The influence of edge sites on the development of surface charge on goethite nanoparticles: A molecular dynamics investigation

Large-scale molecular simulation of proton accumulations were carried out on (i) (110) and (021) slabs immersed in aqueous solution and (ii) a series of model goethite nanoparticles of dimension 2 to 8 nm with systematically varying acicularity and (110)/(021) surface areas. In the slab systems, the (021) surface exhibits 15% more proton charge per unit area than the (110) surface. In the particulate systems, the acicular particles having the highest (110)/(021) ratio accumulate the most charge, opposite to the trend expected from the slab simulations, indicating that, at length scales on the order of 10 nm, the slab results are not a good indicator of the overall charging behavior of the particles. The primary reason for the discrepancy between the particulate systems and slab systems is the preferential accumulation of protons at acute (110)-(110) intersections. Charge accumulates preferentially in this region because excess proton charge at an asperity is more effectively solvated than at a flat interface.     

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.     

Environmental significance of C/C and O/O ratios of modern land-snail shells from the southern great plains of North America

¹³C/¹²C and ¹⁸O/¹⁶O ratios of aragonite shells of modern land snails from the southern Great Plains of North America were measured for samples from twelve localities in a narrow east-west corridor that extended from the Flint Hills in North Central Oklahoma to the foothills of the Sangre de Cristo Mountains in Northern New Mexico, USA. Across the study area, shell δ¹⁸O values (PDB scale) ranged from −4.1‰ to 1.2‰, while δ¹³C values ranged from −13.2‰ to 0.0‰. δ¹⁸O values of the shell aragonite were predicted with a published, steady state, evaporative flux balance model. The predicted values differed (with one exception) by less than 1‰ from locality averages of measured δ¹⁸O values. This similarity suggests that relative humidity at the time of snail activity is an important control on the δ¹⁸O values of the aragonite and emphasizes the seasonal nature of the climatic information preserved in the shells. Correlated δ¹³C values of coexisting Vallonia and Gastrocopta suggest similar feeding habits and imply that these genera can provide information on variations in southern Great Plains plant ecology. Although there is considerable scatter, multispecies, transect average δ¹³C values of the modern aragonite shells are related to variations in the type of photosynthesis (i.e., C₃, C₄) in the local plant communities. The results of this study emphasize the desirability of obtaining isotope ratios representing averages of many shells in a locale to reduce possible biases associated with local variations among individuals, species, etc., and thus better represent the “neighborhood” scale temporal and/or spatial environmental variations of interest in studies of modern and ancient systems.     

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.     

Critical rainfall statistics for predicting watershed flood responses: rethinking the design storm concept

Recent advances have been made to modernize estimates of probable precipitation scenarios; however, researchers and engineers often continue to assume that rainfall events can be described by a small set of event statistics, typically average intensity and event duration. Given the easy availability of precipitation data and advances in desk‐top computational tools, we suggest that it is time to rethink the ‘design storm’ concept. Design storms should include more holistic characteristics of flood‐inducing rain events, which, in addition to describing specific hydrologic responses, may also be watershed or regionally specific. We present a sensitivity analysis of nine precipitation event statistics from observed precipitation events within a 60‐year record for Tompkins County, NY, USA. We perform a two‐sample Kolmogorov–Smirnov (KS) test to objectively identify precipitation event statistics of importance for two related hydrologic responses: (1) peak outflow from the Six Mile Creek watershed and (2) peak depth within the reservoir behind the Six Mile Creek Dam. We identify the total precipitation depth, peak hourly intensity, average intensity, event duration, interevent duration, and several statistics defining the temporal distribution of precipitation events to be important rainfall statistics to consider for predicting the watershed flood responses. We found that the two hydrologic responses had different sets of statistically significant parameters. We demonstrate through a stochastic precipitation generation analysis the effects of starting from a constrained parameter set (intensity and duration) when predicting hydrologic responses as opposed to utilizing an expanded suite of rainfall statistics. In particular, we note that the reduced precipitation parameter set may underestimate the probability of high stream flows and therefore underestimate flood hazard. Copyright © 2016 John Wiley & Sons, Ltd.     

