Distribution and speciation of mercury in soil in the area of an ancient mercury ore roasting site,Frbejžene trate (Idrija area,Slovenia)

In the initial period of mining activities in the Idrija basin (the16^th and the first half of the17^th centuries), Hg ore processing was performed at various small-scale roasting sites in the woods surrounding Idrija, by roasting ore in earthen vessels. The recovery rate of this method was very low; about half of Hg was lost, causing soil contamination and considerable amounts of waste material that could potentially leach Hg into the surrounding environment. The main aims of present geochemical study were to determine the contents, vertical distribution and speciation of Hg in soils at the roasting site at Frbej?ene trate in order to verify the extreme pollution of ancient Hg ore roasting sites in the Idrija area and to establish their significance in the wider spatial contamination of soils and aquatic systems. Soil sampling was performed at the area of the former roasting site. The organic matter-rich surface soil layer (SOM) and underlying mineral soil were sampled at 63 sampling locations. Mercury speciation was performed using Hg thermo-desorption-AAS to distinguish cinnabar from potentially bioavailable forms. The results indicate extremely high Hg concentrations with a maximum of 37,000 mg/kg in SOM and 19,900 mg/kg in mineral soil. The established Hg median in soil was 370 mg/kg and in SOM 96.3 mg/kg. Spatial distributions of Hg in SOM and soil showed very high Hg contents in the central area and decreased rapidly with distance. The results of Hg thermo-desorption measurements indicated the presence of cinnabar (HgS) and Hg bound to organic or mineral soil matter. A significant portion (35–40%) of Hg in the investigated soil and SOM samples was comprised of non-cinnabar compounds, which are potentially bioavailable. It has been shown that soils contain high amounts of potentially transformable non-cinnabar Hg, which is available for surface leaching and runoff into the surrounding environment. Therefore, contaminated soils and roasted residues at the studied area are important for persistent Hg release into the aquatic ecosystem.     

Anthropogenic metal loads and their sources in stream sediments of the Me?a River catchment area (NE Slovenia)

The Me?a River Valley has been a center of mining, ore processing and iron- and steel-based metallurgical industry for more than 300 a. This paper deals with stream sediments draining this area. Loads of potentially toxic metals and metal-bearing phases were investigated 10 a after the cessation of Pb and Zn mining. Sediments in the upper Me?a River Valley show significant pollution with Pb and Zn as a consequence of mining and ore processing. The highest contents of Pb and Zn were found in the Me?a tributaries, which directly drain mine waste deposits (maximum values: 19,300 mg/kg Pb and 37,900 mg/kg Zn). These results reflect transport of contaminated material from mine waste sites and indicate that the inactive mine and its mine wastes are sources of metal contamination in the surrounding environment. Contents of Cr, Ni, Cu and Co are increased in the lower Me?a River Valley, in the area of Ravne, as a result of the iron and steel industry. The contribution of the Me?a River to the metal-load in the Drava River is evident.Metal-bearing phases, identified in stream sediments by SEM/EDS, are assigned to three areas, according to their source and genesis. The Me?ica mining district source area is characterized by ore minerals of geogenic/technogenic origin (cerussite, sphalerite, smithsonite and galena), the Ravne source area is characterized by technogenic trace metal-bearing Fe-alloys, Fe-oxides and spherical trace metal-oxides and the Me?a and Drava River catchment areas are represented by geogenic metal-bearing accessory and common rock-forming minerals, such as zircon, ilmenite, rutile, sphene, barite and monazite. SEM/EDS analyses of stream sediments agree well with the results of chemical analyses and they prove to be a very useful tool for identification of metal-bearing phases and their characterization according to source and genesis.     

