Opacitization conditions of hornblende in Bezymyannyi volcano andesites (March 30, 1956 eruption)

The paper is devoted to the conditions under which opacite rims developed around hornblende grains in andesite of the catastrophic eruption (March 30, 1956) of Bezymyannyi volcano, Kamchatka. The opacite rims were produced by a bimetasomatic reaction between hornblende and melt with the development of the following zoning: hornblende → Px + Pl + Ti-Mag → Px + Pl → Px → melt. Biometasomatic reaction was accompanied by the active removal of CaO from the rim, addition of SiO₂, and more complicated behavior of other components. The hornblende also shows reactions of its volumetric decomposition under near-isochemical conditions. The opacite rims developed under isobaric conditions, at a pressure of approximately 6 kbar. The main reason for the instability of the hornblende was the heating of the magma chamber from 890 to 1005°C due to new hot magma portion injection. The time interval between the injection and the start of eruption was estimated from the thickness of the opacite rims and did not exceed 37 days. Hence, the March 30, 1956, eruption was not related to the volcanic activity in November of 1955 but to the injection of a fresh magma portion in February–March of 1956.     

Chemical composition,volatile components,and trace elements in melts of the Karymskii volcanic center,Kamchatka, and Golovnina volcano,Kunashir Island: Evidence from inclusions in minerals

Melt inclusions were examined in phenocrysts in basalt, andesite, dacite, and rhyodacite from the Karymskii volcanic center in Kamchatka and dacite form Golovnina volcano in Kunashir Island, Kuriles. The inclusions were examined by homogenization and by analyzing glasses in more than 80 inclusions on an electron microscope and ion microprobe. The SiO₂ concentrations in the melt inclusions in plagioclase phenocrysts from basalts from the Karymskii volcanic center vary from 47.4 to 57.1 wt %, these values for inclusions in plagioclase phenocrysts from andesites are 55.7–67.1 wt %, in plagioclase phenocrysts from the dacites and rhyodacites are 65.9–73.1 wt %, and those in quartz in the rhyodacites are 72.2–75.7 wt %. The SiO₂ concentrations in melt inclusions in quartz from dacites from Golovnina volcano range from 70.2 to 77.0 wt %. The basaltic melts are characterized by usual concentrations of major components (wt %): TiO₂ = 0.7–1.3, FeO = 6.8–11.4, MgO = 2.3–6.1, CaO = 6.7–10.8, and K₂O = 0.4–1.7; but these rocks are notably enriched in Na₂O (2.9–7.4 wt % at an average of 5.1 wt %, with the highest Na₂O concentration detected in the most basic melts: SiO₂ = 47.4–52.0 wt %. The concentrations of volatiles in the basic melts are 1.6 wt % for H₂O, 0.14 wt % for S, 0.09 wt % for Cl, and 50 ppm for F. The andesite melts are characterized by high concentrations (wt %) of FeO (6.5 on average), CaO (5.2), and Cl (0.26) at usual concentrations of Na₂O (4.5), K₂O (2.1), and S (0.07). High water concentrations were determined in the dacite and rhyodacite melts: from 0.9 to 7.3 wt % (average of 15 analyses equals 4.5 wt %). The Cl concentration in these melts is 0.15 wt %, and those of F and S are 0.06 and 0.01 wt %, respectively. Melt inclusions in quartz from the dacites of Golovnina volcano are also rich in water: they contain from 5.0 to 6.7 wt % (average 5.6 wt %). The comparison of melt compositions from the Karymskii volcanic center and previously studied melts from Bezymyannyi and Shiveluch volcanoes revealed their significant differences. The former are more basic, are enriched in Ti, Fe, Mg, Ca, Na, and P but significantly depleted in K. The melts of the Karymskii volcanic center are most probably less differentiated than the melts of Bezymyannyi and Shiveluch volcanoes. The concentrations of water and 20 trace elements were measured in the glasses of 22 melt inclusions in plagioclase and quartz from our samples. Unusually high values were obtained for Li concentrations (along with high Na concentrations) in the basaltic melts from the Karymskii volcanic center: from 118 to 1750 ppm, whereas the dacite and rhyolite melts contain 25 ppm Li on average. The rhyolite melts of Golovnina volcano are much poorer in Li: 1.4 ppm on average. The melts of the Karymskii volcanic center are characterized by relative minima at Nb and Ti and maxima at B and K, as is typical of arc magmas.     

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d’Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.     

