Supergene mineral assemblage from sediments affected by contact and hydrothermal metamorphism, locality Dobrá – Staré Město near Frýdek-Místek (Czech Republic)

Abstract

At locality Dobrá – Staré Město, series of outcrops occur on both banks of the Morávka River. The river cuts through the sediments on the tectonic contact between the Silesian and Subsilesian units of the Outer Western Carpathians. Clayey facies of the Hradiště Formation (Early Cretaceous, Valanginian to Aptian) contains numerous tectonic fragments reaching hundreds meters in size of strongly altered (carbonatized, smectitized) subaquatic volcanic rocks of the Teschenite Association. These volcanic rocks are dominated by fine-grained to aphanitic rocks, possibly of both effusive and intrusive origin. The host sediments affected by the contact metamorphism (contact adinole) also occur. Framboidal pyrite is abundant in majority of sediments of the studied area, giving rise to efflorescences of gypsum, baryte, celestine, and a mineral of alunite group (Figure 1). A more varied assemblage of supergene minerals was recognized on a small rock outcrop at GPS coordinates N 49° 39.992’ E 018° 23.810’ (Figure 2), where it developed relatively recently after the big floods in 2010 that washed away the previous mineralization. During the first years, only gypsum crusts were detectable, while in 2023, we recognized 4 macroscopic and 5 microscopic minerals forming thin botryoidal crusts. These crusts show faint zoning, with gooey, gel-like X-ray amorphous material in the humid upper part , middle zone with abundant fibroferrite and the lower part dominated by gypsum. Gypsum forms well-developed, but frequently corroded crystals with various habitus (Figure 4A, B). Fibroferrite is present as fibrous aggregates with individual crystals of up to ca. 100–150 µm long and <1 µm thick (Figure 4C). It forms directly from the gel-like substance (Figure 4D). Rhombohedral crystals and rossete aggregates of hydroniumjarosite vary from 2 µm to 5 µm in size (Figure 4E), but the most common are dust-like coatings on rock fissures with particle size <1 µm. Rusty coatings of schwertmannite (Figure 4F), in some places accompanied by gypsum, with Fe/S at. % ratios near 4–5 are common. In some cases, the Al/Fe at. % ratio exceed 1, which might indicate presence of yet undescribed Al-analogue of schwertmannite, ill-defined alumogel, or an amorphous precursor of aluminite. Presence of ferrihydrite is possible but not confirmed. The above-mentioned Fe-rich phases are frequently accompanied by diplobacilli-shaped bacteria (Figure 4F). Slavíkite, pickeringite-halotrichite, alunogen, copiapite group mineral, hexahydrite, and melanterite (Figure 5) were also recognized by EDS and PXRD. Slavíkite and copiapite group minerals seem to be alteration products of fibroferrite. Unit-cell parameters refined from the X-ray powder diffraction are presented for all recognized phases (Table 1). Surprisingly, secondary sulfates are present on the metasediments with abundant calcite (Figure 3), which should serve as a neutralization buffer. The reason is the restricted amount of calcite available on the rock fissure surfaces, and water infiltration partially blocked by newly-formed gypsum. The albite in contact adinole (Figure 3) is unaffected by the acid rock drainage, since Na ions are not present in significant quantities in supergene phases. Since there is still enough available unaltered pyrite, we expect a shift towards more stable mineral assemblage in future. The limited amount of secondary sulfates does not present any significant harm to the environment.