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1. Constraining the provenance of black shales using rare earth elements and neodymium isotopes, Midcontinent United States

   https://doi.org/10.1130/B37264.1  

   Morris, Noah; Potra, Adriana; Samuelsen, John R. (March 2024, Geological Society of America Bulletin)

   We conducted research to determine neodymium model dates (TDM), εNd values, and the relative proportions of rare earth elements (REEs) of Paleozoic black shales from the Midcontinent United States to constrain their sediment sources. Twenty-one Cambrian to Pennsylvanian shale formations of the Illinois, Cherokee, Forest City, and Arkoma basins, the Ozark Dome, and the Ouachita Mountains were examined. Findings reveal that these midcontinental shales consist primarily of felsic detrital minerals that originated from the craton. The Cambrian Mt. Simon, Eau Claire, and Tunnel City shales of the northern Illinois Basin exhibit REE patterns and Nd isotopic signatures similar to those of the Ordovician Mazarn and Womble shales of the Ouachita Mountains, which indicates derivation from a similar sediment source. Sediment was likely derived from the Superior and/or Trans-Hudson cratonic provinces. The dominant sediment source shifted during deposition of the Middle Ordovician Womble Shale due to the uplift of the Appalachian Mountains during the Taconic orogeny, as suggested by the younger TDM dates, less negative εNd values, and similar REE patterns compared to those of the older Cambrian and Early Ordovician shales. The Grenville province and Appalachian Basin remained the primary sediment source into the Pennsylvanian. 

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2. 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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3. Hydrogeochemical evolution of formation waters responsible for sandstone bleaching and ore mineralization in the Paradox Basin, Colorado Plateau, USA

   https://doi.org/10.1130/B36078.1  

   Kim, Ji-Hyun; Bailey, Lydia; Noyes, Chandler; Tyne, Rebecca L.; Ballentine, Chris J.; Person, Mark; Ma, Lin; Barton, Mark; Barton, Isabel; Reiners, Peter W.; et al (February 2022, GSA Bulletin)

   The Paradox Basin in the Colorado Plateau (USA) has some of the most iconic records of paleofluid flow, including sandstone bleaching and ore mineralization, and hydrocarbon, CO2, and He reservoirs, yet the sources of fluids responsible for these extensive fluid-rock reactions are highly debated. This study, for the first time, characterizes fluids within the basin to constrain the sources and emergent behavior of paleofluid flow resulting in the iconic rock records. Major ion and isotopic (δ18Owater; δDwater; δ18OSO4; δ34SSO4; δ34SH2S; 87Sr/86Sr) signatures of formation waters were used to evaluate the distribution and sources of fluids and water-rock interactions by comparison with the rock record. There are two sources of salinity in basinal fluids: (1) diagenetically altered highly evaporated paleo-seawater-derived brines associated with the Pennsylvanian Paradox Formation evaporites; and (2) dissolution of evaporites by topographically driven meteoric circulation. Fresh to brackish groundwater in the shallow Cretaceous Burro Canyon Formation contains low Cu and high SO4 concentrations and shows oxidation of sulfides by meteoric water, while U concentrations are higher than within other formation waters. Deeper brines in the Pennsylvanian Honaker Trail Formation were derived from evaporated paleo-seawater mixed with meteoric water that oxidized sulfides and dissolved gypsum and have high 87Sr/86Sr indicating interaction with radiogenic siliciclastic minerals. Upward migration of reduced (hydrocarbon- and H2S-bearing) saline fluids from the Pennsylvanian Paradox Formation along faults likely bleached sandstones in shallower sediments and provided a reduced trap for later Cu and U deposition. The distribution of existing fluids in the Paradox Basin provides important constraints to understand the rock record over geological time. 

