The effect of mineralogy on the mobility of heavy metals in mine tailings: a case study in the Samsanjeil mine,Korea

This study examined the chemical speciation and mobility of As and heavy metals in a tailings impoundment in Samsanjeil mine located in Gosung, Korea, as well as the factors affecting them. XRD, SEM, and 5-step sequential extraction were used to examine the samples at two sampling sites (NN and SN sites). The pH of the tailings decreased with increasing depth at the NN site (from 7.2 to 2.8), whereas no significant differences were observed at the SN site (8.1–8.8). The samples at the SN site showed a larger amount of calcite than those at the NN site, indicating that calcite plays an important role buffering the pH in the study sites. Jarosite was found only at the lower part of the NN site, where calcite was not found. The mineralogical observation of jarosite and calcite was also confirmed by SEM. The concentrations of As and heavy metals in the tailings were as follows: Cu > As > Zn > > Pb > Co > Cr > Ni > Cd. The total concentrations of Ni, Zn, Co, and Cd were higher at the SN site than those at the NN site. On the other hand, the concentrations of As and Cr existing as oxyanions were higher at the NN site, which can be explained by the mobility changes of those elements affected by pH variations. At the NN site, the fractions of heavy metals bound to the Fe/Mn oxides, except for As and Cr, decreased, and Cu, Zn, and Co showed an increasing fraction of exchangeable metals with increasing depth. This suggests that the pH and resulting surface charge of minerals, such as goethite and jarosite, are the dominant factors controlling the chemical speciation of metals. These results highlight the importance of mineralogy in controlling the mobility and possible bioavailability of heavy metals in tailings.     

Combined particle swarm optimization and linear discriminant analysis for landslide image classification: application to a case study in Taiwan

In Taiwan many reservoirs are constructed in mountain areas. Unfortunately, several earthquakes shook the soil, and typhoons brought a huge amount of water to the reservoir zone. In the past studies, remote-sensing image data were used to effectively monitor the landslide near reservoirs. In recent years, linear discriminant analysis (LDA) has become a well-known method for image classification. However, there are few studies to optimize the linear classification function. While the ancillary information has been adopted easily by new methodologies, the ancillary information must be examined by a landslide image classification system. To explore the effects of optimization on the LDA equations, three approaches were compared: (a) conventional LDA; (b) combined discrete rough sets and LDA (DRS + LDA), which identify the core factors and the corresponding thresholds of landslide occurrence; and (c) combined particle swam optimization algorithm and LDA (PSO + LDA), which optimizes the parameters of LDA equation to attain the best classification outcomes. The above methods were applied to a reservoir region in Taiwan, and the following classification results were obtained. The application of DRS + LDA in our case study reduced the number of ancillary attributes from 14 to 5, and resulted in an accuracy rate of 0.83. On the other hand, the application of PSO + LDA resulted in the same accuracy rate as that of DRS + LDA, whereas the accuracy rate of conventional LDA was found to be 0.78.     

Stochastic Fracture Propagation Modelling for Enhanced Geothermal Systems

Fractures and fracture networks are the fundamental components of enhanced geothermal systems and determine their technical and economic viability. A realistic fracture model that can adequately describe a fracture-stimulated reservoir is critical for subsequent flow and heat transfer analyses of the system. Fractures in these systems are essentially the product of hydraulic stimulations of the reservoir that, together with ground conditions and the local stress regime, determine how fractures are formed and propagated. This paper describes three methods for generating realistic fracture models for enhanced geothermal systems; two of them incorporate the fracture propagation process in the modelling and hence provide a stochastic fracture propagation model. The methods are: a Bayesian framework in the form of Markov Chain Monte Carlo simulation, an extended Random Sampling Consensus model and a Point and Surface Association Consensus model. The conditioning data used in these methods are seismic events recorded during fracture stimulation. Geodynamics’ Habanero reservoir in the Cooper Basin of South Australia is used as a case study to test these methods.     

