Computer simulation studies of Crystallization under confinement conditions

Crystallization under confinement conditions is a very important process in geochemistry and geophysics. Computer simulations of fluids in nanometer scale pore spaces can provide a unique microscopic insight into the structure, dynamics and forces arising from the crystallization process. We discuss in this paper molecular dynamics computer simulations of crystallization in pores of nanometer dimensions. The crystallization pressure due to the freezing of a model of Argon in a nanopore is computed using molecular dynamics simulations. We also investigate the influence of pore geometry in determining the dynamics of confined fluids, as well as mass separation in binary mixtures. It turns out that the pore geometry reveals itself as an important variable, leading to 1) new mechanisms for fast diffusion in confined spaces, and 2) accumulation of solute in specific regions inside the pore.     

Study of geothermal water intrusion due to groundwater exploitation in the Puebla Valley aquifer system, Mexico

Significant intrusion of geothermal water into fresh groundwater takes place in the Puebla Valley aquifer system, Mexico. The decline in the potentiometric surface due to the overexploitation of the groundwater induces this intrusion. This hydrological system comprises three aquifers located in Plio-Quaternary volcanic sediments and Mesozoic calcareous rocks. The hydraulic balance of the aquifer shows that the annual output exceeds the natural inputs by 12 million m³. Between 1973 and 2002, a drop in the potentiometric surface, with an 80 m cone of depression, was identified in a 5-km-wide area located southwest of the city of Puebla. Chemical analyses performed on water samples since 1990 have shown an increase in total dissolved solids (TDS) of more than 500 mg/L, coinciding with the region showing a cone of depression in the potentiometric surface. A three-dimensional flow and transport model, based on the hydrogeological and geophysical studies, was computed by using the MODFLOW and MT3D software. This model reproduces the evolution of the aquifer system during the last 30 years and predicts for 2010 an additional drawdown in the potentiometric surface of 15 m, and an increase in the geothermal water intrusion.     

3D numerical modelling of fluid flow in the Val-d’Or orogenic gold district: major crustal shear zones drain fluids from overpressured vein fields

Fluid flow patterns have been determined using oxygen isotope isopleths in the Val-d’Or orogenic gold district. 3D numerical modelling of fluid flow and oxygen isotope exchange in the vein field shows that the fluid flow patterns can be reproduced if the lower boundary of the model is permeable, which represents middle or lower crustal rocks that are infiltrated by a metamorphic fluid generated at deeper levels. This boundary condition implies that the major crustal faults so conspicuous in vein fields do not act as the only major channel for upward fluid flow. The upper model boundary is impermeable except along the trace of major crustal faults where fluids are allowed to drain out of the vein field. This upper impermeable boundary condition represents a low-permeability layer in the crust that separates the overpressured fluid from the overlying hydrostatic fluid pressure regime. We propose that the role of major crustal faults in overpressured vein fields, independent of tectonic setting, is to drain hydrothermal fluids out of the vein field along a breach across an impermeable layer higher in the crust and above the vein field. This breach is crucial to allow flow out of the vein field and accumulation of metals in the fractures, and this breach has major implications for exploration for mineral resources. We propose that tectonic events that cause episodic metamorphic dehydration create a short-lived pulse of metamorphic fluid to rise along zones of transient permeability. This results in a fluid wave that propagates upward carrying metals to the mineralized area. Earthquakes along crustal shear zones cause dilation near jogs that draw fluids and deposit metals in an interconnected network of subsidiary shear zones. Fluid flow is arrested by an impermeable barrier separating the hydrostatic and lithostatic fluid pressure regimes. Fluids flow through the evolving and interconnected network of shear zones and by advection through the rock matrix. Episodic breaches in the impermeable barrier along the crustal shear zones allow fluid flow out of the vein field.     

Are Natural Climate Forcings Able to Counteract the Projected Anthropogenic Global Warming?

A two-dimensional global climate model is used to assessthe climatic changes associated with the new IPCC SRES emissions scenarios and to determine which kind of changes in total solar irradiance and volcanic perturbations could mask the projected anthropogenic global warming associated to the SRES scenarios. Our results suggest that only extremely unlikely changes in total solar irradiance and/or volcanic eruptions would be able to overcome the simulated anthropogenic global warming over the century. Nevertheless, in the critical interval of the next two decades the externally-driven natural climate variability might possibly confuse the debate about temperature trends and impede detection of the anthropogenic climate change signal.     

U–Pb ages of the Dalsfjord Complex, SW Norway, and their bearing on the correlation of allochthonous crystalline segments of the Scandinavian Caledonides

The Dalsfjord Complex is an allochthonous crystalline unit in the hanging wall of a major extensional detachment of the Caledonian orogen on the western coast of Norway. U-Pb geochronology has been carried out to test a previously proposed correlation between this unit and the Jotun Nappe Complex, a member of the Middle Allochthon now occupying a foreland position to the east. A monzonite sample of the Dalsfjord suite yields a zircon age of 1,634Dž Ma, whereas a crosscutting gabbro was formed at 1,464Lj Ma. Both rocks were strongly overprinted during the Sveconorwegian orogeny, especially the monzonite whose zircons U-Pb data were strongly pulled towards a lower intercept age of 882ᆱ Ma, and whose titanite indicates a two-stage growth history at >960 Ma and <920 Ma. These relationships support the correlation of these units with the Jotun Complex, and to some degree also with the Lindås Nappe in the Bergen Arcs.     

A Re–Os study of sulfide minerals from the Bagdad porphyry Cu–Mo deposit, northern Arizona, USA

Rhenium and osmium isotopes in sulfide minerals from the Bagdad porphyry Cu–Mo deposit have been used to determine timing of mineralization and the source of osmium and, by inference, ore metals. Molybdenite, chalcopyrite and pyrite were analyzed mainly from the quartz monzonite and porphyritic quartz monzonite units, which are characterized by moderate to strong potassic alteration (secondary biotite and K-feldspar). Rhenium concentrations in molybdenite are between 330 and 642 ppm. Four Re–Os analyses of two molybdenite samples from the quartz monzonite and porphyritic quartz monzonite yield a weighted average age of 71.8±0.2 Ma (2s). Analyses of a third sample from a molybdenite vein in Precambrian rocks, outside of the main ore zone, yield a weighted average age of 75.9±0.2 Ma (2s), and provide evidence of two separate mineralization episodes. Chalcopyrite samples contain 6 to 12 ppt Os and 1.7 to 4.1 ppb Re; ¹⁸⁷Os/ ¹⁸⁸Os initial ratios are between 0.1 and 0.8. Pyrite samples have osmium and rhenium concentrations varying in the range 8–17 ppt and 3.9–6.8 ppb, respectively. Analyses from these pyrite samples yield an eight-point isochron with an age of 77±15 Ma (2s) and an initial ¹⁸⁷Os/ ¹⁸⁸Os ratio of 2.1±0.8 (MSWD=0.90). The results presented here add to the growing body of work indicating that porphyry-type mineralization is produced by long-term, multiple episodes of magmatism and associated mineralization. The data also support the hypothesis that a significant part of the metals and magmas may have a crustal source, as has been suggested for other copper deposits and districts in Arizona.     

Groundwater-flow modeling in the Yucatan karstic aquifer, Mexico

The current conceptual model of the unconfined karstic aquifer in the Yucatan Peninsula, Mexico, is that a fresh-water lens floats above denser saline water that penetrates more than 40 km inland. The transmissivity of the aquifer is very high so the hydraulic gradient is very low, ranging from 7–10 mm/km through most of the northern part of the peninsula. The computer modeling program AQUIFER was used to investigate the regional groundwater flow in the aquifer. The karstified zone was modeled using the assumption that it acts hydraulically similar to a granular, porous medium. As part of the calibration, the following hypotheses were tested: (1) karstic features play an important role in the groundwater-flow system; (2) a ring or belt of sinkholes in the area is a manifestation of a zone of high transmissivity that facilitates the channeling of groundwater toward the Gulf of Mexico; and (3) the geologic features in the southern part of Yucatan influence the groundwater-flow system. The model shows that the Sierrita de Ticul fault, in the southwestern part of the study area, acts as a flow barrier and head values decline toward the northeast. The modeling also shows that the regional flow-system dynamics have not been altered despite the large number of pumping wells because the volume of water pumped is small compared with the volume of recharge, and the well-developed karst system of the region has a very high hydraulic conductivity. Electronic Publication     

Simultaneous use of geochemical and geophysical methods to characterise abandoned landfills

. Groundwater sampling and geophysical methods determined a serious contamination problem associated with refilled exploitation sites at the Cal Dimoni area, Llobregat delta, Barcelona, Spain. To characterise this process, hydrogeochemical analyses were performed and showed the following modifications to groundwater chemical composition: increasing pH values, changing redox conditions, significant increases in total organic carbon (TOC) and certain trace elements, and high groundwater conductivity values. Major ion content accumulations were found under the refilled area. In contrast, elements involved in the oxidation–reduction processes, such as iron, manganese and nitrates, clearly diminished. Electromagnetic prospecting methods were also performed and delineated the contamination plume extent. These methods also showed separate sources of contamination, one clearly related to the groundwater–refilled zone leachate interaction, another as a consequence of the manure–accumulation surface site. Geochemical and geophysical methods have shown similar results for locating groundwater contamination sources, and for determining leachate generation mechanisms and flow paths.     

Spatial and temporal variation of the nekton and hyperbenthos from a temperate European estuary with regulated freshwater inflow

The aquatic macrofauna of the Guadalquivir estuary were sampled (1 mm mesh persiana net) at 5 sampling sites located along the entire (except the tidal freshwater region) estuarine gradient of salinity (outer 50 km). A total of 134 fish and macroinvertebrate species was collected but only 62 were considered common or regularly present in the estuary. Univariate measures of the community structure showed statistically significant differences among sampling sites: species richness, abundance, and biomass decreased in the upstream direction, being positively correlated with the salinity. Temporal differences of these three variables were also statistically significant. While a clear seasonal pattern (minimum densities in winter and maximum in spring-summer) was observed for abundance and biomass, no such pattern existed for the number of species. Mysids was the most dominant group throughout the estuary (96% to 99% of abundance; 49% to 85% of biomass), although fish biomass was also important at the outer estuary (36% to 38%). Multivariate analyses indicated highly significant spatial variation in the macrofaunal communities observed along the salinity gradient. These analyses suggest that the underlying structure was a continuum with more or less overlapping distributions of the species dependent on their ability to tolerate different physicochemical conditions. There were also significant temporal (intermonthly + interannual) variation of the estuarine community; the relative multivariate dispersion indicated that monthly variation was more considerable (relative multivariate dispersion >1) at the outer part of the estuary during the wet year (last 20 km) and was higher in the inner stations during the dry year (32 to 50 km from the river mouth). Since a clear negative exponential relationship was observed between the freshwater input (from a dam located 110 km upstream) and water salinity at all sampling stations, it is concluded that the human freshwater management is probably affecting the studied estuarine communities. While the higher seasonal (long-term) stability of the salinity gradient, due to the human control of the freshwater input, may facilitate the recruitment of marine species juveniles during the meteorologically unstable early-spring, the additional (short-term) salinity fluctuations during the warm period may negatively affect species that complete their lifecycle within the estuary.