The role of volcanic-derived clays in the preservation of Ediacaran biota from the Itajaí Basin (ca. 563 Ma, Brazil).

The early evolution of metazoans has been reconstructed by studies on exceptionally preserved molds in siliciclastic rocks from the Ediacaran Period. However, there remains considerable controversy regarding the formation mechanisms of this unusual 'Ediacaran-style' preservation. Proposed hypotheses usually include early authigenesis of minerals, but evidence for this is scarce. In a recently discovered deposit of Ediacaran biota in Brazil, we show that the classic moldic preservation is related to clay mineral authigenesis. Specifically, these clays originated from the alteration of original pyroclastic sediments, likely enhanced by microbial activity, leading to early illitization and morphological templating of the fossiliferous surfaces at a micrometric scale. Such high-fidelity preservation was made possible by rapid burial during volcanic events and the in-situ templating of tissue by clays via microbially-mediated mineralization. This newly described Lagerstätte demonstrates that a number of minerals can facilitate preservation, and that perhaps 'Ediacaran-style' preservation result from different processes leading to the same broad style of preservation.

A 571 million-year-old alkaline volcanic lake photosynthesizing microbial community, the Anti-atlas, Morocco.

The Ediacaran period coincides with the emergence of ancestral animal lineages and cyanobacteria capable of thriving in nutrient deficient oceans which together with photosynthetic eukaryotic dominance, culminated in the rapid oxygenation of the Ediacaran atmosphere. However, ecological evidence for the colonization of the Ediacaran terrestrial biosphere by photosynthetic communities and their contribution to the oxygenation of the biosphere at this time is very sparse. Here, we expand the repertoire of Ediacaran habitable environments to a specific microbial community that thrived in an extreme alkaline volcanic lake 571 Myr ago in the Anti-atlas of Morocco. The microbial fabrics preserve evidence of primary growth structures, comprised of two main microbialitic units, with the lower section consisting of irregular and patchy thrombolytic mesoclots associated with composite microbialitic domes. Calcirudite interbeds, dominated by wave-rippled sandy calcarenites and stromatoclasts, fill the interdome troughs and seal the dome tops. A meter-thick epiclastic stromatolite bed grading upwards from a dominantly flat to wavy laminated base, transitions into low convex laminae consisting of decimeter to meter-thick dome-shaped stromatolitic columns, overlies the thrombolitic and composite microbialitic facies. Microbialitic beds constructed during periods of limited clastic input, and underlain by coarse-grained microbialite-derived clasts and by the wave-rippled calcarenites, suggest high-energy events associated with lake expansion. High-resolution microscopy revealed spherulitic aggregates and structures reminiscent of coccoidal microbial cell casts and mineralized extra-polymeric substances (EPS). The primary fabrics and multistage diagenetic features, represented by active carbonate production, photosynthesizing microbial communities, photosynthetic gas bubbles, gas escape structures, and tufted mats, suggest specialized oxygenic photosynthesizers thriving in alkaline volcanic lakes, contributed toward oxygen variability in the Ediacaran terrestrial biosphere.

Organism motility in an oxygenated shallow-marine environment 2.1 billion years ago.

Evidence for macroscopic life in the Paleoproterozoic Era comes from 1.8 billion-year-old (Ga) compression fossils [Han TM, Runnegar B (1992) Science 257:232-235; Knoll et al. (2006) Philos Trans R Soc Lond B 361:1023-1038], Stirling biota [Bengtson S et al. (2007) Paleobiology 33:351-381], and large colonial organisms exhibiting signs of coordinated growth from the 2.1-Ga Francevillian series, Gabon. Here we report on pyritized string-shaped structures from the Francevillian Basin. Combined microscopic, microtomographic, geochemical, and sedimentologic analyses provide evidence for biogenicity, and syngenicity and suggest that the structures underwent fossilization during early diagenesis close to the sediment-water interface. The string-shaped structures are up to 6 mm across and extend up to 170 mm through the strata. Morphological and 3D tomographic reconstructions suggest that the producer may have been a multicellular or syncytial organism able to migrate laterally and vertically to reach food resources. A possible modern analog is the aggregation of amoeboid cells into a migratory slug phase in cellular slime molds at times of starvation. This unique ecologic window established in an oxygenated, shallow-marine environment represents an exceptional record of the biosphere following the crucial changes that occurred in the atmosphere and ocean in the aftermath of the great oxidation event (GOE).

Organic matter interactions with natural manganese oxide and synthetic birnessite.

