Mercury in Eastern Kentucky coals: Geologic aspects and possible reduction strategies

Mercury emissions from US coal-fired power plants will be regulated by the US Environmental Protection Agency (USEPA) before the end of the decade. Because of this, the control of Hg in coal is important. Control is fundamentally based on the knowledge of the amounts of Hg in mined, beneficiated, and as-fired coal. Eastern Kentucky coals, on a reserve district level, have Hg contents similar to the USA average for coal at mines. Individual coals show greater variation at the bench scale, with Hg enrichment common in the top bench, often associated with enhanced levels of pyritic sulfur. Some of the variation between parts of eastern Kentucky is also based on the position relative to major faults. The Pine Mountain thrust fault appears to be responsible for elemental enrichment, including Hg, in coals on the footwall side of the thrust.Eastern Kentucky coals shipped to power plants in 1999, the year the USEPA requested coal quality information on coal deliveries, indicate that coals shipped from the region have 0.09 ppm Hg, compared to 0.10 ppm for all delivered coals in the USA. On an equal energy basis, and given equal concentrations of Hg, the high volatile bituminous coals from eastern Kentucky would emit less Hg than lower rank coals from other USA regions.     

Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

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.     

Deducing the spatial variability of exchange within a longitudinal channel water balance

Developing an appropriate data collection scheme to infer stream–subsurface interactions is not trivial due to the spatial and temporal variability of exchange flowpaths. Within the context of a case study, this paper presents the results from a number of common data collection techniques ranging from point to reach scales used in combination to better understand the spatial complexity of subsurface exchanges, infer the hydrologic conditions where individual influences of hyporheic and groundwater exchange components on stream water can be characterized, and determine where gaps in information arise. We start with a tracer‐based, longitudinal channel water balance to quantify hydrologic gains and losses at a sub‐reach scale nested within two consecutive reaches. Next, we look at groundwater and stream water surface levels, shallow streambed vertical head gradients, streambed and aquifer hydraulic conductivities, water chemistry, and vertical flux rates estimated from streambed temperatures to provide more spatially explicit information. As a result, a clearer spatial understanding of gains and losses was provided, but some limitations in interpreting results were identified even when combining information collected over various scales. Due to spatial variability of exchanges and areas of mixing, each technique frequently captured a combination of groundwater and hyporheic exchange components. Ultimately, this study provides information regarding technique selection, emphasizes that care must be taken when interpreting results, and identifies the need to apply or develop more advanced methods for understanding subsurface exchanges. Copyright © 2013 John Wiley & Sons, Ltd.     

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.