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.     

Symplectite formation in the presence of a reactive fluid: insights from hydrothermal experiments

This study describes the microstructural and chemical development of symplectites, obtained in fluid‐mediated mineral replacement experiments. During the experiments polymineralic feldspar‐rich samples were exposed to aqueous Na–SiO₂ solution at 600 °C and 2 kbar confining pressures for durations of 12 h to 20 days. The resulting reaction rims display high mineralogical and structural complexity and contain two varieties of symplectites, represented by nanometre‐scale intergrowths of gehlenite–zeolite and grossular–zeolite grains. The experimental fluid was enriched in ¹⁸O isotope in order to trace oxygen redistribution during the reaction. The elevated ¹⁸O concentration in the reaction products and the heterogeneity in its distribution suggest that symplectite formation was controlled by dissolution–precipitation mechanisms rather than volume‐diffusion processes. Microstructural and chemical observations suggest that symplectite formation occurred in multiple stages in response to spatially heterogeneous and temporarily evolving fluid composition at the reaction interfaces. Hence, our results shed light on the fundamental processes involved in symplectite formation improving our ability to interpret symplectite microstructures.     

The effect of silica activity on the diffusion of Ni and Co in olivine

The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg₂SiO₄) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO₂ and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D _M (M = Ni or Co) for the combined data set can be fitted to the equation:

$$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$

with E_a(Ni) = ? 284.3 kJ mol^?1 and E_a(Co) = ? 275.9 kJ mol^?1, with an uncertainty of ±10.2 kJ mol^?1. This equation fits the data (24 experiments) to ±0.1 in log D _M. The dependence of diffusion on \(a_{{{\text{SiO}}_{2} }}\) is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg_1.8Fe_0.2SiO₄ at 1,300 °C give a slightly small dependence on \(a_{{{\text{SiO}}_{2} }}\), with D \(\propto\) (\(a_{{{\text{SiO}}_{2} }}^{0.5}\)), presumably because the Mg-site vacancies increase with incorporation of Fe³⁺ in the Fe-bearing olivines. However, the dependence on fO₂ is small, with D \(\propto\) (fO₂)^0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO₂ magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO₂ magmas, such as tholeiitic basalts, at equal temperatures and fO₂.

     

Tycho's Star and the supernov ae of Uranographia Britannica

Kevin J Kilburn describes how a recently discovered 18th century star atlas can shed new light on old supernovae.
The discovery in the library of Manchester Astronomical Society of a first impression of John Bevis's Uranographia Britannica has led to a reappraisal of these early observations. In particular, his observations of Tycho's Star suggest a new interpretation of the supernovae responsible.     

Forecasting volcanic events: some contemporary issues

As the regions around active volcanoes succumb to large increases in population, particularly in the developing world where most of the high-risk volcanoes are located, the threat posed by eruptions becomes increasingly serious. Improvements in eruption forecasting are critical to combat this situation, for reducing injury and loss of life, and for minimizing the detrimental effects to local economies and to the fabric of society. Better-constrained forecasts are strongly dependent on geophysical and other data gathered during a program of volcano surveillance, and we reveal how, if interpreted in terms of static rock fracturing, analysis of changes in volcanic seismicity and ground deformation may be used to forecast more accurately the onset of eruptive activity. As illustrated by recent events at several volcanoes, studies of previous activity, increased levels of monitoring, and improved training of scientists are also all crucial to improving forecasts of impending eruptions.     

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.

     

Earliest microbially mediated pyrite oxidation in ~ 3.4 billion-year-old sediments

Pyrite (FeS₂) oxidation in modern sedimentary environments is neither a purely chemical nor purely microbial process, but it is significantly enhanced by the activity of microorganisms that use reduced forms of iron and sulphur in their metabolisms. On the early Earth, where oxygen levels were thought to be < 10^?5 of the present atmospheric level and chemical oxidants scarce, such biological mediation may have been critical in the redox cycles of iron and sulphur. Here, we show that detrital sedimentary pyrite grains in a ~ 3.4 billion-year-old sandstone were colonised by microbial communities. The detrital pyrite comes from the basal quartz arenite member of the 3.43–3.35 Ga Strelley Pool Formation (SPF) in the East Strelley greenstone belt of the Pilbara Craton, Western Australia. Rock chips and petrographic thin sections of black sandstones occurring on two ridges close to the SPF type locality of Strelley Pool were investigated using optical microscopy, SEM, TEM, laser Raman and NanoSIMS. The detrital pyrite grains exhibit laminated carbonaceous coatings of early Archean age, with localised enrichments of nitrogen that are interpreted as the in situ remains of biofilms growing on these nutrient-rich minerals. Pyrite surfaces contain spherical pits, chains of pits and channels that are morphologically distinct from abiotic alteration features. The pits and channels are widespread, have a clustered distribution typical of microbial colonisation, and are closely comparable to biologically mediated microstructures in the younger rock record and those created by extant Fe- and S-oxidising microbes in the laboratory. They are thus interpreted as trace fossils formed by the attachment of bacteria to the pyrite surfaces. A nano-layer and discreet nano-grains of secondary mineral precipitates, namely Fe-oxides belonging to the magnetite-maghaemite group, attest to pyrite oxidation. These are intimately associated with the biofilms and trace fossils, and are interpreted to represent the fossilised mineral products of biologically mediated pyrite oxidation. These data extend the geological range of microbes capable of metabolising reduced Fe and/or S compounds back to the early Archean and indicate that pyrite-rich sedimentary rocks provide promising targets in the search for extraterrestrial life.     

Rock fracture as a precursor to lava dome eruptions at Mount St Helens from June 1980 to October 1986

Following its plinian eruption on 18 May 1980, Mount St Helens (Washington State, USA) entered a period of intermittent lava-dome extrusion until 1986. Renewed extrusion was frequently preceded by accelerating rates of seismicity, with more precursory seismicity observed prior to eruptions later in the sequence. Here the failure forecasting method (FFM) is used to investigate changes in the observed rate of volcano–tectonic (VT) seismicity. The analysis indicates that: (1) all VT crises resulted in an eruption within 3 weeks (usually less than 10 days), (2) the majority of eruptions had VT precursors, and (3) patterns of precursory seismicity showed fluctuations about the ideal model trend. Thus, although these seismic events could be used to warn of an impending eruption, specific forecasts were subject to an uncertainty of weeks or more. It is proposed that: (1) increased seismicity prior to later eruptions is a result of a larger and more solidified dome acting as a greater impediment to magma ascent; (2) the consistency of seismic swarms resulting in an eruption indicates that stresses high enough to initiate fracturing in the country rock and lava dome carapace were only achieved once the approach to an eruption had already begun; and (3) discrepancies between models of accelerating rock fracture and the observed seismicity may arise due to a significant amount of the rocks deforming through ductile mechanisms rather than seismogenic fracture.