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This chapter discusses how radiogenic and stable isotopes can be used in the study of metallic mineral deposits. Although the chapter is mostly focused on the radiogenic (Pb, Os) and heavy stable (Fe, Cu, Zn) isotopes of metallic elements, we complement the discussion highlighting also the power of stable isotopes of light elements, which are major to significant components of hydrothermal fluids and rocks (e.g., H, B, C, N, O, S), as well as of radiogenic isotopes of elements (Sr, Nd, Hf ) that are useful in tracing fluid/magma sources and their interaction with the host rocks. In the first part of this chapter we discuss general aspects of isotopes clarifying the differences between stable non-radiogenic and stable radiogenic isotopes and, consequently, their different applicability to metallogenic studies. Due to their properties, stable non-radiogenic isotopes record mass-dependent fractionation that occur in many reactions associated with the formation of mineral deposits. Mass-dependent fractionation of stable non-radiogenic isotopes occurs both under equilibrium and non-equilibrium (kinetic) conditions of the reactions leading to ore mineral deposition and is controlled by various physico-chemical parameters, like, among the principal ones, temperature, oxygen fugacity, and biological activity. Therefore, stable non-radiogenic isotopes can inform us about the physico-chemical and, eventually, biological processes that control ore mineral deposition and also on the sources of some metals (e.g., transition metal isotopes of elements like Fe, Cu, Zn) or of the fluids (e.g., H, C, O, N, S isotopes) and even of metal ligands (e.g., S, Cl). We conclude the first part of the chapter providing some hints on the strategy of sampling and on the instrumentation related to isotopic studies. In the second part we discuss radioactive-radiogenic isotope systems and their applications in metallogenic studies of metallic mineral deposits. Stable radiogenic isotopes are characterized by relative variations that are controlled, in each geological system, by the addition of a radiogenic component of an isotope, derived from the decay of a radioactive parent, to the same radiogenic isotope already present in the Earth since its formation  4.55 Gyr ago. This relative variation is usually expressed as the ratio of a radiogenic isotope of an element to a non-radiogenic isotope of the same element. The ratio of these two isotopes has increased since the Earth formation and the magnitude of its variations depends on the radioactive/ radiogenic isotope ratios in different geological systems and on the time elapsed since the system has formed. The Earth is  4.55 Gyr old and has evolved from an initially homogeneous isotopic composition to reservoirs (e.g., mantle, crust) and crustal rocks with very variable radioactive/radiogenic isotope ratios due to magmatic, metamorphic, weathering, atmospheric and biologic processes, among others. This has resulted in extremely large variations of radiogenic isotopes in rocks and reservoirs of the Earth which can track various geological processes. In ore geology, stable radiogenic isotopes are best suited for tracing metal (e.g., Pb, Os) sources from different rocks and reservoirs (e.g., mantle, upper crust, lower crust), fluid-rock interactions (i.e., the hydrothermal plumbing system), or magma-host rock interactions (e.g., host rock assimilation by magmas associated with magmatic-hydrothermal deposits). Radioactive-radiogenic isotope systems allow us to determine also absolute ages of suitable minerals that are found in mineral deposits. This is an essential information in metallogeny that allows us to link the formation of a mineral deposit to a specific geological process and/or to specific periods of the Earth’s history. We discuss various dating methods that are extensively applied to date mineral deposits. These methods can be subdivided into those that allow a direct dating of ore minerals (e.g., RedOs dating of molybdenite, UdPb dating of cassiterite) and those that allow dating of minerals that are demonstrably related with the mineralization (e.g., UdPb dating of zircon from magmatic rocks associated with magmatic-hydrothermal deposits; Ar/Ar dating of K-bearing minerals resulting from alteration associated with various types of mineral deposits). We discuss pros and cons of using these various methods and also mention methods that are less used (because potentially less accurate and precise), but sometimes represent the only possibility to provide an age to deposit types that are notoriously difficult to date (e.g., MVT and Carlin-type deposits). We highlight the power of both stable radiogenic and non-radiogenic isotopes in unravelling the genesis of metallic mineral deposits through a series of conceptual and real examples applied to a broad range of mineral deposit types such as porphyry systems (i.e., porphyry deposits, high- and intermediate-sulfidation epithermal deposits, skarn, carbonate replacement deposits, sediment-hosted Au deposits), low-sulfidation epithermal deposits, IOCG deposits, ortho-magmatic deposits, volcanic-hosted massive sulfide deposits (VHMS), sediment-hosted deposits (stratiform copper, MVT), and supergene deposits. In the third part of the chapter, we discuss the use of transition metal stable non-radiogenic isotopes to mineral deposits. Although in its infancy, the application of transition metal isotopes to mineral deposit investigation is quickly growing because these isotopes allow us to address different aspects of the formation of mineral deposits compared to radiogenic isotopes. In particular, isotopes of transition metals (like stable isotopes of light elements) undergo mass-dependent fractionation processes that may be associated with different types of equilibrium and non-equilibrium chemical, physical and biological reactions occurring during the formation of mineral deposits. We focus on the applications of the isotopes of Cu, Fe and Zn to various deposit types, because isotopes of these transition metals are those that have been most extensively used in mineral deposit studies. Mass-independent fractionation may also occur for isotopes of some elements and could be a developing field that has not yet been extensively explored in the study of mineral deposits. 

