Weathering of Bi-bearing tennantite

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Marco E. Ciriotti
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Weathering of Bi-bearing tennantite

Messaggio da Marco E. Ciriotti » mar 09 ott, 2018 18:32

▪ Keim, M.F., Staude, S., Marquardt, K., Bachmann, K., Opitz, J., Markl, G.(2018): Weathering of Bi-bearing tennantite. Chemical Geology, 497,

The tennantite-tetrahedrite solid-solution series [called fahlore; (Cu,Ag)6Cu4(Fe,Zn,Cu,Hg,Cd)2(Sb,As,Bi,Te)4(S,Se)13] is widespread in many geological environments. Since it incorporates heavy metals and toxic elements, a better understanding of its weathering behaviour and details of its weathering process is important to evaluate environmental risks (emerging mainly from the mobilization of As-Sb-Bi) and local and global metal fluxes in stream waters and oceans. In this study, weathering of Bi-rich members of this mineral group was investigated using microscopy, EMPA, SEM, TEM, LA-ICP-MS, Raman, μXRD, and MLA.
Observations reveal a succession of four distinct stages of weathering: During stage 1, irregular tubes within fahlore show an assemblage of nm- to μm-sized roméite group minerals, tripuhyite, crystalline Cu-oxides and Cu-sulfides. Stage 1 textures and secondary sulfides indicate a low redox-potential and a low fluid/rock ratio, typical of cementation zones. Mass balance calculations show that during this stage all Zn and the majority of As and S are released to the weathering fluids. Bismuth is immobile in this stage and Sb and Fe are immobile, if Bi is sufficiently available from fahlore, but both are partly released, if the fahlore did not contain sufficient Bi. During stage 2, amorphous and nano-crystalline arsenates replace fahlore as weathering fronts. Such assemblages indicate a higher redox-potential than in stage 1, typical for oxidation zones. Mass balance calculations reveal that Zn, Sb, S and partially Cu are lost. Arsenic and Bi are immobile. Stage 3 occurs only locally, dissolving former weathering stages and/or precipitating amorphous Cu-arsenates/silicates reflecting processes in micro-compartments, not characteristic for the general weathering process. Stage 4 is characterized by the formation of crystalline Bi-, Cu-, Ba-, Ca- or Al-bearing arsenates and Cu-carbonates, spatially independent of the precursor fahlore. Copper and As originate from older weathering assemblages, whereas many other elements are derived externally (Ca, Ba, Al). This stage reflects the increasing importance of the local host rock and gangue mineralogy, as it is typical in near-surface environments of oxidation zones or on mine dumps, where elements are highly mobile and a high fluid/rock ratio prevails (gossan mineralization).
The temporal evolution of fahlore weathering textures reflects the transition from fresh ore to cementation zone, oxidation zone and gossan assemblages in one hand specimen. Thus, one fahlore grain can record the uplift and erosion and the increasing fluid/rock interaction of a weathered ore deposit with time. Tube-like textures similar to the ones observed in stage 1 have been reported from other weathering environments and from a variety of element, oxide, arsenide, and sulfide phases. They also were produced during experimental work in ilmenite. This is clear evidence, that the diffusive process during the first contact with alteration fluids is a basic physical process and that it is not only valid for fahlore.
The importance of Bi to stabilize Sb-bearing supergene phases (and thereby for the immobilization of toxic Sb) shown in the present work, may stimulate further investigations on the environmental immobilization of toxic elements by “companion metals” during weathering processes.
Marco E. Ciriotti

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