Crystal chemistry of titanite-structured compounds: the CaTi1-x Zr x OSiO4 (x≤0.5) series

Inhomogeneous aggregates of late-stage titanite enriched in Zr have been described recently from post-magmatic parageneses in silica-undersaturated rocks. In the natural samples, simple isovalent substitution of the large Zr (^[vi]R⁴⁺=0.72 Å) for Ti (^[vi]R⁴⁺=0.605 Å) is limited to an empirical maximum of 0.25 afu (15.3 wt.% ZrO₂). As the natural material is not suitable for crystallographic study, a series of CaTi_1-xZr_xOSiO₄ titanite samples have been synthesized by standard ceramic methods at ambient pressure in air, and their crystal structure determined by Rietveld refinement of laboratory powder X-ray diffraction patterns. All of the synthetic Zr-doped titanite varieties adopt space group A2/a and consist of distorted CaO₇ polyhedra together with less distorted (Ti_1-xZr_x)O₆ octahedra and SiO₄ tetrahedra. Cell dimensions and atomic coordinates together with volumes and distortion indices are given for all polyhedra. The empirical limit for Zr substitution in synthetic (F,OH)-free titanite is 0.5 afu (29.6 wt.% ZrO₂). The existence of a Zr analogue of titanite in nature is considered to be unlikely.     

Kamafugitic diatremes: their textures and field relationships with examples from the Goiás alkaline province, Brazil

Kamafugitic rocks intruded the Precambrian basement and Phanerozoic sediments at the northeast border of the Paraná basin as part of the Late Cretaceous Goiás alkaline province (GAP). Plutonic complexes dominate the north of the province, whereas lavas and pyroclastic rocks prevail in the south. The central GAP is characterized by kamafugitic diatremes, which may crop out continuously for up to 850 m and consist of a central breccia body, surrounded and overlain by lava flows and crosscut by dykes. The breccias contain some special spheroidal juvenile fragments—namely, accretionary and armored lapilli, frozen droplets, spinning droplets, and wrapped fragments—whose textural and mineralogical aspects are described in detail. Irregularly shaped tuff pockets that occur within the breccias contain textures and structures similar to those of subaerial surge deposits and formed in confined, high gas to solid+liquid ratio domains in the conduit. Diatreme emplacement affected the country rock through thermal metamorphism, development of columnar jointing, and formation of peperite-like mixtures. There is no evidence of phreatomagmatic activity in the diatremes, and CO₂, rather than H₂O, seems to have been the major volatile component of the kamafugitic magmas. This finding implies that features such as accretionary lapilli and peperites are not exclusively associated with H₂O-dominated processes.     

Gas hydrate systems at Hydrate Ridge offshore Oregon inferred from molecular and isotopic properties of hydrate-bound and void gases

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C₂₊ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO₂ and H₂S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.     

Glacial flood pulse effects on benthic fauna in equatorial high‐Andean streams

Equatorial glacier‐fed streams present unique hydraulic patterns when compared to glacier‐fed observed in temperate regions as the main variability in discharge occurs on a daily basis. To assess how benthic fauna respond to these specific hydraulic conditions, we investigated the relationships between flow regime, hydraulic conditions (boundary Reynolds number, Re*), and macroinvertebrate communities (taxon richness and abundance) in a tropical glacier‐fed stream located in the high Ecuadorian Andes (> 4000 m). Both physical and biotic variables were measured under four discharge conditions (base‐flow and glacial flood pulses of various intensities), at 30 random points, in two sites whose hydraulic conditions were representative to those found in other streams of the study catchment. While daily glacial flood pulses significantly increased hydraulic stress in the benthic habitats (appearance of Re* > 2000), low stress areas still persisted even during extreme flood events (Re* < 500). In contrast to previous research in temperate glacier‐fed streams, taxon richness and abundance were not significantly affected by changes in hydraulic conditions induced by daily glacial flood pulses. However, we found that a few rare taxa, in particular rare ones, preferentially occurred in highly stressed hydraulic habitats. Monte‐Carlo simulations of benthic communities under glacial flood reduction scenarios predicted that taxon richness would be significantly reduced by the loss of high hydraulic stress habitats following glacier shrinking. This pioneer study on the relationship between hydraulic conditions and benthic diversity in an equatorial glacial stream evidenced unknown effects of climate change on singular yet endangered aquatic systems. Copyright © 2013 John Wiley & Sons, Ltd.     

