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• We present a model of magmatic fluid transport in and out of cooling hydrous magmas. • The depth and water content of magma chambers control their outgassing patterns. • Some scenarios lead to focused outgassing, a requirement for economic ore deposits. Volatile outgassing from hydrous magma intrusions emplaced and cooling in the Earth's upper crust is key to a number of geologic processes including volcanic eruptions and ore deposition, yet the physical interactions between production, storage and transport of a magmatic volatile phase within magmatic intrusions and their large-scale thermal evolution have remained elusive. We performed numerical simulations of aqueous volatile transport in generic magma chambers as they crystallize in response to conductive and convective cooling and thereby transition from a crystal - volatile - melt suspension to a mush and eventually to a rigid rock. We used simplified but realistic material properties based on published phase equilibrium experiments, published grain-scale modeling results and general geological constraints. We found that the intrusion depth and water content exert decisive control on the rates and mechanisms of intrusion outgassing. Above a critical volatile content, highly permeable capillary tubes develop in crystal mush regions with intermediate crystal volume fractions (∼ 0.5 to 0.7), and such grain-scale tubes provide rapid intrusion-scale degassing paths. These tubes are located in a ring-like mush region inside the intrusion, allowing strongly lateral flow and focusing towards the top of the intrusion. If the water content of the magma is close to saturation at the time of emplacement (5 to 6 wt% H 2 O) and the depth of the magma chamber roof is at least 4 km deep, initially distributed breakthrough points may coalesce to a single area of fluid release. Large-scale intrusion geometry determines this location of focused fluid release, and cooling rate and size of the intrusion determine overall fluid flux. Feedbacks between local hydrofracturing and heat advection break up the focused fluid expulsion into many short-lived pulses. These conditions for large-scale fluid focusing favor the formation of porphyry copper deposits, but might also trigger caldera-forming ignimbrite eruptions. [ABSTRACT FROM AUTHOR]

The formation of world class porphyry copper deposits reflect magmatic processes that take place in a deeper and much larger underlying magmatic system, which provides the source of porphyry magmas, as well as metal and sulphur-charged mineralising fluids. Reading the geochemical record of this large magmatic source region, as well as constraining the time-scales for creating a much smaller porphyry copper deposit, are critical in order to fully understand and quantify the processes that lead to metal concentration within these valuable mineral deposits. This study focuses on the Bajo de la Alumbrera porphyry copper deposit in Northwest Argentina. The deposit is centred on a dacitic porphyry intrusive stock that was mineralised by several pulses of porphyry magma emplacement and hydrothermal fluid injections. To constrain the duration of ore formation, we dated zircons from four porphyry intrusions, including pre-, syn- and post-mineralisation porphyries based on intersection relations between successive intrusion and vein generations, using high precision CA-ID-TIMS. Based on the youngest assemblages of zircon grains, which overlap within analytical error, all four intrusions were emplaced within 29 ka, which places an upper limit on the total duration of hydrothermal mineralisation. Re/Os dating of hydrothermal molybdenite fully overlaps with this high-precision age bracket. However, all four porphyries contain zircon antecrysts which record protracted zircon crystallisation during the ∼200 ka preceding the emplacement of the porphyries. Zircon trace element variations, Ti-in-zircon temperatures, and Hf isotopic compositions indicate that the four porphyry magmas record a common geochemical and thermal history, and that the four intrusions were derived from the same upper-crustal magma chamber. Trace element zoning within single zircon crystals confirms a fractional crystallisation trend dominated by titanite and apatite crystallisation. However, zircon cathodoluminescence imaging reveals the presence of intermediate low luminescent (dark) growth zones in many crystals from all intrusions, characterised by anomalously high Th, U and REE concentrations and transient excursions in trace element ratios. A return to the same fractionation trend after this excursion excludes external compositional forcing such as magma mixing. Instead we interpret the “dark-zones” to record zircon crystallisation during a transient event of rapid growth that resulted from mafic magma injection into the base of the magma chamber, releasing a CO 2 -rich vapour phase into the dacitic crystal mush. We propose that this vapour phase then migrated upwards to the apical part of the magma chamber from where it was expelled, together with successive batches of magma, to form the porphyry copper deposit within a short time-span of less than a few 10,000 years. The short duration of host rock emplacement, hydrothermal alteration and mineralisation presented in this study provides critical constraints on fluid storage in magma chambers and the genesis of large porphyry copper deposits. [ABSTRACT FROM AUTHOR]