Mercury in river sediments, floodplains and plants growing thereon in the drainage area of the Idrija mine, Slovenia

Half a millennium mercury production at Idrija is reflected in increased mercury contents in all environmental segments. The bulk of roasting residues from the middle of the 19th century to 1977 was discharged directly into the Idrijca River, and the material was carried at high waters to the Soca River and farther into the Adriatic Sea. It has been estimated that 45500 tons of mercury were emitted into the environment during the operating period of the mine, which ceased production in 1994. In the lower reaches of the Idrijca the riverine deposits with high mercury contents have been, and will be in the future a source of mercury polluted sediment. Stream sediments were monitored at the same locations along the Idrijca and Soca rivers （70 kin） every 5 years since 1991 （1991-2005）. Grain size distribution was determined by dry sieving and fractions for geochemical analysis were prepared （〈0.04 and 〈0.125 mm）. Soils on river terraces were sampled at 5 localities in the lower course of Idrijca. At two locations of the terrace profiles the samples of averaged meadow forage and plantain （Plantago lanceolata） were collected within a 50-meters radius. We found that there was no decrease in mercury concentration in active river sediments during the last 20 years. Upstream from the Idrija Town the mercury concentrations in active river sediments vary from 1 to 10 mg/kg （average 3.3 mg/kg）. From Idrija to Spodnja Idrija the mercury concentrations increase extremely and vary greatly （32-4,121 mg/kg, the average is 734 mg/kg）. From Spodnja ldrija to the Idrijca-Soca confluence is the average 218 mg/kg, and 57 mg/kg downstream in the Soca River sediments.     

Hydrogeochemical characterization and evolution of a regional karst aquifer in the Cuatrociénegas area,Mexico

The Cuatrociénegas area is useful for the investigation of the effect of groundwater extraction in the Chihuahuan freshwater xeric ecoregion. It has been investigated at this time using a selection of geochemical indicators (major, minor and trace elements) and δ³⁴S data, to characterize the origin of groundwater, the main geochemical processes and the mineral/groundwater interactions controlling the baseline geochemistry. The area is composed of limestones of Mesozoic age, with a composite thickness of about 500 m, overlaid by basin fill (poorly consolidated young sediments). Substantial water extraction and modification of natural discharges from the area along the last century have produced a detrimental impact on ecosystem structure and function. Water–rock interactions, mixing and evaporative processes dominate the baseline groundwater quality. Natural recharge is HCO₃–Ca type in equilibrium with calcite, low salinity (TDS?<?500 mg/L), Cl^? lower than 11 mg/L and average Li⁺ concentration of 0.005 mg/L. Along the groundwater flow systems, δ³⁴S evidence and mass transfer calculations indicate that Cretaceous gypsum dissolution and dedolomitization reactions adjust water composition to the SO₄–Ca type. The increase of water–rock interaction is reflected by Cl^? values increase (average 68 mg/L), TDS up to about 1500 mg/L and an average Li⁺ concentration of 0.063 mg/L. Calculations with chemical geothermometers indicate that temperature at depth could be at maximum of 15–20 °C higher than field-measured temperature for pozas. After groundwater is discharged to the surface, chemical evolution continues; water evaporation, CO₂ degassing and precipitation of minerals such as gypsum, calcite and kaolinite represent the final processes and reactions controlling water chemical composition.     

The characteristics of the chemical flow within the Motru catchment area, south — west Romania

The present paper, with reference to the Motru catchment area, contributes to the hydrochemical studies at an international level and to the completion of the characteristics regarding the chemical flow in Romania. In this regard, it emphasizes once again the dependence between the content of dissolved salts (fixed residue — mg/l) on the one hand and the lithological conditions, human activity, flow and the surface of the catchments on the other hand. The calculation and the analysis of the chemical flow for the Motru catchment area (located in the south-west of Romania) was performed on the basis of two parameters: the average flow of dissolved chemical substances (mg/s) and specific average chemical flow (t/kmp year) recorded at the monitoring stations on the Motru River and its tributaries during the period 2005–2009. The values obtained (for example: 2.63 mg/s and 47.7 t/km² year, at the Fata Motrului station, on the Motru River, in 2009) confirm the importance of the areal factors of natural background in the analysis of chemical flow as a morpho-dynamic process and implicitly for the chemical quality of surface waters.     

