40Ar/39Ar geochronological constraints on the evolution of lateritic iron deposits in the Quadrilatero Ferrifero, Minas Gerais, Brazil

Weathering profiles overlying the Sapecado, Pico and Andaime iron ore deposits, Quadrilátero Ferrífero (QF), Minas Gerais, Brazil, reach depths of 150–400 m and host world-class supergene iron orebodies. In addition to hosting supergene ore bodies of global economic significance, weathered banded iron-formations at the Quadrilátero Ferrífero and elsewhere (e.g., Carajás, Hamersley) are postulated to underlie some of the most ancient continuously exposed weathering profiles on earth. Laser incremental-heating 40Ar/39Ar results for 69 grains of hollandite-group manganese oxides extracted from 23 samples collected at depths ranging from 5 to 150 m at the Sapecado, Pico and Andaime deposits reveal ages ranging from ca. 62 to 14 Ma. Older Mn-oxides occur near the surface, while younger Mn-oxides occur at depth. However, many samples collected at the weathering–bedrock interface yield ages in the 51–41 Ma range, suggesting that the weathering profiles in the Quadrilátero Ferrífero had already reached their present depth in the Paleogene. The antiquity of the weathering profiles in the Quadrilátero Ferrífero is comparable to the antiquity of dated weathering profiles on banded iron-formations in the Carajás Region (Brazil) and the Hamersley Province, Western Australia. The age versus depth distributions obtained in this study, but not available for other regions containing similar supergene iron deposits, suggest that little further advance of the weathering front has occurred in the Quadrilátero Ferrífero lateritic profiles during the Neogene. The results suggest that weathering in some of these ancient landscapes is not controlled by the steady-state advance of weathering fronts through time, but may reflect climatic and geomorphological conditions prevailing in a remote past. The geochronological results also confirm that the ancient landsurfaces in the Quadrilátero Ferrífero probably remained immune to erosion for tens of millions of years. Deep weathering, mostly in the Paleogene, combined with low erosion rates, account for the abundance and widespread distribution of supergene iron, manganese, and aluminum orebodies in this region.

Ultrastructure, aggregation-state, and crystal growth of biogenic nanocrystalline sphalerite and wurtzite

In this study, we investigated the size, submicrometer-scale structure, and aggregation state of ZnS formed by sulfate-reducing bacteria (SRB) in a SRB-dominated biofilm growing on degraded wood in cold (Tsimilar to8degreesC), circumneutral-pH (7.2-8.5) waters draining from an abandoned, carbonate-hosted Pb-Zn mine. High-resolution transmission electron microscope (HRTEM) data reveal that the earliest biologically induced precipitates are crystalline ZnS nanoparticles 1-5 nm in diameter. Although most nanocrystals have the sphalerite structure, nanocrystals of wurtzite are also present, consistent with a predicted size dependence for ZnS phase stability. Nearly all the nanocrystals are concentrated into 1-5 mum diameter spheroidal aggregates that display concentric banding patterns indicative of episodic precipitation and flocculation. Abundant disordered stacking sequences and faceted, porous crystal-aggregate morphologies are consistent with aggregation-driven growth of ZnS nanocrystals prior to and/or during spheroid formation. Spheroids are typically coated by organic polymers or associated with microbial cellular surfaces, and are concentrated roughly into layers within the biofilm. Size, shape, structure, degree of crystallinity, and polymer associations will all impact ZnS solubility, aggregation and coarsening behavior, transport in groundwater, and potential for deposition by sedimentation. Results presented here reveal nanometer- to micrometer-scale attributes of biologically induced ZnS formation likely to be relevant to sequestration via bacterial sulfate reduction (BSR) of other potential contaminant metal(loid)s, such as Pb2+, Cd2+, As3+ and Hg2+, into metal sulfides. The results highlight the importance of basic mineralogical information for accurate prediction and monitoring of long-term contaminant metal mobility and bioavailability in natural and constructed bioremediation systems. Our observations also provoke interesting questions regarding the role of size-dependent phase stability in biomineralization and provide new insights into the origin of submicrometer- to millimeter-scale petrographic features observed in low-temperature sedimentary sulfide ore deposits.

