Microanalytical trace element techniques (such as ion probe or laser ablation ICP-MS) are hampered by a lack of well characterized, homogeneous standards. Two silicate glass reference materials produced by National Institute of Standards and Technology (NIST), NIST SRM 610 and NIST SRM 612, have been shown to be homogeneous and are spiked with up to sixty one trace elements at nominal concentrations of 500 μg g-1 and 50 μg g-1 respectively. These samples (supplied as 3 mm wafers) are equivalent to NIST SRM 611 and NIST SRM 613 respectively (which are supplied as 1 mm wafers) and are becoming more widely used as potential microanalytical reference materials. NIST however, only certifies up to eight elements in these glasses. Here we have compiled concentration data from approximately sixty published works for both glasses, and have produced new analyses from our laboratories. Compilations are presented for the matrix composition of these glasses and for fifty eight trace elements. The trace element data includes all available new and published data, and summaries present the overall average and standard deviation, the range, median, geometric mean and a preferred average (which excludes all data outside ± one standard deviation of the overall average). For the elements which have been certified, there is a good agreement between the compiled averages and the NIST data. This compilation is designed to provide useful new working values for these reference materials.

A Compilation of New and Published Major and Trace Element Data for NIST SRM 610 and NIST SRM 612 Glass Reference Materials

Porphyry Cu systems host some of the most widely distributed mineralization types at convergent plate boundaries, including porphyry deposits centered on intrusions; skarn, carbonate-replacement, and sediment-hosted Au deposits in increasingly peripheral locations; and superjacent high- and intermediate-sulfidation epithermal deposits. The systems commonly define linear belts, some many hundreds of kilometers long, as well as occurring less commonly in apparent isolation. The systems are closely related to underlying composite plutons, at paleodepths of 5 to 15 km, which represent the supply chambers for the magmas and fluids that formed the vertically elongate (>3 km) stocks or dike swarms and associated mineralization. The plutons may erupt volcanic rocks, but generally prior to initiation of the systems. Commonly, several discrete stocks are emplaced in and above the pluton roof zones, resulting in either clusters or structurally controlled alignments of porphyry Cu systems. The rheology and composition of the host rocks may strongly influence the size, grade, and type of mineralization generated in porphyry Cu systems. Individual systems have life spans of ~100,000 to several million years, whereas deposit clusters or alignments as well as entire belts may remain active for 10 m.y. or longer.

The alteration and mineralization in porphyry Cu systems, occupying many cubic kilometers of rock, are zoned outward from the stocks or dike swarms, which typically comprise several generations of intermediate to felsic porphyry intrusions. Porphyry Cu ± Au ± Mo deposits are centered on the intrusions, whereas carbonate wall rocks commonly host proximal Cu-Au skarns, less common distal Zn-Pb and/or Au skarns, and, beyond the skarn front, carbonate-replacement Cu and/or Zn-Pb-Ag ± Au deposits, and/or sediment-hosted (distal-disseminated) Au deposits. Peripheral mineralization is less conspicuous in noncarbonate wall rocks but may include base metal- or Au-bearing veins and mantos. High-sulfidation epithermal deposits may occur in lithocaps above porphyry Cu deposits, where massive sulfide lodes tend to develop in deeper feeder structures and Au ± Ag-rich, disseminated deposits within the uppermost 500 m or so. Less commonly, intermediate-sulfidation epithermal mineralization, chiefly veins, may develop on the peripheries of the lithocaps. The alteration-mineralization in the porphyry Cu deposits is zoned upward from barren, early sodic-calcic through potentially ore-grade potassic, chlorite-sericite, and sericitic, to advanced argillic, the last of these constituting the lithocaps, which may attain >1 km in thickness if unaffected by significant erosion. Low sulfidation-state chalcopyrite ± bornite assemblages are characteristic of potassic zones, whereas higher sulfidation-state sulfides are generated progressively upward in concert with temperature decline and the concomitant greater degrees of hydrolytic alteration, culminating in pyrite ± enargite ± covellite in the shallow parts of the litho-caps. The porphyry Cu mineralization occurs in a distinctive sequence of quartz-bearing veinlets as well as in disseminated form in the altered rock between them. Magmatic-hydrothermal breccias may form during porphyry intrusion, with some of them containing high-grade mineralization because of their intrinsic permeability. In contrast, most phreatomagmatic breccias, constituting maar-diatreme systems, are poorly mineralized at both the porphyry Cu and lithocap levels, mainly because many of them formed late in the evolution of systems.

