Experimental partitioning of Tc, Mo, Ru, and Re between solid and liquid during crystallization in Fe-Ni-S

Technetium isotopes ⁹⁷Tc, ⁹⁸Tc and ⁹⁹Tc decay to ⁹⁷Mo, ⁹⁸Ru and ⁹⁹Ru, with half-lives of 2.6 My, 4.1 My, and 0.21 My respectively. If there were early solar system processes that resulted in significant fractionation of Tc from the daughter elements, decay of extant Tc could have led to the creation of Mo and Ru isotopic heterogeneities. To assess the potential of metallic core crystallization to fractionate these elements, we examine the partitioning behavior of Tc relative to Re, Mo and Ru in the Fe-Ni-S system between solid metal and liquid metal alloy. The experimental evidence shows that Tc behaves more like the modestly compatible siderophile element Ru than the more highly compatible siderophile element Re, and that Tc is substantially more compatible than Mo. We also demonstrate a pressure effect in the partitioning of Mo during the crystallization of Fe-Ni-S melts. For a sulfur concentration in the liquid fraction of the core of 10 wt% (16.3 at%), the Jones and Malvin (1990) parameter is −ln(1-2 × 1.09 × 0.163) ≅ 0.44, which yields: D(Re) ≅ 4.1; D(Ru) ≅ 2.3; D(Tc) ≅ 1.7; D(Mo)_Lo-P ≅ 1.0;.and D(Mo)_Hi-P ≅ 0.5. Our results suggest that detectable Tc-induced isotopic anomalies (≥0.1 ε unit) in Ru and Mo could only be produced by unrealistically extreme degrees of crystallization of metal during asteroidal core fractionation, regardless of the time scales and initial Tc abundances involved.     

Barite deposition resulting from phototrophic sulfide-oxidizing bacterial activity

Barite (BaSO₄) deposits generally arise from mixing of soluble barium-containing fluids with sulfate-rich fluids. While the role of biological processes in modulating barium solubility has been shown, no studies have shown that the biological oxidation of sulfide to sulfate leads to barite deposition. Here we present an example of microbially mediated barite deposition in a continental setting. A spring in the Anadarko Basin of southwestern Oklahoma produces water containing abundant barium and sulfide. As emergent water travels down a stream to a nearby creek, sulfate concentration increases from 0.06 mM to 2.2 mM while Ba²⁺ concentration drops from 0.4 mM to less than 7 μM. Stable isotope analysis, microbial activity studies, and in situ experiments provide evidence that as sulfide-rich water flows down the stream, anaerobic, anoxygenic, phototrophic bacteria play a dominant role in oxidizing sulfide to sulfate. Sulfate then precipitates with Ba²⁺ producing barite as travertine, cements, crusts, and accumulations on microbial mats. Our studies suggest that phototrophic sulfide oxidation and concomitant sulfur cycling could prove to be important processes regulating the cycling of barium in continental sulfur-containing systems.     

Exhumation of high-pressure rocks of the Kokchetav massif: facts and models

The exhumation of ultrahigh-pressure (UHP) metamorphic units from depths more than 100-120 km is one of the most intriguing questions in modern petrology and geodynamics. We use the diamondiferous Kumdy-Kol domain in the Kokchetav Massif to show that exhumation models should take into consideration initially high uplift velocities (from 20 down to 6 cm/year) and the absence of the deformation of UHP assemblages. The high rate of exhumation are indicated by ion microprobe (SHRIMP) dating of zircons from diamondiferous rocks and supported by the low degree of nitrogen aggregation in metamorphic diamonds.Diamondiferous rocks in the Kumdy-Kol domain occur as steeply dipping (60°-80°) thin slices (few hundred metres) within granite-gneiss. Using geological, petrological and isotopic-geochemical data, we show that partial melting of diamondiferous metamorphic rocks occurred; a very important factor which has not been taken into account in previous models.Deformation of diamondiferous rocks at Kumdy-Kol is insignificant; diamond inclusions in garnet are often intergrown with mica crystals carrying no traces of deformation. All these facts could be explained by partial melting of metapelites and granitic rocks in the Kumdy-Kol domain. The presence of melt is responsible for an essential reduction of viscosity and a density difference (Δρ) between crustal rocks and mantle material and reduced friction between the upwelling crustal block, the subducting and overriding plates. Besides Δρ, the exhumation rate seems to depend on internal pressure in the subducting continental crustal block which can be regarded as a viscous layer between subducting continental lithosphere and surrounding mantle.We construct different models for the three stages of exhumation: a model similar to “corner flow” for the first superfast exhumation stage, an intermediate stage of extension (most important from structural point of view) and a very low rate of exhumation in final diapir+erosional uplift.     