Redox reactions of inorganic and organic contaminants on manganese oxides have been widely studied. However, these reactions are strongly affected by the presence of natural organic matter (NOM) at the surface of the manganese oxide. Interestingly, the mechanism behind NOM adsorption onto manganese oxides remains unclear. Therefore, in this study, the adsorption kinetics and equilibrium of different NOM isolates to synthetic manganese oxide (birnessite) and natural manganese oxide (Mn sand) were investigated. Natural manganese oxide is composed of both amorphous and well-crystallised Mn phases (i.e., lithiophorite, birnessite, and cryptomelane). NOM adsorption on both manganese oxides increased with decreasing pH (from pH7 to 5), in agreement with surface complexation and ligand exchange mechanisms. The presence of calcium enhanced the rate of NOM adsorption by decreasing the electrostatic repulsion between NOM and Mn sand. Also, the adsorption was limited by the diffusion of NOM macromolecules through the Mn sand pores. At equilibrium, a preferential adsorption of high molecular weight molecules enriched in aromatic moieties was observed for both the synthetic and natural manganese oxide. Hydrophobic interactions may explain the adsorption of organic matter on manganese oxides. The formation of low molecular weight UV absorbing molecules was detected with the synthetic birnessite, suggesting oxidation and reduction processes occurring during NOM adsorption. This study provides a deep insight for both environmental and engineered systems to better understand the impact of NOM adsorption on the biogeochemical cycle of manganese.

Effect of low frequency ultrasound on the surface properties of natural aluminosilicates.

Structural and surface properties of different natural aluminosilicates (layered, chain and framework structural types) exposed of 20 kHz ultrasound irradiation (0-120 min) in aqueous and 35 wt%. aqueous H2O2 dispersions were studied by X-ray diffraction (XRD), dynamic light scattering (DLS), nitrogen adsorption-desorption, thermal analysis, and Fourier transform infrared spectroscopy (FTIR) techniques. It was confirmed that sonication caused slight changes in the structure of investigated minerals whereas their textural properties were significantly affected. The aqueous dispersions of montmorillonite (Mt), clinoptilolite (Zlt), glauconite (Glt) and palygorskite (Pal) were represented by several particles size fractions according to DLS-study. Ultrasound irradiation produced a decrease of the average particle diameter by 4-6 times in water and by 1.3-5 times in H2O2 dispersions except for Pal, which underwent strong agglomeration. A significant increase of total pore volume and pore diameter was observed for Glt sonicated in H2O2 dispersions whereas for Pal mainly micropore volume sharply increased in both aqueous and H2O2 dispersions.

The 2.1 Ga old Francevillian biota: biogenicity, taphonomy and biodiversity.

The Paleoproterozoic Era witnessed crucial steps in the evolution of Earth's surface environments following the first appreciable rise of free atmospheric oxygen concentrations ∼2.3 to 2.1 Ga ago, and concomitant shallow ocean oxygenation. While most sedimentary successions deposited during this time interval have experienced thermal overprinting from burial diagenesis and metamorphism, the ca. 2.1 Ga black shales of the Francevillian B Formation (FB2) cropping out in southeastern Gabon have not. The Francevillian Formation contains centimeter-sized structures interpreted as organized and spatially discrete populations of colonial organisms living in an oxygenated marine ecosystem. Here, new material from the FB2 black shales is presented and analyzed to further explore its biogenicity and taphonomy. Our extended record comprises variably sized, shaped, and structured pyritized macrofossils of lobate, elongated, and rod-shaped morphologies as well as abundant non-pyritized disk-shaped macrofossils and organic-walled acritarchs. Combined microtomography, geochemistry, and sedimentary analysis suggest a biota fossilized during early diagenesis. The emergence of this biota follows a rise in atmospheric oxygen, which is consistent with the idea that surface oxygenation allowed the evolution and ecological expansion of complex megascopic life.

Large colonial organisms with coordinated growth in oxygenated environments 2.1 Gyr ago.

The evidence for macroscopic life during the Palaeoproterozoic era (2.5-1.6 Gyr ago) is controversial. Except for the nearly 2-Gyr-old coil-shaped fossil Grypania spiralis, which may have been eukaryotic, evidence for morphological and taxonomic biodiversification of macroorganisms only occurs towards the beginning of the Mesoproterozoic era (1.6-1.0 Gyr). Here we report the discovery of centimetre-sized structures from the 2.1-Gyr-old black shales of the Palaeoproterozoic Francevillian B Formation in Gabon, which we interpret as highly organized and spatially discrete populations of colonial organisms. The structures are up to 12 cm in size and have characteristic shapes, with a simple but distinct ground pattern of flexible sheets and, usually, a permeating radial fabric. Geochemical analyses suggest that the sediments were deposited under an oxygenated water column. Carbon and sulphur isotopic data indicate that the structures were distinct biogenic objects, fossilized by pyritization early in the formation of the rock. The growth patterns deduced from the fossil morphologies suggest that the organisms showed cell-to-cell signalling and coordinated responses, as is commonly associated with multicellular organization. The Gabon fossils, occurring after the 2.45-2.32-Gyr increase in atmospheric oxygen concentration, may be seen as ancient representatives of multicellular life, which expanded so rapidly 1.5 Gyr later, in the Cambrian explosion.

Formation of methyl iodide on a natural manganese oxide.

This paper demonstrates that manganese oxides can initiate the formation of methyl iodide, a volatile compound that participates to the input of iodine into the atmosphere. The formation of methyl iodide was investigated using a natural manganese oxide in batch experiments for different conditions and concentrations of iodide, natural organic matter (NOM) and manganese oxide. Methyl iodide was formed at concentrations