Porphyry Cu systems are initiated by injection of oxidized magma saturated with S- and metal-rich, aqueous fluids from cupolas on the tops of the subjacent parental plutons. The sequence of alteration-mineralization events charted above is principally a consequence of progressive rock and fluid cooling, from >700° to <250°C, caused by solidification of the underlying parental plutons and downward propagation of the lithostatic-hydrostatic transition. Once the plutonic magmas stagnate, the high-temperature, generally two-phase hyper-saline liquid and vapor responsible for the potassic alteration and contained mineralization at depth and early overlying advanced argillic alteration, respectively, gives way, at <350°C, to a single-phase, low- to moderate-salinity liquid that causes the sericite-chlorite and sericitic alteration and associated mineralization. This same liquid also causes mineralization of the peripheral parts of systems, including the overlying lithocaps. The progressive thermal decline of the systems combined with synmineral paleosurface degradation results in the characteristic overprinting (telescoping) and partial to total reconstitution of older by younger alteration-mineralization types. Meteoric water is not required for formation of this alteration-mineralization sequence although its late ingress is commonplace.

Many features of porphyry Cu systems at all scales need to be taken into account during planning and execution of base and precious metal exploration programs in magmatic arc settings. At the regional and district scales, the occurrence of many deposits in belts, within which clusters and alignments are prominent, is a powerful exploration concept once one or more systems are known. At the deposit scale, particularly in the porphyry Cu environment, early-formed features commonly, but by no means always, give rise to the best ore-bodies. Late-stage alteration overprints may cause partial depletion or complete removal of Cu and Au, but metal concentration may also result. Recognition of single ore deposit types, whether economic or not, in porphyry Cu systems may be directly employed in combination with alteration and metal zoning concepts to search for other related deposit types, although not all those permitted by the model are likely to be present in most systems. Erosion level is a cogent control on the deposit types that may be preserved and, by the same token, on those that may be anticipated at depth. The most distal deposit types at all levels of the systems tend to be visually the most subtle, which may result in their being missed due to overshadowing by more prominent alteration-mineralization.

Porphyry Copper Systems

Orogenic gold deposits : A proposed classification in the context of their crustal distribution and relationship to other gold deposit types

Magmatic fluids, both vapour and hypersaline liquid, are a primary source of many components in hydrothermal ore deposits formed in volcanic arcs. These components, including metals and their ligands, become concentrated in magmas in various ways from various sources, including subducted oceanic crust. Leaching of rocks also contributes components to the hydrothermal fluid—a process enhanced where acid magmatic vapours are absorbed by deeply circulating meteoric waters. Advances in understanding the hydrothermal systems that formed these ore deposits have come from the study of their active equivalents, represented at the surface by hot springs and volcanic fumaroles.

The role of magmas in the formation of hydrothermal ore deposits

Orogenic gold and geologic time: a global synthesis

Porphyry Cu-(Mo-Au) deposits are relatively rare but reproducible products of subduction-related magmatism. No unique processes appear to be required for their formation, although additive combinations of common tectono-magmatic processes, or optimization of these processes, can affect the grade and size as well as the location of the resulting deposits. These various contributing processes are reviewed, from partial melting in the mantle wedge overlying the subducting plate, through processes of magma interaction with the lithosphere, to mechanisms for magma emplacement and volatile exsolution in the upper crust. Specific ore-forming processes, such as magmatic-hydrothermal fluid evolution, are not discussed. Hot, hydrous, relatively oxidized, sulfur-rich mafic magmas (predominantly basalts) generated in the metasomatized mantle wedge above a subducting oceanic slab rise buoyantly to the base of the overlying crust where they stall due to density contrasts. Because these magmas are oxidized, sulfur is dominantly present as sulfate, and chalcophile elements such as Cu and Au are incompatible (i.e., they are retained in the melt). As these magmas begin to crystallize they release heat which causes partial melting of crustal rocks. Mixing between crustal- and mantle-derived magmas yields evolved (andesitic to dacitic), volatile-rich, metalliferous, hybrid magmas, which are of sufficiently low density to rise through the crust. Magma ascent is driven primarily by buoyancy forces and is dominantly a fracture-controlled phenomenon. As such, crustal stress and strain patterns play an important role in guiding the ascent of magma from the lower crust. In particular, translithospheric, orogen-parallel, strike-slip structures serve as a primary control on magma emplacement in many volcanic arcs worldwide. A feedback mechanism operates, whereby preexisting faults facilitate magma ascent, the heat from which further weakens the crust and focuses strain. Certain structural geometries, such as fault jogs, step-overs, and fault intersections, offer low-stress extensional volumes during transpressional strain. Such sites represent vertical conduits of relatively high permeability, up which magmas will preferentially ascend. Large upper crustal plutonic complexes may therefore be localized within these structural settings. Having delivered a sufficient volume of evolved, fertile arc magma to a focused position in the upper crust, magmatic fractionation, recharge, and volatile exsolution lead to the development of ore-forming magmatic-hydrothermal systems. To a first approximation, the size of the resulting deposit will be limited by the magma volume delivered to the upper crustal magma chamber. System-specific details such as magmatic-hydrothermal evolution, the nature of the country rocks, and subsequent erosional and weathering history will ultimately control the value of the deposit, but these factors fall outside the scope of this paper.

