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

Anatexis and fluid regime of the deep continental crust: New clues from melt and fluid inclusions in metapelitic migmatites from Ivrea Zone (NW Italy)

We investigate the inclusions hosted in peritectic garnet from metapelitic migmatites of the Kinzigite Formation (Ivrea Zone, NW Italy) to evaluate the starting composition of the anatectic melt and fluid regime during anatexis throughout the upper amphibolite facies, transition, and granulite facies zones. Inclusions have negative crystal shapes, sizes from 2 to 10 mu m and are regularly distributed in the core of the garnet. Microstructural and micro-Raman investigations indicate the presence of two types of inclusions: crystallized silicate melt inclusions (i.e., nanogranitoids, NI), and fluid inclusions (FI). Microstructural evidence suggests that FI and NI coexist in the same cluster and are primary (i.e., were trapped simultaneously during garnet growth). FI have similar compositions in the three zones and comprise variable proportions of CO2, CH4, and N-2, commonly with siderite, pyrophyllite, and kaolinite, suggesting a COHN composition of the trapped fluid. The mineral assemblage in the NI contains K-feldspar, plagioclase, quartz, biotite, muscovite, chlorite, graphite and, rarely, calcite. Polymorphs such as kumdykolite, cristobalite, tridymite, and less commonly kokchetavite, were also found. Rehomogenized NI from the different zones show that all the melts are leucogranitic but have slightly different compositions. In samples from the upper amphibolite facies, melts are less mafic (FeO + MgO = 2.0-3.4 wt%), contain 860-1700 ppm CO2 and reach the highest H2O contents (6.5-10 wt%). In the transition zone melts have intermediate H2O (4.8-8.5 wt%), CO2 (457-1534 ppm) and maficity (FeO + MgO = 2.3-3.9 wt%). In contrast, melts at granulite facies reach highest CaO, FeO + MgO (3.2-4.7 wt%), and CO2 (up to 2,400 ppm), with H2O contents comparable (5.4-8.3 wt%) to the other two zones. Our results represent the first clear evidence for carbonic fluid-present melting in the Ivrea Zone. Anatexis of metapelites occurred through muscovite and biotite breakdown melting in the presence of a COH fluid, in a situation of fluid-melt immiscibility. The fluid is assumed to have been internally derived, produced initially by devolatilization of hydrous silicates in the graphitic protolith, then as a result of oxidation of carbon by consumption of Fe3+-bearing biotite during melting. Variations in the compositions of the melts are interpreted to result from higher T of melting. The H2O contents of the melts throughout the three zones are higher than usually assumed for initial H2O contents of anatectic melts. The CO2 contents are highest at granulite facies, and show that carbon-contents of crustal magmas are not negligible at high T. The activity of H2O of the fluid dissolved in granitic melts decreases with increasing metamorphic grade. Carbonic fluid-present melting of the deep continental crust represents, together with hydrate-breakdown melting reactions, an important process in the origin of crustal anatectic granitoids

Andalusite and Na- and Li-rich cordierite in the La Costa pluton, Sierras Pampeanas, Argentina: textural and chemical evidence for a magmatic origin

The La Costa pluton in the Sierra de Velasco (NW Argentina) consists of S-type granitoids that can be grouped into three igneous facies: the alkali-rich Santa Cruz facies (SCF, SiO2 *67 wt%) distinguished by the presence of andalusite and Na- and Li-rich cordierite (Na2O = 1.55–1.77 wt% and Li2O = 0.14–0.66 wt%), the Anillaco facies (SiO2 *74 wt%) with a significant proportion of Mn-rich garnet, and the Anjullo´n facies (SiO2 *75 wt%) with abundant albitic plagioclase. The petrography, mineral chemistry and whole-rock geochemistry of the SCF are compatible with magmatic crystallization of Na- and Li-rich cordierite, andalusite and muscovite from the peraluminous magma under moderate P–T conditions (*1.9 kbar and ca. 735C). The high Li content of cordierite in the SCF is unusual for granitic rocks of intermediate composition