Application of Distributed Temperature Sensing for coupled mapping of sedimentation processes and spatio‐temporal variability of groundwater discharge in soft‐bedded streams

The delineation of groundwater discharge areas based on Distributed Temperature Sensing (DTS) data of the streambed can be difficult in soft‐bedded streams where sedimentation and scouring processes constantly change the position of the fibre optic cable relative to the streambed. Deposition‐induced temperature anomalies resemble the signal of groundwater discharge while scouring will cause the cable to float in the water column and measure stream water temperatures. DTS applied in a looped layout with nine fibre optic cable rows in a 70 × 5 m section of a soft‐bedded stream made it possible to detect variability in streambed temperatures between October 2011 and January 2012. Detailed monthly streambed elevation surveys were carried out to monitor the position of the fibre optic cable relative to the streambed and to quantify the effect of sedimentation processes on streambed temperatures. Based on the simultaneous interpretation of streambed temperature and elevation data, a method is proposed to delineate potential high‐groundwater discharge areas and identify deposition‐induced temperature anomalies in soft‐bedded streams. Potential high‐discharge sites were detected using as metrics the daily minimum, maximum and mean streambed temperatures as well as the daily amplitude and standard deviation of temperatures. The identified potential high‐discharge areas were mostly located near the channel banks, also showing temporal variability because of the scouring and redistribution of streambed sediments, leading to the relocation of pool‐riffle sequences. This study also shows that sediment deposits of 0.1 m thickness already resulted in an increase in daily minimum streambed temperatures and decrease in daily amplitude and standard deviation. Scouring sites showed lower daily minimum streambed temperatures and higher daily amplitude and standard deviation compared with areas without sedimentation and scouring. As a limitation of the approach, groundwater discharge occurring at depositional and scouring areas cannot be identified by the metrics applied. Copyright © 2015 John Wiley & Sons, Ltd.     

Improved algorithms for generalized finite element simulations of three-dimensional hydraulic fracture propagation

This paper reports improvements to algorithms for the simulation of 3-D hydraulic fracturing with the Generalized Finite Element Method (GFEM). Three optimizations are presented and analyzed. First, an improved initial guess based on solving a 3-D elastic problem with the pressure from the previous step is shown to decrease the number of Newton iterations and increase robustness. Second, an improved methodology to find the time step that leads to fracture propagation is proposed and shown to decrease significantly the number of iterations. Third, reduced computational cost is observed by properly recycling the linear part of the coupled stiffness matrix. Two representative examples are used to analyze these improvements. Additionally, a methodology to include the leak-off term is presented and verified against asymptotic analytical solutions. Conservation of mass is shown to be well satisfied in all examples.     

Soil cracking effects on hydrological and erosive processes: a study case in Mediterranean cultivated vertisols

Shrink–swell soils, such as those in a Mediterranean climate regime, can cause changes in terms of hydrological and erosive responses because of the changing soil water storage conditions. Only a limited number of long‐term studies have focused on the impacts on both hydrological and erosive responses and their interactions in an agricultural environment. In this context, this study aims to document the dynamics of cracks, runoff and soil erosion within a small Mediterranean cultivated catchment and to quantify the influence of crack processes on the water and sediment supplied to a reservoir located at the catchment outlet using water and sediment measurements at a cultivated field outlet as baseline. Detailed monitoring of the presence of topsoil cracks was conducted within the Kamech catchment (ORE OMERE, Tunisia), and runoff and suspended sediment loads were continuously measured over a long period of time (2005–2012) at the outlets of a field (1.32 ha) and a catchment (263 ha). Analysis of the data showed that topsoil cracks were open approximately half of the year and that the rainfall regime and water table level conditions locally control the seasonal cracking dynamics. Topsoil cracks appeared to seriously affect the generation of runoff and sediment concentrations and, consequently, sediment yields, with similar dynamics observed at the field and catchment outlets. A similar time lag in the seasonality between water and sediment delivery was observed at these two scales: although the runoff rates were globally low during the presence of topsoil cracks, most sediment transport occurred during this period associated with very high sediment concentrations. This study underlines the importance of a good prediction of runoff during the presence of cracks for reservoir siltation considerations. In this context, the prediction of cracking effects on runoff and soil erosion is a key factor for the development of effective soil and water management strategies and downstream reservoir preservation. Copyright © 2016 John Wiley & Sons, Ltd.