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.

Inheritance of early Archaean Pb-isotope variability from long-lived Hadean protocrust

Comparison of initial Pb-isotope signatures of several early Archaean (3.65-3.82 Ga) lithologies (orthogneisses and metasediments) and minerals (feldspar and galena) documents the existence of substantial isotopic heterogeneity in the early Archaean, particularly in the Pb-207/Pb-204 ratio. The magnitude of isotopic variability at 3.82-3.65 Ga requires source separation between 4.3 and 4.1 Ga, depending on the extent of U/Pb fractionation possible in the early Earth. The isotopic heterogeneity could reflect the coexistence of enriched and depleted mantle domains or the separation of a terrestrial protocrust with a U-238/Pb-204 (mu) that was ca. 20-30% higher than coeval mantle. We prefer this latter explanation because the high-p signature is most evident in metasediments (that formed at the Earth's surface). This interpretation is strengthened by the fact that no straightforward mantle model can be constructed for these high-mu lithologies without violating bulk silicate Earth constraints. The Pb-isotope evidence for a long-lived protocrust complements similar Hf-isotope data from the Earth's oldest zircons, which also require an origin from an enriched (low Lu/Hf) environment. A model is developed in which greater than or equal to3.8-Ga tonalite and monzodiorite gneiss precursors (for one of which we provide zircon U-Pb data) are not mantle-derived but formed by remelting or differentiation of ancient (ca. 4.3 Ga) basaltic crust which had evolved with a higher U/Pb ratio than coeval mantle in the absence of the subduction process. With the initiation of terrestrial subduction at, we propose, ca. 3.75 Ga, most of the greater than or equal to3.8-Ga basaltic shell (and its differentiation products) was recycled into the mantle, because of the lack of a stabilising mantle lithosphere. We argue that the key event for preservation of all greater than or equal to3.8-Ga terrestrial crust was the intrusion of voluminous granitoids immediately after establishment of global subduction because of complementary creation of a lithospheric keel. Furthermore, we argue that preservation of !3.8-Ga material (in situ rocks and zircons) globally is restricted to cratons with a high U/Pb source character (North Atlantic, Slave, Zimbabwe, Yilgarn, and Wyoming), and that the Pb-isotope systematics of these provinces are ultimately explained by reworking of material that was derived from ca. 4.3 Ga (i.e. Hadean) basaltic crust.

Importance of water for Archaean granitoid petrology: a comparative study of TTG and potassic granitoids from Barberton Mountain Land, South Africa

A new model for Archaean granitoid magmatism is presented which reconciles the most important geochemical similarities and differences between tonalite-trondhjemite-granodiorite (TTG) and potassic granitoids. Trace element abundances reveal a strong arc magmatism signature in all studied granitoids from Barberton Mountain Land. Characteristic features include HFSE depletion as well as distinct enrichment peaks of fluid-sensitive trace elements such as Pb in N-MORB normalisation, clearly indicating that all studied granitoids are derived from refertilised mantle above subduction zones. We envisage hydrous basaltic (s.l.) melts as parental liquids, which underwent extensive fractional crystallisation. Distinctive residual cumulates evolved depending on initial water content. High-H2O melts crystallised garnet/amphibole together with pyroxenes and minor plagioclase, but no olivine. This fractionation path ultimately led to TTG-like melts. Less hydrous basaltic melts also crystallised garnet/amphibole, but the lower compatible element content indicates that olivine was also a liquidus phase. Pronounced negative Eu-anomalies of the granitic melts, correlating with Na, Ca and Al, indicate plagioclase to be of major importance. In the context of our model, the post-Archaean disappearance of TTG and concomitant preponderance of granites (s.l.), therefore, is explained with secular decrease of aqueous fluid transport into subduction zones and/or efficiency of deep fluid release from slabs.

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.

The igneous charnockite—high-K alkali-calcic I-type granite—incipient charnockite association in Trivandrum Block, southern India

The Pan-African (640 Ma) Chengannoor granite intrudes the NW margin of the Neoproterozoic high-grade metamorphic terrain of the Trivandrum Block (TB), southern India, and is spatially associated with the Cardamom hills igneous charnockite massif (CM). Geochemical features characterize the Chengannoor granite as high-K alkali-calcic I-type granite. Within the constraints imposed by the high temperature, anhydrous, K-rich nature of the magmas, comparison with recent experimental studies on various granitold source compositions, and trace- and rare-earth-element modelling, the distinctive features of the Chengannoor granite reflect a source rock of igneous charnockitic nature. A petrogenetic model is proposed whereby there was a period of basaltic underplating; the partial melting of this basaltic lower crust formed the CM charnockites. The Chengannoor granite was produced by the partial melting of the charnoenderbites from the CM, with subsequent fractionation dominated by feldspars. In a regional context, the Chengannoor I-type granite is considered as a possible heat source for the near-UHT nature of metamorphism in the northern part of the TB. This is different from previous studies, which favoured CM charnockite as the major heat source. The Occurrence of incipient charnockites (both large scale as well as small scale) adjacent to the granite as well as pegmatites (which contain CO2, CO2-H2O, F and other volatiles), suggests that the fluids expelled from the alkaline magma upon solidification generated incipient charnockites through fluid-induced lowering of water activity. Thus the granite and associated alkaline pegmatites acted as conduits for the transfer of heat and volatiles in the Achankovil Shear Zone area, causing pervasive as well as patchy charnockite formation. The transport Of CO2 by felsic melts through the southern Indian middle crust is suggested to be part of a crustal-scale fluid system that linked mantle heat and CO2 input with upward migration of crustally derived felsic melts and incipient charnockite formation, resulting in an igneous charnockite - I-type granite - incipient charnockite association.

Clay mineralogical, geochemical and isotopic tracing of the evolution of the Woodleigh impact structure, Southern Carnarvon Basin, Western Australia

Chaotically structured diamictite from the inner ring syncline surrounding the central uplift of the Woodleigh impact structure contains shocked metamorphic and impact melt-rock fragments, largely derived from Ordovician and Devonian target sandstones. Coarse illite fractions (< 2 mu m) from the sandstones containing no K-feldspar yield K-Ar ages of around 400 Ma, whereas the K-Ar ages of authigenic clays of > 0.2 mu m fractions from the diamictite without smectite and K-feldspar cluster around 360 Ma, consistent with Rb-Sr data. Crystallisation of newly formed illite in the impact melt rock clasts and recrystallisation of earlier formed illite in the sandstone clasts preserved in the diamictite, are attributed to impact-induced hydrothermal processes in the Late Devonian. The illitic clays from the diamictite and from the sandstones have very similar trace element compositions, with significantly enriched incompatible lithophile elements, which increase in concentrations correlatively with those of the compatible ferromagnesian elements. The unusual trace element associations in the clays may be due to the involvement of hot gravity-driven basinal fluids that interacted with rocks of the Precambrian craton to the east of the study area, or with such material transported and reworked in the studied sedimentary succession.