Marine Volcaniclastic Record of Early Arc Evolution in the Eastern Ritter Range Pendant, Central Sierra Nevada, California

Marine volcaniclastic rocks in the Sierra Nevada preserve a critical record of silicic magmatism in the early Sierra Nevada volcanic arc, and this magmatic record provides precise minimum age constraints on subduction inception and tectonic evolution of the early Mesozoic Cordilleran convergent margin at this latitude. New zircon Pb/U ages from the Ritter Range pendant and regional correlations indicate arc inception no later than mid‐Triassic time between 37 and 38°N. The regional first‐order felsic magma eruption rate as recorded by marine volcanic arc rocks was episodic, with distinct pulses of ignimbrite emplacement at ca. 221 to 216 Ma and 174 to 167 Ma. Ignimbrites range from dacite to rhyolite in bulk composition, and are petrographically similar to modern arc‐type, monotonous intermediate dacite or phenocryst‐poor, low‐silica rhyolite. Zircon trace element geochemistry indicates that Jurassic silicic melts were consistently Ti‐ and light rare earth‐enriched and U‐depleted in comparison to Triassic melts of the juvenile arc, suggesting Jurassic silicic melts were hotter, drier, and derived from distinct lithospheric sources not tapped in the juvenile stage of arc construction. Pulses of ignimbrite deposition were coeval with granodioritic to granitic components of the underlying early Mesozoic Sierra Nevada batholith, suggesting explosive silicic volcanism and batholith construction were closely coupled at one‐ to two‐million‐year time scales

In situ multiple sulfur isotope analysis by SIMS of pyrite, chalcopyrite, pyrrhotite, and pentlandite to refine magmatic ore genetic models

With growing interest in the application of in situ multiple sulfur isotope analysis to a variety of mineral systems, we report here the development of a suite of sulfur isotope standards for distribution relevant to magmatic, magmatic-hydrothermal, and hydrothermal ore systems. These materials include Sierra pyrite (FeS2), Nifty-b chalcopyrite (CuFeS2), Alexo pyrrhotite (Fe(1 −x)S), and VMSO pentlandite ((Fe,Ni)9S8) that have been chemically characterized by electron microprobe analysis, isotopically characterized for δ33S, δ34S, and δ36S by fluorination gas-source mass spectrometry, and tested for homogeneity at the micro-scale by secondary ion mass spectrometry. Beam-sample interaction as a function of crystallographic orientation is determined to have no effect on δ34S and Δ33S isotopic measurements of pentlandite. These new findings provided the basis for a case study on the genesis of the Long-Victor nickel-sulfide deposit located in the world class Kambalda nickel camp in the southern Kalgoorlie Terrane of Western Australia. Results demonstrate that precise multiple sulfur isotope analyses from magmatic pentlandite, pyrrhotite and chalcopyrite can better constrain genetic models related to ore-forming processes. Data indicate that pentlandite, pyrrhotite and chalcopyrite are in isotopic equilibrium and display similar Δ33S values + 0.2‰.This isotopic equilibrium unequivocally fingerprints the isotopic signature of the magmatic assemblage. The three sulfide phases show slightly variable δ34S values (δ34Schalcopyrite = 2.9 ± 0.3‰, δ34Spentlandite = 3.1 ± 0.2‰, and δ34Spyrrhotite = 3.9 ± 0.5‰), which are indicative of natural fractionation. Careful in situ multiple sulfur isotope analysis of multiple sulfide phases is able to capture the subtle isotopic variability of the magmatic sulfide assemblage, which may help resolve the nature of the ore-forming process. Hence, this SIMS-based approach discriminates the magmatic sulfur isotope signature from that recorded in metamorphic- and alteration-related sulfides, which may not be resolved during bulk rock fluorination analysis. The results indicate that, unlike the giant dunite-hosted komatiite systems that thermo-mechanically assimilated volcanogenic massive sulfides proximal to vents and display negative Δ33S values, the Kambalda ores formed in relatively distal environments assimilating abyssal sulfidic shales

An atmospheric source of S in Mesoarchaean structurally-controlled gold mineralisation of the Barberton Greenstone Belt

