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.     

Inclusions of silicate and sulfate melts in chrome diposide from the Inagli deposit,Yakutia, Russia

Melt inclusions were studied in chrome diopside from the Inagli deposit of gemstones in the Inagli massif of alkaline ultrabasic rocks of potassic affinity in the northwestern Aldan shield, Yakutia, Russia. The chrome diopside is highly transparent and has an intense green color. Its Cr₂O₃ content varies from 0.13 to 0.75 wt %. Primary and primary-secondary polyphase inclusions in chrome diopside are dominated by crystal phases (80–90 vol %) and contain aqueous solution and a gas phase. Using electron microprobe analysis and Raman spectroscopy, the following crystalline phases were identified. Silicate minerals are represented by potassium feldspar, pectolite [NaCa₂Si₃O₈(OH)], and phlogopite. The most abundant minerals in the majority of inclusions are sulfates: glaserite (aphthitalite) [K₃Na(SO₄)₂], glauberite [Na₂Ca(SO₄)₂], aluminum sulfate, anhydrite (CaSO₄), gypsum (CaSO₄ × 2H₂O), barite (BaSO₄), bloedite [Na₂Mg(SO₄)₂ × 4H₂O], thenardite (NaSO₄), polyhalite [K₂Ca₂Mg(SO₄)₄ × 2H₂O], arcanite (K₂SO₄), and celestite (SrSO₄). In addition, apatite was detected in some inclusions. Chlorides are probably present among small crystalline phases, because some analyses of aggregates of silicate and sulfate minerals showed up to 0.19–10.3 wt % Cl. Hydrogen was identified in the gas phase of polyphase inclusions by Raman spectroscopy. The composition of melt from which the chrome diopside crystallized was calculated on the basis of the investigation of silicate melt inclusions. This melt contains 53.5 wt % SiO₂, considerable amounts of CaO (16.3 wt %), K₂O (7.9 wt %), Na₂O (3.5 wt %), and SO₃ (1.4 wt %) and moderate amounts of Al₂O₃ (7.5 wt %), MgO (5.8 wt %), FeO (1.1 wt %), and H₂O (0.75 wt %). The content of Cr₂O₃ in the melt was 0.13 wt %. Many inclusions were homogenized at 770–850°C, when all of the crystals and the gas phase were dissolved. The material of inclusions heated up to the homogenization temperature became heterogeneous even during very fast quenching (two seconds) producing numerous small crystals. This fact implies that most of the inclusions contained a salt (rather than silicate) melt of sulfate-dominated composition. Such inclusions were formed from salt globules (with a density of about 2.5 g/cm³) occurring as an emulsion in the denser (2.6 g/cm³) silicate melt from which the chrome diopside crystallized.     

Conditions of Quaternary magmatism at Spitsbergen Island

Petrological and geochemical data obtained on the Quaternary lavas of volcanoes at Spitsbergen Island indicate that the rocks were produced via the deep-seated crystallization of parental alkaline magmas at 8–10 kbar. The character of clinopyroxene enrichment in incompatible elements indicates that the mineral crystallized from more enriched melts than those inferred from the composition of the host lavas. These melts were close to the parental melts previously found as veinlets in mantle hyperbasite xenoliths in the lavas. According to the character of their enrichment in Pb and Sr radiogenic isotopes and depletion in Nd, the basalts from Spitsbergen Island define a single trend with the weakly enriched tholeiites of the Knipovich Ridge, a fact suggesting the closeness of the enriched sources beneath the continental margin of Spitsbergen and beneath the spreading zone. Magmatic activity at Spitsbergen was related to the evolution of the Norwegian-Greenland basin, which evolved in pulses according to the shift of the spreading axes. The most significant of the latter events took place in the Neogene, when the Knipovich Ridge obtained its modern position near the western boundary of Spitsbergen. Early in the course of the evolution, the emplacement of alkaline melts generated at Spitsbergen into the oceanic mantle could form the enriched mantle, which was later involved in the melting process beneath the spreading zone.     