Age of Gimli beach of Lake Agassiz based on new OSL dating

Gimli beach in Manitoba is one of the lowest elevation beaches in the southern Lake Agassiz basin, and is a distinct ridge composed of bedded sand and gravel that rises above the lake plain and extends for more than 40 km. Ten new optically stimulated luminescence (OSL) ages from Gimli beach yield ages mostly ranging from 9.7 ± 0.7 to 10.5 ± 0.8 ka (average 10.3 ± 0.5 ka), which is older by 0.6 to >1.0 ka than age estimates of previous researchers. Two of our new OSL ages are notably older than the others, dating to ~11.3 ± 0.8 and 13.9 ± 1.0 ka, which we attribute to poorly bleached sands. We ascribe an age of about 10 ka to Gimli beach, which is several centuries before overflow from Lake Agassiz and its vast drainage basin shifted from the western Great Lakes to glacial Lake Ojibway and the St. Lawrence Valley.     

Landscape controls on long‐term runoff in subhumid heterogeneous Boreal Plains catchments

We compared median runoff (R) and precipitation (P) relationships over 25 years from 20 mesoscale (50 to 5,000 km²) catchments on the Boreal Plains, Alberta, Canada, to understand controls on water sink and source dynamics in water‐limited, low‐relief northern environments. Long‐term catchment R and runoff efficiency (RP^?1) were low and varied spatially by over an order of magnitude (3 to 119 mm/year, 1 to 27%). Intercatchment differences were not associated with small variations in climate. The partitioning of P into evapotranspiration (ET) and R instead reflected the interplay between underlying glacial deposit texture, overlying soil‐vegetation land cover, and regional slope. Correlation and principal component analyses results show that peatland‐swamp wetlands were the major source areas of water. The lowest estimates of median annual catchment ET (321 to 395 mm) and greatest R (60 to 119 mm, 13 to 27% of P) were observed in low‐relief, peatland‐swamp dominated catchments, within both fine‐textured clay‐plain and coarse‐textured glacial deposits. In contrast, open‐water wetlands and deciduous‐mixedwood forest land covers acted as water sinks, and less catchment R was observed with increases in proportional coverage of these land covers. In catchments dominated by hummocky moraines, long‐term runoff was restricted to 10 mm/year, or 2% of P. This reflects the poor surface‐drainage networks and slightly greater regional slope of the fine‐textured glacial deposit, coupled with the large soil‐water and depression storage and higher actual ET of associated shallow open‐water marsh wetland and deciduous‐forest land covers. This intercatchment study enhances current conceptual frameworks for predicting water yield in the Boreal Plains based on the sink and source functions of glacial landforms and soil‐vegetation land covers. It offers the capability within this hydro‐geoclimatic region to design reclaimed catchments with desired hydrological functionality and associated tolerances to climate or land‐use changes and inform land management decisions based on effective catchment‐scale conceptual understanding.     

Dynamic storage: a potential metric of inter‐basin differences in storage properties

The potential for dynamic storage to serve as a metric of basin behaviour was assessed using data from five drainage basins with headwaters on the thick sand and gravel deposits of the Oak Ridges Moraine in southern Ontario, Canada. Dynamic storage was directly correlated with the ratio of variability of δ²H in streamflow relative to that in precipitation. This ratio has previously been shown to be inversely related to basin mean transit time (MTT), suggesting an inverse relationship between dynamic storage and MTT for the study basins. Dynamic storage was also directly correlated with interannual variability in stream runoff, baseflow and baseflow:runoff ratio, implying that basins with smaller dynamic storage have less interannual variability in their streamflow regimes. These preliminary results suggest that dynamic storage may serve as a readily derived and useful metric of basin behaviour for inter‐basin comparisons. Copyright © 2016 John Wiley & Sons, Ltd.     

Modeling the 2D behavior of dry‐stone retaining walls by a fully discrete element method

The dry‐stone retaining walls (DSRW) have been tipped as a promising solution for sustainable development. However, before recently, their behavior is relatively obscure. In this study, discrete element method (DEM) approach was applied to simulate the plane strain failure of these walls. A commercial DEM package (PFC2D™) was used throughout this study. The authors used a fully discrete approach; thus, both the wall and the backfill were modeled as discrete elements. The methodology for obtaining the micromechanical parameters was discussed in detail; this includes the three mechanical sub‐systems of DSRWs: wall, backfill and interface. The models were loaded progressively until failure, and then the results were compared with the full‐scale experimental results where the walls were loaded, respectively, with hydrostatic load and backfill. Despite its complexity and its intensive calculation time, DEM model can then be used to validate a more simplified approach. Copyright © 2015 John Wiley & Sons, Ltd.