Environmental impacts of the abandoned mercury mine in Podljubelj, Slovenia

The Podljubelj mercury mine lies in the NW part of Slovenia. The ore is of hydrothermal-vein type. The ore deposit was exploited between the years 1557 and 1902. Total production of the mine was 110000 tons of ore （360 tons of Hg）. A smelter located close to the mine had been in operation since 1855. The waste material from the mine and the smelter was dumped in close vicinity of the mine. Total quantity of the waste has been estimated at 170000 tons. In order to establish environmental impacts, soil and stream sediment samples were investigated. Soil samples were collected at two different depths （horizons A and B） in a 100 m grid within an 88 ha area. In the vast area also 11 samples of stream sediments were considered. Heavy metals were determined by means of cold vapor atomic absorption spectrometry CV-AAS after aqua regia digestion. Based on the chemical analyses of samples, the estimated mercury mean for soils is 3.67 mg/kg （0.35-244 mg/kg） for horizon A and 1.39 mg/kg （0.17-71.7 mg/kg） for horizon B. The estimated mercury mean for stream sediments is 0.64 mg/kg （0.065-1.36 mg/kg）. The concentrations of mercury in soils generally decrease with depth and distance from the mine. The highest content of Hg was determined in a sample taken in the immediate vicinity of the smelter （719 mg/kg）. The results have shown that on the 9 ha of the study area, the contents of Hg in soils exceeded the officially set limit value for soils （10 mg/kg）. High contents of Hg in soil around the abandoned smelter are a consequence of former atmospheric emissions and technological losses. High contents of Hg were also found in the mine and smelter waste dump. At the edges of the study area and in the samples of stream sediments, Hg concentrations are low.     

Chemical composition and evolution of tourmaline-supergroup minerals from the Sb hydrothermal veins in Rožňava area,Western Carpathians,Slovakia

Mineralogy and Petrology - Tourmaline-supergroup minerals are common gangue minerals in Sb-hydrothermal veins on Betliar – Straková, Čučma – Gabriela and...     

Wavelet analysis of Fuenmayor karst spring,San Julián de Banzo,Huesca, Spain

Fuenmayor spring has been monitored continuously for identification purposes to study the behavior of a karst groundwater system. This paper initially deals with linear methods employing system engineering techniques for the analysis and identification of a hydrological system, considered as a black box model, which disregards information on the internal structure of the aquifer. Under a linear time invariant hypothesis, the application of the simple correlation of spectral analysis and parametric identification of transfer function generated some interesting results in the monitored spring. These tools have historically been successful in studying a large number of karst springs and continue to be practical approximations in initial attempts to obtain a draft model. Because of the nonlinear and nonstationary nature of karst, more effective systemic techniques are required to cover certain aspects of analysis that the linear system cannot reveal adequately. This paper presents interesting results using Fuenmayor spring data, collected over almost 10 years, to show the ability of wavelet techniques in the identification of a karst spring system.     

Hydrodynamic characteristics of the western Doñana Region (area of El Abalario), Huelva,Spain

