Gold Ores Related to Shear Zones, West Santa Comba Fervenza Area (Galicia, NW Spain): A Mineralogical Study

Recent research has discovered high-grade Au ores in NNE-SSW trending shear zones in metamorphic proterozoic and palaeozoic terranes, some 40 km NW of Santiago de Compostela (NW Spain). The orebodies are bound to late-stage Hercynian structures, mainly due to brittle deformation, which are superimposed on earlier ductile shear zones, cutting through various catazonal lithologies, including ortho- and paragneisses, amphibolites, eclogites, and granites. Ore mineralogy, alteration, and ore textures define a frame whose main features are common to all prospects in the area. Main minerals are arsenopyrite and pyrite - accompanied by quartz, adularia, sericite, + (tourmaline, chlorite, carbonates, graphite), as main gangue minerals - with subordinate amounts of boulangerite, bismuthinite, kobellite, jamesonite, chalcopyrite, marcasite, galena, sphalerite, rutile, titanite, scheelite, beryl, fluorite, and minor native gold, electrum, native bismuth, fahlore, pyrrhotite, mackinawite, etc., defining a meso-catathermal paragenesis. Detailed microscopic study allows the author to propose a general descriptive scheme of textural classification for this type of ore. Most of the ores fill open spaces or veins, seal cracks or cement breccias; disseminated ores with replacement features related to alteration (mainly silicification, sericitization, and adularization) are also observed. Intensive and repeated cataclasis is a common feature of many ores, suggesting successive events of brittle deformation, hydrothermal flow, and ore precipitation. Gold may be transported and accumulated in any of these events, but tends to be concentrated in later ones. The origin of the gold ores is explained in terms of hydrotherreal discharge, associated with mainly brittle deformation and possibly related to granitic magmas, in the global tectonic frame of crustal evolution of West Galicia. The mineralogical and textural study suggests some criteria which will be of practical value for exploration and for ore processing. Ore grades can be improved by flotation of arsenopyrite. Non-conventional methods, such as pressure or bacterial leaching, may subsequently obtain a residue enriched in gold.

Biochemical evolution II: Origin of life in tubular microstructures on weathered feldspar surfaces

Mineral surfaces were important during the emergence of life on Earth because the assembly of the necessary complex biomolecules by random collisions in dilute aqueous solutions is implausible. Most silicate mineral surfaces are hydrophilic and organophobic and unsuitable for catalytic reactions, but some silica-rich surfaces of partly dealuminated feldspars and zeolites are organophilic and potentially catalytic. Weathered alkali feldspar crystals from granitic rocks at Shap, north west England, contain abundant tubular etch pits, typically 0.4–0.6 μm wide, forming an orthogonal honeycomb network in a surface zone 50 μm thick, with 2–3 × 106 intersections per mm2 of crystal surface. Surviving metamorphic rocks demonstrate that granites and acidic surface water were present on the Earth’s surface by ∼3.8 Ga. By analogy with Shap granite, honeycombed feldspar has considerable potential as a natural catalytic surface for the start of biochemical evolution. Biomolecules should have become available by catalysis of amino acids, etc. The honeycomb would have provided access to various mineral inclusions in the feldspar, particularly apatite and oxides, which contain phosphorus and transition metals necessary for energetic life. The organized environment would have protected complex molecules from dispersion into dilute solutions, from hydrolysis, and from UV radiation. Sub-micrometer tubes in the honeycomb might have acted as rudimentary cell walls for proto-organisms, which ultimately evolved a lipid lid giving further shelter from the hostile outside environment. A lid would finally have become a complete cell wall permitting detachment and flotation in primordial “soup.” Etch features on weathered alkali feldspar from Shap match the shape of overlying soil bacteria.

The origin of atmospheric oxygen on Earth: The innovation of oxygenic photosynthesis

The evolution of O2-producing cyanobacteria that use water as terminal reductant transformed Earth's atmosphere to one suitable for the evolution of aerobic metabolism and complex life. The innovation of water oxidation freed photosynthesis to invade new environments and visibly changed the face of the Earth. We offer a new hypothesis for how this process evolved, which identifies two critical roles for carbon dioxide in the Archean period. First, we present a thermodynamic analysis showing that bicarbonate (formed by dissolution of CO2) is a more efficient alternative substrate than water for O2 production by oxygenic phototrophs. This analysis clarifies the origin of the long debated “bicarbonate effect” on photosynthetic O2 production. We propose that bicarbonate was the thermodynamically preferred reductant before water in the evolution of oxygenic photosynthesis. Second, we have examined the speciation of manganese(II) and bicarbonate in water, and find that they form Mn-bicarbonate clusters as the major species under conditions that model the chemistry of the Archean sea. These clusters have been found to be highly efficient precursors for the assembly of the tetramanganese-oxide core of the water-oxidizing enzyme during biogenesis. We show that these clusters can be oxidized at electrochemical potentials that are accessible to anoxygenic phototrophs and thus the most likely building blocks for assembly of the first O2 evolving photoreaction center, most likely originating from green nonsulfur bacteria before the evolution of cyanobacteria.

Biochemical evolution III: Polymerization on organophilic silica-rich surfaces, crystal–chemical modeling, formation of first cells, and geological clues

Catalysis at organophilic silica-rich surfaces of zeolites and feldspars might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and other geological sources. Crystal–chemical modeling yielded packings for amino acids neatly encapsulated in 10-ring channels of the molecular sieve silicalite-ZSM-5-(mutinaite). Calculation of binding and activation energies for catalytic assembly into polymers is progressing for a chemical composition with one catalytic Al–OH site per 25 neutral Si tetrahedral sites. Internal channel intersections and external terminations provide special stereochemical features suitable for complex organic species. Polymer migration along nano/micrometer channels of ancient weathered feldspars, plus exploitation of phosphorus and various transition metals in entrapped apatite and other microminerals, might have generated complexes of replicating catalytic biomolecules, leading to primitive cellular organisms. The first cell wall might have been an internal mineral surface, from which the cell developed a protective biological cap emerging into a nutrient-rich “soup.” Ultimately, the biological cap might have expanded into a complete cell wall, allowing mobility and colonization of energy-rich challenging environments. Electron microscopy of honeycomb channels inside weathered feldspars of the Shap granite (northwest England) has revealed modern bacteria, perhaps indicative of Archean ones. All known early rocks were metamorphosed too highly during geologic time to permit simple survival of large-pore zeolites, honeycombed feldspar, and encapsulated species. Possible microscopic clues to the proposed mineral adsorbents/catalysts are discussed for planning of systematic study of black cherts from weakly metamorphosed Archaean sediments.