Abstract: The global supply of Mo and much of Cu and Au comes from porphyry-type ore deposits associated with hydrous magmas of broadly calc-alkaline composition, thought to be generated by contemporaneous subduction zone processes. Molybdenum is generally considered to be derived from the continental crust while Cu and Au are sourced in the mantle wedge above subducting slabs. Here we show that neither contemporaneous subduction nor derivation of Mo from crustal sources is required to explain the genesis of porphyry–Cu–Mo–Au deposits on Proterozoic lithosphere in the eastern Rocky Mountains. Uniform Pb isotope ratios measured by LA-MC-ICP-MS in individual fluid inclusions from distinct Cu–Au and later Mo ore-forming stages at Bingham Canyon, USA, demonstrate a common metal source. Uranogenic Pb isotope ratios are particularly non-radiogenic (17.494< 206Pb/204Pb<17.534; 15.553< 207Pb/204Pb<15.588) and plot to the left of the geochron and above the mantle Pb evolution line. In 207Pb/206Pb vs. 208Pb/206Pb space, the fluid Pb isotope data cluster at the non-radiogenic end of a mixing line described by >80 feldspar data from igneous rocks intimately associated with magmatic-hydrothermal ore formation, which extends to modern depleted mantle or upper crust. Forward Monte Carlo simulations require three events for the U–Th–Pb isotope evolution of the fluid: (1) Late Archean formation of enriched crust is followed by (2) preferential extraction of Pb from this aged crust into a subduction fluid characterized by drastically reduced U/Pb that metasomatized lithospheric mantle at ∼1.8Ga. This mantle reservoir then evolved to produce the retarded uranogenic Pb isotope signatures of the Bingham Canyon Cu–Mo–Au deposit in the Cenozoic (3). Similarly retarded uranogenic Pb isotope data characterize the giant porphyry–Mo and Climax-type Mo deposits of Henderson, Questa, Butte, and SE Arizona that occur in Proterozoic sutures of the central and eastern Rocky Mountains. We propose that Cenozoic melting of subcontinental lithospheric mantle metasomatized by subduction fluids during early Proterozoic amalgamation of terranes to the Wyoming Craton provides the metal endowment and subduction flavour to the giant magmatic-hydrothermal Cu–Mo–Au ore deposits in western North America, which together constitute the world''s major molybdenum ore province. [Copyright &y& Elsevier]

Abstract: Essential resources of many rare metals including copper, zinc, molybdenum, silver and gold occur in natural sulfide mineral deposits. Understanding the origin of these metal resources has been limited by a lack of data about the geochemistry of sulfur, the most important and abundant element of ore deposits. We report the first directly measured sulfur concentrations in high-temperature fluids, together with their ore-metal contents, using a new method for sulfur quantification in fluid inclusions by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Co-genetic brine and vapor inclusions from magmatic–hydrothermal ore deposits and granitic intrusions show an excess of sulfur over ore metals, as required for efficient ore-mineral precipitation. The results demonstrate that S, Cu and Au are highly enriched in vapor-like magmatic fluids, implying that such low-salinity fluids are the key agent for the formation of porphyry copper and epithermal gold deposits. [Copyright &y& Elsevier]