The Doñana region, in southwestern Spain, comprises a large and important nature reserve, the wetlands of which are affected by human activity. Planting of an extensive eucalyptus forest in the 1950s and, more recently, the use of aquifers for irrigation and water supply for some coastal tourist resorts, have altered the natural groundwater-flow system. The area of the study is the western sector of the region, called El Abalario, which is a gentle topographic elevation between the Atlantic coast and La Rocina Creek (Arroyo de la Rocina). Underneath a variable layer of eolian sands with high dunes near the coast, thick Plio-Quaternary detritic strata, mostly fine silica sands, overlie marls. Near the base there is a variable, deltaic-origin layer of coarse sands and gravels. The dome-shaped water table, inside the sands, is close to the surface everywhere except beneath the dune belt, and small, temporary, shallow lagoons are numerous. The coarse sand and gravel layer conditions groundwater flow and behaves as a semiconfined layer between sands. A cross section through the area was simulated with a model to check the validity of the conceptual groundwater-flow pattern and its sensitivity to the hydraulic parameters. The model was calibrated using parameter values obtained by pumping tests and multilevel piezometric data, and checked against the estimated groundwater discharge into La Rocina Creek. Groundwater flows peripherally to the sea coast, to La Rocina Creek, or directly east and southeastward into the Doñana marshlands, in the Guadalquivir River delta. The average net aquifer recharge rate was calculated to be between 100 and 200 mm year^–1 for the area covered by brush, but is remarkably lower in the areas of eucalyptus trees. The transient-state model shows that recharge varies spatially and is not clearly proportional to annual precipitation. Phreatic evapotranspiration plays an important role in decreasing the net value of aquifer recharge to approximately 0.4–0.6 of that calculated with a soil-balance model. The cross section model was used to study the effect of groundwater abstraction on water-table depth by subtracting the contribution of vertical flow, calculated by a well-hydraulics formula, to the semiconfined deep aquifer. The result was a decrease in phreatic evapotranspiration, flow into La Rocina Creek, and lagoon-inundation frequency. Replacement of the eucalyptus forest with native vegetation may raise water-table levels and even reactivate old tributaries to La Rocina Creek.

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Resumen La región de Doñana, situada en el sudoeste de España, incluye una gran e importante reserva natural, cuyos humedales están siendo afectados por la actividad humana. La extensa plantación de eucaliptus en la década de 1950 y el uso más reciente de los acuíferos para riego y para abastecimiento de centros turísticos costeros han modificado el sistema de flujo del agua subterránea en esta zona. Este estudio se ha realizado en el sector occidental, llamado El Abalario. Se trata de una elevación suave situada entre el océano Atlántico y el arroyo de La Rocina. Debajo de un manto variable de arenas eólicas, que forma un alto cordón dunar costero, se encuentran sedimentos detríticos plio-cuaternarios formados por arenas silíceas finas, que hacia la base incluyen una capa de arenas gruesas y gravas de origen deltrico, los que a su vez yacen sobre margas. El flujo de agua subterránea está relacionado con niveles de gravas y gravillas semiconfinadas por las arenas fluvio-marinas que contienen el nivel freático. El nivel freático es somero excepto debajo del cordón dunar. Son frecuentes pequeñas lagunas temporales. Se ha simulado el flujo de agua subterránea en una sección para comprobar el modelo de flujo conceptual y la sensibilidad a variaciones de los parámetros. El modelo fue calibrado usando los valores de los parámetros hidráulicos obtenidos en ensayos de bombeo y datos piezométricos medidos a diferentes profundidades, y la descarga estimada al arroyo de La Rocina. La recarga de agua subterránea drena lateralmente, por un lado hacia la costa y por otro lado a través del arroyo de La Rocina, o directamente hacia las Marismas de Doñana situadas en el delta del río Guadalquivir. Con una lluvia media anual entre 550 y 600 mm, la recarga neta media estacionaria anual del acuífero, considerando periodos de tiempo largos, se estima entre 100 y 200 mm en las zonas de vegetación autóctona, y es notablemente menor en las zonas de plantación de eucaliptos. El modelo transitorio indica que la recarga varia espacialmente y no es claramente proporcional a la precipitación para periodos de un año. La evapotranspiración freática varia espacialmente y juega un papel importante; disminuye el valor neto de la recarga al acuífero para dejarlo en 0,4 a 0,6 de lo que se calcula mediante un balance de agua en el suelo. La sección modelada sirve para estudiar el efecto de la extracción de agua subterránea sobre la profundidad del nivel freático mediante la substracción del flujo vertical, que se calcula mediante una fórmula de hidráulica de pozos para el acuífero semiconfinado profundo. El resultado es una disminución de la evapotranspiración freática, del flujo al arroyo de la Rocina y de la frecuencia de inundación de las lagunas. La substitución del bosque de eucaliptus por vegetación nativa puede elevar los niveles freáticos e incluso reactivar antiguos "caños" tributarios al arroyo de La Rocina.

