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.

Colloidal transport and flocculation are the cause of the hyperenrichment of gold in nature.

Aqueous complexation has long been considered the only viable means of transporting gold to depositional sites in hydrothermal ore-forming systems. A major weakness of this hypothesis is that it cannot readily explain the formation of ultrahigh-grade gold veins. This is a consequence of the relatively low gold concentrations typical of ore fluids (tens of parts per billion [ppb]) and the fact that these "bonanza" veins can contain weight-percent levels of gold in some epithermal and orogenic deposits. Here, we present direct evidence for a hypothesis that could explain these veins, namely, the transport of the gold as colloidal particles and their flocculation in nanoscale calcite veinlets. These gold-bearing nanoveinlets bear a remarkable resemblance to centimeter-scale ore veins in many hydrothermal gold deposits and give unique insight into the scale invariability of colloidal flocculation in forming hyperenriched gold deposits. Using this evidence, we propose a model for the development of bonanza gold veins in high-grade deposits. We argue that gold transport in these systems is largely mechanical and is the result of exceptionally high degrees of supersaturation that preclude precipitation of gold crystals and instead lead to the formation of colloidal particles, which flocculate and form much larger masses. These flocculated masses aggregate locally, where they are seismically pumped into fractures to locally form veins composed largely of gold. This model explains how bonanza veins may form from fluids containing ppb concentrations of gold and does not require prior encapsulation of colloidal gold particles in silica gel, as proposed by previous studies.

Challenging the thorium-immobility paradigm.

Thorium is the most abundant actinide in the Earth's crust and has universally been considered one of the most immobile elements in natural aqueous systems. This view, however, is based almost exclusively on solubility data obtained at low temperature and their theoretical extrapolation to elevated temperature. The occurrence of hydrothermal deposits with high concentrations of Th challenges the Th immobility paradigm and strongly suggests that Th may be mobilized by some aqueous fluids. Here, we demonstrate experimentally that Th, indeed, is highly mobile at temperatures between 175 and 250 °C in sulfate-bearing aqueous fluids due to the formation of the highly stable Th(SO4)2 aqueous complex. The results of this study indicate that current models grossly underestimate the mobility of Th in hydrothermal fluids, and thus the behavior of Th in ore-forming systems and the nuclear fuel cycle needs to be re-evaluated.

The origin of rare alkali metals in geothermal fluids of southern Tibet, China: A silicon isotope perspective.

Geothermal waters from the Semi, Dagejia and Kawu hot springs in the Shiquanhe-Yarlung Zangbo geothermal field of southern Tibet (China) are highly enriched in rare alkali metals (RAM). However, the enrichment mechanism is still hotly debated. Here, we report the first silicon isotope data of these geothermal waters to unravel the origin of the extreme RAM enrichments. Sinter precipitation in the spring vents and water-rock interaction in the deep reservoir controlled both the silicon budget and silicon isotope fractionation. The rates of water-rock interaction and sinter precipitation in three spring sites decrease in the sequences Semi > Kawu > Dagejia, and Dagejia > Kawu > Semi respectively. Silicon isotope fractionation during sinter precipitation (i.e. Δ30Siprecipitate-solution < -0.1‰) is less than that due to water-rock interaction (i.e. Δ30Sisolution-rocks at least as high as -0.47‰), which makes it possible to use the δ30Si signatures of springs to evaluate the intensity of water-rock interaction. Based on the available evidence, a conceptual model of RAM enrichment is proposed: (i) persistent magmatic activity in southern Tibet provided the initial enrichment of the RAM in host rocks and a heat sources for the deep reservoirs of geothermal systems; (ii) the high Cl- content and long residence time (thousands of years) promote the leaching of RAM from the silicate host rocks.

Uranium transport in acidic brines under reducing conditions.

The behavior of uranium in environments, ranging from those of natural systems responsible for the formation of uranium deposits to those of nuclear reactors providing 11% of the world's electricity, is governed by processes involving high-temperature aqueous solutions. It has been well documented that uranium is mobile in aqueous solutions in its oxidized, U6+ state, whereas in its reduced, U4+ state, uranium has been assumed to be immobile. Here, we present experimental evidence from high temperature (>100 °C) acidic brines that invalidates this assumption. Our experiments have identified a new uranium chloride species (UCl4°) that is more stable under reducing than oxidized conditions. These results indicate that uranium is mobile under reducing conditions and necessitate a re-evaluation of the mobility of uranium, particularly in ore deposit models involving this metal. Regardless of the scenario considered, reducing conditions can no longer be considered a guarantee of uranium immobility.

Steel slag carbonation in a flow-through reactor system: the role of fluid-flux.

Steel production is currently the largest industrial source of atmospheric CO2. As annual steel production continues to grow, the need for effective methods of reducing its carbon footprint increases correspondingly. The carbonation of the calcium-bearing phases in steel slag generated during basic oxygen furnace (BOF) steel production, in particular its major constituent, larnite {Ca2SiO4}, which is a structural analogue of olivine {(MgFe)2SiO4}, the main mineral subjected to natural carbonation in peridotites, offers the potential to offset some of these emissions. However, the controls on the nature and efficiency of steel slag carbonation are yet to be completely understood. Experiments were conducted exposing steel slag grains to a CO2-H2O mixture in both batch and flow-through reactors to investigate the impact of temperature, fluid flux, and reaction gradient on the dissolution and carbonation of steel slag. The results of these experiments show that dissolution and carbonation of BOF steel slag are more efficient in a flow-through reactor than in the batch reactors used in most previous studies. Moreover, they show that fluid flux needs to be optimized in addition to grain size, pressure, and temperature, in order to maximize the efficiency of carbonation. Based on these results, a two-stage reactor consisting of a high and a low fluid-flux chamber is proposed for CO2 sequestration by steel slag carbonation, allowing dissolution of the slag and precipitation of calcium carbonate to occur within a single flow-through system.

Physicochemical conditions and timing of rodingite formation: evidence from rodingite-hosted fluid inclusions in the JM Asbestos mine, Asbestos, Québec.

Fluid inclusions and geological relationships indicate that rodingite formation in the Asbestos ophiolite, Québec, occurred in two, or possibly three, separate episodes during thrusting of the ophiolite onto the Laurentian margin, and that it involved three fluids. The first episode of rodingitization, which affected diorite, occurred at temperatures of between 290 and 360 degrees C and pressures of 2.5 to 4.5 kbar, and the second episode, which affected granite and slate, occurred at temperatures of between 325 and 400 degrees C and pressures less than 3 kbar. The fluids responsible for these episodes of alteration were moderately to strongly saline (approximately 1.5 to 6.3 m eq. NaCl), rich in divalent cations and contained appreciable methane. A possible third episode of alteration is suggested by primary fluid inclusions in vesuvianite-rich bodies and secondary inclusions in other types of rodingite, with significantly lower trapping temperatures, salinity and methane content. The association of the aqueous fluids with hydrocarbon-rich fluids containing CH4 and higher order alkanes, but no CO2, suggests strongly that the former originated from the serpentinites. The similarities in the composition of the fluids in all rock types indicate that the ophiolite had already been thrust onto the slates when rodingitization occurred.