Extreme shifts in pyrite sulfur isotope compositions reveal the path to bonanza gold.

Pyrite is the most common sulfide mineral in hydrothermal ore-forming systems. The ubiquity and abundance of pyrite, combined with its ability to record and preserve a history of fluid evolution in crustal environments, make it an ideal mineral for studying the genesis of hydrothermal ore deposits, including those that host critical metals. However, with the exception of boiling, few studies have been able to directly link changes in pyrite chemistry to the processes responsible for bonanza-style gold mineralization. Here, we report the results of high-resolution secondary-ion mass spectrometry and electron microprobe analyses conducted on pyrite from the Brucejack epithermal gold deposit, British Columbia. Our δ34S and trace element results reveal that the Brucejack hydrothermal system experienced abrupt fluctuations in fluid chemistry, which preceded and ultimately coincided with the onset of ultra-high-grade mineralization. We argue that these fluctuations, which include the occurrence of extraordinarily negative δ34S values (e.g., -36.1‰) in zones of auriferous, arsenian pyrite, followed by sharp increases of δ34S values in syn-electrum zones of nonarsenian pyrite, were caused by vigorous, fault valve-induced episodic boiling (flashing) and subsequent inundation of the hydrothermal system by seawater. We conclude that the influx of seawater was the essential step to forming bonanza-grade electrum mineralization by triggering, through the addition of cationic flocculants and cooling, the aggregation of colloidal gold suspensions. Moreover, our study demonstrates the efficacy of employing high-resolution, in situ analytical techniques to map out individual ore-forming events in a hydrothermal system.

Boron-oxygen complex yields n-type surface layer in semiconducting diamond.

Diamond is a wide-bandgap semiconductor possessing exceptional physical and chemical properties with the potential to miniaturize high-power electronics. Whereas boron-doped diamond (BDD) is a well-known p-type semiconductor, fabrication of practical diamond-based electronic devices awaits development of an effective n-type dopant with satisfactory electrical properties. Here we report the synthesis of n-type diamond, containing boron (B) and oxygen (O) complex defects. We obtain high carrier concentration (∼0.778 × 1021 cm-3) several orders of magnitude greater than previously obtained with sulfur or phosphorous, accompanied by high electrical conductivity. In high-pressure high-temperature (HPHT) boron-doped diamond single crystal we formed a boron-rich layer ∼1-1.5 µm thick in the {111} surface containing up to 1.4 atomic % B. We show that under certain HPHT conditions the boron dopants combine with oxygen defects to form B-O complexes that can be tuned by controlling the experimental parameters for diamond crystallization, thus giving rise to n-type conduction. First-principles calculations indicate that B3O and B4O complexes with low formation energies exhibit shallow donor levels, elucidating the mechanism of the n-type semiconducting behavior.

Dense hydrated Mg-silicates in diamond: Implications for transport of H2O into the mantle.

Water in Earth's upper mantle is a minor and yet critically important component that dictates mantle properties such as strength and melting behavior. Minerals with stoichiometric water, such as those of the humite group, are important yet poorly characterized potential reservoirs for volatiles in the upper mantle. Here, we report observation of hydroxyl members of the humite group as inclusions in mantle-derived diamond. Hydroxylchondrodite and hydroxylclinohumite were found coexisting with olivine, magnesiochromite, Mg-bearing calcite, dolomite, quartz, mica, and a djerfisherite-group mineral in a diamond from Brazil. The olivine is highly forsteritic (Mg# 97), with non-mantle-like oxygen isotope composition (δ18O +6.2‰), and is associated with fluid inclusions and hydrous minerals-features that could be inherited from a serpentinite protolith. Our results constitute direct evidence for the presence of deserpentinized peridotitic protoliths in subcratonic mantle keels, placing important constraints on the stability of hydrous phases in the mantle and the origin of diamond-forming fluids.

Oxidized sulfur-rich arc magmas formed porphyry Cu deposits by 1.88 Ga.

Most known porphyry Cu deposits formed in the Phanerozoic and are exclusively associated with moderately oxidized, sulfur-rich, hydrous arc-related magmas derived from partial melting of the asthenospheric mantle metasomatized by slab-derived fluids. Yet, whether similar metallogenic processes also operated in the Precambrian remains obscure. Here we address the issue by investigating the origin, fO2, and S contents of calc-alkaline plutonic rocks associated with the Haib porphyry Cu deposit in the Paleoproterozoic Richtersveld Magmatic Arc (southern Namibia), an interpreted mature island-arc setting. We show that the ca. 1886-1881 Ma ore-forming magmas, originated from a mantle-dominated source with minor crustal contributions, were relatively oxidized (1‒2 log units above the fayalite-magnetite-quartz redox buffer) and sulfur-rich. These results indicate that moderately oxidized, sulfur-rich arc magma associated with porphyry Cu mineralization already existed in the late Paleoproterozoic, probably as a result of recycling of sulfate-rich seawater or sediments from the subducted oceanic lithosphere at that time.

Sulfur isotopes in diamonds reveal differences in continent construction.

Neoproterozoic West African diamonds contain sulfide inclusions with mass-independently fractionated (MIF) sulfur isotopes that trace Archean surficial signatures into the mantle. Two episodes of subduction are recorded in these West African sulfide inclusions: thickening of the continental lithosphere through horizontal processes around 3 billion years ago and reworking and diamond growth around 650 million years ago. We find that the sulfur isotope record in worldwide diamond inclusions is consistent with changes in tectonic processes that formed the continental lithosphere in the Archean. Slave craton diamonds that formed 3.5 billion years ago do not contain any MIF sulfur. Younger diamonds from the Kaapvaal, Zimbabwe, and West African cratons do contain MIF sulfur, which suggests craton construction by advective thickening of mantle lithosphere through conventional subduction-style horizontal tectonics.