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Résumé La région de Doñana, située dans le sud ouest de l'Espagne, comprend une importante réserve naturelle avec des zones humides, affectée par l'activité humaine. L'exploitation de vastes plantations d'eucalyptus pendant les années 50 et l'usage plus récent des nappes souterraines pour l'irrigation et l'alimentation en eau des centres touristiques côtiers ont modifié le système de flux d'eau souterraine dans cette zone. La présente étude a été réalisée dans le secteur occidental, appelé El Abalario. Ce secteur consiste en une légère élévation située entre l'Océan Atlantique et la ravine de La Rocina. Une couverture variable de sables éoliens, formant une haute crête dunaire côtière, recouvre des sédiments detritiques plio-quaternaires, déposés eux même sur des sables siliceux lesquels reposent à leur tour sur des marnes. Près de la base se trouvent des sables grossiers et des graviers d'origine deltaïque, dont l'épaisseur varie spatialement. Le flux d'eau souterraine est conditionné par l'aquifère semi confinés des graviers et des sables grossiers. Le niveau phréatique de l'aquifère libre des sables fluvio-marins est peu profond, excepté sous les dunes. On y trouve souvent des petites lagunes temporaires peu profondes. Le flux de l'eau souterraine a été simulé dans une section verticale pour vérifier le modèle hydrogéologique conceptuel et la sensibilité aux variations des paramètres. Le modèle a été calé en utilisant d'une part les valeurs des paramètres hydrauliques obtenus par des essais de pompage et d'après les données piezométriques mesurées à différentes profondeurs, et d'autre part l'apport estimé de la ravine de La Rocina. L'écoulement d'eau souterraine s'effectue par drainage latérale dans trois directions, d'une part vers la côte, d'autre part à travers la ravine de La Rocina et finalement directement vers les Marais de Doñana situés à l'est et sud-est dans le delta du fleuve Guadalquivir. Avec une pluviométrie moyenne comprise entre 550 et 600 mm, la recharge nette moyenne annuelle des nappes, pour des périodes de temps assez longues, est estimée entre 100 et 200 mm dans les aires de végétation autochtone, et elle est nettement inférieure dans les aires plantées d´eucalyptus. Le modèle transitoire montre que la recharge varie dans l'espace et qu'elle n'est pas clairement proportionnelle aux précipitations annuelles. L'évapotranspiration phréatique joue un rôle important et diminue la valeur nette de la recharge des nappes de 0,4 à 0,6 de la valeur calculée avec un modèle de bilan d'eau dans le sol. La section modélisée est utilisée pour étudier l'effet de l'extraction d'eau souterraine sur la profondeur du niveau phréatique en soustrayant le flux vertical, calculé grâce à une formule d'hydraulique des puits, de la nappe profonde semi-confinée. Le résultat de cette extraction est une diminution de l'évapotranspiration phréatique, du flux au niveau de la ravine de La Rocina et de la fréquence d'inondation des lagunes. La substitution de forêts d'eucalyptus par de la végétation autochtone peut permettre la remonté des niveaux phréatiques et même réactiver d'anciens ravins affluents à La Rocina.

     

