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.     

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.     

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.     

High-P (P = 1.5–1.8 GPa) blueschist from Elba: Implications for underthrusting and exhumation of continental units in the Northern Apennines

The Acquadolce Subunit on the Island of Elba, Italy, records blueschist facies metamorphism related to the Oligocene–early Miocene stages of continental collision in the Northern Apennines. The blueschist facies metamorphism is represented by glaucophane- and lawsonite-bearing metabasite associated with marble and calcschist. These rock types occur as lenses in a schistose complex representing foredeep deposits of early Oligocene age. Detailed petrological analyses on metabasic and metapelitic protoliths, involving mineral and bulk-rock chemistry coupled with P–T and P–T–X(Fe₂O₃) pseudosection modelling using PERPLE_X, show that the Acquadolce Subunit recorded nearly isothermal exhumation from peak pressure–temperature conditions of 1.5–1.8 GPa and 320–370°C. During exhumation, peak lawsonite- and possibly carpholite- or stilpnomelane-bearing assemblages were overprinted and partially obliterated by epidote-blueschist and, subsequently, albite-greenschist facies metamorphic assemblages. This study sheds new light on the tectonic evolution of Adria-derived metamorphic units in the Northern Apennines, by showing (a) the deep underthrusting of continental crust during continental collision and (b) rapid exhumation along ‘cold’ and nearly isothermal paths, compatible with syn-orogenic extrusion.     

Hammond Hill Research Catchment: Supporting hydrologic investigations of rooting zone and vegetation water dynamics under climate change

The Hammond Hill Research Catchment (HH) is a small (120 ha), temperate, second order tributary to Six Mile Creek, Cayuga Lake, and the Great Lakes (42.42°, −76.32°). The HH has been monitored since January 2017 for the purpose of understanding how recent infiltration mixes with antecedent soil water on hillslope forest floors and the spatial and temporal patterns of Root Water Uptake (RWU) by temperate northeastern US tree species (eastern hemlock [Tsuga canadensis], American beech [Fagus grandifolia], and sugar maple [Acer saccharum]). These data are informing us about the hydrologic consequences of anticipated tree species composition change and supporting the development of more refined ecohydrological models. The glaciated catchment is underlain by a shallow confining siltstone layer (1–1.5 m depth) and densely covered with an approximately 60 year old regrowth mixed species forest of hemlock, beech, and other deciduous tree species common to the northeastern US. Current datasets from the HH include precipitation snow water equivalent, discharge, and associated isotopic water compositions, δ²H & δ¹⁸O. Measurements of (top 10 cm) soil water content, as well as bulk soil water and hemlock and beech xylem isotopic compositions are made at several locations across a topographic wetness gradient. The near-term role of the HH is to support an understanding of the environmental and ecological drivers of plant RWU competition. All data from the HH are publicly available.