The role of aluminium in the preservation of microbial biosignatures

Demonstrating the biogenicity of presumptive microfossils in the geological record often requires supporting chemical signatures, including isotopic signatures. Understanding the mechanisms that promote the preservation of microbial biosignatures associated with microfossils is fundamental to unravelling the palaeomicrobiological history of the material. Organomineralization of microorganisms is likely to represent the first stages of microbial fossilisation and has been hypothesised to prevent the autolytic degradation of microbial cell envelope structures. In the present study, two distinct fossilisation textures(permineralised microfossils and iron oxide encrusted cell envelopes)identified throughout iron-rich rock samples were analysed using nanoscale secondary ion mass spectrometry(NanoSIMS). In this system, aluminium is enriched around the permineralised microfossils, while iron is enriched within the intracellularly, within distinct cell envelopes. Remarkably,while cell wall structures are indicated, carbon and nitrogen biosignatures are not preserved with permineralised microfossils. Therefore, the enrichment of aluminium, delineating these microfossils appears to have been critical to their structural preservation in this iron-rich environment. In contrast,NanoSIMS analysis of mineral encrusted cell envelopes reveals that preserved carbon and nitrogen biosignatures are associated with the cell envelope structures of these microfossils. Interestingly, iron is depleted in regions where carbon and nitrogen are preserved. In contrast aluminium appears to be slightly enriched in regions associated with remnant cell envelope structures. The correlation of aluminium with carbon and nitrogen biosignatures suggests the complexation of aluminium with preserved cell envelope structures before or immediately after cell death may have inactivated autolytic activity preventing the rapid breakdown of these organic, macromolecular structures.Combined, these results highlight that aluminium may play an important role in the preservation of microorganisms within the rock record.     

The golden ark: arsenopyrite crystal plasticity and the retention of gold through high strain and metamorphism

Quantitative electron backscatter diffraction analysis and ion microprobe imaging of gold‐rich arsenopyrites provide the first insights into the crystal plasticity and element mobility behaviour of arsenopyrites through metamorphism (340°–460° and 2 kbar). Remarkably, the gold‐rich arsenopyrites remained structurally and chemically robust during high strain deformation. It was only during a superimposed lower strain deformation event, at a high angle to the preferred orientation of the arsenopyrites, that small amounts of crystal plasticity affected the arsenopyrites. During the low strain event, a dissolution–reprecipitation reaction resulted in loss of gold from the crystal lattice, facilitated by localised domains of recrystallisation, most likely due to fluid percolation along sub‐ and new grain boundaries. We suggest that the abundance and rheologically robust nature of gold‐rich arsenopyrite in giant gold deposits, affected by greenschist–amphibolite metamorphism, is actually critical in the preservation of those deposits.     

Intermobility of barium,strontium, and lead in chloride and sulfate leach solutions

Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2–0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t_50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t_50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.