Fluoride exposure in the endemic fluorosis area of Guizhou, China

The dental and skeletal fluorosis is highly prevalent in Zhijin, Guizhou, especially at Hualuo Village, Hehua Village and Majiazhuang Village. The contents of fluorine in coal, clay used for coal combustion, mixed fuel of coal and clay, corn, and chili from households of the three villages were determined by the pyrohydrolysis-fluorine ion-selective electrode method. The average contents of fluorine in the above samples respectively are 237 mg/g, 2262 mg/g, 828 mg/g, 1419 mg/g, and 110 mg/g. The clay used for coal combustions is the main fluorine source of endemic fluorosis and the inferior coal and weathered coal are the secondary source of fluorine. During the combustion of mixed fuel of coal and clay, about eighty percent of fluorine was volatilized, approximately two thirds of which was from the clay and the other one third from the coal. The occurrence of fluorine in clay used for coal combustion is closely related to apatite and hornblende. The contents of fluorine in corn and chili, dried by coal-clay mixed fuel are about 1400 and 73 times higher than the permitted level of fluorine in foods according to the Chinese Standard. It is worth paying attention to the high-fluorine indoor surroundings, such as coal, clay, corn, and chili, particularly ash from boiler bottom with the fluorine content of 15738 μg/g. Besides the technologies of fluorine fixation during the combustion,     

The largest karst cave discovered in a tunnel during motorway construction in Slovenia’s Classical Karst (Kras)

Karst researchers of the Karst Research Institute ZRC SAZU are regularly consulted during the planning of Slovenia’s motorways and invited to observe and monitor construction in the karst areas. More than 350 caves have been discovered in the course of building 60 km of new motorways over the past decade. Access to the most important caves is preserved by concrete tubes closed with metal covers at the roadside. The largest cave system in a tunnel, named LC-S647, is almost entirely preserved. The protection of this cave will serve as a good example for the preservation of natural heritage in the future. Construction work for the motorway uncovered a high degree of karstification. In particular, the discovery of this cave in the Kastelec tunnel LC-S647 showed the existence of a major cave system in the geological and speleological past. A number of unconnected passages have also been found. Caves discovered during highway construction have brought new knowledge about the cavernosity and the geological history of this part of the karst.     

Application of the content–area (C–A) fractal model and prediction–area (P–A) plot for mineral prospectivity modeling in the Luchun area of Yunnan Province,China

This method of assigning weights based on expert opinion introduces bias when we are evaluating the relative importance of evidence values. In this paper, we used a prediction–area (P–A) plot method and content–area (C–A) fractal model to estimate the weight of each evidence map. In this paper, we used the content region (C–A) fractal model to divide the evidence maps to the threshold of the corresponding dimensions. The P–A plot approach is an objective data-driven approach for evaluating map weights. Using geochemical layer and remote sensing, hydroxyl layers as weight evidence maps are the highlights of this study. We use the P–A method from which we can evaluate the predictive ability of each evidence map with respect to the known ore occurrences. We used the P–A plot for weighting each evidence map and choosing the appropriate threshold for predictor maps in the Luchun area of Yunnan Province, China. The method adopted in this paper can improve the prediction efficiency of ore prospecting.     

Multi-tracer tests to evaluate the hydraulic setting of a complex aquifer system (Brévilles spring catchment, France)

For good management of groundwater resources, and to comply with European and national regulations, a detailed understanding of an aquifer’s hydraulic setting is required. In order to better characterize a sandy aquifer that is affected by diffuse pollution (Brévilles spring catchment, Val d’Oise, France), and to quantify the transfer time in the saturated zone, a multi-tracer test involving a new technique, the ‘finite volume point dilution method’, has been performed in natural flow conditions. In November 2005, injections of four different tracers took place in four piezometers involving different locations and depths in the aquifer. Recovery of the tracers was observed at two different places near the aquifer outlet. A particularly long and unusual monitoring exercise (27 months) demonstrated the existence of several different velocities within the sandy layer, which seems to be linked to the decrease of hydraulic conductivity with depth. The new insight and parameter quantification brought by interpretation of these tests contribute to a better characterization of the saturated zone. The particularly long-term monitoring exercise also gives new information to understand and forecast the trend and persistence of groundwater contamination by pesticides in the catchment.     

