Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO₄·2H₂O), ferric arsenates, arseniosiderite (Ca₂Fe₃(AsO₄)₃O₂·3H₂O), Ca-Fe arsenates, pharmacosiderite (KFe₄(AsO₄)₃(OH)₄·6-7H₂O), jarosite (K₂Fe₆(SO₄)₄(OH)₁₂) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%.Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As⁵⁺in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 Å and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides.The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore.     

Contemporary Tectonic Movements of the Western Caucasus and the Ciscaucasia Based on Satellite-Geodetic Observations

Geotectonics - The paper presents the velocity field of the Western Caucasus and Ciscaucasia based on GNSS observations. In the ITRF2014 reference frame, this field shows the coordinated movement...     

Comparative geochemistry of platinum-group elements of nickel-copper sulfide occurrences associated with mafic-ultramafic intrusions in the Appalachian Orogen

Numerous tholeiitic mafic-ultramafic intrusions occurring in the Avalon and the Gander terranes of the Appalachian Orogen host magmatic Ni-Cu sulfide accumulations. The sulfide occurrences of the Gander terrane are depleted in the platinum-group elements (PGE). Total PGE abundances in these intrusions do not exceed several hundreds of ppb. The Mechanic intrusion occurring in the Avalon terrane, on the other hand, has PGE concentrations as high as 2400 ppb. Low PGE levels in the Gander terrane can be explained by equilibration of the immiscible sulfide melt with a low proportion of silicate magma. One possible explanation would be that the parental magmas for these intrusions were sulfur saturated before leaving their source region. An early sulfide fractionation during migration to the upper crustal levels, or immediately after entering the magma chamber is another possibility. Differences in the PGE geochemistry of the two groups can be explained by the different source region characteristics and different environments in which the magmas evolved.     

Soil H<Subscript>2</Subscript> and CO<Subscript>2</Subscript> Surveys at Several Active Faults in Japan

Soil H₂ and CO₂ surveys were carried out along seven active faults and around the aftershock region of the 2000 Tottori-ken Seibu earthquake in Japan. Diffuse CO₂ effluxes were also measured along one fault and around the 2000 aftershock region. The results show highly variable H₂ concentration in space and time and it seems that the maximum H₂ concentration at each active fault correlates with fault activity as exemplified by the time of the latest big earthquakes. Even though observed H₂ concentrations in four faults were markedly lower than those collected previously in the latter half of the 1970s, it is evident that the higher H₂ concentrations in this study are due to the addition of the fault gases. Comparing the chemical composition of trapped gases (H₂: 5–20% and CO₂/H₂: 0.5–12) in fractured rocks of drill cores bored at the Nojima fault, a soil gas sample with the highest H₂ concentration showed large amounts of the trapped fault gas, diluted with atmospheric component. The profile experiment across a fracture zone at the Yamasaki fault showed higher H₂ concentrations and lower CO₂/H₂ ratios as was observed in soil gas from the fracture zone. A few days after the 2000 Tottori-kei Seibu earthquake, no CO₂ effluxes related to the occurrence of earthquakes were observed at the aftershock region. However, only above the epicenter zone, relatively high H₂ concentrations in soil gases were observed.     

Mineralogical constraints on the determination of neutralization potential and prediction of acid mine drainage

 Acid-base accounting tests, commonly used as a screening tool in acid mine drainage (AMD) predictions, have limitations in (1) measuring with confidence the amount of neutralizers present in samples and (2) affording an interpretation of what the test results mean in terms of predicting the occurrence of acid mine drainage. Aside from the analytical difficulties inherent to the conventional methods, a potential source of error in neutralization potential (NP) measurements is the contribution from the dissolution of non-carbonate minerals. Non-carbonate alkalinity measured during static tests may or may not be available to neutralize acidity produced in the field. In order to assess the value-added of extending the NP with the knowledge of mineralogical composition and evaluate potential sources of errors in NP measurements, a suite of samples were examined and characterized in terms of their mineralogical and chemical compositions. The results indicate that although the acid-base accounting tests work well for simple compositions, the tests may result in overestimation or underestimation of NP values for field samples. Mineralogical constraint diagrams relating NP determinations to Ca, Mg and CO₂ concentrations were developed with the purpose to serve as supplementary guides to conventional static tests in identifying possible NP contributions from non-carbonate minerals and checking the quality of the chemical testing results. Mineralogical NP makes it possible to interpret the meaning of NP results and to assess the behaviour of samples over time by predicting the onset of AMD and calculating NP values for individual size fractions. Received: 1 June 1998 · Accepted: 6 October 1998     

An isobaric–isenthalpic magma mixing model for the Hasan Dagi volcano,Central Anatolia,Turkey

