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1. Origin of Au-Rich Carbonate-Hosted Replacement Deposits of the Kassandra Mining District, Northern Greece: Evidence for Late Oligocene, Structurally Controlled, and Zoned Hydrothermal Systems

   https://doi.org/10.5382/econgeo.4664  

   Siron, Chris R.; Thompson, John F.H.; Baker, Tim; Darling, Robert; Dipple, Gregory (November 2019, Economic Geology)

   Abstract The Au-rich polymetallic massive sulfide orebodies of the Kassandra mining district belong to the intrusion-related carbonate-hosted replacement deposit class. Marble lenses contained within the Stratoni fault zone host the Madem Lakkos and Mavres Petres deposits at the eastern end of the fault system, where paragenetically early skarn and massive sulfide are spatially associated with late Oligocene aplitic and porphyritic dikes. Skarn transitions into predominant massive and banded replacement sulfide bodies, which are overprinted by a younger assemblage of boulangerite-bearing, quartz-rich sulfide and late quartz-rhodochrosite vein breccias. The latter style of mineralization is most abundant at the Piavitsa prospect at the western end of the exposed fault system. The sulfide orebodies at the Olympias deposit are hosted by marble in association with the Kassandra fault, where textural and mineralogical similarities to the sulfide bodies within the Stratoni fault zone suggest a genetic relationship. Estimated trapping temperatures and pressures based on fluid inclusion data indicate that carbonate replacement mineralization took place at depths less than about 5.9 km. Carbon and oxygen isotope patterns in carbonate from the Stratoni fault zone support isotopic exchange principally through fluid–wall-rock interaction, whereas decarbonation and fluid-rock exchange reactions were important at the Olympias deposit. Carbonate minerals associated with skarn and replacement sulfide throughout the district have isotopic compositions that are consistent with formation from a hydrothermal fluid of magmatic origin. Lower homogenization temperatures and salinities in the younger quartz-rich sulfide assemblage and quartz-rhodochrosite vein breccias, together with low δ18O values of gangue carbonate, suggest dilution of a primary magmatic fluid with meteoric water late in the evolution of the hydrothermal system in both the Olympias area and the Stratoni fault zone. The replacement sulfide orebodies in the district likely inherited their uniform Pb isotope composition from a late Oligocene igneous source and the isotopically heterogeneous metamorphic basement units. Metal distribution patterns at the scale of the Stratoni fault zone show diminishing Cu concentration with decreasing Pb/Zn and Ag/Au ratios from Madem Lakkos to Mavres Petres and the Piavitsa prospect in the west. The sulfide orebodies at the Olympias deposit exhibit elevated Cu values in the east with increasing Pb/Zn and Ag/Au ratios down-plunge to the south-southwest. Metal concentration and ratios support zoning related to temperature and solubility changes with increasing distance from a probable magmatic source. Structural and igneous relationships, together with fluid inclusion microthermometric and carbon-oxygen isotope data and metal distribution patterns, are supportive of a zoned hydrothermal system that exceeded 12 km along the Stratoni fault zone, sourced by an igneous intrusion to the southeast of the Madem Lakkos deposit. The Olympias replacement sulfide orebodies, associated with the Kassandra fault, resulted from a local hydrothermal system that was likely derived from a concealed igneous intrusion to the east of the deposit. 

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2. A Continuum from Iron Oxide Copper-Gold to Iron Oxide-Apatite Deposits: Evidence from Fe and O Stable Isotopes and Trace Element Chemistry of Magnetite

   https://doi.org/10.5382/econgeo.4752  

   Rodriguez-Mustafa, Maria A.; Simon, Adam C.; del Real, Irene; Thompson, John F.H.; Bilenker, Laura D.; Barra, Fernando; Bindeman, Ilya; Cadwell, David (November 2020, Economic Geology)

