Saturation of groundwaters with respect to minerals of the host rocks

Calculations of the saturation of groundwaters with respect to minerals of the rocks hosting these waters indicate that most of the analyzed groundwaters were saturates with respect to calcite, dolomite, and quartz. Brines of chloride-calcic composition were determined to be saturated with respect to calcite, whereas brines of chloride-sodic composition are saturated with respect to dolomite and quartz. The solution was simultaneously saturated with respect to six minerals for the association ankerite-calcite-dolomite-pyrite-quartz-strontianite. An increase in the number of minerals with respect to which solution is saturated is correlated with an increase in the diversity of types of groundwaters and an increase in the runoff rate. The paper proposes possible avenues for searches for relations between hydrogeological and geochemical parameters that make it possible to adapt the thermodynamic models to real geological-hydrogeological conditions. The research was centered on the testing of groundwaters for their saturation with respect to minerals of the rocks hosting these waters. This parameter plays a significant part in forming the geochemical type of natural waters because it reflects the crystallization of a mineral from a solution and, consequently, the removal of an element from the aqueous solution.     

Metamorphic rocks of the Murmansk domain (Kola Peninsula) as compared with the oldest rock associations of the northeastern Baltic shield,Canada, and Greenland

Rock associations characterized by heterogeneous sets of petrogeochemical parameters were compared by quantifying the degree of their similarity-dissimilarity and searching for discrimination trends between them. Using procedures specially developed for this purpose, it was demonstrated for the first time that the lithotectonic complexes of the Murmansk domain are fundamentally different from those of typical granulite-gneiss terrains and resemble the granite-greenstone terrains of the Baltic shield, Greenland, and Canada. Based on the whole data set, the Murmansk domain can be considered as a deeply eroded Archean granite-greenstone terrain retaining only the tonalite-trondhjemite-gneiss basement with abundant supracrustal enclaves. A trend of the compositional difference between the older and younger rock associations is similar to that between the tholeiitic and boninitic volcanic series. It was suggested that the petrogeochemical “age” trend reflects the initial stage of the compositional evolution of the metamagmatic rocks of the region from metamorphic rocks similar to tholeiites at the early stages to the Paleoproterozoic boninite-like rocks, which are believed to be linked to the unique PGE-bearing province of the northeastern Baltic shield. This implies that the specific metallogenic features of the region emerged already in the Archean, which supported the suggestion on the long duration of geological processes in the Early Precambrian.     

Surface complexation effects on phosphate adsorption to ferric iron oxyhydroxides along pH and salinity gradients in estuaries and coastal aquifers

Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg²⁺ and Ca²⁺ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.     

Oxygen Isotope Evidence for Chemical Interaction of Ki lauea Historical Magmas with Basement Rocks

Klauea historical summit lavas have a wide range in matrix ¹⁸O_VSMOWvalues (4·9–5·6) with lower values in rockserupted following a major summit collapse or eruptive hiatus.In contrast, ¹⁸O values for olivines in most of these lavasare nearly constant (5·1 ± 0·1). The disequilibriumbetween matrix and olivine ¹⁸O values in many samples indicatesthat the lower matrix values were acquired by the magma afterolivine growth, probably just before or during eruption. BothMauna Loa and Klauea basement rocks are the likely sources ofthe contamination, based on O, Pb and Sr isotope data. However,the extent of crustal contamination of Klauea historical magmasis probably minor (< 12%, depending on the assumed contaminant)and it is superimposed on a longer-term, cyclic geochemicalvariation that reflects source heterogeneity. Klauea's heterogeneoussource, which is well represented by the historical summit lavas,probably has magma ¹⁸O values within the normal mid-ocean ridgebasalt mantle range (5·4–5·8) based on thenew olivine ¹⁸O values. KEY WORDS: Hawaii; Klauea; basalt; oxygen isotopes; crustal contamination     

Geochronology of Pliocene volcanism in the Dzhavakheti Highland (the Lesser Caucasus). Part 1: Western part of the Dzhavakheti Highland

Isotopic-geochronological study of the Pliocene magmatic activity in western part of the Dzhavakheti Highland (northwestern region of the Lesser Caucasus) is carried out. The results obtained imply that the Pliocene magmatic activity lasted in this part of the highland approximately 2 million years from 3.75 to 1.75–1.55 Ma. As is established, the studied volcanic rocks correspond in composition mostly to K-Na subalkaline and more abundant normal basalts. Time constraints of main phases in development of basic volcanism within the study region are figured out. We assume that individual pulses of silicic to moderately silicic volcanism presumably took place in the Dzhavakheti Highland about 3.2 and 2.5 Ma ago.     

The Ruiga intrusion: A typical example of a shallow-facies paleoproterozoic peridotite-gabbro-komatiite-basaltic association of the Vetreny Belt,Southeastern Fennoscandia

The Ruiga differentiated mafic-ultramafic intrusion in the northwestern part of the Vetreny Belt paleorift was described for the first time based on geological, petrological, geochronological, and geochemical data. The massif (20 km² in exposed area) is a typical example of shallow-facies peridotite-gabbro-komatiite-basalt associations and consists of three zones up to 810 m in total thickness (from bottom to top): melanogab-bronorite, peridotite, and gabbro. In spite of pervasive greenschist metamorphism, the rocks contain locally preserved primary minerals: olivine (Fo _75–86), bronzite, augite of variable composition, labradorite, and Cr-spinels. A mineral Sm-Nd isochron on olivine melanogabbronorite from the Ruiga Massif defines an age of 2.39 ± 0.05 Ga, while komatiitic basalts of the Vetreny Belt Formation were dated at 2.40–2.41 Ga (Puchtel et al., 1997). The rocks of the Ruiga intrusion and lava flows of Mt. Golets have similar major, rare-earth, and trace element composition, which suggests their derivation from a single deep-seated source. Their parent magma was presumably a high-Mg komatiitic basalt. In transitional crustal chambers, its composition was modified by olivine-controlled fractionation and crustal contamination, with the most contaminated first portions of the ejected melt. In terms of geology and geochemistry, the considered magmatic rocks of the Vetreny Belt are comparable with the Raglan Ni-PGE komatiite gabbro-peridotite complex in Canada (Naldrett, 2003).     

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.     

Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.