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  1. Free, publicly-accessible full text available October 1, 2023
  2. Free, publicly-accessible full text available August 1, 2023
  3. The disappearance of mass-independent sulfur isotope fractionation (S-MIF) within the c. 2.3-billion-year-old (Ga) Rooihoogte Formation has been heralded as a chemostratigraphic marker of permanent atmospheric oxygenation. Reports of younger S-MIF, however, question this narrative, leaving significant uncertainties surrounding the timing, tempo, and trajectory of Earth’s oxygenation. Leveraging a new bulk quadruple S-isotope record, we return to the South African Transvaal Basin in search of support for supposed oscillations in atmospheric oxygen beyond 2.3 Ga. Here, as expected, within the Rooihoogte Formation, our data capture a collapse in Δ 3× S values and a shift from Archean-like Δ 36 S/Δ 33 S slopes to their mass-dependent counterparts. Importantly, the interrogation of a Δ 33 S-exotic grain reveals extreme spatial variability, whereby atypically large Δ 33 S values are separated from more typical Paleoproterozoic values by a subtle grain-housed siderophile-enriched band. This isotopic juxtaposition signals the coexistence of two sulfur pools that were able to escape diagenetic homogenization. These large Δ 33 S values require an active photochemical sulfur source, fingerprinting atmospheric S-MIF production after its documented cessation elsewhere at ∼2.4 Ga. By contrast, the Δ 33 S monotony observed in overlying Timeball Hill Formation, with muted Δ 33 S values (<0.3‰)more »and predominantly mass-dependent Δ 36 S/Δ 33 S systematics, remains in stark contrast to recent reports of pronounced S-MIF within proximal formational equivalents. If reflective of atmospheric processes, these observed kilometer-scale discrepancies disclose heterogenous S-MIF delivery to the Transvaal Basin and/or poorly resolved fleeting returns to S-MIF production. Rigorous bulk and grain-scale analytical campaigns remain paramount to refine our understanding of Earth’s oxygenation and substantiate claims of post-2.3 Ga oscillations in atmospheric oxygen.« less
    Free, publicly-accessible full text available March 29, 2023
  4. Free, publicly-accessible full text available February 1, 2023
  5. Abstract This study addresses the question of how and where arc magmas obtain their chemical and isotopic characteristics. The Wooley Creek batholith and Slinkard pluton are a tilted, mid- to upper-crustal part of a vertically extensive, late-Jurassic, arc-related magmatic system in the Klamath Mountains, northern California. The main stage of the system is divided into an older lower zone (c. 159 Ma) emplaced as multiple sheet-like bodies, a younger upper zone (c. 158–156 Ma), which is gradationally zoned upward from mafic tonalite to granite, and a complex central zone, which represents the transition between the lower and upper zones. Xenoliths are common and locally abundant in the lower and central zones and preserve a ghost stratigraphy of the three host terranes. Bulk-rock Nd isotope data along with ages and Hf and oxygen isotope data on zircons were used to assess the location and timing of differentiation and assimilation. Xenoliths display a wide range of εNd (whole-rock) and εHf (zircon), ranges that correlate with rocks in the host terranes. Among individual pluton samples, zircon Hf and oxygen isotope data display ranges too large to represent uniform magma compositions, and very few data are consistent with uncontaminated mantle-derived magma. In addition, zoning of Zrmore »and Hf in augite and hornblende indicates that zircon crystallized at temperatures near or below 800 °C; these temperatures are lower than emplacement temperatures. Therefore, the diversity of zircon isotope compositions reflects in situ crystallization from heterogeneous magmas. On the basis of these and published data, the system is interpreted to reflect initial MASH-zone differentiation, which resulted in elevated δ18O and lowered εHf in the magmas prior to zircon crystallization. Further differentiation, and particularly assimilation–fractional crystallization, occurred at the level of emplacement on a piecemeal (local) basis as individual magma batches interacted with partial melts from host-rock xenoliths. This piecemeal assimilation was accompanied by zircon crystallization, resulting in the heterogeneous isotopic signatures. Magmatism ended with late-stage emplacement of isotopically evolved granitic magmas (c. 156 Ma) whose compositions primarily reflect reworking of the deep-crustal MASH environment.« less