Primary melt from Sannome-gata volcano,NE Japan arc: constraints on generation conditions of rear-arc magmas

The conditions under which rear-arc magmas are generated were estimated using primary basalts from the Sannome-gata volcano, located in the rear of the NE Japan arc. Scoriae from the volcano occur with abundant crustal and mantle xenoliths, suggesting that the magma ascended rapidly from the upper mantle. The scoriae show significant variations in their whole-rock compositions (7.9–11.1 wt% MgO). High-MgO scoriae (MgO > ~9.5 wt%) have mostly homogeneous ⁸⁷Sr/⁸⁶Sr ratios (0.70318–0.70320), whereas low-MgO scoriae (MgO < ~9 wt%) have higher ⁸⁷Sr/⁸⁶Sr ratios (>0.70327); ratios tend to increase with decreasing MgO content. The high-MgO scoriae are aphyric, containing ~5 vol% olivine microphenocrysts with Mg# [100 × Mg/(Mg + Fe²⁺)] of up to 90. In contrast, the low-MgO scoriae have crustal xenocrysts of plagioclase, alkali feldspar, and quartz, and the mineralogic modes correlate negatively with whole-rock MgO content. On the basis of these observations, it is inferred that the high-MgO scoriae represent primary or near-primary melts, while the low-MgO scoriae underwent considerable interaction with the crust. Using thermodynamic analysis of the observed petrological features of the high-MgO scoriae, the eruption temperature of the magmas was constrained to 1,160–1,220 °C. Given that the source mantle was depleted MORB-source mantle, the primary magma was plausibly generated by ~7 % melting of a garnet-bearing spinel peridotite; taking this into consideration, and considering the constraints of multi-component thermodynamics, we estimated that the primary Sannome-gata magma was generated in the source mantle with 0.5–0.6 wt% H₂O at 1,220–1,230 °C and at ~1.8 GPa, and that the H₂O content of the primary magma was 6–7 wt%. The rear-arc Sannome-gata magma was generated by a lower degree of melting of the mantle at greater depths and lower temperatures than the frontal-arc magma from the Iwate volcano, which was also estimated to be generated by ~15 % melting of the source mantle with 0.6–0.7 wt% H₂O at ~1,250 °C and at ~1.3 GPa.     

Fractional crystallization of primitive,hydrous arc magmas: an experimental study at 0.7 GPa

Differentiation of mantle-derived, hydrous, basaltic magmas is a fundamental process to produce evolved intermediate to SiO₂-rich magmas that form the bulk of the middle to shallow continental and island arc crust. This study reports the results of fractional crystallization experiments conducted in a piston cylinder apparatus at 0.7 GPa for hydrous, calc-alkaline to arc tholeiitic magmas. Fractional crystallization was approached by synthesis of starting materials representing the liquid composition of the previous, higher temperature experiment. Temperatures ranged from near-liquidus at 1,170 °C to near-solidus conditions at 700 °C. H₂O contents varied from 3.0 to more than 10 wt%. The liquid line of descent covers the entire compositional range from olivine–tholeiite (1,170 °C) to high-silica rhyolite (700 °C) and evolves from metaluminous to peraluminous compositions. The following crystallization sequence has been established: olivine → clinopyroxene → plagioclase, spinel → orthopyroxene, amphibole, titanomagnetite → apatite → quartz, biotite. Anorthite-rich plagioclase and spinel are responsible for a marked increase in SiO₂-content (from 51 to 53 wt%) at 1,040 °C. At lower temperatures, fractionation of amphibole, plagioclase and Fe–Ti oxide over a temperature interval of 280 °C drives the SiO₂ content continuously from 53 to 78 wt%. Largest crystallization steps were recorded around 1,040 °C and at 700 °C. About 40 % of ultramafic plutonic rocks have to crystallize to generate basaltic–andesitic liquids, and an additional 40 % of amphibole–gabbroic cumulate to produce granitic melts. Andesitic liquids with a liquidus temperature of 1,010 °C only crystallize 50 % over an 280 °C wide range to 730 °C implying that such liquids form mobile crystal mushes (<50 % crystals) in long-lived magmatic systems in the middle crust, allowing for extensive fractionation, assimilation and hybridization with periodic replenishment of more mafic magmas from deeper magma reservoirs.     