PCB-anomalies around the urban karst area in ZADAR (CROATIA) as consequence of war action and /or industrial contamination

A great part of the former Yugoslavia has recently been encompassed by warfare. Research on the environmental impact of warfare has shown that many sorts of highly stable organic contaminants have entered the environment. The karstic region and in many ca…     

Geodynamic evolution of the Salinas de Añana diapir in the Basque-Cantabrian Basin,Western Pyrenees

The Salinas de Añana diapir is located in the Basque-Cantabrian basin part of the great evaporite basin, along with the Gulf of Mexico and the Central European basin, when the fragmentation of Pangea started. The evolution of these basins can only be achieved by understanding the control of salt in the sedimentary and tectonic evolution of these basins.Sedimentation began with clastic Buntsandstein sediments and minor Muschelkalk limestones. Subsequent Keuper evaporites are the bottom of sedimentary cover constituted by Jurassic limestones and marls, a clastic Lower Cretaceous and an alternant limestone and marl Upper Cretaceous, whose deposition has been conditioned by salt tectonics. The emplacement of salt extends from the Aptian until now, favored by the duplication of the salt thickness associated with the thrust of Sierra Cantabria, so it is an excellent example to study changes in the regime of intrusion along the time. The geodynamic evolution of the Salinas de Añana diapir was determined through the interpretation of 45 reprocessed seismic lines, along with information from three wells. Migration of the salt in this diapir, conditioned by N120E and N30E pre-Alpine basement lineations, was determined using time isopach maps of the various rock layers. Vertical evolution of the diapir was determined through the reconstruction of a north-south section at various geologic times by flattening the respective seismic horizons. A minimum of salt flow into the diapir coincides with a minimum rate of sedimentation during the Turonian. Similarly, maximum flows of salt into the diapir occurred during the Coniacian and Lower Santonian and again from the end of the Lower Miocene to the present, coinciding with maximum rates of sedimentation during these times. In the Tertiary, probably during the Oligocene, the diapir was displaced to the south by the Sierra Cantabria thrust, maintaining the contact between the evaporites of diapir and the same evaporites of the lower block. Since the Oligocene, the salts of the lower block migrated towards and into the diapir, deforming the trace of the overthrust.     

Iron–bentonite interactions in the Kawasaki bentonite deposit,Zao area,Japan

Greenish veins occurring in brecciated bentonite were found in the Kawasaki bentonite deposit of the Zao region in Miyagi Prefecture, Japan. Their occurrence possibly indicates the interaction of bentonite with Fe-rich hydrothermal solutions. In order to prove the hypothesis and understand the long-term mineralogical and petrographic evolution of bentonite during such interactions, the greenish veins and the surrounding altered bentonite were analyzed using X-ray fluorescence (XRF), scanning electron microscopy (SEM), X-ray diffraction (XRD), electron probe micro-analysis (EPMA), scanning transmission electron microscopy with energy dispersed spectroscopy (STEM-EDS) and micro X-ray absorption near-edge structure (XANES). The greenish veins resulting from hydrothermal solution are composed of mixed-layer minerals consisting of smectite and glauconite (glaucony), pyrite and opal. The occurrences indicate that glaucony and pyrite formed almost simultaneously from hydrothermal solution prior to opal precipitation. The mineral assemblages of the greenish veins and their surroundings indicate that the hydrothermal activity had most likely taken place at a temperature of less than 100 °C and that the pH and Eh conditions of the reacted solution were neutral to alkaline pH and reducing. The unaltered bentonite is composed mainly of Al smectite and opal. These minerals coexist as a mixture within the resolution level of the microprobe analyses. On the other hand, the bentonite in contact with the greenish veins consists of discrete opal grains and dioctahedral Al smectite containing Fe and was altered mineralogically and petrographically by the hydrothermal activity. Both the clay minerals and the opal were formed by dissolution and subsequent precipitation from the interaction of the original bentonite with the hydrothermal solution.     