Quantitative textural analysis of packings of elongate crystals

The spatial distribution of grains in a solidifying igneous rock controls the physical properties of the crystal mush, and in turn is controlled by the rate of crystal growth and accumulation. A predominant non-spherical habit for igneous minerals brings into question the use of spherical particles in reference packings used for quantification of spatial distribution. Furthermore, variations of crystal clustering/ordering with length scale require spatial statistics which take into account the distribution of particles beyond nearest neighbours. Using random close packings of spherocylinders, we demonstrate the importance of aspect ratio for the aggregation index (usually known as R) and show that packings of spherical particles have more structure than packings of rods. The spatial distribution functions demonstrate that the plagioclase grains in the colonnade from the Holyoke basalt are clustered on a length scale of 0.5 mm. Understanding the controls on grain spatial distribution in igneous rocks will depend on the application of these techniques to well-understood environments.     

Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rocks: the Erongo granite and tourmalinites in the Damara Belt,Namibia

Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ¹¹B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ¹¹B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ¹¹B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Basaltic explosive volcanism: Constraints from deposits and models

Basaltic pyroclastic volcanism takes place over a range of scales and styles, from weak discrete Strombolian explosions (～10²–10³ kg s^?1) to Plinian eruptions of moderate intensity (10⁷–10⁸ kg s^?1). Recent well-documented historical eruptions from Etna, Kīlauea and Stromboli typify this diversity. Etna is Europe's largest and most voluminously productive volcano with an extraordinary level and diversity of Strombolian to subplinian activity since 1990. Kīlauea, the reference volcano for Hawaiian fountaining, has four recent eruptions with high fountaining (>400 m) activity in 1959, 1960, 1969 (–1974) and 1983–1986 (–2008); other summit (1971, 1974, 1982) and flank eruptions have been characterized by low fountaining activity. Stromboli is the type location for mildly explosive Strombolian eruptions, and from 1999 to 2008 these persisted at a rate of ca. 9 per hour, briefly interrupted in 2003 and 2007 by vigorous paroxysmal eruptions. Several properties of basaltic pyroclastic deposits described here, such as bed geometry, grain size, clast morphology and vesicularity, and crystal content are keys to understand the dynamics of the parent eruptions.The lack of clear correlations between eruption rate and style, as well as observed rapid fluctuations in eruptive behavior, point to the likelihood of eruption style being moderated by differences in the fluid dynamics of magma and gas ascent and the mechanism by which the erupting magma fragments. In all cases, the erupting magma consists of a mixture of melt and gaseous bubbles. The depth and rate of degassing, melt rheology, bubble rise and coalescence rates, and extent of syn-eruptive microlite growth define complex feedbacks that permit reversible shifts between fragmentation mechanisms and in eruption style and intensity. However, many basaltic explosive eruptions end after an irreversible shift to open-system outgassing and microlite crystallization in melt within the conduit.Clearer understanding of the factors promoting this diversity of basaltic pyroclastic eruptions is of fundamental importance in order to improve understanding of the range of behaviors of these volcanoes and assess hazards of future explosive events at basaltic volcanoes. The three volcanoes used for this review are the sites of large and growing volcano-tourism operations and there is a public need both for better knowledge of the volcanoes’ behavior and improved forecasting of the likely course of future eruptions.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

Reaction mechanism of uranyl in the presence of zero-valent iron nanoparticles

The current study provides an investigation of abiotic reduction of an oversaturated uranyl solution driven by iron nanoparticle oxidation. The reactivity of nano-scale zero-valent iron (ZVI) under mildly oxic conditions (1.2% O₂ and 0.0017% CO₂) was studied in 1000 ppm uranyl solution in the pH range 3-7, at reaction times from 10 min to 4 h. Reductive precipitation of UO₂ was observed as the main process responsible for the removal of uranium from solution with the kinetics of reaction becoming increasingly favourable at higher pH. Despite working with an oversaturated uranium solution, the precipitation of UO₂ occurred in preference to precipitation of UO₃·2H₂O (metaschoepite) at reaction times between 1 and 4 h and for uranyl solutions initially set up at pH ?5. Characterisation of both solid and solution phases was performed using X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) imaging, X-ray diffraction (XRD) and inductively coupled plasma atomic emission spectroscopy (ICP-AES).     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol⁻¹, which is within the range reported in the literature for anaerobic processes.