Evidence for a dominantly reducing Archaean ambient mantle from two redox proxies, and low oxygen fugacity of deeply subducted oceanic crust.

Oxygen fugacity (ƒO2) is an intensive variable implicated in a range of processes that have shaped the Earth system, but there is controversy on the timing and rate of oxidation of the uppermost convecting mantle to its present ƒO2 around the fayalite-magnetite-quartz oxygen buffer. Here, we report Fe3+/ΣFe and ƒO2 for ancient eclogite xenoliths with oceanic crustal protoliths that sampled the coeval ambient convecting mantle. Using new and published data, we demonstrate that in these eclogites, two redox proxies, V/Sc and Fe3+/ΣFe, behave sympathetically, despite different responses of their protoliths to differentiation and post-formation degassing, seawater alteration, devolatilisation and partial melting, testifying to an unexpected robustness of Fe3+/ΣFe. Therefore, these processes, while causing significant scatter, did not completely obliterate the underlying convecting mantle signal. Considering only unmetasomatised samples with non-cumulate and little-differentiated protoliths, V/Sc and Fe3+/ΣFe in two Archaean eclogite suites are significantly lower than those of modern mid-ocean ridge basalts (MORB), while a third suite has ratios similar to modern MORB, indicating redox heterogeneity. Another major finding is the predominantly low though variable estimated ƒO2 of eclogite at mantle depths, which does not permit stabilisation of CO2-dominated fluids or pure carbonatite melts. Conversely, low-ƒO2 eclogite may have caused efficient reduction of CO2 in fluids and melts generated in other portions of ancient subducting slabs, consistent with eclogitic diamond formation ages, the disproportionate frequency of eclogitic diamonds relative to the subordinate abundance of eclogite in the mantle lithosphere and the general absence of carbonate in mantle eclogite. This indicates carbon recycling at least to depths of diamond stability and may have represented a significant pathway for carbon ingassing through time.

Subcellular imaging of isotopically labeled carbon compounds in a biological sample by ion microprobe (NanoSIMS).

Here we demonstrate the technique of nanoscale secondary ion mass spectrometry, utilizing the Cameca NanoSIMS50 ion microprobe, to detect and image the metabolism of an isotopically labeled compound (NaH(13)CO(3)) in a biological sample. In particular, we have designed and verified protocols for imaging the subcellular distribution and determining the relative abundance of labeled (13)C, within the coral Galaxea fascicularis. Analyses were conducted on 1-mum thick sections of resin-embedded material, using both scanned (mapping) and static (spot analysis) Cs(+) primary ion beam of approximately 100 nm diameter. Using these samples we establish that NanoSIMS has adequate mass resolution to reliably distinguish (13)C from potential isobaric interference by (12)C(1)H and that data extracted from ion maps are comparable to those acquired by spot analyses. Independent of the method of acquisition, ratioing of (13)C to the naturally abundant (12)C is essential if meaningful data, which can be statistically compared to standard and control samples, are to be obtained. These results highlight the potential of NanoSIMS for intracellular tracking of a variety of organic and inorganic compounds labeled with stable isotopes of C, N, O, S, P, and halogens.

Rapid heterogeneous assembly of multiple magma reservoirs prior to Yellowstone supereruptions.

Large-volume caldera-forming eruptions of silicic magmas are an important feature of continental volcanism. The timescales and mechanisms of assembly of the magma reservoirs that feed such eruptions as well as the durations and physical conditions of upper-crustal storage remain highly debated topics in volcanology. Here we explore a comprehensive data set of isotopic (O, Hf) and chemical proxies in precisely U-Pb dated zircon crystals from all caldera-forming eruptions of Yellowstone supervolcano. Analysed zircons record rapid assembly of multiple magma reservoirs by repeated injections of isotopically heterogeneous magma batches and short pre-eruption storage times of 10(3) to 10(4) years. Decoupled oxygen-hafnium isotope systematics suggest a complex source for these magmas involving variable amounts of differentiated mantle-derived melt, Archean crust and hydrothermally altered shallow-crustal rocks. These data demonstrate that complex magma reservoirs with multiple sub-chambers are a common feature of rift- and hotspot related supervolcanoes. The short duration of reservoir assembly documents rapid crustal remelting and two to three orders of magnitude higher magma production rates beneath Yellowstone compared to continental arc volcanoes. The short pre-eruption storage times further suggest that the detection of voluminous reservoirs of eruptible magma beneath active supervolcanoes may only be possible prior to an impending eruption.

Bilaterian burrows and grazing behavior at >585 million years ago.

Based on molecular clocks and biomarker studies, it is possible that bilaterian life emerged early in the Ediacaran, but at present, no fossils or trace fossils from this time have been reported. Here we report the discovery of the oldest bilaterian burrows in shallow-water glaciomarine sediments from the Tacuarí Formation, Uruguay. Uranium-lead dating of zircons in cross-cutting granite dykes constrains the age of these burrows to be at least 585 million years old. Their features indicate infaunal grazing activity by early eumetazoans. Active backfill within the burrow, an ability to wander upward and downward to exploit shallowly situated sedimentary laminae, and sinuous meandering suggest advanced behavioral adaptations. These findings unite the paleontological and molecular data pertaining to the evolution of bilaterians, and link bilaterian origins to the environmental changes that took place during the Neoproterozoic glaciations.