ELA-ICP-MS U-Pb zircon geochronology of regional volcanism hosting the Bajo de la Alumbrera Cu-Au deposit: implications for porphyry-related mineralization

ELA-ICP-MS U-Pb zircon geochronology has been used to show that the porphyritic intrusions related to the formation of the Bajo de la Alumbrera porphyry Cu-Au deposit, NW Argentina, are cogenetic with stratigraphically well-constrained volcanic and volcaniclastic rocks of the Late Miocene Farallon Negro Volcanic Complex. Zircon geochronology for intrusions in this deposit and the host volcanic sequence show that multiple mineralized porphyries were emplaced in a volcanic complex that developed over 1.5 million years. Volcanism occurred in a multivent volcanic complex in a siliciclastic intermontane basin. The complex evolved from early mafic-intermediate effusive phases to a later silicic explosive phase associated with mafic intrusions. Zircons from the basal mafic-intermediate lavas have ages that range from 8.46 +/- 0.14 to 7.94 +/- 0.27 Ma. Regionally extensive silicic explosive volcanism occurred at similar to8.0 Ma (8.05 +/- 0.13 and 7.96 +/- 0.11 Ma), which is co-temporal with intrusion of the earliest mineralized porphyries at Bajo de la Alumbrera (8.02 +/- 0.14 and 7.98 +/- 0.14 Ma). Regional uplift and erosion followed during which the magmatic-hydrothermal system was probably unroofed. Shortly thereafter, dacitic lava domes were extruded (7.95 +/- 0.17 Ma) and rhyolitic diatremes (7.79 +/- 0.13 Ma) deposited thick tuff blankets, across the region. Emplacement of large intermediate composition stocks occurred at 7.37 +/- 0.22 Ma, shortly before renewed magmatism occurred at Bajo de la Alumbrera (7.10 +/- 0.07 Ma). The latest porphyry intrusive event is temporally associated with new ore-bearing magmatic-hydrothermal fluids. Other dacitic intrusions are associated with subeconomic deposits that formed synchronously with the mineralized porphyries at Bajo de la Alumbrera. However, their emplacement continued (from 7.10 +/- 0.06 to 6.93 +/- 0.07 Ma) after the final intrusion at Bajo de al Alumbrera. Regional volcanism had ceased by 6.8 Ma (6.92 +/- 0.07 Ma). The brief history of the volcanic complex hosting the Bajo de la Alumbrera Cu-Au deposit differs from that of other Andean provinces hosting porphyry deposits. For example, at the El Salvador porphyry copper district in Chile, magmatism related to Cu mineralization was episodic in regional igneous activity that occurred over tens of millions of years. Bajo de la Alumbrera resulted from the superposition of multiple porphyry-related hydrothermal systems, temporally separated by a million years. It appears that the metal budget in porphyry ore deposits is not simply a function of their longevity and/or the superposition of multiple porphyry systems. Nor is it a function of the duration of the associated cycle of magmatism. Instead, the timing of processes operating in the parental magma body is the controlling factor in the formation of a fertile porphyry-related ore system.

Theoretical and numerical analysis of large-scale heat transfer problems with temperature-dependent pore-fluid densities

