Implications of Reactions Between SO2 and Basaltic Glasses for the Mineralogy of Planetary Crusts

Basalts are ubiquitous in volcanic systems on several planetary bodies, including the Earth, Mars, Venus, and Jupiter's moon Io, and are commonly associated with sulfur dioxide (SO2) degassing. We present the results of an experimental study of reactions between SO2 and basaltic glasses. We examined Fe‐free basalt, and Fe‐bearing tholeiitic and alkali basalts with a range of Fe3+/Fetotal (0.05 to 0.79) that encompass the oxygen fugacities proposed for most terrestrial planetary bodies. Tholeiitic and alkali basalts were exposed to SO2 at 600, 700, and 800 C for 1 hr and 24 hr. Surface coatings formed on the reacted basalts; these contain CaSO4, MgSO4, Na2SO4, Na2Ca(SO4)2, Fe2O3, Fe3O4, Fe‐Ti‐(Al)‐oxides, and TiO2. Additionally, the SO2‐basalt reaction drives nucleation of crystalline phases in the substrate to form pyroxenes and possible Fe‐oxides. A silica‐rich layer forms between the substrate and sulfate coatings. More oxidized basalts may readily react with SO2 to form coatings dominated by large Ca‐sulfate and oxide grains. On less oxidized basalts (NNO−1.5 to NNO−5), reactions with SO2 will form thin, fine‐grained aggregates of sulfates; such materials are less readily detected by spectroscopy and spectrometry techniques. In contrast, in very reduced basalts (lower than NNO−5), typical of the Moon and Mercury, SO2 is typically a negligible component in the magmatic gas, and sulfides are more likely.This research was supported by the Australian Research Council funding to King (DP150104604 and FT130101524). Renggli was supported by an ANU PhD scholarship. Palm was supported by the John and Kerry Lovering Scholarship (RSES, ANU). The Ion Probe Facility at the University of Western Australia is supported by the Australian Microscopy and Microanalysis Research Facility, AuScope, the Science and Industry Endowment Fund, and the State Government of Western Australia

Coping with Incomplete Data: Recent Advances

Handling incomplete data in a correct manner is a notoriously hard problem in databases. Theoretical approaches rely on the computationally hard notion of certain answers, while practical solutions rely on ad hoc query evaluation techniques based on three-valued logic. Can we find a middle ground, and produce correct answers efficiently? The paper surveys results of the last few years motivated by this question. We re-examine the notion of certainty itself, and show that it is much more varied than previously thought. We identify cases when certain answers can be computed efficiently and, short of that, provide deterministic and probabilistic approximation schemes for them. We look at the role of three-valued logic as used in SQL query evaluation, and discuss the correctness of the choice, as well as the necessity of such a logic for producing query answers

Metal remobilization and ore-fluid perturbation during episodic replacement of auriferous pyrite from an epizonal orogenic gold deposit

Mineral-scale episodic replacement of auriferous pyrite by texturally-complex pyrite, marcasite and minor arsenopyrite occurred in breccia ores from the Daqiao epizonal orogenic gold deposit, West Qinling Orogen, China. This study uses a novel combination of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), Nanoscale secondary ion mass spectrometry (NanoSIMS), and secondary ion mass spectrometry (SIMS) to investigate the remobilization and re-concentration of gold and other trace elements during this complex replacement process and the probable mechanism. Several lines of evidence including some degree of preservation of external morphology, sharp contacts and compositional differences between the parent pyrite and product pyrite and marcasite, and reaction-induced porosity suggest that the replacement of parent pyrite proceeds via a two-step replacement via a dissolution and reprecipitation mechanism, plus an additional marcasite overgrowth. During the replacement of euhedral pyrite, depletion of gold and other trace elements (Te, Se, Zn, Co, Tl, Ni, W, and As) in porous product pyrite relative to its precursor indicate exsolution and remobilization of these metals from crystal lattice of the original pyrite. In the subsequent replacement of porous pyrite by two types of marcasite and minor arsenopyrite, euhedral product marcasite contains low contents of trace elements, possibly due to high metal solubility in the acidic fluids favorable for marcasite precipitation. The complex-zoned marcasite significantly enriched in gold and other metals relative to porous pyrite (W, Tl, As, Sb, Ag, Se, and Zn) is thought to have formed via precipitation triggered by further oxidation and/or immediate reduction in threshold supersaturation. Dissolution of the impurity-rich pyrite and precipitation of new pyrite and marcasite generations could have occurred at low pH plus high concentrations of dissolved Fe2+ condition caused by partial oxidation of aqueous H2S and/or S2- in ore fluids. The fluid oxidation is evidenced by a general decreasing trend of d34S values from the parent euhedral pyrite, to product porous pyrite, euhedral marcasite, and complex-zoned marcasite. The isotopic results are consistent with ore fluid oxidation controlled by pressure fluctuations during multistage hydraulic fracturing in a fault-valve regime at Daqiao deposit. This quantitative study emphasizes that the pressure-driven hydrothermal process plays a key role in the micron- to nano-scale redistribution and re-enrichment of gold and other trace metals during episodic replacement of auriferous pyrite in brittle rheological zones from epizonal orogenic gold systems

