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

Hydrothermal technologies are broadly defined as chemical and physical transformations in high-temperature (200–600 °C), high-pressure (5–40 MPa) liquid or supercritical water. This thermochemical means of reforming biomass may have energetic advantages, since, when water is heated at high pressures a phase change to steam is avoided which avoids large enthalpic energy penalties. Biological chemicals undergo a range of reactions, including dehydration and decarboxylation reactions, which are influenced by the temperature, pressure, concentration, and presence of homogeneous or heterogeneous catalysts. Several biomass hydrothermal conversion processes are in development or demonstration. Liquefaction processes are generally lower temperature (200–400 °C) reactions which produce liquid products, often called “bio-oil” or “bio-crude”. Gasification processes generally take place at higher temperatures (400–700 °C) and can produce methane or hydrogen gases in high yields.

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Thermochemical biofuel production in hydrothermal media: A review of sub- and supercritical water technologies

Preface.- Contributors.- List of Abbreviations.- Section 1: Basic Principles: Introduction.-Sources of Heavy Metals and Metalloids in Soils.- Chemistry of Heavy Metals and Metalloids in Soils.- Methods for the Determination of Heavy Metals and Metalloids in Soils.- Effects of Heavy Metals and Metalloids on Soil Organisms.- Soil-Plant Relationships of Heavy Metals and Metalloids.- Heavy Metals and Metalloids as Micronutrients for Plants and Animals.-Critical Loads of Heavy Metals for Soils.- Section 2: Key Heavy Metals And Metalloids: Arsenic.- Cadmium.- Chromium and Nickel.- Cobalt and Manganese.- Copper.-Lead.- Mercury.- Selenium.- Zinc.- Section 3: Other Heavy Metals And Metalloids Of Potential Environmental Significance: Antimony.- Barium.- Gold.- Molybdenum.- Silver.- Thallium.- Tin.- Tungsten.- Uranium.- Vanadium.- Glossary of Specialized Terms.- Index.

Heavy metals in soils : trace metals and metalloids in soils and their bioavailability

Geothermal solute equilibria. Derivation of Na-K-Mg-Ca geoindicators

4. Structure of Ionic Hydration Shells 1351 4.1. Results from Diffraction Experiments 1351 4.1.1. X-ray Diffraction 1351 4.1.2. Neutron Diffraction 1351 4.2. Results from Computer Simulations 1352 4.3. Results from Spectroscopic Measurements 1354 4.3.1. Vibrational Spectroscopic Measurements 1354 4.3.2. EXAFS Spectroscopy 1354 4.3.3. NMR Relaxation Studies 1355 4.3.4. Dielectric Relaxation Studies 1355 4.4. Summary of the Structure of Ionic Hydration Shells 1355

Effect of ions on the structure of water: structure making and breaking.

Thio complexes of gold and the transport of gold in hydrothermal ore solutions

Hydrosulphide complexing of Au (I) in hydrothermal solutions from 150–400°C and 500–1500 bar

Fluid-phase stability relations combined with thermodynamic modeling using fluid-inclusion analyses and new gold-solubility experiments lead to an integrated geological interpretation linking epithermal gold mineralization and porphyry-style ore formation to the cooling of hydrous magma chambers. The essential chemical requirement for gold transport to low temperatures is an initial excess of sulfide over Fe in the magmatic fluid, which is best achieved by condensing out Fe-rich brine from a buoyant, low- to medium-salinity vapor enriched in volatile S. This vapor can contract directly to an aqueous liquid, by cooling at elevated pressure above the critical curve of the salt-water fluid system. Physical and chemical conditions are matched when magmatic fluid is released through a gradually downward-retracting interface of crystallizing magma beneath a porphyry stock, predicting the consistent zoning and overprinting relations of alteration and mineralization observed in magmatic hydrothermal systems.

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Terry M. Seward

Papers

Thio complexes of gold and the transport of gold in hydrothermal ore solutions

Hydrosulphide complexing of Au (I) in hydrothermal solutions from 150–400°C and 500–1500 bar

Magmatic vapor contraction and the transport of gold from the porphyry environment to epithermal ore deposits

Gold(I) complexing in aqueous sulphide solutions to 500°C at 500 bar

Dissolution kinetics of fosteritic olivine at 90–150 °C including effects of the presence of CO2