Nature's refineries — Metals and metalloids in arc volcanoes
Chemical data for fumaroles and for atmospheric gas and ash plumes from active arc volcanoes provide glimpses of the rates of release of metal and metalloids, such as Tl and Cd, from shallow and mid-crust magmas. Data from copper deposits formed in ancient volcanoes at depths of up to about 1500 m in the fractures below paleo-fumaroles, and at around 2000–4000 m in association with sub-volcanic intrusions (porphyry copper deposits) provide evidence of sub-surface deposition of Cu–Au–Ag–Mo and a range of other minor elements including Te, Se, As and Sb. These deposits, or ‘sinks’, of metals consistently record sustained histories of magmatic gas streaming through volcanic systems interspersed by continuing intrusive and eruptive activity. Here we integrate data from ancient and modern volcanic systems and show that the fluxes of metals and metalloids are controlled by a) the maintenance of fracture permeability in the stressed crust below volcanoes and b) the chemical processes that are triggered as magmatic gas, initially undersaturated with metals and metalloids, expands from lithostatic to very low pressure conditions through fracture arrays. The recognition of gas streaming may also account for the phenomenon of ‘excess degassing’, and defines an integral, but generally understated, component of active volcanic systems – a volcanic gas core – that is likely to be integral to the progression of eruptions to Plinean state. Destabilization of solvated molecular metal and metalloid species in magmatic gas mixtures and changes in their redox state are triggered, as it expands to the surface by abrupt pressure drops, or throttles' in the fracture array that guides expansion to the surface. The electronically harder, low electronegativity metals, such as copper and iron, deposit rapidly in response to expansion followed more slowly by arsenic with antimony as sulfosalts. Heavy, large radius, softer elements such as bismuth, lead, and thallium along with cadmium are strongly fractionated along the way, eventually venting their excess along with SO 2 , CO 2 , and other components of the carrier gas, into the atmosphere. These elements, many of which are toxic, may also be dispersed by mixing with groundwater in the permeable crust below volcanoes and generate potential health risks due to Hg, As, and Se contamination of drinking water resources.