Purpose - In many scientific and engineering fields, large-scale heat transfer problems with temperature-dependent pore-fluid densities are commonly encountered. For example, heat transfer from the mantle into the upper crust of the Earth is a typical problem of them. The main purpose of this paper is to develop and present a new combined methodology to solve large-scale heat transfer problems with temperature-dependent pore-fluid densities in the lithosphere and crust scales. Design/methodology/approach - The theoretical approach is used to determine the thickness and the related thermal boundary conditions of the continental crust on the lithospheric scale, so that some important information can be provided accurately for establishing a numerical model of the crustal scale. The numerical approach is then used to simulate the detailed structures and complicated geometries of the continental crust on the crustal scale. The main advantage in using the proposed combination method of the theoretical and numerical approaches is that if the thermal distribution in the crust is of the primary interest, the use of a reasonable numerical model on the crustal scale can result in a significant reduction in computer efforts. Findings - From the ore body formation and mineralization points of view, the present analytical and numerical solutions have demonstrated that the conductive-and-advective lithosphere with variable pore-fluid density is the most favorite lithosphere because it may result in the thinnest lithosphere so that the temperature at the near surface of the crust can be hot enough to generate the shallow ore deposits there. The upward throughflow (i.e. mantle mass flux) can have a significant effect on the thermal structure within the lithosphere. In addition, the emplacement of hot materials from the mantle may further reduce the thickness of the lithosphere. Originality/value - The present analytical solutions can be used to: validate numerical methods for solving large-scale heat transfer problems; provide correct thermal boundary conditions for numerically solving ore body formation and mineralization problems on the crustal scale; and investigate the fundamental issues related to thermal distributions within the lithosphere. The proposed finite element analysis can be effectively used to consider the geometrical and material complexities of large-scale heat transfer problems with temperature-dependent fluid densities.

Bajo de la Alumbrera copper-gold deposit: Stable isotope evidence for a porphyry-related hydrothermal system dominated by magmatic aqueous fluids

Alteration zones at the gold-rich Bajo de la Alumbrera porphyry copper deposit in northwestern Argentina are centered on several porphyritic intrusions. They are zoned from a central copper-iron sulfide and gold-mineralized potassic (biotite-K-feldspar +/- quartz) core outward to propylitic (chlorite-illite-epidote-calcite) assemblages. A mineralized intermediate argillic alteration assemblage (chlorite-illite +/- pyrite) has overprinted the potassic alteration zone across the top and sides of the deposit and is itself zoned outward into phyllic (quartzinuscovite-illite +/- pyrite) alteration. This study contributes new data to previously reported delta(18)O and delta D compositions of fluids responsible for the alteration at Bajo de la Alumbrera, and the data are used to infer likely ore-forming processes. Measured and calculated delta(18)O and delta D values of fluids (+8.3 to +10.2 and -33 to -81 parts per thousand, respectively) confirm a primary magmatic origin for the earliest potassic alteration phase. Lower temperature potassic alteration formed from magmatic fluids with lower delta D values (down to -123 parts per thousand). These depleted compositions are distinct from meteoric water and consistent with degassing and volatile exsolution of magmatic fluids derived from an underlying magma. Variability in the calculated composition of fluid associated with potassic alteration is explained in terms of phase separation (or boiling). if copper-iron sulfide deposition occurred during cooling (as proposed elsewhere), this cooling was largely a result of phase separation. Magmatic water was directly involved in the formation of overprinting intermediate argillic alteration assemblages at Bajo de la Alumbrera. Calculated delta(18)O and delta D values of fluids associated with this alteration range from +4.8 to +8.1 and -31 to -71 per mil, respectively Compositions determined for fluids associated with phyllic alteration (-0.8 to +10.2 and -31 to -119 parts per thousand) overlap with the values determined for the intermediate argillic alteration. We infer that phyllic alteration assemblages developed during two stages; the first was a high-temperature (400 degrees-300 degrees C) stage with D-depleted water (delta D = -66 to -119 parts per thousand). This compositional range may have resulted from magma degassing and/or the injection of new magmatic water into a compositionally evolved hydrothermal system. The isotopic variations also can be explained by increased fluid-rock interaction. The second stage of phyllic alteration occurred at a lower temperature (similar to 200 degrees C), and variations in the modeled isotopic compositions imply mixing of magmatic and meteoric waters. Ore deposition that occurred late in the evolution of the hydrothermal system was probably associated with further cooling of the magmatic fluid, in part caused by fluid-rock interaction and phase separation. Changing pH and/or oxygen fuoracity may have caused additional ore deposition. The ingress of meteoric water appears to postdate the bulk of mineralization and occurred as the system at Bajo de la Alumbrera waned.