The Barberton Greenstone Belt of southern Africa hosts several Mesoarchaean gold deposits. The ores were mostly formed in greenschist facies conditions, and occur as hydrothermal alteration zones around extensional faults that truncate and post-date the main compressional structures of the greenstone belt. Ore deposition was accompanied by the intrusion of porphyries, which has led to the hypothesis that gold may have been sourced from magmas. Because the transport of Au in the hydrothermal fluids is widely believed to have involved S complexes, tracing the origin of S may place strong constraints on the origin of Au. We measured multiple S isotopes in sulfide ore from Sheba and Fairview mines of the Barberton Greenstone Belt to distinguish “deep” S sources (e.g. magmas) from “surface” S sources (i.e. rocks of the volcano-sedimentary succession that contain S processed in the atmosphere preserved as sulfide and sulfate minerals). Ion probe (SIMS) analyses of pyrite from ore zones indicate mass-independent fractionation of S isotopes (Δ33S = −0.6‰ to +1.0‰) and the distribution of the analyses in the Δ33S–δ34S space matches the distribution peak of previously published analyses of pyrite from the entire volcano-sedimentary succession. Notwithstanding that the H2O–CO2 components of the fluids may have been introduced from a deep source external to the greenstone belt rocks, the fact that S bears an atmospheric signature suggests the hypothesis that the source of Au should also be identified in the supracrustal succession of the greenstone belt. Our findings differ from conclusions of previous studies of other Archaean shear-hosted Au deposits based on mineralogical and isotopic evidence, which suggested a magmatic or mantle source for Au, and imply that there is no single model that can be applied to this type of mineralisation in the Archaean

A stable (Li, O) and radiogenic (Sr, Nd) isotope perspective on metasomatic processes in a subducting slab

Two distinct types of eclogites from the Raspas Complex (Ecuador), which can be distinguished based on petrography and trace element geochemistry, were analyzed for their stable (Li, O) and radiogenic (Sr, Nd) isotope signature to constrain metasomatic changes due to fluid-overprinting in metabasaltic rocks at high-pressure conditions and to identify fluid sources. MORB-type eclogites are characterized by a relative LREE depletion similar to MORB. High-pressure (HP) minerals from this type of eclogite have highly variable oxygen isotope compositions (garnet: + 4.1 to + 9.8 ‰; omphacite: + 6.1 to + 11.0 ‰; phengite: 8.7 to 10.4 ‰; amphibole: 6.2 to 10.1 ‰) and generally show equilibrium oxygen isotope fractionation. Initial 87Sr/86Sr isotope ratios are also variable (0.7037-0.7063), whereas εNd130Ma values (+ 8.3 to + 11.0) are relatively similar. Sr and O isotopic compositional differences among rocks on outcrop scale, the preservation of O isotopic compositions of low-temperature altered oceanic crust, and Sr-Nd isotopic trends typical for seafloor alteration suggest inheritance from variably altered oceanic crust. However, decreasing δ7Li values (-0.5 to -12.9 ‰) with increasing Li concentrations (11-94 ppm) indicate Li isotope fractionation by diffusion related to fluid-rock interaction. Li isotopes prove to be a very sensitive tracer of metasomatism, although the small effects on the Sr-Nd-O isotope systems suggest that the fluid-induced metasomatic event in the MORB-type eclogites was small-scale at low-water/rock ratios. This metasomatic fluid is thought to predominantly derive from in situ dehydration of MORB-type rocks. Zoisite eclogites, the second eclogite type from the Raspas Complex, are characterized by the presence of zoisite and enrichment in many incompatible trace elements compared to the MORB-type eclogites. The zoisite eclogites have a homogenous Sr-Nd isotopic signature (Initial 87Sr/86Sr = 0.7075-0.7081, εNd130Ma = -6.7 to -8.7), interpreted to reflect a metasomatic overprint. The isotopic signature can be attributed to the metasomatic formation of zoisite because associated zoisite veins are isotopically similar. Relatively homogenous O isotope values for garnet (10.9-12.3 ‰) omphacite (9.4 to 10.8 ‰), amphibole (10.0-10.1 ‰) and zoisite (10.5-11.9 ‰) and inter-mineral O isotopic disequilibria are consistent with a metasomatic overprint via open-system fluid input. Li concentrations (46-76 ppm) and δ7Li values of the zoisite eclogites overlap the range of the MORB-type eclogites. The large amount of fluid required for isotopic homogenization, combined with the results from fluid inclusion studies, suggests that deserpentinization played a major role in generating the metasomatic fluid that altered the zoisite eclogites. However, influence of a (meta)sedimentary source is required based on Sr-Nd isotope data and trace element enrichments. The significant geochemical variation in the various eclogites generated by interaction with metasomatic fluids has to be considered in attempts to constrain recycling at convergent margins

Tracing the effects of high-pressure metasomatic fluids and seawater alteration in blueschist-facies overprinted eclogites: Implications for subduction channel processes

