Conventional wisdom holds that aqueous solutions are the only non-magmatic fluids capable of concentrating metals in the Earth's crust. The role of hydrocarbons in metal concentration is relegated to providing geochemical barriers at which the metals are reduced and immobilised. Liquid hydrocarbons, however, are also known to be able to carry appreciable concentrations of metals, and travel considerable distances. Here we report the results of an experimental determination of bulk solubilities of Au, Zn, and U in a variety of crude oils at temperatures up to 300 °C and of the benchtop-scale transport experiments that simulate hydrocarbon-mediated re-deposition of Zn at 25-200 °C. It has been demonstrated that the metal concentrations obtained in solubility experiments are within the range of concentrations that are typically considered sufficient for aqueous fluids to form ore bodies. It has also been shown that Zn can be efficiently transported and re-deposited by hydrocarbons. These results provide direct evidence of the ability of natural crude oils to mobilise metals available in hydrocarbon-associated host rocks, and transport them in concentrations sufficient to contribute to ore-forming processes.
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.
In a companion paper in this issue, the authors reviewed the properties of cobalt, its mineralogy, and the processes that concentrate it to exploitable levels. Using this information and knowledge of the geology of the principal types of cobalt deposits, the present paper assesses the conditions and controls of cobalt transport and deposition and develops/refines plausible models for the genesis of these deposits. Economic cobalt deposits owe their origins to the compatible nature of Co2+, which causes it to concentrate in the mantle, mainly in olivine, and to be released to magmas only after high degrees of partial melting (i.e., to komatiitic and basaltic magmas). Thus, there is a very close association between cobalt deposits and mafic and ultramafic rocks. Magmatic deposits, in which Co is subordinate to Ni, develop through sulfide-silicate liquid immiscibility as a result of the very strong preference of these metals for the sulfide liquid. Predictably, these deposits reach their highest grades where hosted by olivine-rich ultramafic rocks. Approximately 60% of the world’s cobalt resource is of hydrothermal origin and is contained in sediment-hosted copper deposits in the Democratic Republic of the Congo. Using a combination of thermodynamic data and geologic information, we have refined a model in which Co is leached from mafic and ultramafic rocks by oxidized, chloride-rich hydrothermal fluids, derived from evaporation, and deposited in response to decreasing fO2 in carbonaceous sediments that accumulated in intracratonic rift basins. Economic Co deposits also develop as hydrothermal vein systems, in which Co is the primary ore metal. In the only deposits of this type that are currently being exploited (Bou Azzer, Morocco), the source of the Co was an adjacent serpentinized peridotite. The ore fluid was an oxidized, high-salinity brine derived from evaporites, and deposition occurred in response to pH neutralization by the felsic to intermediate igneous host. The final major class of Co deposits is laterite-hosted and develops on olivine-rich ultramafic rocks or their serpentinized equivalents. Our thermodynamic modeling shows that Co is leached from an ultramafic source by mildly acidic fluids as Co2+ and is transported down the laterite profile, eventually concentrating by a combination of adsorption on Mn oxides, incorporation in the structure of absolane (an Mn oxide), and precipitation as heterogenite (HCoO2). The dissolution of cobalt at the surface and its deposition at depth are controlled mainly by pH, which decreases downward; oxygen fugacity, which also decreases downward, has the opposite effect, inhibiting dissolution of cobalt at the surface and promoting it at depth. It is our hope that this introduction to the economic geology of cobalt and the processes responsible for the formation of cobalt-bearing ores will help guide future studies of cobalt ore genesis and strategies for the exploration of this critical metal.
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