Tectono-Magmatic Precursors for Porphyry Cu-(Mo-Au) Deposit Formation

Based on a compilation of published sources, rocks referred to as adakites show the following geochemical and isotopic characteristics: SiO2 ≥56 wt percent, Al2O3 ≥15 wt percent, MgO normally <3 wt percent, Mg number ≈0.5, Sr ≥400 ppm, Y ≤18 ppm, Yb ≤1.9 ppm, Ni ≥20 ppm, Cr ≥30 ppm, Sr/Y ≥20, La/Yb ≥20, and 87Sr/86Sr ≤0.7045. Rocks with such compositions have been interpreted to be the products of hybridization of felsic partial melts from subducting oceanic crust with the peridotitic mantle wedge during ascent and are not primary magmas. High Mg andesites have been interpreted to be related to adakites by partial melting of asthenospheric peridotite contaminated by slab melts. The case for these petrogenetic models for adakites and high Mg andesites is best made in the Archean, when higher mantle geotherms resulted in subducting slabs potentially reaching partial melting temperatures at shallow depths before dehydration rendered the slab infusible. In the Phanerozoic these conditions were likely only met under certain special tectonic conditions, such as subduction of young (≤25-m.y.-old) oceanic crust.

Key adakitic geochemical signatures, such as low Y and Yb concentrations and high Sr/Y and La/Yb ratios, can be generated in normal asthenosphere-derived tholeiitic to calc-alkaline arc magmas by common upper plate crustal interaction and crystal fractionation processes and do not require slab melting. An assessment of several arc volcanic suites from around the world shows that most adakite-like compositions are generated in this way and do not reflect source processes. Similarly, rare adakite-like intrusive rocks associated with some porphyry Cu deposits are the evolved products of extensive crustal-level processing of calc-alkaline basalt-andesite-dacite-rhyolite series magmas. If slab melts contribute to such magmas, their geochemical signatures would have been obliterated or rendered ambiguous by subsequent extensive open-system processes. In Archean terranes, where adakitic and high Al tonalite-trondhjemite-granodiorite (TTG) magma series rocks are more common, porphyry Cu deposits are rare and, where found, are associated with normal calc-alkaline suites rather than adakites. The two different magma series are compositionally distinct in terms of several major and trace element parameters.

Common upper plate magmatic processes such as melting-assimilation-storage-homogenization (MASH) and assimilation-fractional-crystallization (AFC) affecting normal arc magmas can be demonstrated to explain the distinctive compositions of most adakite-like arc rocks, including high Mg andesites and especially those rare examples associated with porphyry Cu deposits. In contrast, slab melting can in most cases neither be proved nor disproved and is therefore unsatisfactory as a unique factor in porphyry Cu genesis.

Special Paper: Adakite-Like Rocks: Their Diverse Origins and Questionable Role in Metallogenesis

Porphyry Deposits: Characteristics and Origin of Hypogene Features

Porphyry Cu ± Mo ± Au and some epithermal Au deposits are formed from hydrothermal fluids exsolved from cooling, water-rich, calc-alkaline magmas emplaced in volcanoplutonic arcs above subduction zones. These magmas originate by partial melting of the metasomatized asthenospheric mantle wedge. However, there is increasing evidence for the existence of a suite of porphyry Cu-Au and epithermal Au deposits related to magmas generated after subduction beneath the arc has ceased. Associated magmas tend to be mildly alkaline, relatively sulfur poor, and emplaced as isolated complexes rather than in voluminous volcanoplutonic arcs. They are likely formed by remelting of previously subduction-modified arc lithosphere, triggered by postsubduction lithospheric thickening, lithospheric extension, or mantle lithosphere delamination. Metasomatized mantle lithosphere or hydrous lower crustal cumulates residual from first-stage arc magmatism contain small amounts of chalcophile and siderophile element–rich sulfides, and constitute a fertile source for hydrous, Au-rich, but relatively sulfur-poor magmas during later remelting. The recognition that porphyry Cu-Au and related epithermal Au systems can also form in postsubduction and collisional tectonic settings expands the range of geological environments and geographical terranes that are prospective for such deposits.

Jeremy P. Richards

Papers

Tectono-Magmatic Precursors for Porphyry Cu-(Mo-Au) Deposit Formation

Special Paper: Adakite-Like Rocks: Their Diverse Origins and Questionable Role in Metallogenesis

Porphyry Deposits: Characteristics and Origin of Hypogene Features

Postsubduction porphyry Cu-Au and epithermal Au deposits: Products of remelting of subduction-modified lithosphere

Magmatic to hydrothermal metal fluxes in convergent and collided margins