Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

Application of organic petrology and geochemistry to coal waste studies

Coal wastes produced during mining activities are commonly deposited in nearby dumps. These wastes mostly composed of minerals and variable amounts (usually 20-30%) of organic matter start to weather immediately after deposition. Oxidation of the organic matter can lead to self heating and self combustion as a result of organic and mineral matter transformations. The degree of alteration depends on the properties of the wastes, i.e., the maceral and microlithotype composition of the organic matter and its rank.Alteration of wastes also depends on the heating history, i.e., the rate of heating, final heating temperature, duration of heating, and the degree of air access. Although air is probably necessary to initiate and drive the heating processes, these usually take place under relatively oxygen depleted conditions. With slow heating, color of organic matter particles changes, irregular cracks and oxidation rims develop around edges and cracks, and bitumen is expelled. As a result, massive and detritic isotropic and strongly altered organic matter forms. On the other hand, higher heating rates cause the formation of devolatilization pores, oxidation rims around these pores and along cracks, vitrinite-bands-mantling particles, and bitumen expulsions.Organic compounds generated from the wastes include n-alkanes, iso-alkanes, alkylcyclohexanes, acyclic isoprenoids, mainly pristane, phytane and, in some cases, farnesane, sesquiterpanes, tri- and tetracyclic diterpanes, tri- and pentacyclic triterpanes, and steranes, polycyclic aromatic hydrocarbons (mostly with two- to five rings, rarely six rings), and phenols. The compounds formed change during the heating history. The fact that phenols are found in dumps where heating has not yet been completed, but are absent in those where heating ceased previously suggests the presence of water washing. The organic compounds formed may migrate within the dumps. However, when they migrate out of the dumps, they become a hazard to environment.This paper is a review on transformations of organic matter (both maceral composition and reflectance and chemical composition) in coal wastes deposited in coal waste dumps. Immediately after deposition the wastes are exposed to weathering conditions and sometimes undergo self heating processes.     

Plesiosaurs

Plesiosaurs are an unusual and intriguing group of extinct aquatic reptiles ( Fig. 1 ). They are sauropterygians, a group known from an array of semi‐aquatic forms during the Triassic period: placodonts, pachypleurosaurs and nothosaurs. The first plesiosaurs are known from the very latest Triassic, but by the Early Jurassic plesiosaurs were cosmopolitan in distribution and lasted successfully to the latest Cretaceous, when they became victims of the K‐T extinction event. Plesiosaurs were predominantly marine organisms, although their fossils are not uncommon in brackish or even fresh water deposits. We know that all plesiosaurs were carnivorous; many of them were top predators in their respective ecosystems. But with no living descendants (or analogues) plesiosaurs are mysterious fossil organisms—as we will see, many questions regarding their biology remain unanswered or contentious. However, plesiosaurs are currently undergoing renewed scientific attention.

Figure 1 Open in figure viewer PowerPoint The beautifully preserved skeleton of the plesiosaur Rhomaleosaurus victor seen in ventral view, from the Lower Jurassic (Toarcian) of Holzmaden, Germany (total length 3.44 m). Redrawn from Fraas (1910).     

Effects of an Omnivorous Katydid,Salinity, and Nutrients on a Planthopper-<Emphasis Type="Italic">Spartina</Emphasis> Food Web

Top–down and bottom–up effects interact to structure communities, especially in salt marshes, which contain strong gradients in bottom–up drivers such as salinity and nutrients. How omnivorous consumers respond to variation in prey availability and plant quality is poorly understood. We used a mesocosm experiment to examine how salinity, nutrients, an omnivore (the katydid Orchelimum fidicinium) and an herbivore (the planthopper Prokelisia spp.) interacted to structure a simplified salt marsh food web based on the marsh grass Spartina alterniflora. Bottom–up effects were strong, with both salinity and nutrients decreasing leaf C/N and increasing Prokelisia abundance. Top–down effects on plants were also strong, with both the herbivore and the omnivore affecting S. alterniflora traits and growth, especially when nutrients or salt were added. In contrast, top–down control by Orchelimum of Prokelisia was independent of bottom–up conditions. Orchelimum grew best on a diet containing both Spartina and Prokelisia, and in contrast to a sympatric omnivorous crab, did not shift to an animal-based diet when prey were present, suggesting that it is constrained to consume a mixed diet. These results suggest that the trophic effects of omnivores depend on omnivore behavior, dietary constraints, and ability to suppress lower trophic levels, and that omnivorous katydids may play a previously unrecognized role in salt marsh food webs.     