Meteoric water convection has long been recognized as an efficient means to cool magmatic intrusions in the Earth's upper crust. This interplay between magmatic and hydrothermal activity thus exerts a primary control on the structure and evolution of volcanic, geothermal and ore-forming systems. Incursion of meteoric water into magmatic–hydrothermal systems has been linked to tin ore deposition in granitic plutons. In contrast, evidence from porphyry copper ore deposits suggests that crystallizing subvolcanic magma bodies are only affected by meteoric water incursion in peripheral zones and during late post-ore stages. We apply high-resolution secondary ion mass spectrometry (SIMS) to analyze oxygen isotope ratios of individual growth zones in vein quartz crystals, imaged by cathodo-luminescence microscopy (SEM-CL). Existing microthermometric information from fluid inclusions enables calculation of the oxygen isotope composition of the fluid from which the quartz precipitated, constraining the relative timing of meteoric water input into these two different settings. Our results confirm that incursion of meteoric water directly contributes to cooling of shallow granitic plutons and plays a key role in concurrent tin mineralization. By contrast, data from two porphyry copper deposits suggest that downward circulating meteoric water is counteracted by up-flowing hot magmatic fluids. Our data show that porphyry copper ore deposition occurs close to a magmatic–meteoric water interface, rather than in a purely magmatic fluid plume, confirming recent hydrological modeling. On a larger scale, the expulsion of magmatic fluids against the meteoric water interface can shield plutons from rapid convective cooling, which may aid the build-up of large magma chambers required for porphyry copper ore formation. [ABSTRACT FROM AUTHOR]

Subduction-related magmas have higher volatile contents than mid-ocean ridge basalts, which affects the dynamics of associated submarine hydrothermal systems. Interaction of saline magmatic fluids with convecting seawater may enhance ore metal deposition near the seafloor, making active submarine arcs a preferred modern analogue for understanding ancient massive sulfide deposits. We have constructed a quantitative hydrological model for sub-seafloor fluid flow based on observations at Brothers volcano, southern Kermadec arc, New Zealand. Numerical simulations of multi-phase hydrosaline fluid flow were performed on a two-dimensional cross-section cutting through the NW Caldera and the Upper Cone sites, two regions of active venting at the Brothers volcanic edifice, with the former hosting sulfide mineralization. Our aim is to explore the flow paths of saline magmatic fluids released from a crystallizing magma body at depth and their interaction with seawater circulating through the crust. The model includes a 3 × 2 km 2 sized magma chamber emplaced at ∼ 2.5 km beneath the seafloor connected to the permeable cone via a ∼ 200 m wide feeder dike. During the simulation, a magmatic fluid was temporarily injected from the top of the cooling magma chamber into the overlying convection system, assuming hydrostatic conditions and a static permeability distribution. The simulations predict a succession of hydrologic regimes in the subsurface of Brothers volcano, which can explain some of the present-day hydrothermal observations. We find that sub-seafloor phase separation, inferred from observed vent fluid salinities, and the temperatures of venting at Brothers volcano can only be achieved by input of a saline magmatic fluid at depth, consistent with chemical and isotopic data. In general, our simulations show that the transport of heat, water, and salt from magmatic and seawater sources is partly decoupled. Expulsion of magmatic heat and volatiles occurs within the first few hundred years of magma emplacement in the form of rapidly rising low-salinity vapor-rich fluids. About 95% of the magmatically derived salt is temporarily trapped in the crust, either as dense brine or as precipitated halite. This retained salt can only be expelled by later convection of seawater during the waning period of the hydrothermal system (i.e., “brine mining”). While the abundant mineralization of the NW Caldera vent field at Brothers could not be classified as an economic ore deposit, our model has important implications for submarine metal enrichment and the origin of distinct ore types known from exposed systems on land. Sulfide-complexed metals (notably Au) will preferentially ascend during early vapor-dominated fluid expulsion, potentially forming gold ± copper rich vein and replacement deposits in near-seafloor zones of submarine volcanoes. Dense magmatic brine will initially accumulate chloride-complexed base metals (such as Cu, Fe, Pb and Zn) at depth before they are mobilized by seawater convection. The resulting mixed brines can become negatively buoyant when they reach the seafloor and may flow laterally towards depressions, potentially forming layers of base metal sulphides with distinct zonation of metals. [ABSTRACT FROM AUTHOR]