Abstract The Smithian–Spathian boundary interval is characterised by a positive carbon isotopic excursion in both δ¹³C_carband δ¹³C_org, concurrent with a major marine ecosystem reorganisation and the resurgence of microbialite facies. While these δ¹³C records have been traditionally interpreted as capturing global carbon cycle behaviour, recent studies have suggested that at least some excursions in early Triassic δ¹³C values may incorporate influences from authigenic or early diagenetic processes. To examine the mechanistic drivers of Smithian–Spathian boundary geochemistry, the carbonate geochemistry of a core from Georgetown, Idaho (USA), was analysed using a coupled δ^44/40Ca, δ²⁶Mg and trace‐metal framework. While the δ¹³C record in the Georgetown core is broadly similar to other Smithian–Spathian boundary sections, portions of the record coincide with substantial shifts in δ^44/40Ca, δ²⁶Mg and trace‐metal compositions that cannot feasibly be interpreted as primary. Furthermore, these geochemical variations correspond with lithology: The δ¹³C record is modulated by variations in the extent of dolomitisation, and the diagenetic styles recognised here coincide with individual lithostratigraphic units. A primary shift in local sea water δ¹³C values is inferred from the most geochemically unaltered strata, fromca3‰ in the middle Smithian toca5‰ in the early Spathian, although the timing and pathway through which this occurs cannot be readily identified nor extrapolated globally. Therefore, the Georgetown core may not directly record exogenic carbon cycle evolution, showing that there is a need for the careful reconsideration of the Smithian–Spathian boundary—and more broadly, Early Triassic—geochemical records to examine potential local and diagenetic influences on sedimentary geochemistry. 

Abstract The solubility of CO2 in hydrous basaltic andesite was examined in fO2-controlled experiments at a temperature of 1125 °C and pressures between 310–1200 MPa. Concentrations of dissolved H2O and CO2 in experimental glasses were determined by ion microprobe calibrated on a subset of run glasses analyzed by high-temperature vacuum manometry. Assuming that the solubility of H2O in mafic melt is relatively well known, estimates of XH2Ofluid and PH2Ofluid in the saturating fluid were modeled, and by difference, values for XCO2fluid and PCO2fluid were obtained (XCO2 ~0.5–0.9); fCO2 could be then calculated from the fluid composition, temperature, and pressure. Dissolved H2O over a range of 2.3–5.5 wt% had no unequivocal influence on the dissolution of CO2 at the pressures and fluid compositions examined. For these H2O concentrations, dissolved CO2 increases with fCO2 following an empirical power-law relation: dissolved CO2 (ppmw) = 14.9−3.5+4.5[fCO2 (MPa)]0.7±0.03. The highest-pressure results plot farthest from this equation but are within its 1 standard-error uncertainty envelope. We compare our experimental data with three recent CO2-H2O solubility models: Papale et al. (2006); Iacono-Marziano et al. (2012); and Ghiorso and Gualda (2015). The Papale et al. (2006) and Iacono-Marizano et al. (2012) models give similar results, both over-predicting the solubility of CO2 in a melt of the Pavlof basaltic andesite composition across the fCO2 range, whereas the Ghiorso and Gualda (2015) model under-predicts CO2 solubility. All three solubility models would indicate a strong enhancement of CO2 solubility with increasing dissolved H2O not apparent in our results. We also examine our results in the context of previous high-pressure CO2 solubility experiments on basaltic melts. Dissolved CO2 correlates positively with mole fraction (Na+K+Ca)/Al across a compositional spectrum of trachybasalt-alkali basalt-tholeiite-icelandite-basaltic andesite. Shortcomings of current solubility models for a widespread arc magma type indicate that our understanding of degassing in the deep crust and uppermost mantle remains semi-quantitative. Experimental studies systematically varying concentrations of melt components (Mg, Ca, Na, K, Al, Si) may be necessary to identify solubility reactions, quantify their equilibrium constants, and thereby build an accurate and generally applicable solubility model.