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

Gaseous mercury emissions from urban surfaces: Controls and spatiotemporal trends

The spatial and temporal variability of Hg emissions from urban paved surfaces was assessed through repeated measurements under varying environmental conditions at six sample sites in Toronto, Ontario, Canada. The results show significant spatial variability of the Hg emissions with median values ranging from below detection limit to 5.2 ng/m²/h. Two of the sites consistently had higher Hg emissions (on several occasions >20 ng/m²/h) than the other 4, which were equivalently low (maximum emission: 2.1 ng/m²/h). A surrogate measure of the pavement Hg concentrations was obtained during each day of sampling through the collection of street dust. The median street dust concentration also showed significant spatial variability (ranging from 9.6 to 44.5 ng/g). Regression analysis showed that the spatial variability of the Hg emissions was significantly related to the street dust concentrations. Controlled experiments using Hg amended street dust confirmed the relationship between Hg surface concentration and emission magnitude. Within a given sample site, Hg emissions varied temporally and multiple regression analysis showed that within-site variability was significantly influenced by changes in solar radiation with only a minor effect from surface temperature. Controlled experiments using shade cloths confirmed that solar radiation can have a large influence on the magnitude of Hg emissions within a given site. The emissions measured in Toronto were contextualized through comparison sampling in Austin, Texas. The Hg emissions measured in Austin were within the range detected in Toronto and also showed significant correlation with Hg street dust concentrations between sites. To provide a holistic assessment of Hg emissions from urban environments, samples were also collected from other common urban surfaces (soil, roofs, and windows). Soils consistently had higher emissions than all the other surfaces (7.3 ng/m²/h, n = 39).     

Paleogeographic regionalization of Triassic seas based on conodontophorids

Geographic differentiation of conodontophorids between northern and southern latitudes commenced in the Triassic since the early Induan. Cosmopolitan long-lived genera of predominantly smooth morphotypes without sculpturing were characteristic of high-latitude basins of the Panboreal Superrealm. Since the early Olenekian until the Carnian inclusive, this superrealm consisted of the Siberian Realm that extended over Northeast Asia and the Canada-Svalbard Realm that included the Svalbard Archipelago and northern regions of Canada. Throughout the Triassic period, conodontophorids characteristic of the Tethys-Panthalassa Superrealm spanning the Tethys and low-latitude zones of the Pacific were highly endemic, very diverse in taxonomic aspect, having well-developed sculpturing and tempos of morphological transformations. Distinctions between the Early-Middle Triassic conodontophorids from northern and southern zones were not as great as afterward, and their impoverished assemblages from southern Tethyan basins were close in some respects to the Boreal ones. Their habitat basins of that time can be grouped into the Mediterranean-Pacific and India-Pakistan realms. Hence, the extent of geographic differentiation of conodontophorids was not constant and gradually grew, as their taxonomic diversity was reducing in northern basins but relatively increasing in southern ones. The Panboreal e Tethys-Panthalassa superrealms of conodontophorids, which are most clearly recognizable, are close to first-rank paleobiochores (superrealms) established earlier for ammonoids and bivalve mollusks. Main factor that controlled geographic differentiation of Triassic conodontophorids was climatic zoning. Initially lower diversity of southern Tethyan assemblages points probably to relatively cooler water regime in the peri-Gondwanan part of the Tethys. The established patterns in geographic distribution of conodontophorids characterize most likely the real trend of their differentiation and evolution, i.e., the distribution area contraction prior to complete extinction at the end of the Triassic     

Geochemical characterization of surface waters and groundwater resources in the Managua area (Nicaragua,Central America)

This paper reports new geochemical data on dissolved major and minor constituents in surface waters and ground waters collected in the Managua region (Nicaragua), and provides a preliminary characterization of the hydrogeochemical processes governing the natural water evolution in this area. The peculiar geological features of the study site, an active tectonic region (Nicaragua Depression) characterized by active volcanism and thermalism, combined with significant anthropogenic pressure, contribute to a complex evolution of water chemistry, which results from the simultaneous action of several geochemical processes such as evaporation, rock leaching, mixing with saline brines of natural or anthropogenic origin. The effect of active thermalism on both surface waters (e.g., saline volcanic lakes) and groundwaters, as a result of mixing with variable proportions of hyper-saline geothermal Na–Cl brines (e.g., Momotombo geothermal plant), accounts for the high salinities and high concentrations of many environmentally-relevant trace elements (As, B, Fe and Mn) in the waters. At the same time the active extensional tectonics of the Managua area favour the interaction with acidic, reduced thermal fluids, followed by extensive leaching of the host rock and the groundwater release of toxic metals (e.g., Ni, Cu). The significant pollution in the area, deriving principally from urban and industrial waste-water, probably also contributes to the aquatic cycling of many trace elements, which attain concentrations above the WHO recommended limits for the elements Ni (∼40 μg/l) and Cu (∼10 μg/l) limiting the potential utilisation of Lake Xolotlan for nearby Managua.