Eclogites from the Tian Shan high-pressure/low-temperature (HP/LT) metamorphic belt show evidence for successively increasing metasomatic alteration with increasing retrograde, blueschist-facies overprint. To constrain the source(s) of the metasomatizing fluid and to evaluate elemental and isotopic changes during this overprint, two sequences of eclogite-blueschist transitions were investigated: A layered transition from eclogite to blueschist (FTS 9–1 sequence) and blueschist-facies overprinted pillow metabasalts (FTS 4 samples). Geochemical trends based on the relationships of K, Ba, Rb and Th are consistent with HP metasomatism, but distinct from typical seafloor alteration trends. In contrast, oxygen isotope ratios in garnet (δ18OV-SMOW = 7.3–8.7‰) and omphacite (δ18OV-SMOW = 8.2–9.7‰) are similar to δ18OV-SMOW in bulk low-temperature altered oceanic crust (AOC), suggesting O isotopic preservation of a seafloor alteration signature. Carbonate crystallization related to the metasomatic overprint demonstrate CO2 mobility during subduction and potential C storage in HP metamorphic rocks. Carbon isotope ratios in the two sequences differ markedly: Disseminated calcite in the layered FTS 9–1 sequence has δ13CV-PDB = − 9.14 ± 0.19‰, whereas vein-forming ankerite in the pillow metabasalts has δ13CV-PDB = − 2.08 ± 0.12‰. The ankerite reflects an inorganic marine/hydrothermal signature, as observed in ophiolites, whereas the low δ13CV-PDB values from the calcite point to a contribution of organic carbon. The time when the metasomatic overprint occurred is estimated to be ~ 320 ± 11 Ma based on a Rb-Sr isochron age of six blueschist samples from the pillow metabasalts, which is in agreement with active subduction in this region. Initial (T = 320 Ma) 87Sr/86Sr ratios for all HP/LT rocks range from 0.7059 – 0.7085, and εNd320Ma varies from − 0.4 to + 10.9. Both eclogite-blueschist sequences have initial Sr isotope compositions (87Sr/86Sr ~ 0.707) that are significantly higher than those of typical oceanic mantle-derived basalts. They are thought to derive from a fluid that preserved the Sr isotopic signature of seawater by fluid-rock interaction with seawater-altered oceanic lithosphere in a subduction channel. Mixing models between eclogite and various fluids suggest that the contribution of a sediment-derived fluid was likely less than 20%. A fluid predominantly derived from seawater-altered oceanic lithosphere is also supported by the calculated O isotope composition of the fluids (10.2 – 11.2‰). It is thus evident that subduction channel fluids carry complex, mixed elemental and isotopic signatures, which reflect the composition of their source rocks modified by interaction with various other lithologies. Highlights ► Eclogites from the Tian Shan show blueschist-facies metasomatic overprint ► Fluid-induced metasomatism occurred at 320 ± 11 Ma ► Fluid predominantly derived from seawater-altered oceanic lithosphere ► Carbonates reflect C sequestration of mixture of organic and inorganic component

The History, Relevance, and Applications of the Periodic System in Geochemistry

Geochemistry is a discipline in the earth sciences concerned with understanding the chemistry of the Earth and what that chemistry tells us about the processes that control the formation and evolution of Earth materials and the planet itself. The periodic table and the periodic system, as developed by Mendeleev and others in the nineteenth century, are as important in geochemistry as in other areas of chemistry. In fact, systemisation of the myriad of observations that geochemists make is perhaps even more important in this branch of chemistry, given the huge variability in the nature of Earth materials – from the Fe-rich core, through the silicate-dominated mantle and crust, to the volatile-rich ocean and atmosphere. This systemisation started in the eighteenth century, when geochemistry did not yet exist as a separate pursuit in itself. Mineralogy, one of the disciplines that eventually became geochemistry, was central to the discovery of the elements, and nineteenth-century mineralogists played a key role in this endeavour. Early “geochemists” continued this systemisation effort into the twentieth century, particularly highlighted in the career of V.M. Goldschmidt. The focus of the modern discipline of geochemistry has moved well beyond classification, in order to invert the information held in the properties of elements across the periodic table and their distribution across Earth and planetary materials, to learn about the physicochemical processes that shaped the Earth and other planets, on all scales. We illustrate this approach with key examples, those rooted in the patterns inherent in the periodic law as well as those that exploit concepts that only became familiar after Mendeleev, such as stable and radiogenic isotopes