Multi-stage zeolite facies mineralization in the Hvalfjördur area,Iceland

The Hvalfjördur area, 30 km north of Iceland’s capital Reykjavik, belongs to the sequence of Late Tertiary to early Quaternary flood basalts with minor intercalations of hyaloclastites and rhyolites. The basalts are affected by progressive low-temperature metamorphism, caused by the burial of the lava succession and higher heat flow from nearby central volcanoes. Low-grade zeolite facies metamorphism of basaltic lavas in the Hvalfjördur area results in two distinct mineral parageneses that can be correlated to events in the burial and hydrothermal history of the lava pile. Stage Ia represents syn-eruptive near-surface alteration in which celadonite and silica were precipitated along primary pores. During regional burial metamorphism (stage Ib), hydrolysis of olivine and glass led to the formation of mixed-layer chlorite/smectite clays. The chlorite content of stage Ib phyllosilicate vesicle rims increases with increasing burial depth and temperature. Stage II occurred after the burial and is marked by zeolite mineralization caused by higher heat flow from the Laxárvogur and Hvalfjördur central volcanoes. Altogether 11 different zeolites were found in the Hvalfjördur area: analcime, chabazite, epistilbite, heulandite, laumontite, levyne, mesolite, stilbite, stellerite, thomsonite and yugawaralite. In total, three separate depth and temperature-controlled “zeolite zones” occur in the Hvalfjördur area.     

Sulfur isotope variations from orebody to hand-specimen scale at the Mežica lead–zinc deposit, Slovenia: a predominantly biogenic pattern

The Mississippi Valley-type (MVT) Pb–Zn ore district at Mežica is hosted by Middle to Upper Triassic platform carbonate rocks in the Northern Karavanke/Drau Range geotectonic units of the Eastern Alps, northeastern Slovenia. The mineralization at Mežica covers an area of 64 km² with more than 350 orebodies and numerous galena and sphalerite occurrences, which formed epigenetically, both conformable and discordant to bedding. While knowledge on the style of mineralization has grown considerably, the origin of discordant mineralization is still debated. Sulfur stable isotope analyses of 149 sulfide samples from the different types of orebodies provide new insights on the genesis of these mineralizations and their relationship. Over the whole mining district, sphalerite and galena have δ ³⁴ S values in the range of –24.7 to –1.5‰ VCDT (–13.5 ± 5.0‰) and –24.7 to –1.4‰ (–10.7 ± 5.9‰), respectively. These values are in the range of the main MVT deposits of the Drau Range. All sulfide δ ³⁴ S values are negative within a broad range, with δ ³⁴ S _pyrite <δ ³⁴ S _sphalerite <δ ³⁴ S _galena for both conformable and discordant orebodies, indicating isotopically heterogeneous H₂S in the ore-forming fluids and precipitation of the sulfides at thermodynamic disequilibrium. This clearly supports that the main sulfide sulfur originates from bacterially mediated reduction (BSR) of Middle to Upper Triassic seawater sulfate or evaporite sulfate. Thermochemical sulfate reduction (TSR) by organic compounds contributed a minor amount of ³⁴S-enriched H₂S to the ore fluid. The variations of δ ³⁴ S values of galena and coarse-grained sphalerite at orefield scale are generally larger than the differences observed in single hand specimens. The progressively more negative δ ³⁴ S values with time along the different sphalerite generations are consistent with mixing of different H₂S sources, with a decreasing contribution of H₂S from regional TSR, and an increase from a local H₂S reservoir produced by BSR (i.e., sedimentary biogenic pyrite, organo-sulfur compounds). Galena in discordant ore (–11.9 to –1.7‰; –7.0 ± 2.7‰, n = 12) tends to be depleted in ³⁴ S compared with conformable ore (–24.7 to –2.8‰, –11.7 ± 6.2‰, n = 39). A similar trend is observed from fine-crystalline sphalerite I to coarse open-space filling sphalerite II. Some variation of the sulfide δ ³⁴ S values is attributed to the inherent variability of bacterial sulfate reduction, including metabolic recycling in a locally partially closed system and contribution of H₂S from hydrolysis of biogenic pyrite and thermal cracking of organo-sulfur compounds. The results suggest that the conformable orebodies originated by mixing of hydrothermal saline metal-rich fluid with H₂S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralization.