Computer simulations of the Al-Si disorder in synthetic cordierites: Configuraltional entropy constrained by 29Si NMR data

The published ²⁹Si NMR data on synthetic Mg-cordierites have been used to estimate the changes in configurational Al-Si entropy of the samples due to metastable disorder. The results show that with the increase of the time of annealing in the range of 2 min-2000 h at 1185 °C the entropy of disorder in cordierite decreases from 17.1 to 6.4 J/mol K, while at 1400 °C in the range of 2 min–88 h the entropy changes from 15.4 to 8.8 J/mol K. The decrease in entropy is followed by the appearance and increase of long-range ordering which is reflected in changes of T₁ and T₂ site occupancies, decrease in the number of Si-O-Si and Al-O-Al groupings around O1 oxygens and in a decrease in the number of Al-O-Si-O-Al contacts among hexagonal 6T₂-rings. The derived values of entropy effects together with published calorimetric data suggest that the enthalpy of metastable disordering strongly depends on the temperature of annealing.     

Tectono-sequence stratigraphy and U–Pb zircon ages of the Rincón Blanco Depocenter,northern Cuyo Rift,Argentina

Extensional processes that followed the Gondwanan Orogeny rise to the development of a series of rift basins along the continental margin over older accreted Eopaleozoic terranes. Stratigraphic, structural, paleontological, and isotopic studies are presented in this work in order to constrain the ages of the sedimentary infilling and to analyze the tectosedimentary evolution of one of the Cuyo basin depocenters, known as Rincón Blanco. This asymmetrical half-graben was filled by continental sediments under a strong tectonic control. The infilling was strongly controlled by tectonics which in term produced distinctive features along the whole sedimentary sequence. Using a combination of lithological and structural data the infilling was subdivided into packages of genetically linked units bounded by regional extended surfaces. Several tuffs and acid volcanic rocks have been collected across the whole section of the Rincon Blanco sub-basin for SHRIMP and LA-MC-ICPMS U–Pb zircon dating. The ages obtained range from 246.4 ± 1.1 Ma to 230.3 ± 1.5 Ma which is the time elapsed for the deposition of three tectono-sequence units separated by regional unconformities and mainly constrained to the Middle Triassic. They are interpreted as a result of a reactivation of the extensional system that has evolved along strike as segments of faults that linked together and/or as laterally propagating faults. Regional correlation with coeval rift basins permits to establish north-south propagation in the extensional regime along the western margin of SW Gondwana. This trending started in the lowermost Triassic and extended until the latest Triassic. Two of them were precisely correlated with Cerro Puntudo and Cacheuta half-graben systems. The new data indicate that the three sequences were mostly deposited during the Middle Triassic (246 to 230 Ma), with no evidence of sedimentation during Norian and Rhaetian, which is in conflict with some previous biostratigraphic studies.     

Subtidal distribution of barnacles (Cirripedia: Balanidae) in Chesapeake Bay,Maryland

From 1977 to 1980, samples of barnacles were collected (as opportunities arose) from 61 subtidal locations (mostly oyster beds) around Chesapeake Bay, Maryland. Three species were identified from the area.Balanus improvisus dominated, comprising 83% of the 8,231 barnacles identified, and was collected at all locations but one. It occurred over a collection salinity range of 0.8‰ to 17.9‰.Balanus subalbidus (14% of the barnacles identified) was collected over the same salinity range, but mainly in lower salinity waters.Balanus eburneus was scarce (2% of the barnacles identified) and was collected at higher salinities (8.5‰ to 17.1‰).     

The study of metal contamination in urban topsoils of Mexico City using GIS

This research presents and discusses information concerning the spatial distribution of heavy metals (Pb, Cu, Zn, Ba, Co, Cr, Ni and V) in the urban environments of Mexico City using geographical information system and statistical analysis. Superficial soil samples (n = 146) were analyzed. The highest contamination indices were found in the north and center zone of the metropolitan area. In contrast, the surrounding rural fields show a lower impact grade. The higher concentrations of Pb, Cu, Zn and Ba were observed as being related to high vehicular traffic, nevertheless other elements such as Co, Cr, Ni and V do not show anthropogenic influence and their content can be attributed to the parental rock. The results are compared with previous surveys carried out in 2003 in order to evaluate temporal deposition trends. No changes were found on reported concentrations except for Cu and Zn, whose concentration has increased in later years. The results suggest that spatial distribution analysis and results in comparison with previous studies could be useful for the management and sustainable development of the metropolitan area of Mexico City.     

