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.     

Isotopic variability in the aragonite shells of freshwater gastropods living in springs with nearly constant temperature and isotopic composition

We conducted a year-long, intensive monitoring program of live aquatic gastropods (Helisoma duryi, Melanoides tuberculata, Physa virgata, Pyrgulopsis sp., and Tyronia sp.) and their host springs in the Ash Meadows National Wildlife Refuge of southern Nevada. Our purpose was to constrain the degree of natural variation in the isotopic values of shell aragonite for gastropods living in near-constant conditions. Inter- and intraspecies variations, as well as within-shell variations, of δ¹⁸O and δ¹³C values for all taxa were larger than predicted based on variations in environmental conditions alone. This result suggests that different organisms growing in identical or nearly identical environmental conditions may not produce shells with equilibrium isotopic compositions and that these offsets from equilibrium may differ by small, but statistically significant amounts. For the gill-breathing, fully aquatic gastropods M. tuberculata, Pyrgulopsis sp., and Tyronia sp., the deviation of measured isotopic values compared to predicted values based on average environmental conditions were consistent with differences between taxa in the seasonal timing of shell growth. Measured values for the lung-breathing gastropods H. duryi and P. virgata were higher for δ¹⁸O and lower for δ¹³C than predicted at isotopic equilibrium, even when accounting for seasonality effects. We suggest that explaining the differences between the shell isotopic composition of lung- and gill-breathing snails requires a combination of both behavioral and physiologic factors. Our results illustrate the potential complexities of interpreting stable isotopic data from fossil gastropod shells even when environmental conditions are nearly constant, and place limitations on the paleoenvironmental deductions that can be made from the isotopic measurements on fossil gastropods.     

Assessing regional‐scale spatio‐temporal patterns of groundwater–surface water interactions using a coupled SWAT‐MODFLOW model

Interaction between groundwater and surface water in watersheds has significant impacts on water management and water rights, nutrient loading from aquifers to streams, and in‐stream flow requirements for aquatic species. Of particular importance are the spatial patterns of these interactions. This study explores the spatio‐temporal patterns of groundwater discharge to a river system in a semi‐arid region, with methods applied to the Sprague River Watershed (4100 km²) within the Upper Klamath Basin in Oregon, USA. Patterns of groundwater–surface water interaction are explored throughout the watershed during the 1970–2003 time period using a coupled SWAT‐MODFLOW model tested against streamflow, groundwater level and field‐estimated reach‐specific groundwater discharge rates. Daily time steps and coupling are used, with groundwater discharge rates calculated for each model computational point along the stream. Model results also are averaged by month and by year to determine seasonal and decadal trends in groundwater discharge rates. Results show high spatial variability in groundwater discharge, with several locations showing no groundwater/surface water interaction. Average annual groundwater discharge is 20.5 m³/s, with maximum and minimum rates occurring in September–October and March–April, respectively. Annual average rates increase by approximately 0.02 m³/s per year over the 34‐year period, negligible compared with the average annual rate, although 70% of the stream network experiences an increase in groundwater discharge rate between 1970 and 2003. Results can assist with water management, identifying potential locations of heavy nutrient mass loading from the aquifer to streams and ecological assessment and planning focused on locations of high groundwater discharge. Copyright © 2016 John Wiley & Sons, Ltd.     

Stratigraphy of Pleistocene glaciations in the St Elias Mountains,southwest Yukon,Canada

