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.     

Weibull statistical analysis of granite bending strength

Summary  This paper describes and discusses the adequacy of Weibull statistical analysis to analyse the bending strength of granite. The experimental results show that strength variability is related with a specific origin of failure. This conclusion is based on analysing the influence of the surface condition (extrinsic defects) on the bending strength results treated by the Weibull statistics. The conclusions drawn from this study have been validated by analysing the results of the critical flaw dimension estimated by applying the linear elastic fracture mechanics (LEFM) formulae. Results obtained from fractographic examination also have been used to describe the location of the origin of the fracture and understand the distribution of defects; i.e., there is a unimodal distribution of defects (intrinsic defects), despite the fact that some outlier values are normally observed in the fractured surfaces. Correspndence: P. M. Amaral, Department of Materials Engineering, Instituto Superior Técnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisboa, Portugal     

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.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: I. Effect of hydraulic retention time

Sulfate-reducing passive bioreactors have proved to be an effective technology for the treatment of acid mine drainage (AMD) contaminated waters over relatively short periods of time (1–5 a). However, long-term efficiency can be limited by several factors including problems related to the hydraulic properties of the reactive mixture. In this study, the effect of two hydraulic retention times (HRTs) of 7.3 d and 10 d on the performance of passive bioreactors was evaluated over an 11-month period for the treatment of a highly contaminated AMD. Evolution of the porosity and hydraulic conductivity of the reactive mixture was also evaluated during the 15-month operation of two bioreactors. Results indicated that bioreactors were effective at both HRTs for increasing the pH and alkalinity of contaminated water and for SO₄ and metal removal (60–82% for Fe and up to 99.9% for Cd, Ni and Zn). Although the quality of treated effluent was significantly improved with the 10 d HRT compared to the 7.3 d HRT, results showed that the higher HRT reduced the porosity and the permeability of the reactive mixture which might lead to hydraulic related problems and, eventually, to limited efficiency in long-term operation compared to a shorter HRT. The choice of HRT for a passive bioreactor must therefore consider both the desired quality of treated effluent and the potential for deterioration of hydraulic properties in the reactive mixture.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.