Building zoned ignimbrites by recycling silicic cumulates: insight from the 1,000 km<Superscript>3</Superscript> Carpenter Ridge Tuff,CO

The ~1,000 km³ Carpenter Ridge Tuff (CRT), erupted at 27.55 Ma during the mid-tertiary ignimbrite flare-up in the western USA, is among the largest known strongly zoned ash-flow tuffs. It consists primarily of densely welded crystal-poor rhyolite with a pronounced, highly evolved chemical signature (high Rb/Sr, low Ba, Zr, Eu), but thickly ponded intracaldera CRT is capped by a more crystal-rich, less silicic facies. In the outflow ignimbrite, this upper zone is defined mainly by densely welded crystal-rich juvenile clasts of trachydacite composition, with higher Fe–Ti oxide temperatures, and is characterized by extremely high Ba (to 7,500 ppm), Zr, Sr, and positive Eu anomalies. Rare mafic clasts (51–53 wt% SiO₂) with Ba contents to 4,000–5,000 ppm and positive Eu anomalies are also present. Much of the major and trace-element variations in the CRT juvenile clasts can be reproduced via in situ differentiation by interstitial melt extraction from a crystal-rich, upper-crustal mush zone, with the trachydacite, crystal-rich clasts representing the remobilized crystal cumulate left behind by the melt extraction process. Late recharge events, represented by the rare mafic clasts and high-Al amphiboles in some samples, mixed in with parts of the crystal cumulate and generated additional scatter in the whole-rock data. Recharge was important in thermally remobilizing the silicic crystal cumulate by partially melting the near-solidus phases, as supported by: (1) ubiquitous wormy/sieve textures and reverse zoning patterns in feldspars and biotites, (2) absence of quartz in this very silicic unit stored at depths of >4–5 km, and (3) heterogeneous melt compositions in the trachydacite fiamme and mafic clasts, particularly in Ba, indicating local enrichment of this element due mostly to sanidine and biotite melting. The injection of hot, juvenile magma into the upper-crustal cumulate also imparted the observed thermal gradient to the deposits and the mixing overprint that partly masks the in situ differentiation process. The CRT provides a particularly clear perspective on processes of in situ crystal-liquid separation into a lower crystal-rich zone and an upper eruptible cap, which appears common in incrementally built upper-crustal magma reservoirs of high-flux magmatic provinces.     

Re–Os isotope and platinum-group element geochemistry of the Pobei Ni–Cu sulfide-bearing mafic–ultramafic complex in the northeastern part of the Tarim Craton

A number of mafic–ultramafic intrusions that host Ni–Cu sulfide mineralization occur in the northeastern Tarim Craton and the eastern Tianshan Orogenic Belt (NW China). The sulfide-mineralized Pobei mafic–ultramafic complex is located in the northeastern part of the Tarim Craton. The complex is composed of gabbro and olivine gabbro, cut by dunite, wehrlite, and melatroctolite of the Poyi and Poshi intrusions. Disseminated Ni–Cu sulfide mineralization is present towards the base of the ultramafic bodies. The sulfide mineralization is typically low grade (<0.5 wt.% Ni and <2 wt.% S) with low platinum-group element (PGE) concentrations (<24.5 ppb Pt and <69 ppb Pd); the abundance of Cu in 100 % sulfide is 1–8 wt.%, and Ni abundance in 100 % sulfide is typically >4 wt.%. Samples from the Pobei complex have εNd (at 280 Ma) values up to +8.1, consistent with the derivation of the magma from an asthenospheric mantle source. Fo 89.5 mol.% olivine from the ultramafic bodies is consistent with a primitive parental magma. Sulfide-bearing dunite and wehrlite have high Cu/Pd ratios ranging from 24,000 to 218,000, indicating a magma that evolved under conditions of sulfide saturation. The grades of Ni, Cu, and PGE in 100 % sulfide show a strong positive correlation. A model for these variations is proposed where the mantle source of the Pobei magma retained ~0.033 wt.% sulfide during the production of a PGE-depleted parental magma. The parental magma migrated from the mantle to the crust and underwent further S saturation to generate the observed mineralization along with its high Cu/Pd ratio at an R-factor varying from 100 to 1,200. The mineralization at Poshi and Poyi has very high γOs (at 280 Ma) values (+30 to +292) that are negatively correlated with the abundance of Os in 100 % sulfide (5.81–271 ppb) and positively correlated with the Re/Os ratios; this indicates that sulfide saturation was triggered by the assimilation of crustal sulfide with both high γOs and Re/Os ratios. When compared to other Permian mafic–ultramafic intrusions with sulfide mineralization in the East Tianshan, the Poyi and Poshi ultramafic bodies were formed from more primitive magmas, and this helps to explain why the sulfide mineralization has high Ni tenor.     