At least five Middle to Late Pleistocene advances of the northern Cordilleran Ice Sheet are preserved at Silver Creek, on the northeastern edge of the St Elias Mountains in southwest Yukon, Canada. Silver Creek is located 100 km up‐ice of the Marine Isotope Stage (MIS) 2 McConnell glacial limit of the St Elias lobe. This site contains ~3 km of nearly continuous lateral exposure of glacial and non‐glacial sediments, including multiple tills separated by thick gravel, loess and tilted lake beds. Infrared‐stimulated luminescence (IRSL) and AMS radiocarbon dating constrain the glacial deposits to MIS 2, 4, either MIS 6 or mid‐MIS 7, and two older Middle Pleistocene advances. This chronology and the tilt of the lake beds suggest Pleistocene uplift rates of up to 1.9 mm a^?1 along the Denali Fault since MIS 7. The non‐glacial sediment consists of sand, gravel, loess and organic beds from MIS 7, MIS 3 and the early Holocene. The MIS 3 deposits date to between 30–36 ¹⁴C ka BP, making Silver Creek one of the few well‐constrained MIS 3‐aged sites in Yukon. This confirms that ice receded close to modern limits in MIS 3. Pollen and macrofossil analyses show that a meadow‐tundra to steppe‐tundra mosaic with abundant herbs and forbs and few shrubs or trees, dominated the environment at this time. The stratigraphy at Silver Creek provides a palaeoclimatic record since at least MIS 8 and comprises the oldest direct record of Pleistocene glaciation in southwest Yukon.     

High‐temperature gold‐copper extraction with chloride flux in lava tubes of Tolbachik volcano (Kamchatka)

Subvolcanic environments in supra‐subduction zones are renowned for hosting epithermal deposits that often contain electrum and native gold, including bonanza examples. This study examined mineral assemblages and processes occurring in shallow‐crust volcanic settings using recent eruption (2012–2013) of the basaltic Tolbachik volcano in the Kamchatka arc. The Tolbachik eruptive system is characterized by an extensive system of lava tubes. After cessation of magma input, the tubes maintained the flow of hot oxidized gases that episodically interacted with the lava surfaces and sulphate‐chloride precipitates from volcanic gases on these surfaces. The gas‐rock interaction had strong pyrometamorphic effects that resulted in the formation of molten salt, oxidized (tenorite, hematite, Cu‐rich magnesioferrite) and skarn‐like silicate mineral assemblages. By analogy with experimental studies, we propose that a combination of these processes was responsible for extraction of metals from the basaltic wall rocks and deposition of Cu‐, Fe‐ and Cu‐Fe‐oxides and native gold.     

Primary aragonite and high‐Mg calcite in the late Cambrian (Furongian). Potential evidence from marine carbonates in Oman

Transient aragonite seas occurred in the early Cambrian but several models suggest the late Cambrian was a time of calcite seas. Here, evidence is presented from the Andam Group, Huqf High, Oman (Gondwana) that suggests a transient Furongian (late Cambrian) aragonite sea, characterized by the precipitation of aragonite and high‐Mg calcite ooids and aragonite isopachous, fibrous, cements. Stable carbon isotope data suggest that precipitation occurred just before and during the SPICE (Steptoean Positive Carbonate Isotope Excursion). Aragonite and high‐Mg calcite precipitation can be accounted for if mMg:Ca ratios were around 1.2 given the very high atmospheric CO₂ at that time and if precipitation occurred in warm waters associated with the SPICE. This, together with reported occurrences of early Furongian aragonite ooids from various locations in North America (Laurentia), suggests that aragonite and high‐Mg calcite precipitation from seawater may have been more than just a local phenomenon.     

Segmentation and kinematics of the North America‐Caribbean plate boundary offshore Hispaniola

We explored the submarine portions of the Enriquillo–Plantain Garden Fault zone (EPGFZ) and the Septentrional–Oriente Fault zone (SOFZ) along the Northern Caribbean plate boundary using high‐resolution multibeam echo‐sounding and shallow seismic reflection. The bathymetric data shed light on poorly documented or previously unknown submarine fault zones running over 200 km between Haiti and Jamaica (EPGFZ) and 300 km between the Dominican Republic and Cuba (SOFZ). The primary plate‐boundary structures are a series of strike‐slip fault segments associated with pressure ridges, restraining bends, step overs and dogleg offsets indicating very active tectonics. Several distinct segments 50–100 km long cut across pre‐existing structures inherited from former tectonic regimes or bypass recent morphologies formed under the current strike‐slip regime. Along the most recent trace of the SOFZ, we measured a strike‐slip offset of 16.5 km, which indicates steady activity for the past ~1.8 Ma if its current GPS‐derived motion of 9.8 ± 2 mm a^?1 has remained stable during the entire Quaternary.     