   Abstract Iron oxide copper-gold (IOCG) and iron oxide-apatite (IOA) deposits are major sources of Fe, Cu, and Au. Magnetite is the modally dominant and commodity mineral in IOA deposits, whereas magnetite and hematite are predominant in IOCG deposits, with copper sulfides being the primary commodity minerals. It is generally accepted that IOCG deposits formed by hydrothermal processes, but there is a lack of consensus for the source of the ore fluid(s). There are multiple competing hypotheses for the formation of IOA deposits, with models that range from purely magmatic to purely hydrothermal. In the Chilean iron belt, the spatial and temporal association of IOCG and IOA deposits has led to the hypothesis that IOA and IOCG deposits are genetically connected, where S-Cu-Au–poor magnetite-dominated IOA deposits represent the stratigraphically deeper levels of S-Cu-Au–rich magnetite- and hematite-dominated IOCG deposits. Here we report minor element and Fe and O stable isotope abundances for magnetite and H stable isotope abundances for actinolite from the Candelaria IOCG deposit and Quince IOA prospect in the Chilean iron belt. Backscattered electron imaging reveals textures of igneous and magmatic-hydrothermal affinities and the exsolution of Mn-rich ilmenite from magnetite in Quince and deep levels of Candelaria (>500 m below the bottom of the open pit). Trace element concentrations in magnetite systematically increase with depth in both deposits and decrease from core to rim within magnetite grains in shallow samples from Candelaria. These results are consistent with a cooling trend for magnetite growth from deep to shallow levels in both systems. Iron isotope compositions of magnetite range from δ56Fe values of 0.11 ± 0.07 to 0.16 ± 0.05‰ for Quince and between 0.16 ± 0.03 and 0.42 ± 0.04‰ for Candelaria. Oxygen isotope compositions of magnetite range from δ18O values of 2.65 ± 0.07 to 3.33 ± 0.07‰ for Quince and between 1.16 ± 0.07 and 7.80 ± 0.07‰ for Candelaria. For cogenetic actinolite, δD values range from –41.7 ± 2.10 to –39.0 ± 2.10‰ for Quince and from –93.9 ± 2.10 to –54.0 ± 2.10‰ for Candelaria, and δ18O values range between 5.89 ± 0.23 and 6.02 ± 0.23‰ for Quince and between 7.50 ± 0.23 and 7.69 ± 0.23‰ for Candelaria. The paired Fe and O isotope compositions of magnetite and the H isotope signature of actinolite fingerprint a magmatic source reservoir for ore fluids at Candelaria and Quince. Temperature estimates from O isotope thermometry and Fe# of actinolite (Fe# = [molar Fe]/([molar Fe] + [molar Mg])) are consistent with high-temperature mineralization (600°–860°C). The reintegrated composition of primary Ti-rich magnetite is consistent with igneous magnetite and supports magmatic conditions for the formation of magnetite in the Quince prospect and the deep portion of the Candelaria deposit. The trace element variations and zonation in magnetite from shallower levels of Candelaria are consistent with magnetite growth from a cooling magmatic-hydrothermal fluid. The combined chemical and textural data are consistent with a combined igneous and magmatic-hydrothermal origin for Quince and Candelaria, where the deeper portion of Candelaria corresponds to a transitional phase between the shallower IOCG deposit and a deeper IOA system analogous to the Quince IOA prospect, providing evidence for a continuum between both deposit types. 

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3. Coupled antimony and sulfur isotopic composition of stibnite as a window to the origin of Sb mineralization in epithermal systems (examples from the Kremnica and Zlatá Baňa deposits, Slovakia)

   https://doi.org/10.1007/s00126-024-01333-9  

   Koděra, Peter; Mathur, Ryan; Zhai, Degao; Milovský, Rastislav; Bačo, Pavel; Majzlan, Juraj (December 2024, Mineralium Deposita)

   Abstract Stibnite is a relatively common mineral in epithermal deposits, with little known about Sb transport and efficient stibnite precipitation. The famous Kremnica Au-Ag low-sulfidation deposit and Zlatá Baňa intermediate-sulfidation Pb-Zn-Cu-Au-Ag-Sb deposit are hosted in two different Neogene volcanic fields in Western Carpathians, Slovakia. In both deposits, stibnite-rich veins occur outside of major vein structures, accompanied by illite, illite/smectite, and kaolinite alteration, and affiliated to late-stage fluids (< 2 wt% NaCl eq., < 150 °C). Sulfur isotopic composition of stibnite and sulfides is different at both deposits, likely due to a different magmatic-hydrothermal evolution of the parental magmatic chambers in the Central and Eastern Slovak Volcanic Fields. The Sb isotopes (δ¹²³Sb), however, show similar values and trends of gradual simultaneous increase with δ³⁴S values, explained by a progressive precipitation of stibnite and its fractionation with the fluid. The data were modeled by two coupled Rayleigh fractionation models, (for Sb and for S), assuming a predominant Sb transport in HSb₂S₄^–with a variable amount of S species. Higher molality ratio m_S/m_Sbof fluids was found in Kremnica (~ 3–4) than in Zlatá Baňa (~ 2). At both deposits, the heaviest δ¹²³Sb values are accompanied by a decrease in the δ³⁴S values probably due to the commencement of pyrite/marcasite precipitation. According to thermodynamic models of solubility of Sb(III) complexes and observations from active geothermal fields, stibnite precipitation was triggered by temperature decrease accompanied by mixing with a mildly acidic fluid (pH 4–5) of a steam-heated CO₂-rich condensate on margins and in the final stages of epithermal systems. The proposed model for the origin of stibnite-bearing veins in epithermal systems can be used for their better targeting and efficient mineral exploration. 

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4. Natural growth of gold dendrites within silica gels

   https://doi.org/10.1130/G48927.1  

   Monecke, Thomas; Reynolds, T. James; Taksavasu, Tadsuda; Tharalson, Erik R.; Zeeck, Lauren R.; Guzman, Mario; Gissler, Garrett; Sherlock, Ross (January 2023, Geology)

   Abstract High-grade ores in low-sulfidation epithermal precious metal deposits include banded quartz veins that contain gold dendrites. The processes by which dendrite growth takes place have been subject to debate for decades, especially given that these deposits are known to form from dilute thermal liquids that contain only trace amounts of gold. It is shown here that growth of gold dendrites in epithermal veins at the McLaughlin deposit in California (western USA) originally took place within bands of gel-like noncrystalline silica. The gel provided a framework for the delicate dendrites to form. The high permeability of the gel allowed the diffusion and advection of gold from the thermal liquids flowing across the top of the silica layers to the sites of crystal growth within the gel. Over time, the gel hardened to form opal-AG. This silica phase is thermodynamically unstable and recrystallized to quartz that has a distinct mosaic texture. 

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5. Applications of radiogenic and transition metal isotopes to the study of metallic mineral deposits

   https://doi.org/10.1016/b978-0-323-99762-1.00010-3  

   Chiaradia, Massimo; Mathur, Ryan; Vennemann, Torsten; Simon, Adam (January 2025, Elsevier)

   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. 

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