Iron and silica systems constitute widely recognized preservation agents for mineralized biosignatures in biogeochemical environments spanning from deep-sea hydrothermal vents and metal mineralization to terrestrial sulfide mineralization subjected to supergene oxidation/weathering (gossan) (e.g. Cady and Farmer, 1996; Westall et al., 2006; Peng and Jones, 2012; Williams et al., 2015).
Here we employ mainly imaging using SEM at various resolutions with secondary electron (SE) technique, combined with energy dispersive spectroscopy (EDS) and XRD, in order to describe and evaluate morphological characteristics of mainly Fe-mineralized bio-morphous microstructures, i.e. filamentous, coccoidal and rod-shaped, as putative biosignatures, and related abiotic crystalline solids, in supergene oxidation zones of carbonate-replacement Pb-Ag-Zn mineralization, Lavrion District, Attica, Greece (Skarpelis and Argyraki, 2009).
Underground sampling included solids, streams of gravity-driven material in water flow and acid mine drainage water samples from the old underground mines of Ilarion (Mine No.50), Serpieri, Jean Baptiste (Mine No.1) and Christiana shaft (Mine No. 132) at Kamariza. Surface sampling included solids of the oxidized ore and efflorescent salts, just outside the shaft No. 160 in Plaka, Lavrion. Based on the mineralogy and mineral chemistry, the underground samples (solids and suspended particulate material) have been classified as members of the "Zone of iron oxides containing secondary ore minerals" (mainly secondary minerals of Zn, Cu and As) while surface gossan belongs to the "Zone of leached iron oxides" with prevailing goethite (Blain and Andrew, 1977).
Microscale crystal habits and mineral textures identified include: bladed (devilline, gypsum), tabular (chonichalcite, scorodite), platy (chonichalcite, muscovite, gypsum), prismatic (gypsum), rhombohedral - scalenohedral (smithsonite, hematite), orthorhombic (scorodite), wedge-like prisms (adamite), polygonal (scorodite), reniform - botryoidal (hematite, goethite, malachite), acicular (goethite, chenevixite), "orzo-like" (conichalcite), rosette-arranged (unidentified arsenate), dipyramidal (scorodite, adamite), bundled (halotrichite group minerals), fibrous (halotrichite group minerals), radiating (goethite), stalactitic (goethite), columnar (gypsum), monoclinic (gypsum) and drop/film-like efflorescences.
A number of filamentous, coccoidal and rod-shaped morphological microstructures were identified with obvious differences in structural organization from the surrounding crystal matrix and were interpreted as potential microfossils. Specifically they were interpreted as microbial filaments, coccoids and rods (bacillus), possibly of acidophilic iron-oxidizing bacteria and fungi. Additionally their associations were described as microbial colonies and the multispecies associations as microbial biofilms; and all these features were associated with EPS (extracellular polymeric substances), according to the criteria used by Westall et al (2006). The microbial filaments identified were divided into three categories: 1) Plexi of twisted filaments likely of fungal origin, 2) Multi-branching filaments connected with EPS and 3) Smooth tubular filaments, curvilinear or erect in various sizes, with the largest filament 96 κm long and the smallest just 4 κm . This interpretation resulted from the fulfillment of specific criteria for potential biogenicity (Westall et al., 2006; Williams et al., 2015) which include the geological context (i.e. gossan) that is highly plausible for microbial life and the similarity of the microstructures identified, to biological morphologies in terms of size, shape and morphological characteristics, i.e. cell division, sinuosity, shrinkage, degradation and preserved central filament lumen.
EDS spot analysis made on the different categories of filaments identified, detected only Fe and O. This is interpreted as fossilization possibly associated with Fe3+- (oxy) hydroxide coating as a result of precipitation and nucleation on preexisting bare microbial filaments (Williams et al., 2015). Secondly, the diversity and frequency of biomorphs identified in Plaka surface samples was much wider than in the underground samples in Kamariza mines. Therefore it seems that preservation depends on the level of natural leaching and it is facilitated by rising leaching of iron oxides in gossan. Finally, based on morphological similarities between our putative microfossils and those from Brick Flat Gossan, Iron Mountain, California (Williams et al., 2015), and if the Lavrion microstructures are proven biogenic on the basis of future work involving joint evidence from mineralogy, chemistry, and morphology, the Lavrion gossan may serve as a mineralogical analogue to some ancient martian environments.