Volcanic setting of the Bajo de la Alumbrera porphyry Cu-Au deposit, Farallon Negro Volcanics, Northwest Argentina

The late Miocene Farallon Negro volcanics, comprising basaltic to rhyodacitic volcano-sedimentary rocks, host the Bajo de la Alumbrera porphyry copper-gold deposit in northwest Argentina. Early studies of the geology of the district have underpinned the general model for porphyry ore deposits where hydrothermal alteration and mineralization develop in and around porphyritic intrusions emplaced at shallow depths (2.5-3.5 km) into stratovolcanic assemblages. The Farallon Negro succession is dominated by thick sequences of volcano-sedimentary breccias, with lavas forming a minor component volumetrically. These volcaniclastic rocks conformably overlie crystalline basement-derived sedimentary rocks deposited in a developing foreland basin southeast of the Puna-Altiplano plateau. Within the Farallon Negro volcanics, volcanogenic accumulations evolved from early mafic to intermediate and silicic compositions. The younger and more silicic rocks are demonstrably coeval and comagmatic with the earliest group of mineralized porphyritic intrusions at Bajo de la Alumbrera. Our analysis of the volcanic stratigraphy and facies architecture of the Farallon Negro volcanics indicates that volcanic eruptions evolved from effusive to mixed effusive and explosive styles, as magma compositions changed to more intermediate and silicic compositions. Air early phase of mafic to intermediate voleanism was characterized by small synsedimentary intrusions with peperitic contacts, and lesser lava units scattered widely throughout the district, and interbedded with thick and extensive successions of coarse-grained sedimentary breccias. These sedimentary breccias formed from numerous debris- and hyperconcentrated flow events. A later phase of silicic volcanism included both effusive eruptions, forming several areally restricted lavas, and explosive eruptions, producing more widely dispersed (up to 5 kin) tuff units, some tip to 30-m thickness in proximal sections. Four key features of the volcanic stratigraphy suggest that the Farallon Negro volcanics need not simply record the construction of a large steep-sided polygenetic stratovolcano: (1) sheetlike, laterally continuous debris-flow and other coarse-grained sedimentary deposits are dominant, particularly in the lower sections; (2) mafic-intermediate composition lavas are volumetrically minor; (3) peperites are present throughout the sequence; and (4) fine-grained lacustrine sandstone-siltstone sequences occur in areas previously thought to be proximal to the summit region of the stratovolcano. Instead, the nature, distribution, and geometry of volcanic and volcaniclastic facies suggest that volcanism occurred as a relatively low relief, multiple-vent volcanic complex at the eastern edge of a broad, > 200-km-wide late Miocene volcanic belt and oil ail active foreland sedimentary basin to the Puna-Altiplano. Volcanism that occurred synchronously with the earliest stages of porphyry-related mineralization at Bajo de la Alumbrera apparently developed in an alluvial to ring plain setting that was distal to larger volcanic edifices.

Dating paleochannel iron ore by (U-Th)/He analysis of supergene goethite, Hamersley province, Australia

(U-Th)/He dating of late-stage authigenic goethite, combined with corrections for diffusive loss of He-4 by the He-4/He-3 methodology, reveals strong correlation between a sample's age and its depth in ferruginized channel sediments from the Yandicoogina deposit, Western Australia. Corrected ages, ranging from ca. 18 Ma near the surface to ca. 5 Ma at the bottom of the profile, indicate that ferruginization of the aggraded channels becomes progressively younger with depth. This trend is consistent with goethite precipitation at the groundwater-atmosphere interface during water table drawdown driven by the aridification of Western Australia during the Neogene. The results demonstrate that the (U-Th)/He system is ideal for dating goethite if diffusive loss corrections are applied. The approach is suitable for dating weathering reactions on Earth and should also be suitable for dating Fe oxyhydroxides in the Martian regolith.

