on the effects of C&R on estuarine-dependent species. Cape stumpnose Rhabdosargus holubi dominates the recreational fisheries catch and provides an important source of food for subsistence fishers in some temperate South African estuaries. The health and survival of R. holubi exposed to a C&R event was investigated by examining their physiological stress response (blood glucose and lactate), reflex impairment (reflex action mortality predictors [RAMP]) and short-term (12-hour) survival. Fish were captured and exposed to one of three air-exposure treatments: 0 s, 30 s or 90 s. Stress and health were measured either immediately (immediate) or one hour after (delayed) the C&R event. There was no significant difference in blood glucose between air-exposure treatments, but there was a significant difference between the mean immediate and delayed glucose levels within each treatment (F_(2,143) = 81.8, p < 0.01). In contrast, blood lactate level was significantly higher in the 90-s treatment (p < 0.05). Immediate blood lactate levels were significantly lower than the delayed samples for each treatment (F = 4.29, p = 0.02; n = 169). Although all fish exhibited at least one reflex impairment, the RAMP score was significantly higher in the 90-s air-exposure treatment (H_(2,86) = 9.73, p = 0.007). Also, RAMP scores were significantly lower in the delayed samples (p < 0.01). Although short-term mortality was relatively low (2.3%) for this species, it was highest in the 90-s treatment (7%). These results suggest that physiological stress is higher when R. holubi are exposed to longer periods of air exposure and that the physiological stress of fish subject to a C&R event is best measured after a delay.     

Stochastic evaluation of fluvial to marginal marine sealing facies

Hydrocarbon top seal analyses are particularly difficult in fluvial and marginal marine settings. Although these settings often contain beds comprised of a low-permeability, clay-rich lithology associated with high quality seals, their presence does not guarantee an effective seal because individual beds within the stratal unit may be laterally discontinuous. Lateral facies changes, truncation of fine-grained beds, or the presence of crevasse splays may provide cross-stratal migration pathways, reducing the effective sealing capacity to a magnitude less than the closure height.     

Influence of discrete step size on wind setup component of storm surge

Open coast storm surge water levels consist of wind setup due to wind shear at the water surface; a wave setup component caused by wind induced waves transferring momentum to the water column; an atmospheric pressure head component due to the atmospheric pressure deficit over the spatial extent of the storm system; a Coriolis forced setup or setdown component due to the effects of the rotation of the earth acting on the wind driven alongshore current at the coast; a possible seiche component due to resonance effects initiated by moving wind system, and, if astronomical tides are present, an astronomical tide component (although the tide is typically considered to be a forced astronomical event and not really a direct part of the external wind-driven meteorological component of storm surge). Typically the most important component of a storm surge is the wind setup component, especially on the U.S. East Coast and the Gulf of Mexico shorelines. In many approaches to storm surge modeling, a constant depth approximation is invoked over a limited step size in the computational domain. The use of a constant depth approximation has received little attention in the literature although can be very important to the resulting magnitude of the computed storm surge. The importance of discrete step size to the wind setup storm surge component is considered herein with a simple case computation of the wind setup component on a linear slope offshore profile. The present study findings show that the constant depth approximation to wind setup storm surge estimation is biased on the low side (except in extremely shallow water depths) and can provide large errors if discrete step size is not sufficiently resolved. Guidance has been provided on the error that one might encounter for various step sizes on different slopes.     

Benthic macrofauna and productivity regimes in the Barents Sea — Ecological implications in a changing Arctic

Benthic faunal assemblages were analysed from 47 stations in the central and southern parts of the Barents Sea, together with sedimentary and water column parameters, daily ice records and modelled integrated primary productivity. Sampling spanned areas influenced by Atlantic Water (AW) to those lying under Arctic Water (ArW), and included stations with mixed water masses. Ice cover suppressed water column productivity in the northern areas. Three main faunal groups were identified, based on similarity of numerical faunal composition. The northern and southern faunal groups were separated by the northernmost penetration of AW in the bottom water and the third group, the Hopen group, was influenced by modified bank water. Faunal abundances were significantly higher within the southern faunal group relative to the northern group, but the numbers of taxa present were similar. The particularly rich fauna of the Hopen group reflected sediment heterogeneity and tight pelagic–benthic coupling. These results suggest that a retreat and thinning of the ice cover in the Barents Sea likely will result in the northern parts of the Barents Sea becoming more Atlantic in character, with a higher productivity at the sea floor.