A protoceratopsid skeleton with an associated track from the Upper Cretaceous of Mongolia

The Djadokhta Formation of the Gobi Desert is known for the number and diversity of dinosaur and other vertebrate bones and skeletons found there, but only theropod, hadrosaur and supposed ankylosaurid footprints have been reported from this stratum. Dinosaur footprints are also noted from the Nemegt Formation, and occur as typical dinosaur track accumulations (tracksites). An articulated protoceratopsid skeleton - specimen ZPAL Mg D-II/3 - was collected by the Polish-Mongolian Expedition of 1965 from the Djadokhta Formation of Flaming Cliffs in Mongolia. Recently, the natural cast of a tetradactyl digitigrade footprint was found underneath the pelvic girdle while the skeleton and matrix were being prepared. This is possibly the first find of a dinosaur track in close association with an articulated skeleton. Although Protoceratops is an extremely common dinosaur in Mongolia, its footprints have never previously been reported from the Late Cretaceous of the Gobi Desert.     

El Chichón volcano, April 4, 1982: volcanic cloud history and fine ash fallout

This retrospective study focuses on the fine silicate particles (<62 µm in diameter) produced in a large eruption that was otherwise well studied. Fine particles represent a potential hazard to aircraft, because as simple particles they have very low terminal velocities and could potentially stay aloft for weeks. New data were collected to describe the fine particle size distributions of distal fallout samples collected soon after eruption. Although, about half of the mass of silicate particles produced in this eruption of ~1 km³ dense rock equivalent magma were finer than 62 µm in diameter, and although these particles were in a stratospheric cloud after eruption, almost all of these fine particles fell to the ground near (<300 km) the volcano in a day or two. Particles falling out from 70 to 300 km from the volcano are mostly <62 µm in diameter. The most plausible explanation for rapid fallout is that the fine ash nucleates ice in the convective cloud and initiates a process of meteorological precipitation that efficiently removes fine silicates. These observations are similar to other eruptions and we conclude that ice formation in convective volcanic clouds is part of an effective fine ash removal process that affects all or most volcanic clouds. The existence of pyroclastic flows and surges in the El Chichón eruption increased the overall proportion of fine silicates, probably by milling larger glassy pyroclasts.     

Redbed-type gold mineralisation, Kupferschiefer, south-west Poland

A new type of gold mineralisation containing minor amounts of platinum and palladium has been found proximal to the secondary redox interface located below the Cu-Ag Kupferschiefer orebody of the Polkowice-Sieroszowice mine in the south-western part of the Lubin-Sieroszowice district, Poland. This deposit can be classified as redbed-type gold. Our study shows that gold, platinum and palladium occur in secondary red-coloured sections of the basal Zechstein sedimentary rocks and in the uppermost Weissliegendes sandstone. Noble metal mineralisation occurs within an average interval of 0.22 m, which lies directly below the copper ores. The average grade of the horizon is 2.25 ppm Au, 0.138 ppm Pt and 0.082 ppm Pd with a metal content of several tens of tonnes of gold. A transition zone has been recognised between the gold-bearing horizon and the copper deposit. This transition zone is characterised by the presence of low grades of copper (<0.2 wt%) and elevated gold contents (>0.5 ppm). Native gold accompanied by electrum, mercury-bearing gold, haematite, covellite, chalcocite, bornite and chalcopyrite has been identified in the gold-bearing horizon. In some sections, Pd-arsenides, tetra-auricupride, Co-arsenides, clausthalite, tennantite, digenite, yarrowite, spionkopite and galena have also been noted.     

Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part II: synthesis of a S-spiro-like dithiolane triterpenoid

A sulfide with a bicyclic squalene hydrocarbon skeleton present in sediments from various depositional settings and of different geological age has been identified by synthesis of a reference compound. In contrast to previous expectations [cf. Schouten, S., Sinninghe Damsté, J.S., de Leeuw, J.W., 1995. A novel triterpenoid carbon skeleton in immature sulphur-rich sediments. Geochimica et Cosmochimica Acta 59, 953–958; Gug, S., Schaeffer, P., Adam, P., Klein, S., Motsch, E., Albrecht, P., 2009. Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part I: Synthesis of a dithiane triterpenoid. Organic Geochemistry 40, 876–884.], this sulfide bears two “S-spiro type“ thiolane moities, but not the two thiochromane moieties originally envisaged. The synthesis resulted in the formation of a complex isomeric mixture of compounds, all co-eluting in gas chromatography (GC) in the form of one broad peak, as is the case with the geochemical compound. The spiro-type sulfide was formed by intramolecular sulfurization of a polyunsaturated bicyclic squalene derivative of unknown biological origin. The presence of this sulfide in a number of Triassic to Miocene marine sediments from various and contrasting depositional settings (upwelling environments, shallow continental platforms, lagoonal sub-basins, hypersaline environments), all characterized by strongly anoxic conditions, but with or without photic zone anoxia, indicates that the microorganisms biosynthesizing the precursor bicyclic squalene occupy diverse ecological niches.     

Binary gas sorption/desorption experiments on a bituminous coal: Simultaneous measurements on sorption kinetics,volumetric strain and acoustic emission

There is still no clear understanding of the specific interactions between coal and gas molecules. In this context sorption–desorption studies of methane and carbon dioxide, both in a single gas environment and gas mixtures, are of fundamental interest. This paper presents the results of unique simultaneous measurements of sorption kinetics, volumetric strain and acoustic emission (AE) on three tetragonal coal samples subjected to sorption of carbon dioxide and methane mixtures. The coal was a high volatile bituminous C coal taken from the Budryk mine in the Upper Silesia Basin, Poland. Three different gas mixtures were used in the sorption tests, with dominant CO₂, with dominant CH₄ and a 50/50 mixture.The experimental set-up was designed specially for this study. It consisted of three individual units working together: (i) a unit for gas sorption experiments using a volumetric method, (ii) an AE apparatus for detecting, recording and analysing AE, and (iii) a strain meter for measuring strains induced in the coal sample by gas sorption/desorption. All measurements were computer aided.The experiments indicated that the coal tested showed preferential sorption of CH₄ at 2.6 MPa pressure and exhibited comparable affinities for CH₄ and CO₂ at higher pressures (4.0 MPa). The results of chromatographic analysis of the gas released on desorption suggested that the desorption of methane from the coal was favoured. The relationship between the volumetric strain and the amount of sorbed gas was found to be non-linear. These results were contrary to common opinions on the coal behaviour. Furthermore, it appeared that the swelling/shrinkage of coal was clearly influenced by the network of fractures. Besides, the AE and strain characteristics suggested common sources of sorption induced AE and strain.The present results may have implications for the sequestration of carbon dioxide in coal seams and enhanced coalbed methane recovery (ECBM).     

The brecciated texture of polymict eucrites: Petrographic investigations of unequilibrated meteorites from the Antarctic Yamato collection

We report on the petrography and mineralogy of five Yamato polymict eucrites to better constrain the formation and alteration of crustal material on differentiated asteroids. Each sample consists of different lithic clasts that altogether form four dominant textures and therefore appear to originate from closely related petrological areas within Vesta′s crust. The textures range from subophitic to brecciated, porphyritic, and quench‐textured, that differ from section to section. Comparison with literature data for these samples is therefore difficult, which stresses that polymict eucrites are extremely complex in their petrography and investigation of only one thick section may not be representative for the host rock. We also show that sample Y‐793548 consists of more than one lithic unit and must therefore be classified as polymict instead of monomict. The variety and nature of lithic textures in the investigated Yamato meteorites indicate shock events, intense post‐magmatic thermal annealing, and secondary alteration. These postmagmatic features occur in different intensities, varying from clast to clast or among coexisting mineral fragments on a small, local scale. Several clasts within the eucrites studied have been modified by late‐stage alteration processes that caused deposition of Fe‐rich olivine and Fe enrichment along cracks crosscutting pyroxene crystals. However, formation of these secondary phases seems to be independent of the degree of thermal metamorphism observed within every type of clast, which would support a late‐stage metasomatism model for their formation.