  6. Abstract Detrital chromites are commonly reported within Archean metasedimentary rocks, but have thus far garnered little attention for use in provenance studies. Systematic variations of Cr–Fe spinel mineral chemistry with changing tectonic setting have resulted in the extensive use of chromite as a petrogenetic indicator, and so detrital chromites represent good candidates to investigate the petrogenesis of eroded Archean mafic and ultramafic crust. Here, we report the compositions of detrital chromites within fuchsitic (Cr-muscovite rich) metasedimentary rocks from the Jack Hills, situated within the Narryer Terrane, Yilgarn Craton, Western Australia, which are geologically renowned for hosting Hadean (>4000 Ma) zircons. We highlight signatures of metamorphism, including highly elevated ZnO and MnO, coupled with lowered Mg# in comparison with magmatic chromites, development of pitted domains, and replacement of primary inclusions by phases that are part of the metamorphic assemblages within host metasedimentary rocks. Oxygen isotope compositions of detrital chromites record variable exchange with host metasedimentary rocks. The variability of metamorphic signatures between chromites sampled only meters apart further indicates that modification occurred in situ by interaction of detrital chromites with metamorphic fluids and secondary mineral assemblages. Alteration probably occurred during upper greenschist to lower amphibolite facies metamorphism and deformation of host metasedimentarymore »rocks at ∼2650 Ma. Regardless of metamorphic signatures, sampling location or grain shape, chromite cores yield a consistent range in Cr#. Although other key petrogenetic indices, such as Fe2O3 and TiO2 contents, are complicated in Jack Hills chromites by mineral non-stoichiometry and secondary mobility within metasedimentary rocks, we demonstrate that the Cr# of chromite yields significant insights into their provenance. Importantly, moderate Cr# (typically 55–70) precludes a komatiitic origin for the bulk of chromites, reflecting a dearth of komatiites and intrusive equivalents within the erosional catchment of the Jack Hills metasedimentary units. We suggest that the Cr# of Jack Hills chromite fits well with chromites derived from layered intrusions, and that a single layered intrusion may account for the observed chemical compositions of Jack Hills detrital chromites. Where detailed characterization of key metamorphic signatures is undertaken, detrital chromites preserved within Archean metasedimentary rocks may therefore yield valuable information on the petrogenesis and geodynamic setting of poorly preserved mafic and ultramafic crust.« less
  7. Abstract Tellurium-rich (Te) adularia-sericite epithermal Au-Ag deposits are an important current and future source of precious and critical metals. However, the source and evolution of ore-forming fluids in these deposits are masked by traditional bulk analysis of quartz oxygen isotope ratios that homogenize fine-scale textures and growth zones. To advance understanding of the source of Te and precious metals, herein, we use petrographic and cathodoluminescence (CL) images of such textures and growth zones to guide high spatial resolution secondary ion mass spectroscopy (SIMS) oxygen isotope analyses (10 µm spot) and spatially correlated fluid inclusion microthermometric measurements on successive quartz bands in contemporary Te-rich and Te-poor adularia-sericite (-quartz) epithermal Au-Ag vein deposits in northeastern China. The results show that large positive oxygen isotope shifts from –7.1 to +7.7‰ in quartz rims are followed by precipitation of Au-Ag telluride minerals in the Te-rich deposit, whereas small oxygen isotope shifts of only 4‰ (–2.2 to +1.6‰) were detected in quartz associated with Au-Ag minerals in the Te-poor deposits. Moreover, fluid-inclusion homogenization temperatures are higher in comb quartz rims (avg. 266.4 to 277.5 °C) followed by Au-Ag telluride minerals than in previous stages (~250 °C) in the Te-rich deposit. The Te-poor deposit has amore »consistent temperature (~245 °C) in quartz that pre- and postdates Au-Ag minerals. Together, the coupled increase in oxygen isotope ratios and homogenization temperatures followed by precipitation of Au-Ag tellurides strongly supports that inputs of magmatic fluid containing Au, Ag, and Te into barren meteoric water-dominated flow systems are critical to the formation of Te-rich adularia-sericite epithermal Au-Ag deposits. In contrast, Te-poor adularia-sericite epithermal Au-Ag deposits show little or no oxygen isotope or fluid-inclusion evidence for inputs of magmatic fluid.« less
