An experimental study of amphibole stability in low-pressure granitic magmas and a revised Al-in-hornblende geobarometer

We report new experimental data on the composition of magmatic amphiboles synthesised from a variety of granite (sensu lato) bulk compositions at near-solidus temperatures and pressures of 0.8–10 kbar. The total aluminium content (Al$^\text{tot}$) of the synthetic calcic amphiboles varies systematically with pressure ($\small \textit{P}$), although the relationship is nonlinear at low pressures (<2.5 kbar). At higher pressures, the relationship resembles that of other experimental studies, which suggests of a general relationship between Al$^\text{tot}$ and P that is relatively insensitive to bulk composition. We have developed a new Al-in-hornblende geobarometer that is applicable to granitic rocks with the low-variance mineral assemblage: amphibole + plagioclase (An$_{15–80}$) + biotite + quartz + alkali feldspar + ilmenite/ titanite + magnetite + apatite. Amphibole analyses should be taken from the rims of grains, in contact with plagioclase and in apparent textural equilibrium with the rest of the mineral assemblage at temperatures close to the haplogranite solidus (725 ± 75 °C), as determined from amphibole–plagioclase thermometry. Mean amphibole rim compositions that meet these criteria can then be used to calculate $\small \textit{P}$ (in kbar) from Al$^\text{tot}$ (in atoms per formula unit, apfu) according to the expression: $P$ (kbar) = 0.5 + 0.331(8) × Al$^\text{tot}$ + 0.995(4) × (Al$^\text{tot}$)$^2$ This expression recovers equilibration pressures of our calibrant dataset, comprising both new and published experimental and natural data, to within ±16 % relative uncertainty. An uncertainty of 10 % relative for a typical Al$^\text{tot}$ value of 1.5 apfu translates to an uncertainty in pressure estimate of 0.5 kbar, or 15 % relative. Thus the accuracy of the barometer expression is comparable to the precision with which near-solidus amphibole rim composition can be characterised.BHP Billiton, Royal Society (Wolfson Research Merit Award), California Institute of Technology (Moore Scholarship

Amphibole and apatite insights into the evolution and mass balance of Cl and S in magmas associated with porphyry copper deposits

Chlorine and sulfur are of paramount importance for supporting the transport and deposition of ore metals at magmatic–hydrothermal systems such as the Coroccohuayco Fe–Cu–Au porphyry–skarn deposit, Peru. Here, we used recent partitioning models to determine the Cl and S concentration of the melts from the Coroccohuayco magmatic suite using apatite and amphibole chemical analyses. The pre-mineralization gabbrodiorite complex hosts S-poor apatite, while the syn- and post-ore dacitic porphyries host S-rich apatite. Our apatite data on the Coroccohuayco magmatic suite are consistent with an increasing oxygen fugacity (from the gabbrodiorite complex to the porphyries) causing the dominant sulfur species to shift from S2− to S6+ at upper crustal pressure where the magmas were emplaced. We suggest that this change in sulfur speciation could have favored S degassing, rather than its sequestration in magmatic sulfides. Using available partitioning models for apatite from the porphyries, pre-degassing S melt concentration was 20–200 ppm. Estimates of absolute magmatic Cl concentrations using amphibole and apatite gave highly contrasting results. Cl melt concentrations obtained from apatite (0.60 wt% for the gabbrodiorite complex; 0.2–0.3 wt% for the porphyries) seems much more reasonable than those obtained from amphibole which are very low (0.37 wt% for the gabbrodiorite complex; 0.10 wt% for the porphyries). In turn, relative variations of the Cl melt concentrations obtained from amphibole during magma cooling are compatible with previous petrological constraints on the Coroccohuayco magmatic suite. This confirms that the gabbrodioritic magma was initially fluid undersaturated upon emplacement, and that magmatic fluid exsolution of the gabbrodiorite and the pluton rooting the porphyry stocks and dikes were emplaced and degassed at 100–200 MPa. Finally, mass balance constraints on S, Cu and Cl were used to estimate the minimum volume of magma required to form the Coroccohuayco deposit. These three estimates are remarkably consistent among each other (ca. 100 km3) and suggest that the Cl melt concentration is at least as critical as that of Cu and S to form an economic mineralization

Generation of porphyry copper deposits by gas-brine reaction in volcanic arcs

Porphyry copper deposits, that is, copper ore associated with hydrothermal fluids rising from a magma chamber, supply 75% of the world’s copper. They are typically associated with intrusions of magma in the crust above subduction zones, indicating a primary role for magmatism in driving mineralization. However, it is not clear that a single, copper-rich magmatic fluid could trigger both copper enrichment and the subsequent precipitation of sulphide ore minerals within a zone of hydrothermally altered rock. Here we draw on observations of modern subduction zone volcanism to propose an alternative process for porphyry copper formation. We suggest that copper enrichment initially involves metalliferous, magmatic hyper-saline liquids, or brines, that exsolve from large, magmatic intrusions assembled in the shallow crust over tens to hundreds of thousands of years. In a subsequent step, sulphide ore precipitation is triggered by the interaction of the accumulated brines with sulphurrich gases, liberated in short-lived bursts from the underlying mafic magmas. We use high-temperature and high-pressure laboratory experiments to simulate such gas–brine interactions. The experiments yield copper–iron sulphide minerals and hydrogen chloride gas at magmatic temperatures of 700–800 ◦C, with textural and chemical characteristics that resemble those in porphyry copper deposits. We therefore conclude that porphyry copper ore forms in a two-stage process of brine enrichment followed by gas-induced precipitation.We acknowledge research funding from BHP Billiton, a Benjamin Meaker Visiting Professorship to J.M. and a Royal Society Wolfson Research Merit Award and ERC Advanced Grant (CRITMAG) to J.B