The effect of aqueous metal-chlorophenolate complexation on contaminant transport in groundwater systems

Aqueous metals and chlorophenols are common co-contaminants of groundwater systems. However, the importance of aqueous metal-chlorophenolate complexation cannot be accurately assessed because the stability constants for environmentally important aqueous metal-phenolate and metal-chlorophenolate complexes have not been measured. In order to determine the role these complexes play in contaminant transport, this study applies a correlation technique to the limited data that do exist to estimate the stabilities of metal-chlorophenolate complexes of environmental interest. Speciation calculations that are based on these estimated stability constants indicate that aqueous metal-chlorophenolate complexation may significantly affect both aqueous metal and dissolved chlorophenolate species distributions. Therefore, aqueous metal-chlorophenolate complexation may affect the extent of adsorption of both metals and chlorophenolates onto mineral surfaces. In addition, aqueous complexation may significantly enhance dissolution of aquifer aluminosilicate minerals. This study suggests that aqueous complexation between metals and chlorophenolates can significantly affect the mobility of metal and phenolic contaminants.     

Morphology and distribution of dolines on ultramafic rocks from airborne LiDAR data: the case of southern Grande Terre in New Caledonia (SW Pacific)

Dolines are closed geomorphological depressions which are surface manifestations of karstic systems. Usually developed on limestones, they also typify the morphology of the New Caledonian landscape, particularly on the southern massif of the main island (known as Massif du Sud). The specificity of dolines here lies in their development on ultramafic rocks. They are evidences of subsidence, suffosion and collapse phenomena resulting from dissolution weathering of peridotites. However, extensive underground drainage systems are still not yet recognized. Semi‐automatic mapping of dolines is carried out on a 148 km² area of the Massif du Sud from a high accuracy LiDAR digital elevation model. In this area 8601 dolines ranging from 1 m² to 2 km² are identified and morphologically characterized with precision. Most are small, shallow and round‐shaped, yet more complex shapes are locally observed. Size distribution analysis allows the setting of a threshold of 20 000 m² above which surface processes rather than chemical weathering control doline evolution. Doline density analysis reveals high concentrations on flat areas where ferricrete overlies the complete weathering profile, especially in the case of elevated rainy watersheds. Dolines are aligned and elongated along a north 135° ± 5° major fracture direction, which is inherited from the obduction of the Pacific Plate upper mantle in the Late Eocene. Finally, we propose a pioneering morphometric typology of dolines that provides important clues as to pseudokarstic activity. We define collapse, bowl‐shaped and flat bottom dolines. Collapse and bowl‐shaped dolines are assumed to denote active pseudokarst. They may widen and deepen, or eventually be filled by sediments. They are distinguished from flat bottom dolines that are partially to completely filled, which suggests that they are associated with paleo‐pseudokarsts. However the groundwater flow paths associated with the genesis and evolution of dolines must be clarified, thus collapse and bowl‐shaped dolines should be hydrologically monitored. Copyright © 2016 John Wiley & Sons, Ltd.     

Calibration of a three‐component angular distribution model of sky radiance

Abstract

A three‐component (isotropic, circumsolar and horizon‐brightening) model of the angular distribution of sky (short‐wave) radiance has been tested and validated against a data base of measured sky radiance. The data base encompasses cloud cover 0.0 to 1.0 and solar zenith angles 30 to 80°. Empirical constants have been derived for the model enabling the prediction of sky radiances for any sky condition.     

Experimental verification of the fracture density and shear‐wave splitting relationship using synthetic silica cemented sandstones with a controlled fracture geometry

We present laboratory ultrasonic measurements of shear‐wave splitting from two synthetic silica cemented sandstones. The manufacturing process, which enabled silica cementation of quartz sand grains, was found to produce realistic sandstones of average porosity 29.7 ± 0.5% and average permeability 29.4 ± 11.3 mD. One sample was made with a regular distribution of aligned, penny‐shaped voids to simulate meso‐scale fractures in reservoir rocks, while the other was left blank. Ultrasonic shear waves were measured with a propagation direction of 90° to the coincident bedding plane and fracture normal. In the water saturated blank sample, shear‐wave splitting, the percentage velocity difference between the fast and slow shear waves, of <0.5% was measured due to the bedding planes (or layering) introduced during sample preparation. In the fractured sample, shear‐wave splitting (corrected for layering anisotropy) of 2.72 ± 0.58% for water, 2.80 ± 0.58% for air and 3.21 ± 0.58% for glycerin saturation at a net pressure of 40 MPa was measured. Analysis of X‐ray CT scan images was used to determine a fracture density of 0.0298 ± 0.077 in the fractured sample. This supports theoretical predictions that shear‐wave splitting (SWS) can be used as a good estimate for fracture density in porous rocks (i.e., SWS = 100ε_f, where ε_f is fracture density) regardless of pore fluid type, for wave propagation at 90° to the fracture normal.     

Crustal lineament control on magmatism and mineralization in northwestern Argentina: geological, geophysical, and remote sensing evidence