  8. Abstract We present >500 zircon δ18O and Lu-Hf isotope analyses on previously dated zircons to explore the interplay between spatial and temporal magmatic signals in Zealandia Cordillera. Our data cover ~8500 km2 of middle and lower crust in the Median Batholith (Fiordland segment of Zealandia Cordillera) where Mesozoic arc magmatism along the paleo-Pacific margin of Gondwana was focused along an ~100 km wide, arc-parallel zone. Our data reveal three spatially distinct isotope domains that we term the eastern, central, and western isotope domains. These domains parallel the Mesozoic arc-axis, and their boundaries are defined by major crustal-scale faults that were reactivated as ductile shear zones during the Early Cretaceous. The western isotope domain has homogenous, mantle-like δ 18O (Zrn) values of 5.8 ± 0.3‰ (2 St.dev.) and initial εHf (Zrn) values of +4.2 ± 1.0 (2 St.dev.). The eastern isotope domain is defined by isotopically low and homogenous δ18O (Zrn) values of 3.9 ± 0.2‰ and initial εHf values of +7.8 ± 0.6. The central isotope domain is characterized by transitional isotope values that display a strong E-W gradient with δ18O (Zrn) values rising from 4.6 to 5.9‰ and initial εHf values decreasing from +5.5 to +3.7. We find thatmore »the isotope architecture of the Median Batholith was in place before the initiation of Mesozoic arc magmatism and pre-dates Early Cretaceous contractional deformation and transpression. Our data show that Mesozoic pluton chemistry was controlled in part by long-lived, spatially distinct isotope domains that extend from the crust through to the upper mantle. Isotope differences between these domains are the result of the crustal architecture (an underthrusted low-δ18O source terrane) and a transient event beginning at ca. 129 Ma that primarily involved a depleted-mantle component contaminated by recycled trench sediments (10–20%). When data showing the temporal and spatial patterns of magmatism are integrated, we observe a pattern of decreasing crustal recycling of the low-δ18O source over time, which ultimately culminated in a mantle-controlled flare-up. Our data demonstrate that spatial and temporal signals are intimately linked, and when evaluated together they provide important insights into the crustal architecture and the role of both stable and transient arc magmatic trends in Cordilleran batholiths.« less
  9. Abstract The southern Coast Mountain batholith was episodically active from Jurassic to Eocene time and experienced four distinct high magmatic flux events during that period. Similar episodicity has been recognized in arcs worldwide, yet the mechanism(s) driving such punctuated magmatic behavior are debated. This study uses zircon Hf and O isotopes, with whole-rock and mineral geochemistry, to track spatiotemporal changes in southern Coast Mountains batholith melt sources and to evaluate models of flare-up behavior and crust formation in Cordilleran arc systems. Zircon Hf isotope analysis yielded consistently primitive values, with all zircon grains recording initial εHf between +6 and +16. The majority (97%) of zircons analyzed yielded δ18O values between 4.2‰ and 6.5‰, and only five grains recorded values of up to 8.3‰. These isotopic results are interpreted to reflect magmatism dominated by mantle melting during all time periods and across all areas of the southern batholith, which argues against the periodic input of more melt-fertile crustal materials as the driver of episodic arc magmatism. They also indicate that limited crustal recycling is needed to produce the large volumes of continental crust generated in the batholith. Although the isotopic character of intrusions is relatively invariant through time, magmas emplaced duringmore »flare-ups record higher Sr/Y and La/Yb(N) and lower zircon Ti and Yb concentrations, which is consistent with melting in thickened crust with garnet present as a fractionating phase. Flare-ups are also temporally associated with periods when the southern Coast Mountains batholith both widens and advances inboard. We suggest that the landward shift of the arc into more fertile lithospheric mantle domains triggers voluminous magmatism and is accompanied by magmatic and/or tectonic thickening. Overall, these results demonstrate that the magmatic growth of Cordilleran arcs can be spatially and temporally complex without requiring variability in the contributions of crust and/or mantle to the batholith.« less