Dissecting the Re-Os molybdenite geochronometer

Rhenium and osmium isotopes have been used for decades to date the formation of molybdenite (MoS2), a common mineral in ore deposits and the world’s main source of molybdenum and rhenium. Understanding the distribution of parent 187Re and radiogenic daughter 187Os isotopes in molybdenite is critical in interpreting isotopic measurements because it can compromise the accurate determination and interpretation of mineralization ages. In order to resolve the controls on the distribution of these elements, chemical and isotope mapping of MoS2 grains from representative porphyry copper-molybdenum deposits were performed using electron microprobe and nano-scale secondary ion mass spectrometry. Our results show a heterogeneous distribution of 185,187Re and 192Os isotopes in MoS2, and that both 187Re and 187Os isotopes are not decoupled as previously thought. We conclude that Re and Os are structurally bound or present as nanoparticles in or next to molybdenite grains, recording a complex formation history and hindering the use of microbeam techniques for Re-Os molybdenite dating. Our study opens new avenues to explore the effects of isotope nuggeting in geochronometers

Greater functional diversity and redundancy of coral endolithic microbiomes align with lower coral bleaching susceptibility.

The skeleton of reef-building coral harbors diverse microbial communities that could compensate for metabolic deficiencies caused by the loss of algal endosymbionts, i.e., coral bleaching. However, it is unknown to what extent endolith taxonomic diversity and functional potential might contribute to thermal resilience. Here we exposed Goniastrea edwardsi and Porites lutea, two common reef-building corals from the central Red Sea to a 17-day long heat stress. Using hyperspectral imaging, marker gene/metagenomic sequencing, and NanoSIMS, we characterized their endolithic microbiomes together with 15N and 13C assimilation of two skeletal compartments: the endolithic band directly below the coral tissue and the deep skeleton. The bleaching-resistant G. edwardsi was associated with endolithic microbiomes of greater functional diversity and redundancy that exhibited lower N and C assimilation than endoliths in the bleaching-sensitive P. lutea. We propose that the lower endolithic primary productivity in G. edwardsi can be attributed to the dominance of chemolithotrophs. Lower primary production within the skeleton may prevent unbalanced nutrient fluxes to coral tissues under heat stress, thereby preserving nutrient-limiting conditions characteristic of a stable coral-algal symbiosis. Our findings link coral endolithic microbiome structure and function to bleaching susceptibility, providing new avenues for understanding and eventually mitigating reef loss

Oligodendroglia are particularly vulnerable to oxidative damage after neurotrauma in vivo

Loss of function following injury to the central nervous system is worsened by secondary degeneration of neurons and glia surrounding the injury and initiated by oxidative damage. However, it is not yet known which cellular populations and structures are most vulnerable to oxidative damage in vivo Using Nanoscale secondary ion mass spectrometry (NanoSIMS), oxidative damage was semi-quantified within cellular subpopulations and structures of optic nerve vulnerable to secondary degeneration, following a partial transection of the optic nerve in adult female PVG rats. Simultaneous assessment of cellular subpopulations and structures revealed oligodendroglia as the most vulnerable to DNA oxidation following injury. 5-ethynyl-2'-deoxyuridine (EdU) was used to label cells that proliferated in the first 3 days after injury. Injury led to increases in DNA, protein and lipid damage in OPCs and mature oligodendrocytes at 3 days, regardless of proliferative state, associated with a decline in the numbers of OPCs at 7 days. O4+ pre-oligodendrocytes also exhibited increased lipid peroxidation. Interestingly, EdU+ mature oligodendrocytes derived after injury demonstrated increased early susceptibility to DNA damage and lipid peroxidation. However, EdU- mature oligodendrocytes with high 8OHdG immunoreactivity were more likely to be caspase3+. By day 28, newly derived mature oligodendrocytes had significantly reduced MYRF mRNA indicating that the myelination potential of these cells may be reduced. The proportion of caspase3+ oligodendrocytes remained higher in EdU- cells. Innovative use of NanoSIMS together with traditional immunohistochemistry and in situ hybridisation have enabled the first demonstration of subpopulation specific oligodendroglial vulnerability to oxidative damage, due to secondary degeneration in vivo. SIGNIFICANCE STATEMENT. Injury to the central nervous system is characterised by oxidative damage in areas adjacent to the injury. However, the cellular subpopulations and structures most vulnerable to this damage remain to be elucidated. Here we use powerful NanoSIMS techniques to show increased oxidative damage in oligodendroglia and axons and to demonstrate that cells early in the oligodendroglial lineage are the most vulnerable to DNA oxidation. Further immunohistochemical and in situ hybridisation investigation reveals that mature oligodendrocytes derived after injury are more vulnerable to oxidative damage than their counterparts existing at the time of injury and have reduced MYRF mRNA, yet pre-existing oligodendrocytes are more likely to die

Subcellular view of host-microbiome nutrient exchange in sponges: insights into the ecological success of an early metazoan-microbe symbiosis.

