The compressibility of silicate liquids containing Fe2O3 and the effect of composition,temperature, oxygen fugacity and pressure on their redox states

Ultrasonic longitudinal acoustic velocities in oxidized silicate liquids indicate that the pressure derivative of the partial-molar volume of Fe₂O₃ is the same in iron-rich alkali-, alkaline earth- and natural silicate melt compositions at 1 bar. The dV/dP for multicomponent silicate liquids can be expressed as a linear combination of partial-molar constants plus a positive excess term for Na₂O−Al₂O₃ mixing. Partial-molar properties for FeO and Fe₂O₃ components allow extension of the empirical expression of Sack et al. (1980) to permit the calculation of Fe-redox equilibrium in a natural silicate liquid as a function of composition, temperature, fo₂ and pressure; a more formal thermodynamic expression is presented in the Appendix. The predicted equilibrium fo₂ of natural silicate melts, of fixed oxygen content, closely parallels that defined by the metastable assemblage fayalite+magnetite+β-quartz (FMQ), in pressure-temperature space. A silicate melt initially equilibrated at 3 GPa and FMQ, will remain within approximately 0.5 log₁₀ units of FMQ during its closed-system ascent. Thus, for magmas closed to oxygen, iron-redox equilibrium in crystal-poor pristine glassy lavas represents an excellent probe of the relative oxidation state of their source regions.     

Geology, Mineralogy, and Formation Environment of the Disseminated Gold-Silver Telluride Bulawan Deposit, Negros Occidental, Philippines

Abstract: The Bulawan deposit is located in the porphyry copper belt of southwest Negros island, Philippines. Propylitic, K–feldspar, sericitic, and carbonate alteration types can be distinguished in the deposit. Propylite alteration occurs mainly in Cretaceous-Eocene andesitic lavas and agglomerates while K–feldspar, sericite and carbonate alteration types occur mostly in the Middle Miocene dacite porphyry breccia pipes and stocks which were intruded into the andesites. K-feldspar zones occur in the inner parts of the sericitized zone. Sericite alteration overprinted the propylitized and K-feldspar alteration zones, at lower temperature than epidote and chlorite in the propylitized zone. Carbonate alteration is associated with the mineralization in the center of the breccia pipes and along faults. Mineralization consists of gold-silver telluride ores that are hosted by the carbonate– and sericite-altered dacite porphyry breccia pipes. The Bulawan ores occur mainly as disseminations, but unlike many epithermal gold deposits, lack classical epithermal colloform and crustiform quartz veins. The ore minerals are sphalerite, galena, chalcopyrite, pyrite and tetrahedite-tennantite with minor amounts of electrum, calaverite, petzite, sylvanite, hessite, tellurobismuthite, coloradoite, altaite, and rucklidgeite. Electrum and telluride minerals are associated mostly with calcite and dolomite-ankerite minerals. Fluid inclusions in quartz and calcite in clasts of propylitized andesite in the breccia pipes homogenize from about 300° to 400°C while fluid inclusions in quartz, calcite and sphalerite within the dacite porphyry breccia pipes homogenize between 300° to 310°C. The ores were formed around 300°C from hydrothermal solutions with salinity of about 6. 6 wt % NaCl equivalent. The presence of sylvanite and calaverite as intergrowths with each other, and the Ag content of calaverite are consistent with the above temperature estimate. Based on paragenesis, the Bulawan deposit formed in a pyrite-stable environment, with pH between 3. 4 and 5. 5, f_O2 between 10^-32 to 10^-30 atm, f_S2 between 10^-9.8 to 10^-7.8 atm, f_Te2 between 10^-8.9 to 10^-6.5 atm, and total sulfur content about 10^-2.8 molal. The dominant reduced sulfur species in the ore solutions may have been H₂S_(aq), and the likely aqueous tellurium species were H₂Te_(aq) and H₂TeO_3(aq). The ore minerals in the Bulawan deposit were probably formed by mixing of slightly saline and low salinity fluids.     

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.