Water source dynamics of high Arctic river basins

Arctic river basins are amongst the most vulnerable to climate change. However, there is currently limited knowledge of the hydrological processes that govern flow dynamics in Arctic river basins. We address this research gap using natural hydrochemical and isotopic tracers to identify water sources that contributed to runoff in river basins spanning a gradient of glacierization (0–61%) in Svalbard during summer 2010 and 2011. Spatially distinct hydrological processes operating over diurnal, weekly and seasonal timescales were characterized by river hydrochemistry and isotopic composition. Two conceptual water sources (‘meltwater’ and ‘groundwater’) were identified and used as a basis for end‐member mixing analyses to assess seasonal and year‐to‐year variability in water source dynamics. In glacier‐fed rivers, meltwater dominated flows at all sites (typically >80%) with the highest contributions observed at the beginning of each study period in early July when snow cover was most extensive. Rivers in non‐glacierized basins were sourced initially from snowmelt but became increasingly dependent on groundwater inputs (up to 100% of total flow volume) by late summer. These hydrological changes were attributed to the depletion of snowpacks and enhanced soil water storage capacity as the active layer expanded throughout each melt season. These findings provide insight into the processes that underpin water source dynamics in Arctic river systems and potential future changes in Arctic hydrology that might be expected under a changing climate. Copyright © 2013 John Wiley & Sons, Ltd.     

A hydropedological approach to simulate streamflow and soil water contents with SWAT+

Reflecting internal catchment hydrological processes in hydrological models is important for accurate predictions of the impact of climate and land-use change on water resources. Characterizing these processes is however difficult and expensive due to their dynamic nature and spatio-temporal variability. Hydropedology is a relatively new discipline focusing on the synergistic integration of hydrology, soil physics and pedology. Hydropedological interpretations of soils and soil distribution can be used to characterize key hydrological processes, especially in areas with no or limited hydrometric measurements. Here we applied a hydropedological approach to reflect flowpaths through detailed routing in SWAT+ for a 157 ha catchment (Weatherley) in South Africa. We compared the hydropedological approach and a standard (no routing) approach against measured streamflow (two weirs) and soil water contents (13 locations). The catchment was treated as ‘ungauged’ and the model was not calibrated against hydrometric measurements in order to determine the direct contribution of hydropedology on modelling efficiency. Streamflow was predicted well without calibration (NSE > 0.8; R² > 0.82) for both approaches at both weirs. The standard approach yielded slightly better streamflow predictions. The hydropedological approach resulted in considerable improvements in the simulation of soil water contents (R² increased from 0.40 to 0.49 and PBIAS decreased from 40% to 20%). The routing capacity of SWAT+ as employed in the hydropedological approach reduced the underestimation of wetland water regimes drastically and resulted in a more accurate representation of the dominant hydrological processes in this catchment. We concluded that hydropedology can be a valuable source of ‘soft data’ to reflect internal catchment structure and processes and, potentially, for realistic calibrations in other studies, especially those conducted in areas with limited hydrometric measurements.     

The potential for agricultural land use change to reduce flood risk in a large watershed

Effects of agricultural land management practices on surface runoff are evident at local scales, but evidence for watershed‐scale impacts is limited. In this study, we used the Soil and Water Assessment Tool model to assess changes in downstream flood risks under different land uses for the large, intensely agricultural, Raccoon River watershed in Iowa. We first developed a baseline model for flood risk based on current land use and typical weather patterns and then simulated the effects of varying levels of increased perennials on the landscape under the same weather patterns. Results suggest that land use changes in the Raccoon River could reduce the likelihood of flood events, decreasing both the number of flood events and the frequency of severe floods. The duration of flood events were not substantially affected by land use change in our assessment. The greatest flood risk reduction was associated with converting all cropland to perennial vegetation, but we found that converting half of the land to perennial vegetation or extended rotations (and leaving the remaining area in cropland) could also have major effects on reducing downstream flooding potential. We discuss the potential costs of adopting the land use change in the watershed to illustrate the scale of subsidies required to induce large‐scale conversion to perennially based systems needed for flood risk reduction. Copyright © 2013 John Wiley & Sons, Ltd.