Calc-alkaline rocks of the Hasan Dagi volcano (Central Anatolia, Turkey) are products of arc volcanism triggered by continental collision. Volcanic rocks of the Hasan Dagi range in composition from basalt to rhyolite but are dominated by andesite and dacite. Considering only the mass transfer part of the process leads to an incomplete picture of magma chamber processes. The exclusion of simultaneous calculations of heat and mass transfer between mixing magmas, however, has prevented petrologists from gaining new insights into the magma mixing process. Thus, we report our experimental results in conjunction with modeling with MELTS to test the ideas concerning the petrogenesis of Hasan Dagi volcanic rocks and quantitatively model the relevant petrogenetic processes. Our results demonstrate that the chemical diversity of Hasan Dagi volcano is inconsistent with the closed-system crystallization and differentiation. Thus, (1) our experimental modeling, (2) the agreement between the liquid line of descent defined by the natural rock data and the MELTS calculations, and (3) the agreement between the mineralogy of the rocks and calculated mineralogy corroborate the conclusion that the isobaric–isenthalpic magma mixing of basalt and rhyolite is the major controlling process in the petrogenesis of the Hasan Dagi magmas.     

Temporal changes of soft-bottom zoobenthic communities in and around Alsancak Harbor (Izmir Bay, Aegean Sea), with special attention to the autecology of exotic species

Temporal and spatial variation in soft‐bottom benthic communities following recovery from a pollution episode were studied between January and September 2004 in and around Alsancak Harbor, located in the polluted part of Izmir Bay (Aegean Sea, eastern Mediterranean). Samples were collected at seven stations by van Veen grab. Three additional stations were sampled by means of a beam trawl to take into account large mobile animals and for a better estimate of the local biodiversity. A total of 231 species belonging to 10 zoobenthic groups were found. Polychaetes contributed 90% of the total faunal populations and mollusks 87% of the total biomass in the area. Community parameters varied significantly among stations and sampling periods; number of species ranged from 2 to 79 per 0.1 m² grab sample; density from 20 to 81,720 ind·m^?2; biomass from 0.1 to 4190 g·m^?2; Shannon–Wiener diversity index (log₂ base) from 0.4 to 4.4; and Pielou's evenness index from 0.11 to 1.0. Collections indicate that a number of species, including those sensitive to pollution, have colonized the area where azoic conditions had been previously reported. A total of six exotic species, Streblospio gynobranchiata, Polydora cornuta, Hydroides dianthus, Hydroides elegans, Anadara demiri and Fulvia fragilis, probably transferred to the area via ballast water or hull fouling, dominated soft or hard substrata in and near Alsancak Harbor. The first two species accounted for more than 70% of the total population in the area, while A. demiri contributed the most to the biomass (93%, at station 7).     

Synthesis and phase transformations involving scorodite, ferric arsenate and arsenical ferrihydrite: Implications for arsenic mobility

Scorodite, ferric arsenate and arsenical ferrihydrite are important arsenic carriers occurring in a wide range of environments and are also common precipitates used by metallurgical industries to control arsenic in effluents. Solubility and stability of these compounds are controversial because of the complexities in their identification and characterization in heterogeneous media. To provide insights into the formation of scorodite, ferric arsenate and ferrihydrite, series of synthesis experiments were carried out at 70 °C and pH 1, 2, 3 and 4.5 from 0.2 M Fe(SO₄)_1.5 solutions also containing 0.02-0.2 M Na₂HAsO₄. The precipitates were characterized by transmission electron microscopy, X-ray diffraction and X-ray absorption fine structure techniques. Ferric arsenate, characterized by two broad diffuse peaks on the XRD pattern and having the structural formula of FeAsO₄·4-7H₂O, is a precursor to scorodite formation. As defined by As XAFS and Fe XAFS, the local structure of ferric arsenate is profoundly different than that of scorodite. It is postulated that the ferric arsenate structure is made of single chains of corner-sharing Fe(O,OH)₆ octahedra with bridging arsenate tetrahedra alternating along the chains. Scorodite was precipitated from solutions with Fe/As molar ratios of 1 over the pH range of 1-4.5. The pH strongly controls the kinetics of scorodite formation and its transformation from ferric arsenate. The scorodite crystallite size increased from 7 to 33 nm by ripening and aggregation. Precipitates, resulting from continuous synthesis at pH 4.5 from solutions having Fe/As molar ratios ranging from 1 to 4 and resembling the compounds referred to as ferric arsenate, arsenical ferrihydrite and As-rich hydrous ferric oxide in the literature, represent variable mixtures of ferric arsenate and ferrihydrite. When the Fe/As ratio increases, the proportion of ferrihydrite increases at the expense of ferric arsenate. Arsenate adsorption appears to retard ferrihydrite growth in the precipitates with molar Fe/As ratios of 1-4, whereas increased reaction gradually transforms two-line ferrihydrite to six-line ferrihydrite at Fe/As ratios of 5 and greater.