Neoproterozoic Volhynia-Brest magmatic province in the western East European craton: Within-plate magmatism in an ancient suture zone

The reasons for the isotopic and geochemical heterogeneity of magmatism of the Neoproterozoic large Volhynia-Brest igneous province (VBP) are considered. The province was formed at 550 Ma in response to the break up of the Rodinia supercontinent and extends along the western margin of the East European craton, being discordant to the Paleoproterozoic mobile zone that separates Sarmatia and Fennoscandia and the Mesoproterozoic Volhynia-Orsha aulacogen. The basalts of VBP show prominent spatiotemporal geochemical zoning. Based on petrographic, mineralogical, geochemical, and isotopic data, the following types of basalts can be distinguished: olivine-normative subalkaline basalts consisting of low-Ti (sLT, < 1.10–2.0 wt % TiO₂; ε_Nd(550) from ?6.6 to ?2.7) and medium-Ti (sMT, 2.0–3.0 wt % TiO₂, occasionally up to 3.6 wt % TiO₂; ε_Nd(550) from ?3.55 to + 0.6) varieties; normal quartz-normative basalts (tholeiites) including low-Ti (tLT, < 1.75–2.0 wt % TiO₂) and medium-to-high-Ti (tHT1, 2.0–3.6 wt % TiO₂, ε_Nd(550) from ?1.3 to + 1.0) varieties. The hypabyssal bodies are made up of subalkaline low-Ti olivine dolerites (LT, 1.2–1.5 wt % TiO₂; ε_Nd(550) = ?5.8) and subalkaline high-Ti olivine gabbrodolerites (HT2, 3.0–4.5 wt % TiO₂; ε_Nd(550) = ?2.5). Felsic rocks of VBP are classed as volcanic rocks of normal (andesidacites, dacites, and rhyodacites) and subalkaline (trachyrhyodacites) series with TiO₂ 0.72–0.77 wt% and ε_Nd(550) of ?12. The central part of VBP is underlain by a Paleoproterozoic domain formed by continent-arc accretion and contains widespread sills of HT2 dolerites and lavas of LT basalts; the northern part of the province is underlain by the juvenile Paleoproterozoic crust dominated by MT and HT1 basalts. MT and LT basalts underwent significant AFC-style upper crustal contamination. During their long residence in the upper crustal magmatic chambers, the basaltic melts fractionated and caused notable heating of the wall rocks and, correspondingly, nonmodal melting of the upper crustal protolith containing high-Rb phase (biotite), thus producing the most felsic rocks of the province. The basalts of VBP were derived from geochemically different sources: probably, the lithosphere and a deep-seated plume (PREMA type). The HT2 dolerites were generated mainly from a lithospheric source: by 3–4% melting of the geochemically enriched garnet lherzolite mantle. LT dolerites were obtained by partial melting of the modally metasomatized mantle containing volatile-bearing phases. The concepts of VBP formation were summarized in the model of three-stage plume-lithosphere interaction.     

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.     

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.     

Dissolved metals and associated constituents in abandoned coal-mine discharges,Pennsylvania, USA. Part 1: Constituent quantities and correlations

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s⁻¹, with a median of 18.4 L s⁻¹. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-μm pore-size filter) SO₄ (34–2000), Fe (0.046–512), Mn (0.019–74), and Al (0.007–108) varied widely. Predominant metalloid elements were Si (2.7–31.3 mg L⁻¹), B (<1–260 μg L⁻¹), Ge (<0.01–0.57 μg L⁻¹), and As (<0.03–64 μg L⁻¹). The most abundant trace metals, in order of median concentrations (range in μg/L), were Zn (0.6–10,000), Ni (2.6–3200), Co (0.27–3100), Ti (0.65–28), Cu (0.4–190), Cr (<0.5–72), Pb (<0.05–11) and Cd (<0.01–16). Gold was detected at concentrations greater than 0.0005 μg L⁻¹ in 97% of the samples, with a maximum of 0.0175 μg L⁻¹. No samples had detectable concentrations of Hg, Os or Pt, and less than half of the samples had detectable Pd, Ag, Ru, Ta, Nb, Re or Sn. Predominant rare-earth elements, in order of median concentrations (range in μg/L), were Y (0.11–530), Ce (0.01–370), Sc (1.0–36), Nd (0.006–260), La (0.005–140), Gd (0.005–110), Dy (0.002–99) and Sm (<0.005–79). Although dissolved Fe was not correlated with pH, concentrations of Al, Mn, most trace metals, and rare earths were negatively correlated with pH, consistent with solubility or sorption controls. In contrast, As was positively correlated with pH.     

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).     

The presence of anomalous trace element levels in present day Jamaican soils and the geochemistry of Late-Miocene or Pliocene phosphorites

High levels of Cd and Zn in Jamaican soils observed in geochemical surveys are related to the presence of phosphorites of possible Late-Miocene or Pliocene age. The trace element and REE geochemistry of the phosphorites, together with SEM studies, indicate a guano origin for the phosphorites. No specific host minerals for Cd could be identified in the fossiliferous phosphorite which is characterized by uniquely high levels of Cd, Zn, Ag, Be, U and Y. However, in the soil Cd is present in lithiophorite and a complex history of pedological development is preserved in the aluminous–goethite present in the soil. The unique guano signature is preserved in the soil despite the fact that guanos themselves have either not been observed or have been destroyed by continuing karst and soil development. The phosphorite geochemical signature can be traced in the data of a 1988 island-wide soil geochemical survey, identifying areas where the Palaeo-environment that supported bird ‘rookeries’ existed in the Late-Miocene or Pliocene.     

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.