Zinc deposits and related mineralization of the Burketown mineral field, including the world-class Century Deposit, Northern Australia: Fluid inclusion and stable isotope evidence for basin fluid sources

The stratiform Century Zn-Pb deposit and the discordant Zn-Pb lode deposits of the Burketown mineral field, northern Australia, host ore and gangue minerals with primary fluid inclusions that have not been affected by the Isan orogeny, thus providing a unique opportunity to investigate the nature of the ore-forming brines. All of the deposits are hosted in shales and siltstones belonging to the Isa superbasin and comprise sphalerite, pyrite, carbonate, quartz, galena, minor chalcopyrite, and minor illite. According to Pb model ages, the main ore stage of mineralization at Century formed at I575 Ma, some 20 m.y. after deposition of the host shale sequence. Microthermometry on undeformed, primary fluid inclusions hosted in porous sphalerite shows that the Zn at Century was transported to the deposit by a homogeneous, Ca2+- and Na+-bearing brine with a salinity of 21.6 wt percent NaCl equiv. delta D-fluid of the fluid inclusion water ranges from -89 to -83 per mil, consistent with a basinal brine that evolved from meteoric water. Fluid inclusion homogenization temperatures range between 74 degrees and 125 degrees C, which are lower than the 120 degrees to 160 degrees C range calculated from vitrinite reflectance and illite crystallinity data from the deposit. This discrepancy indicates that mineralization likely formed at 50 to 85 Mpa, corresponding to a depth of 1,900 to 3,100 m. Transgressive galena-sphalerite veins that cut stratiform mineralization at Century and breccia-filled quartz-dolomite-sphalerite-galena veins in the discordant Zn-Pb lodes have Pb model ages between 1575 and 1485 Ma. Raman spectroscopy and microthermometry reveal that the primary fluid inclusions in these veins contain Ca2+, Na+. but they have lower salinities between 23 and 10 wt percent NaCl equiv and higher delta D-fluid values ranging from -89 to -61 per mil than fluid inclusions in porous sphalerite from Century. Fluid inclusion water from sphalerite in one of the lode deposits has delta O-18(fluid) values of 1.6 and 2.4 per mil, indistinguishable from delta O-18(fluid) values between -0.3 to +7.4 per mil calculated from the isotopic composition of coexisting quartz, dolomite, and illite. The trend toward lower salinities and higher delta D-fluid values relative to the earlier mineralizing fluids is attributed to mixing between the fluid that formed Century and a seawater-derived fluid from a different source. Based on seismic data from the Lawn Hill platform and paragenetic and geochemical results from the Leichhardt River fault trough to the south, diagenetic aquifers in the Underlying Calvert superbasin appear to have been the most likely sources for the fluids that formed Century and the discordant lode deposits. Paragenetically late sphalerite and calcite cut sphalerite, quartz, and dolomite in the lode deposits and contain Na+-dominated fluid inclusions with much lower salinities than their older counterparts. The isotopic composition of calcite also indicates delta O-18(fluid) from 3.3 to 10.7 per mil, which is larger than the range obtained from synmineralization minerals, supporting the idea that a unique fluid source was involved. The absolute timing of this event is unclear, but a plethora of Pb model, K-Ar, and Ar-40/Ar-39 ages between 1440 and 1300 Ma indicate that a significant volume of fluid was mobilized at this time. The deposition of the Roper superbasin from ca. 1492 +/- 4 Ma suggests that these late veins formed from fluids that may have been derived from aquifers in overlying sediments of the Roper superbasin. Clear, buck, and drusy quartz in veins unrelated to any form of Pb-Zn mineralization record the last major fluid event in the Burketown mineral field and form distinct outcrops and ridges in the district. Fluid inclusions in these veins indicate formation from a low-salinity, 300 degrees +/- 80 degrees C fluid. Temperatures approaching 300 degrees C recorded in organic matter adjacent to faults and at sequence boundaries correspond to K-Ar ages spanning 1300 to 1100 Ma, which coincides with regional hydrothermal activity in the northern Lawn Hill platform and the emplacement of the Lakeview Dolerite at the time of assemblage of the Rodinia supercontinent.