The relationship between long-lived deep crustal lineaments and the locations of magmatic centers and associated mineral deposits has been investigated in the Puna region of northwestern Argentina, through the analysis of regional aeromagnetic surveys, Landsat images, and geological information. The good exposure and excellent preservation of basement and supracrustal geology in this region makes it particularly suitable for such a study. At a regional scale, several contrasting magnetic domains are recognized, which correlate with crustal geology. Two basement domains are separated by a NNE-trending boundary, which is believed to correlate with a Paleozoic suture zone between the Pampia (to the southeast) and Arequipa–Antofalla terranes (to the northwest). Locally overlying these basement terranes is the Cenozoic magmatic domain, which is best developed in the N–S-trending volcanic arc at the western edge of the Puna (the Cordillera Occidental). In addition, four southeast-trending volcanic zones extend for several hundred kilometers across the Puna. Many important mineral deposits and areas of hydrothermal alteration are associated with these volcanic breakouts, and we have selected three such areas for more detailed study: Bajo de la Alumbrera (Argentina's largest porphyry copper deposit), Cerro Galán (the largest ignimbrite caldera in Argentina, with associated hydrothermal alteration zones), and El Queva (a historic polymetallic district located within a major volcanic range). A comparison of lineament maps generated from aeromagnetic and Landsat TM images reveals broad correlation between these different remote sensing techniques, which respectively highlight subsurface magnetic and surface geological features. In addition, the locations of magmatic and hydrothermal centers can be related to the interpreted structural framework, and are seen to occur near the intersections of major lineament zones. It is suggested that in three dimensions, such intersection zones form trans-lithospheric columns of low strength and high permeability during transpressional or transtensional tectonic strain, and may thereby serve as conduits for magma ascent to the shallow crust. Pooling of large volumes of deeply derived magma in shallow crustal magma chambers may then result in voluminous devolatilization and the formation of hydrothermal mineral deposits. It is important to note that in this model, structural intersections serve as facilitators for magma ascent and volatile exsolution, but do not in themselves cause this process—other factors such as magma supply rate and tectonic stress are essential primary ingredients, and local magmatic and volcanic processes affect the ultimate potential for ore formation. Nevertheless, we suggest that lineament analysis provides a valuable framework for guiding the early stages of mineral exploration; other regional and local geological considerations must then be applied to identify priority targets within this framework.     

GGR Biennial Review: Advances in Laser Ablation and Solution ICP-MS from 2008 to 2009 with Particular Emphasis on Sensitivity Enhancements,Mitigation of Fractionation Effects and Exploration of New Applications

Recent developments from 2008 to 2009 in ICP-MS engineering, methods and applications are reviewed here. Of particular emphasis are advances in: (a) maximising sensitivity and reducing elemental/isotopic fractionation during laser ablation processing; (b) developing new analytical techniques to measure major, minor and trace element abundances without depending on matrix-matched calibrating materials, pre-determined internal standard concentrations and/or multiple analytical methods; (c) applying in situ and solution-based ICP-MS techniques to the analysis of forensic materials for criminal and/or nuclear investigations; and (d) improving precision and limits of detection of laser ablation multi-collector ICP-MS measurements of (ultra) trace elemental and isotopic abundances.     

Hydraulic and geomorphic processes in an overbank flood along a meandering,gravel‐bed river: implications for chute formation

Hydraulic interactions between rivers and floodplains produce off‐channel chutes, the presence of which influences the routing of water and sediment and thus the planform evolution of meandering rivers. Detailed studies of the hydrologic exchanges between channels and floodplains are usually conducted in laboratory facilities, and studies documenting chute development are generally limited to qualitative observations. In this study, we use a reconstructed, gravel‐bedded, meandering river as a field laboratory for studying these mechanisms at a realistic scale. Using an integrated field and modeling approach, we quantified the flow exchanges between the river channel and its floodplain during an overbank flood, and identified locations where flow had the capacity to erode floodplain chutes. Hydraulic measurements and modeling indicated high rates of flow exchange between the channel and floodplain, with flow rapidly decelerating as water was decanted from the channel onto the floodplain due to the frictional drag provided by substrate and vegetation. Peak shear stresses were greatest downstream of the maxima in bend curvature, along the concave bank, where terrestrial LiDAR scans indicate initial floodplain chute formation. A second chute has developed across the convex bank of a meander bend, in a location where sediment accretion, point bar development and plant colonization have created divergent flow paths between the main channel and floodplain. In both cases, the off‐channel chutes are evolving slowly during infrequent floods due to the coarse nature of the floodplain, though rapid chute formation would be more likely in finer‐grained floodplains. The controls on chute formation at these locations include the flood magnitude, river curvature, floodplain gradient, erodibility of the floodplain sediment, and the flow resistance provided by riparian vegetation. Copyright © 2015 John Wiley & Sons, Ltd.     

Deep mantle roots and continental emergence: implications for whole-Earth elemental cycling,long-term climate,and the Cambrian explosion

Elevations on Earth are dominantly controlled by crustal buoyancy, primarily through variations in crustal thickness: continents ride higher than ocean basins because they are underlain by thicker crust. Mountain building, where crust is magmatically or tectonically thickened, is thus key to making continents. However, most of the continents have long passed their mountain building origins, having since subsided back to near sea level. The elevations of the old, stable continents are lower than that expected for their crustal thicknesses, requiring a subcrustal component of negative buoyancy that develops after mountain building. While initial subsidence is driven by crustal erosion, thermal relaxation through growth of a cold thermal boundary layer provides the negative buoyancy that causes continents to subside further. The maximum thickness of this thermal boundary layer is controlled by the thickness of a chemically and rheologically distinct continental mantle root, formed during large-scale mantle melting billions of years ago. The final resting elevation of a stabilized continent is controlled by the thickness of this thermal boundary layer and the temperature of the Earth’s mantle, such that continents ride higher in a cooler mantle and lower in a hot mantle. Constrained by the thermal history of the Earth, continents are predicted to have been mostly below sea level for most of Earth’s history, with areas of land being confined to narrow strips of active mountain building. Large-scale emergence of stable continents occurred late in Earth’s history (Neoproterozoic) over a 100–300 million year transition, irreversibly altering the surface of the Earth in terms of weathering, climate, biogeochemical cycling and the evolution of life. Climate during the transition would be expected to be unstable, swinging back and forth between icehouse and greenhouse states as higher order fluctuations in mantle dynamics would cause the Earth to fluctuate rapidly between water and terrestrial worlds.