Sulfur-poor intense acid hydrothermal alteration: A distinctive hydrothermal environment


Kreiner, Douglas C.
Barton, Mark D.

A fundamentally distinct, sulfide-poor variant of intense acid (advanced argillic) alteration occurs at the highest structural levels in iron oxide-rich hydrothermal systems. Understanding the mineralogy, and geochemical conditions of formation in these sulfide-poor mineral assemblages have both genetic and environmental implications. New field observations and compilation of global occurrences of low sulfur advanced argillic alteration demonstrates that in common with the sulfide-rich variants of advanced argillic alteration, sulfide-poor examples exhibit nearly complete removal of alkalis, leaving a residuum of aluminum-silicate + quartz. In contrast, the sulfur-poor variants lack the abundant pyrite ± other sulfides, hypogene alunite, Al-leached rocks (residual ‘‘vuggy” quartz) as well as the Au-Cu-Ag ± As-rich mineralization of some sulfur-rich occurrences. Associated mineralization is dominated by magnetite and/or hematite with accessory elements such as Cu, Au, REE, and P. These observations presented here indicate there must be distinct geologic processes that result in the formation of low-sulfur advanced argillic styles of alteration. Hydrolysis of magmatic SO2 to sulfuric acid is the most commonly recognized mechanism for generating hypogene advanced argillic alteration, but is not requisite for its formation. Low sulfur iron-oxide copper-gold systems are known to contain abundant acid-styles of alteration (e.g. sericitic, chloritic), which locally reaches advanced argillic assemblages. A compilation of mapping in four districts in northern Chile and reconnaissance observations elsewhere show systematic zoning from near surface low-sulfide advanced argillic alteration through chlorite-sericite-albite and locally potassic alteration. The latter is commonly associated with specular hematite-chalcopyrite mineralization. Present at deeper structural levels are higher-temperature styles of sodic-calcic (oligoclase/scapolite – actinolite) alteration associated with magnetite ± chalcopyrite mineralization. These patterns are in contrast to the more sulfur-rich examples which generally zone to higher pyrite and locally alunite-bearing alteration. Fluid inclusion evidence from the systems in northern Chile shows that many fluids contain 25 to >50 wt% NaCleq with appreciable Ca, Fe, and K contents with trapping temperatures >300 C. These geological and geochemical observations are consistent with the origin of the low-sulfur advanced argillic assemblages from HCl generated by precipitation of iron oxides from iron chloride complexes from a high-salinity fluid by reactions such as 3FeCl2 + 4H2O = Fe3O4 + 6HCl + H2. Such HCl-rich (and relatively HSO4 = -poor) fluids can then account for the intense acid, Al-silicate-rich styles of alteration observed at high levels in some iron-oxide-coppe-gold (IOCG) systems. The geochemical differences between the presence of sulfide-rich and sulfur-poor examples of advanced argillic alteration are important to
distinguishing between system types and the acid-producing capacity of the system, including in the modern weathering environment. They have fundamental implications for effective mineral exploration in low-sulfur systems and provide yet another vector of exposed alteration in the enigmatic IOCG clan of mineral deposits. Furthermore, understanding the geochemistry and mineralogy of this distinct geologic environment has applications to understanding the acid generating capacity and deleterious heavy metals associated with advanced argillic alteration. 

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Fig. 9. Synoptic models for the genesis of advanced argillic alteration in IOCG and porphyry environments. SO2-rich magmatic-hydrothermal fluids (right) yield sulfuric acid and high sulfidation assemblages. In contrast, chloride-rich brines, here shown as being of external derivation, yield a metal chloride fluid that generates acid on cooling. These contrasting environments result in sulfide-rich and sulfide-poor advanced argillic alteration, respectively. Abbreviations for mineral assemblages: musc = muscovite, pyroph = pyrophyllite, qz = quartz, chl = chlorite, carb = carbonate, hm = hematite, cpy = chalcopyrite, py = pyrite, bi = biotite, act = actinolite, Kf = potassium feldspar, ab = albite, mt = magnetite, olig = oligoclase, scap = scapolite, hbl = hornblende, px = pyroxene, apat = apatite, en = enargite, cv = covellite, S° = native sulfur, bn = bornite. Double backslash separates proximal assemblage before from distal assemblage after (proximal nn distal). Single forward slash delineates sulfide-oxide minerals from silicate and carbonate
alteration mineral.

Publication Listing 0169-1368/Published by Elsevier B.V.