Analysis of coprolites from the extinct mountain goat Myotragus balearicus

Humans colonized the Balearic Islands 5–4 ka ago. They arrived in a uniquely adapted ecosystem with the Balearic mountain goat Myotragus balearicus (Bovidae, Antilopinae, Caprini) as the only large mammal. This mammal went extinct rapidly after human arrival. Several hypotheses have been proposed to explain the extinction of M. balearicus. For the present study ancient DNA analysis (Sanger sequencing, Roche-454, Ion Torrent), and pollen and macrofossil analyses were performed on preserved coprolites from M. balearicus, providing information on its diet and paleo-environment. The information retrieved shows that M. balearicus was heavily dependent on the Balearic box species Buxus balearica during at least part of the year, and that it was most probably a browser. Hindcast ecological niche modelling of B. balearica shows that local distribution of this plant species was affected by climate changes. This suggests that the extinction of M. balearicus can be related to the decline and regional extinction of a plant species that formed a major component of its diet. The vegetation change is thought to be caused by increased aridity occurring throughout the Mediterranean. Previous hypotheses relating the extinction of M. balearicus directly to the arrival of humans on the islands must therefore be adjusted.     

A temperature-induced reversible transformation between paratacamite and herbertsmithite

The crystal chemistry of paratacamite has been re-evaluated by studying a crystal from the holotype specimen BM86958 of composition Cu_3.71Zn_0.29(OH)₆Cl₂ using single-crystal X-ray diffraction at 100, 200, 300, 353, 393 and 423 K. At 300 K paratacamite has space group $R\bar{3}$ with unit-cell parameters a 13.644 and c 14.035 Å and exhibits a pronounced subcell, a′ = ½a and c′ = c, analogous to that of the closely related mineral herbertsmithite, Cu₃Zn(OH)₆Cl₂. Between 353 and 393 K, paratacamite undergoes a reversible phase transformation to the herbertsmithite-like substructure, space group $R\bar{3}m$ , unit-cell parameters a 6.839 and c 14.072 Å (393 K). The transformation is characterised by a gradual reduction in intensity of superlattice reflections, which are absent at 393 and 443 K. On cooling from 443 to 300 K at ~10 K min^?1, the superlattice reflections reappear and the refined structures ( $R\bar{3}$ ) of the initial and recovered 300 K states are almost identical. The complete reversibility of the transformation establishes that paratacamite of composition Cu_3.71Zn_0.29(OH)₆Cl₂ is thermodynamically stable at ambient temperatures. The nature of the rhombic distortion of the M(2)O₆ octahedron is discussed by considering two possibilities that are dependent upon the nature of cation substitution in the interlayer sites.     

Assessing impact of urban impervious surface on watershed hydrology using distributed object-oriented simulation and spatial regression

In this study, we investigated the relationship between watershed characteristics and hydrology using high spatial resolution impervious surface area (ISA), hydrologic simulations and spatial regression. We selected 20 watersheds at HUC 12 level with different degrees of urbanization and performed hydrologic simulation using a distributed object-oriented rainfall and runoff simulation model. We extracted the discharge per area and ratio of runoff to base flow from simulation results and used them as indicators of hydrology pattern. We derived percentage of ISA, distance from ISA to streams, and stream density as the watershed characteristics to evaluate the relationship with hydrology pattern in watersheds using ordinary least square, spatial error and spatial lag regression models. The comparison indicates that spatial lag regression model can achieve better performance for the evaluation of relationship between ratio of runoff to base flow and watershed characteristics, and that three models provide similar performance for the evaluation of relationship between discharge per area and watershed characteristics. The results from regression analyses demonstrate that ISA plays an important role in watershed hydrology. Ignorance of spatial dependence in analyses will likely cause inaccurate evaluation for relationship between ISA and watershed hydrology. The hydrologic model, regression methods and relationships between watershed characteristics and hydrology pattern provide important tools and information for decision makers to evaluate the effect of different scenarios in land management.