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4. Lead isotopes and rare earth elements geochemistry of global phosphate rocks: Insights into depositional conditions and environmental tracing

   https://doi.org/10.1016/j.chemgeo.2023.121715  

   Wang, Zhen; Hill, Robert; Williams, Gordon; Dwyer, Gary S; Hu, Jun; Schnug, Ewald; Bol, Roland; Sun, Yajie; Coleman, Drew S; Liu, Xiao-Ming; et al (November 2023, Chemical Geology)

   Phosphate rock bears both geologically and environmentally significant information. Rare earth elements and yttrium (i.e., REY) characteristics have been commonly used for reconstructing the redox conditions of depositional environments of and the effects of post-depositional diagenetic alteration on phosphate rock. In addition, phosphate rock is typically enriched in a range of trace elements such as uranium (U) and cadium (Cd) that can be dispersed as contaminants into the environment with phosphate mining and phosphate fertilizer application. Here we report the lead (Pb) isotope compositions combined with Pb and REY concentrations of both global sedimentary and igneous phosphate rocks, aiming to evalute the geological origin of phosphate rocks over time and the potential of using them for environmental tracing. Phopshate rocks samples analyzed in this study were sourced from major economic phosphate deposits in the world, including China, Southern Tethys (e.g., Morocco, Tunisia, Israel), the U.S., India, South Africa and Russia. Our results show a wide range of 208Pb/204Pb (35.70 to 60.58), 207Pb/204Pb (15.20 to 18.25), and 206Pb/204Pb (16.369 to 71.806) ratios in phosphate rocks, with sedimentary phosphate rocks being significantly more radiogenic than igneous rocks. The majority of the sedimentray phosphate rocks show a notable isotopic overprinting by non-radiogenic terrestrial Pb, except for those from Israel and Morocco that have the most radiogenic Pb isotope compositions. Correspondingly, phosphate rocks with more radiogenic Pb isotope ratios show relatively pristine seawater REY features, likely suggesting their preservation of the original oxic seawater conditions and/or minimal diagenetic alteration. In contrast, phosphate rocks with less radiogenic Pb isotope compositions show REY indications for more anoxic seawater redox conditions and/or greater diagenetic alteration. We further evaluate the potential utility of Pb isotopes for tracing the associated contamination with phosphate rock mining and fertilizer application in the environment. In most cases, the radiogenic Pb isotope composition of phosphate rocks and corresponding P-fertilizers is distinctive from both natural crustal Pb and major anthropogenic Pb sources (e.g., Pb ore deposits and pesticides), which provides a great advantage for applying Pb isotopes as environmental tracers for metal(loid) contamination from phosphate sources. The combination of Pb isotope ratios and REY proxies could further constrain the Pb source discrimination. Overall, this study provides new Pb isotopic and REY geochemical data on global phosphate rocks and fertilizers, which lays the groundwork for future regional and local studies on both their geological and environmental implications. 

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5. Diagnostic biosignature transformation under simulated martian radiation in organic-rich sedimentary rocks

   https://doi.org/10.3389/fspas.2022.919828  

   Roussel, A.; McAdam, A. C.; Graham, H. V.; Pavlov, A. A.; Achilles, C. N.; Knudson, C. A.; Steele, A.; Foustoukos, D. I.; Johnson, S. S. (August 2022, Frontiers in Astronomy and Space Sciences)

   As we look for traces of ancient life on Mars, we need to consider the impact of ionizing radiation in the biosignature preservation process. Here, we irradiated two organic rich terrestrial samples (Enspel and Messel shales) that have Martian analog mineralogies, with simulated cosmic rays to a dose of 0.9 MGy, equivalent of 15 million years of radiation exposure on the Martian surface. We compared a range of biosignatures before and after exposure, including total organic carbon, bulk stable carbon isotope ratios, diagnostic lipid biomarkers (hopanes and steranes), and Raman signatures akin to those collected by the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument on Perseverance. While we did not observe a significant difference in total organic carbon, bulk stable carbon isotopes, or Raman G-band signatures, we found that five lipid biomarkers decreased by a factor of two to three in the Enspel shale. This degree of degradation exceeds current predictions by existing models or experimental studies in organic rich samples and challenges our current understanding of complex biosignatures under ionizing irradiation. 

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