Geochemical characteristics, Ar–Ar ages and original tectonic setting of the Band-e-Zeyarat/Dar Anar ophiolite, Makran accretionary prism, S.E. Iran

The Makran accretionary prism in southeastern Iran contains extensive Mesozoic zones of melange and large intact ophiolites, representing remnants of the Tethys oceanic crust that was subducted beneath Eurasia. To the north of the Makran accretionary prism lies the Jaz Murian depression which is a subduction-related back-arc basin. The Band-e-Zeyarat/Dar Anar ophiolite is one of the ophiolite complexes; it is located on the west side of the Makran accretionary prism and Jaz Murian depression, and is bounded by two major fault systems. The principal rock units of this complex are a gabbro sequence which includes low- and high-level gabbros, an extensive sheeted diabase dike sequence, late intrusive rocks which consist largely of trondhjemites and diorites, and volcanic rocks which are largely pillow basalts interbedded with pelagic sedimentary rocks, including radiolarian chert. Chondrite- and primitive-mantle-normalized incompatible trace element data and age-corrected Nd, Pb, and Sr isotopic data indicate that the Band-e-Zeyarat/Dar Anar ophiolite was derived from a midocean ridge basalt-like mantle source. The isotopic data also reveal that the source for basalts was Indian-Ocean-type mantle. Based on the rare earth element (REE) data and small isotopic range, all the rocks from the Band-e-Zeyarat/Dar Anar ophiolite are cogenetic and were derived by fractionation from melts with a composition similar to average E-MORB; fractionation was controlled by the removal of clinopyroxene, hornblende and plagioclase. Three ⁴⁰Ar–³⁹Ar plateau ages of 140.7±2.2, 142.9±3.5 and 141.7±1.0 Ma, and five previously published K–Ar ages ranging from 121±4 to 146±5 Ma for the hornblende gabbros suggest that rocks from this ophiolite were formed during the Late Jurassic–Early Cretaceous. Plate reconstructions suggest that the rocks of this complex appear to be approximately contemporaneous with the Masirah ophiolite which has crystallization age of (150 Ma). Like Masirah, the rocks from the Band-e-Zeyarat/Dar Anar ophiolite complex represent southern Tethyan ocean crust that was formed distinctly earlier than crust preserved in the 90–100 Ma Bitlis-Zagros ophiolites (including the Samail ophiolite).     

Geochronology of anthropogenic pollutants in riparian wetland sediments of the Lippe River (Germany)

Anthropogenic pollutants were determined in a dated sediment core, collected from a riparian wetland of the Lippe River (Ruhr district, Germany). The historical trend in heavy metals, polycyclic aromatic hydrocarbons, organochlorines, polychlorinated biphenyls and linear alkylbenzenes as well as more recent contaminants such as industrial additives, organotins, synthetic musks, methyltriclosan and some other compounds were determined for the time period between 1930 and 1986. Emission sources, information on technical production and usage, as well as on the individual pollution pathways, with appropriate environmental stability, were considered in the interpretation of the sediment contamination over the past 50 years.Contaminants were analysed and interpreted according to two different criteria: (a) the origin of the main contaminants as related to mining and industrial activities as well as municipal sewage and agricultural effluents and (b) the pollution history. Due to a significant appearance of formerly missing contaminants in sediments deposited since 1970, we suggest classifying contaminants as either common (predating 1970) or modern (postdating 1970).In summary, the study provided a comprehensive reconstruction of the pollution history of the Lippe River system.     

The Singapore River thematic zone: sustainable tourism in an urban context

This paper explores the concept of sustainable tourism and how it applies to urban destinations such as Singapore. As tourism is an important industry in Singapore, in terms of employment, business activity and an income generator, the Singapore Tourism Board is continuously looking at potential avenues to make Singapore a competitive destination. We examine the use of thematic zones in Singapore as a strategy to achieve its ambition of becoming a tourism capital of the world. By focusing on a case study of the Singapore River thematic zone (one of the 11 thematic zones identified by the Singapore Tourism Board), we assess the viability of thematic zones in ensuring sustainable urban tourism. The paper closes with some theoretical reflections and policy implications arising from our key findings.