Activity-composition relations in the system CaCO3-MgCO3 predicted from static structure energy calculations and Monte Carlo simulations

Thermodynamic mixing properties and subsolidus phase relations of the rhombohedral carbonate system, (1 − x) · CaCO₃ − x · MgCO₃, were modelled in the temperature range of 623-2023 K with static structure energy calculations based on well-parameterised empirical interatomic potentials. Relaxed static structure energies of a large set of randomly varied structures in a 4 × 4 × 1 supercell of calcite (a = 19.952 Å, c = 17.061 Å) were calculated with the General Utility Lattice Program (GULP). These energies were cluster expanded in a basis set of 12 pair-wise effective interactions. Temperature-dependent enthalpies of mixing were calculated by the Monte Carlo method. Free energies of mixing were obtained by thermodynamic integration of the Monte Carlo results. The calculated phase diagram is in good agreement with experimental phase boundaries.     

Conditions of pocket formation in the Oktyabrskaya tourmaline-rich gem pegmatite (the Malkhan field, Central Transbaikalia, Russia)

Coexisting melt (MI), fluid-melt (FMI) and fluid (FI) inclusions in quartz from the Oktaybrskaya pegmatite, central Transbaikalia, have been studied and the thermodynamic modeling of PVTX-properties of aqueous orthoboric-acid fluids has been carried out to define the conditions of pocket formation. At room temperature, FMI in early pocket quartz and in quartz from the coarse-grained quartz–oligoclase host pegmatite contain crystalline aggregates and an orthoboric-acid fluid. The portion of FMI in inclusion assemblages decreases and the volume of fluid in inclusions increases from the early to the late growth zones in the pocket quartz. No FMI have been found in the late growth zones. Significant variations of solid/fluid ratios in the neighboring FMI result from heterogeneous entrapment of coexisting melts and fluids by a host mineral. Raman spectroscopy, SEM EDS and EMPA indicate that the crystalline aggregates in FMI are dominated by mica minerals of the boron-rich muscovite–nanpingite CsAl₂[AlSi₃O₁₀](OH,F)₂ series as well as lepidolite. Topaz, quartz, potassium feldspar and several unidentified minerals occur in much lower amounts. Fluid isolations in FMI and FI have similar total salinity (4–8 wt.% NaCl eq.) and H₃BO₃ contents (12–16 wt.%). The melt inclusions in host-pegmatite quartz homogenize at 570–600 °C. The silicate crystalline aggregates in large inclusions in pocket quartz completely melt at 615 °C. However, even after those inclusions were significantly overheated at 650±10 °C and 2.5 kbar during 24 h they remained non-homogeneous and displayed two types: (i) glass+unmelted crystals and (ii) fluid+glass. The FMI glasses contain 1.94–2.73 wt.% F, 2.51 wt.% B₂O₃, 3.64–5.20 wt.% Cs₂O, 0.54 wt.% Li₂O, 0.57 wt.% Ta₂O₅, 0.10 wt.% Nb₂O₅, 0.12 wt.% BeO. The H₂O content of the glass could exceed 12 wt.%. Such compositions suggest that the residual melts of the latest magmatic stage were strongly enriched in H₂O, B, F, Cs and contained elevated concentrations of Li, Be, Ta, and Nb. FMI microthermometry showed that those melts could have crystallized at 615–550 °C.

Crystallization of quartz–feldspar pegmatite matrix leads to the formation of H₂O-, B- and F-enriched residual melts and associated fluids (prototypes of pockets). Fluids of different compositions and residual melts of different liquidus–solidus P–T-conditions would form pockets with various internal fluid pressures. During crystallization, those melts release more aqueous fluids resulting in a further increase of the fluid pressure in pockets. A significant overpressure and a possible pressure gradient between the neighboring pockets would induce fracturing of pockets and “fluid explosions”. The fracturing commonly results in the crushing of pocket walls, formation of new fractures connecting adjacent pockets, heterogenization and mixing of pocket fluids. Such newly formed fluids would interact with a primary pegmatite matrix along the fractures and cause autometasomatic alteration, recrystallization, leaching and formation of “primary–secondary” pockets.     

