Groundwater control of mangrove surface elevation: Shrink and swell varies with soil depth

We measured monthly soil surface elevation change and determined its relationship to groundwater changes at a mangrove forest site along Shark River, Everglades National Park, Florida. We combined the use of an original design, surface elevation table with new rod-surface elevation tables to separately track changes in the mid zone (0–4 m), the shallow root zone (0–0.35 m), and the full sediment profile (0–6 m) in response to site hydrology (daily river stage and daily groundwater piezometric pressure). We calculated expansion and contraction for each of the four constituent soil zones (surface [accretion and erosion; above 0 m], shallow zone [0–0.35 m], middle zone [0.35–4 m], and bottom zone [4–6]) that comprise the entire soil column. Changes in groundwater pressure correlated strongly, with changes in soil elevation for the entire profile (Adjusted R² = 0.90); this relationship was not proportional to the depth of the soil profile sampled. The change in thickness of the bottom soil zone accounted for the majority (R² = 0.63) of the entire soil profile expansion and contraction. The influence of hydrology on specific soil zones and absolute elevation change must be considered when evaluating the effect of disturbances, sea level rise, and water management decisions on coastal wetland systems.     

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.     

Multi‐year water balance assessment of a newly constructed wetland,Fort McMurray,Alberta

Oil sands mining in Alberta transforms the boreal landscape of forests and wetlands into open pits, tailings ponds and overburden piles. Whereas reclamation efforts have primarily focused on upland forests, rebuilding wetland systems has recently become a motivation for research. Wetland creation and sustainability in this region is complicated by the sub‐humid climate and salinity of underlying mining material. In 2012, Syncrude Canada Ltd. completed the construction of the Sandhill Fen Watershed (SFW), a 52‐ha upland‐wetland system to evaluate wetland reclamation strategies on soft tailings. SFW includes an active pumping system, upland hummocks, a fen wetland and underdrains. To evaluate the influence of management practices on the hydrology of the system, this study reports the water balance from January 2013 to December 2014, the first 2 years after commissioning. A semi‐distributed approach was taken to examine the fluxes and stores of water in uplands and lowlands. Natural and artificial inputs and outputs were measured using a series of precipitation gauges and pumps, and evapotranspiration was quantified using three eddy covariance towers. A series of near surface wells recorded water table position. Both 2013 and 2014 were normal rainfall years, with 2013 having more and 2014 less snow than normal. In 2013, inflow/outflow from pumping was the predominant hydrological fluxes, resulting in considerable variability in water table position and storage changes throughout the summer. In 2014, the artificial addition of water was negligible, yet the water table remained near the surface in lowland locations, suggesting that wetland conditions could be maintained under current conditions. Evapotranspiration rates between uplands and lowlands were similar between years and sites, ranging from 2.2 ± 1.8 to 2.5 ± 1.2 mm/day and were largely controlled by climate. These rates were less than nearby older upland systems, suggesting that water balance partitioning will change as vegetation develops. Comparison between years and with natural systems provides insight on how management practices influence hydrologic dynamics and the overall water balance of the SFW. Copyright © 2016 John Wiley & Sons, Ltd.     

Mercury and methylmercury biogeochemistry in a thawing permafrost wetland complex,Northwest Territories,Canada

In arctic and sub‐arctic environments, mercury (Hg), more specifically toxic methylmercury (MeHg), is of growing concern to local communities because of its accumulation in fish. In these regions, there is particular interest in the potential mobilization of atmospherically deposited Hg sequestered in permafrost that is thawing at unprecedented rates. Permafrost thaw and the resulting ground surface subsidence transforms forested peat plateaus into treeless and permafrost‐free thermokarst wetlands where inorganic Hg released from the thawed permafrost and draining from the surrounding peat plateaus may be transformed to MeHg. This study begins to characterize the spatial distribution of MeHg in a peat plateau–thermokarst wetland complex, a feature that prevails throughout the wetland‐dominated southern margin of thawing discontinuous permafrost in Canada's Northwest Territories. We measured pore water total Hg, MeHg, dissolved organic matter characteristics and general water chemistry parameters to evaluate the role of permafrost thaw on the pattern of water chemistry. A gradient in vegetation composition, water chemistry and dissolved organic matter characteristics followed a toposequence from the ombrotrophic bogs near the crest of the complex to poor fens at its downslope margins. We found that pore waters in poor fens contained elevated levels of MeHg, and the water draining from these features had dissolved MeHg concentrations 4.5 to 14.5 times higher than the water draining from the bogs. It was determined through analysis of historical aerial images that the poor fens in the toposequence had formed relatively recently (early 1970s) as a result of permafrost thaw. Differences between the fens and bogs are likely to be a result of their differences in groundwater function, and this suggests that permafrost thaw in this landscape can result in hotspots for Hg methylation that are hydrologically connected to downstream ecosystems. Copyright © 2016 John Wiley & Sons, Ltd.     

Do southern Appalachian Mountain summer stream temperatures respond to removal of understory rhododendron thickets?

Dense understory thickets of the native evergreen shrub Rhododendron maximum expanded initially following elimination of American chestnut by the chestnut blight, and later in response to loss of the eastern hemlock due to hemlock woolly adelgid invasion. Rhododendron thickets often blanket streams and their riparian zones, creating cool, low-light microclimates. To determine the effect of such understory thickets on summer stream temperatures, we removed riparian rhododendron understory on 300 m reaches of two southern Appalachian Mountain headwater streams, while leaving two 300 m reference reaches undisturbed. Overhead canopy was left intact in all four streams, but all streams were selected to have a significant component of dead or dying eastern hemlock in the overstory, creating time-varying canopy gaps throughout the reach. We continuously monitored temperatures upstream, within and downstream of treatment and reference reaches. Temperatures were monitored in all four streams in the summer before treatments were imposed (2014), and for two summers following treatment (2015, 2016). Temperatures varied significantly across and within streams prior to treatment and across years for the reference streams. After rhododendron removal, increases in summer stream temperatures were observed at some locations within the treatment reaches, but these increases did not persist downstream and varied by watershed, sensor, and year. Significant increases in daily maxima in treatment reaches ranged from 0.9 to 2.6°C. Overhead canopy provided enough shade to prevent rhododendron removal from increasing summer temperatures to levels deleterious to native cold-water fauna (average summer temperatures remained below 16°C), and local temperature effects were not persistent.