BackgroundSponges are increasingly recognised as key ecosystem engineers in many aquatic habitats. They play an important role in nutrient cycling due to their unrivalled capacity for processing both dissolved and particulate organic matter (DOM and POM) and the exceptional metabolic repertoire of their diverse and abundant microbial communities. Functional studies determining the role of host and microbiome in organic nutrient uptake and exchange, however, are limited. Therefore, we coupled pulse-chase isotopic tracer techniques with nanoscale secondary ion mass spectrometry (NanoSIMS) to visualise the uptake and translocation of 13C- and 15N-labelled dissolved and particulate organic food at subcellular level in the high microbial abundance sponge Plakortis angulospiculatus and the low microbial abundance sponge Halisarca caerulea.ResultsThe two sponge species showed significant enrichment of DOM- and POM-derived 13C and 15N into their tissue over time. Microbial symbionts were actively involved in the assimilation of DOM, but host filtering cells (choanocytes) appeared to be the primary site of DOM and POM uptake in both sponge species overall, via pinocytosis and phagocytosis, respectively. Translocation of carbon and nitrogen from choanocytes to microbial symbionts occurred over time, irrespective of microbial abundance, reflecting recycling of host waste products by the microbiome.ConclusionsHere, we provide empirical evidence indicating that the prokaryotic communities of a high and a low microbial abundance sponge obtain nutritional benefits from their host-associated lifestyle. The metabolic interaction between the highly efficient filter-feeding host and its microbial symbionts likely provides a competitive advantage to the sponge holobiont in the oligotrophic environments in which they thrive, by retaining and recycling limiting nutrients. Sponges present a unique model to link nutritional symbiotic interactions to holobiont function, and, via cascading effects, ecosystem functioning, in one of the earliest metazoan-microbe symbioses. Video abstract

Characterisation of metakaolin-based geopolymers using beam-based and conventional PALS.

The nano-porosity of metakaolin-based geopolymers and the effect of heat-treatment on porosity have been studied with conventional and beam-based positron annihilation lifetime spectroscopy (PALS). Conventional PALS found significant nano-porosity in the geopolymers, as indicated by the presence in the PALS spectrum of two long lifetime components, τ3 = 1.58 ns and τ4 = 47 ns, associated with pore diameters of approximately 0.5 and 3 nm respectively. The lifetime of the shorter component was found to decrease monotonically with successive heat treatments of 300°C and 600°C. Beam-based PALS, conducted at 5 keV, also indicated two long lifetime components, τ3 = 4.84 ns and τ4 = 54.6 ns. These are significantly longer than those observed by conventional PALS and the monotonic decrease of τ3 with successive heat treatments was not observed. As the beam-based PALS probed only the near-surface region, with an average implantation depth of about 350 nm, these results suggest that the near-surface structure may vary significantly from that of the bulk. This could be an inherent property of the samples or an artefact caused by surface effects or sample outgassing.ARC Centre for Antimatter-Matter Studies; Australian National University (ANU); Flinders University; James Cook University (JCU); The Institute of Physics; Australian Government Department of Innovation, Industry, Science and Researc

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

Production of radionuclide-free copper concentrates is dependent on understanding and controlling the deportment of daughter radionuclides (RNs) produced from 238U decay, specifically 226Ra, 210Pb, and 210Po. Sulfuric acid leaching is currently employed in the Olympic Dam processing plant (South Australia) to remove U and fluorine from copper concentrates prior to smelting but does not adequately remove the aforementioned RN. Due to chemical similarities between lead and alkaline earth metals (including Ra), two sets of experiments were designed to understand solution interactions between Sr, Ba, and Pb at various conditions. Nanoscale secondary ion mass spectrometry (NanoSIMS) isotopic spatial distribution maps and laser ablation inductively coupled-plasma mass spectrometry transects were performed on laboratory-grown crystals of baryte, celestite, and anglesite which had been exposed to different solutions under different pH and reaction time conditions. Analysis of experimental products reveals three uptake mechanisms: overgrowth of nearly pure SrSO4 and PbSO4 on baryte; incorporation of minor of Pb and Ba into celestite due to diffusion; and extensive replacement of Pb by Sr (and less extensive replacement of Pb by Ba) in anglesite via coupled dissolution-reprecipitation reactions. The presence of H2SO4 either enhanced or inhibited these reactions. Kinetic modelling supports the experimental results, showing potential for extrapolating the (Sr, Ba, Pb)SO4 system to encompass RaSO4. Direct observation of grain-scale element distributions by nanoSIMS aids understanding of the controlling conditions and mechanisms of replacement that may be critical steps for Pb and Ra removal from concentrates by allowing construction of a cationic replacement scenario targeting Pb or Ra, or ideally all insoluble sulfates. Experimental results provide a foundation for further investigation of RN uptake during minerals processing, especially during acid leaching. The new evidence enhances understanding of micro- to nanoscale chemical interactions and not only aids determination of where radionuclides reside during each processing stage but also guides development of flowsheets targeting their removal.Mark Rollog, Nigel J. Cook, Paul Guagliardo, Kathy Ehrig, Sarah E. Gilbert and Matt Kilbur