6: Classification of VMS deposits: Lessons from the South Uralides

VMS deposits of the South Urals developed within the evolving Urals palaeo-ocean between Silurian and Late Devonian times. Arc-continent collision between Baltica and the Magnitogorsk Zone (arc) in the south-western Urals effectively terminated submarine volcanism in the Magnitogorsk Zone with which the bulk of the VMS deposits are associated. The majority of the Urals VMS deposits formed within volcanic-dominated sequences in deep seawater settings. Preservation of macro and micro vent fauna in the sulphide bodies is both testament to the seafloor setting for much of the sulphides but also the exceptional degree of preservation and lack of metamorphic overprint of the deposits and host rocks. The deposits in the Urals have previously been classified in terms of tectonic setting, host rock associations and metal ratios in line with recent tectono-stratigraphic classifications. In addition to these broad classes, it is clear that in a number of the Urals settings, an evolution of the host volcanic stratigraphy is accompanied by an associated change in the metal ratios of the VMS deposits, a situation previously discussed, for example, in the Noranda district of Canada.Two key structural settings are implicated in the South Urals. The first is seen in a preserved marginal allochthon west of the Main Urals Fault where early arc tholeiites host Cu–Zn mineralization in deposits including Yaman Kasy, which is host to the oldest macro vent fauna assembly known to science. The second tectonic setting for the South Urals VMS is the Magnitogorsk arc where study has highlighted the presence of a preserved early forearc assemblage, arc tholeiite to calc-alkaline sequences and rifted arc bimodal tholeiite sequences. The boninitc rocks of the forearc host Cu–(Zn) and Cu–Co VMS deposits, the latter hosted in fragments within the Main Urals Fault Zone (MUFZ) which marks the line of arc-continent collision in Late Devonian times. The arc tholeiites host Cu–Zn deposits with an evolution to more calc-alkaline felsic volcanic sequences matched with a change to Zn–Pb–Cu polymetallic deposits, often gold-rich. Large rifts in the arc sequence are filled by thick bimodal tholeiite sequences, themselves often showing an evolution to a more calc-alkaline nature. These thick bimodal sequences are host to the largest of the Cu–Zn VMS deposits.The exceptional degree of preservation in the Urals has permitted the identification of early seafloor clastic and hydrolytic modification (here termed halmyrolysis sensu lato) to the sulphide assemblages prior to diagenesis and this results in large-scale modification to the primary VMS body, resulting in distinctive morphological and mineralogical sub-types of sulphide body superimposed upon the tectonic association classification.It is proposed that a better classification of seafloor VMS systems is thus achievable using a three stage classification based on (a) tectonic (hence bulk volcanic chemistry) association, (b) local volcanic chemical evolution within a single edifice and (c) seafloor reworking and halmyrolysis.     

Catchment precipitation processes in the San Francisco valley in southern Ecuador: combined approach using high-resolution radar images and in situ observations

The precise estimation of precipitation quantities in tropical mountain regions is in great demand by ecological and hydrological studies, due to the heterogeneity of the rainfall distribution and the lack of meteorological station data. This study uses radar images and ground station data to provide the required high-resolution precipitation maps. Also wind data are taken into account, due to its influence on the precipitation formation and to demonstrate the relation between synoptic wind, topography and the precipitation distribution inside small mountain valleys. The study analyses the rainfall distribution and amounts of 4 days inside the San Francisco Valley, a small catchment in the tropical Andes of southern Ecuador, representing different seasons and the typical atmospheric flows, which are correlated to the annual precipitation map. The results show that the rainfall distribution and amounts are generally defined by the wind direction and velocity, besides the topographic location in relation to the main barriers and pathways. The dominant wind direction causes a division of the catchment in a wetter eastern and a dryer western part. Moreover, the annual seasons are reversed; the main rainy season for the eastern part occurs between June and August, while the western part reaches the precipitation maximum between January and March. This may have influence on the species composition at the different slopes and the annual hydrological cycle inside the catchment.     

An experimental study of sapped drainage network development

In a basin developed on a stream table, effluent subsurface flow supported a channel network that evolved by a combination of headward growth, lateral widening and divide decay. The area occupied by the developing network increased with time. Circularity was used to characterize network evolution which occurred in three phases (initiation, extension and abstraction). Basin sediment discharge declined exponentially with time. Pronounced quasi-cyclic variability was superimposed upon this general trend. Some of the variability was directly linked to changes in the amount of sediment supplied to the channel. The variation of mean network sediment yield (mean sediment discharge scaled by network area) with time adequately described the general decline in sediment discharge as the network evolved.