Abstract: Magmatic-hydrothermal ore deposits are a major resource of gold. Volatiles exsolving from magmas rising through the Earth''s crust are the key agent for enrichment of gold in these deposits. We report the first experimental determination of gold solubilities in the magmatic volatile phases at conditions typical of most magmas associated with gold deposits (T=1000°C, P=150MPa). We show that gold hydrosulfide complexes supersede gold chloride complexes, and more importantly, that the stability of gold hydrosulfide complexes is greatly increased by the presence of minute concentrations of KCl or NaCl (0.1–0.5mol/kg H2O). The amplifying effect of alkali chlorides on the solubility of gold in H2S bearing volatiles may explain the preferential association of many giant hydrothermal gold deposits with high-potassium alkaline mafic to intermediate igneous rocks, which exsolve volatiles that simultaneously contain both H2S and alkali chlorides in significant concentrations. [Copyright &y& Elsevier]

Abstract: We present new, accurate numerical simulations of 2D models resembling hydrothermal systems active in the high-permeability axial plane of mid-ocean ridges and show that fluid flow patterns are much more irregular and convection much more unstable than reported in previous simulation studies. First, we observe the splitting of hot, rising plumes. This phenomenon is caused by the viscous instability at the interface between hot, low-viscosity fluid and cold, high-viscosity fluid. This process, known as Taylor–Saffman fingering could potentially explain the sudden extinguishing of black smokers. Second, our simulations show that for relatively moderate permeabilities, convection is unsteady resulting in transiently varying vent temperatures. The amplitude of these fluctuations typically is 40 °C with a period of decades or less, depending on the permeability. Although externally imposed events such as dike injections are possible mechanisms, they are not required to explain temperature variations observed in natural systems. Our results also offer a simple explanation of how seismic events cause fluctuating temperatures: Earthquake-induced permeability-increase shifts the hydrothermal system to the unsteady regime with accompanying fluctuating vent temperatures. We demonstrate that realistic modelling of these high-Rayleigh number convection systems does not only require the use of real fluid properties, but also the use of higher order numerical methods capable of handling high-resolution meshes. Less accurate numerical solutions smear out sharp advection fronts and thereby artificially stabilize the system. [Copyright &y& Elsevier]

Abstract: Scanning electron microscope cathodoluminescence imaging is used to map successive generations of fluid inclusions in texturally complex quartz veinlets representing the main stage of ore metal introduction into the porphyry Cu–Au–Mo deposit at Bingham, Utah. Following conventional fluid inclusion microthermometry, laser ablation–inductively coupled plasma–mass spectrometry (LA-ICPMS) is applied to quantify copper and other major and trace-element concentrations in the evolving fluid, with the aim of identifying the ore-forming processes. Textures visible in cathodoluminescence consistently show that the bulk of vein quartz (Q1), characterized by bright luminescence, crystallized early in the vein history. Cu–Fe-sulfides are precipitated later in these veins, in a microfracture network finally filled with a second generation of dull-luminescing Q2 quartz. Mapping of brine and vapor inclusion assemblages in these successive quartz generations in combination with LA-ICPMS microanalysis shows that the fluids trapped before and after Cu–Fe-sulfide precipitation are very similar with respect to their major and minor-element composition, except for copper. Copper concentrations in inclusions associated with ore formation drop by two orders of magnitude, in a tight pressure–temperature interval between 21 and 14 MPa and 425–350 °C, several hundred degrees below the temperature of fluid exsolution from the magma. Copper deposition occurs within a limited P–T region, in which sulfide solubility shows strong normal temperature dependence while quartz solubility is retrograde. This permits copper sulfide deposition while secondary vein permeability is generated by quartz dissolution. The brittle-to-ductile transition of the quartz–feldspar-rich host rocks occurs in the same temperature range, which further enhances vein reactivation and promotes cooling and expansion of fluids ascending across the transition from lithostatic to hydrostatic conditions. [Copyright &y& Elsevier]