Calcite precipitation instability under laminar, open-channel flow

We present a 2D numerical model for the growth of calcite from supersaturated aqueous solutions under laminar, open-channel flow conditions. The model couples solution chemistry, precipitation at solution/calcite interfaces, hydrodynamics, diffusion and degassing. The model output is compared with experimental results obtained using an oversaturated calcite solution produced by mixing CaCl₂ and Na₂CO₃. The precipitation rate is observed to increase when the supersaturated solution flows over an obstruction, leading to a growth instability that causes the formation of terraces. At relatively high flow rates, the most important mechanism for this behaviour seems to be hydrodynamic advection of dissolved species either towards or away from the calcite surface, depending on location relative to the obstruction, which deforms the concentration gradients. At lower flow rates, steepening of diffusion gradients around protrusions becomes important. Enhanced degassing over the obstruction due to shallowing and pressure drop is not important on small scales. Diffusion controlled transport close to the calcite surface can lead to a fingering-type growth instability, which generates porous textures. Our results are consistent with existing diffusive boundary layer theory, but for flow over non-smooth surfaces, simple calcite precipitation models that include empirical correlations between fluid flow rate and calcite precipitation rate are inaccurate.     

Lateral structural variability in zone of eocene island-arc-continent collision,Kamchatka

The lateral variability of structural elements in the collision zone of the Cretaceous-Paleocene Achaivayam-Valagin island arc with the northeastern Asian margin is considered. The similarity and difference of Eocene collision structural elements in the north and the south of Kamchatka are shown. In northern Kamchatka, the continent-arc boundary is traced along the Lesnaya-Vatyn Thrust Fault, which completed its evolution about 45 Ma ago. The thin, near-horizontal allochthon of this thrust, composed of island-arc rocks, overlies the deformed but unmetamorphosed terrigeneous sequences of the Asian margin. The general structure of this suture in the Kamchatka Isthmus and southern Koryakia is comparable with the uppermost subduction zone, where a thin lithospheric wedge overlaps intensely deformed sediments detached from the plunging plate. In southern Kamchatka (Malka Uplift of the Sredinny Range), the arc-continent collision started 55–53 Ma ago with thrusting of island-arc complexes over terrigenous rocks of continental margin. However, the thickness of the allochthon was much greater than in the north. Immediately after this event, both the autochthon and lower part of allochthon were deformed and subsided to a significant depth. This subsidence gave rise to metamorphism of both the autochthon (Kolpakov and Kamchatka groups, Kheivan Formation) and lower allochthon (Andrianovka and Khimka formations). The anomalously fast heating of the crust was most likely related to the ascent of asthenospheric masses due to slab breakoff, when the Eurasian Plate was plunging beneath the Achaivayam-Valagin arc.     

Geobarometry for Peridotites: Experiments in Simple and Natural Systems from 6 to 10 GPa

Experiments with peridotite minerals in simple (MgO–Al₂O₃–SiO₂,CaO–MgO–SiO₂ and CaO–MgO–Al₂O₃–SiO₂)and natural systems were conducted at 1300–1500°Cand 6–10 GPa using a multi-anvil apparatus. The experimentsin simple systems demonstrated consistency with previous lowerpressure experiments in belt and piston–cylinder set-ups.The analysis of spatial variations in pyroxene compositionswithin experimental samples was used to demonstrate that pressureand temperature variations within the samples were less than0·4 GPa and 50°C. Olivine capsules were used in natural-systemexperiments with two mineral mixtures: SC1 (olivine + high-Alorthopyroxene + high-Al clinopyroxene + spinel) and J4 (olivine+ low-Al orthopyroxene + low-Al clinopyroxene + garnet). Theexperiments produced olivine + orthopyroxene + garnet ±clinopyroxene assemblages, occasionally with magnesite and carbonate-richmelt. Equilibrium compositions were derived by the analysisof grain rims and evaluation of mineral zoning. They were comparedwith our previous experiments with the same starting mixturesat 2·8–6·0 GPa and the results from simplesystems. The compositions of minerals from experiments withnatural mixtures show smooth pressure and temperature dependencesup to a pressure of 8 GPa. The experiments at 9 and 10 GPa producedandradite-rich garnets and pyroxene compositions deviating fromthe trends defined by the lower pressure experiments (e.g. higherAl in orthopyroxene and Ca in clinopyroxene). This discrepancyis attributed to a higher degree of oxidation in the high-pressureexperiments and an orthopyroxene–high-P clinopyroxenephase transition at 9 GPa. Based on new and previous resultsin simple and natural systems, a new version of the Al-in-orthopyroxenebarometer is presented. The new barometer adequately reproducesexperimental pressures up to 8 GPa. KEY WORDS: garnet; mineral equilibrium; multi-anvil apparatus; orthopyroxene; geobarometry     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

Characterization and cycling of atmospheric mercury along the central US Gulf Coast

Concentrations of atmospheric Hg species, elemental Hg (Hg^°), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM_2.5) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m⁻³, 4.0 ± 7.5 pg m⁻³ and 2.7 ± 3.4 pg m⁻³, respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m⁻³), but not for Hg^° or Hg-PM_2.5. Elevated RGM concentrations (>25 pg m⁻³) in April and May of 2005 correlated with elevated average daytime O₃ concentrations (>55 ppbv) and high light intensity (>500 W m⁻²). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly (p < 0.05) with peaks in SO₂ concentration and corresponded to periods of high light intensity and lower average daytime O₃ concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg^° by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM.     

Biofacies analysis of Upper Cretaceous deposits in the Ust-Yenisei region: Implications of palynomorphs

The results of palynomorph biofacies analysis in the Upper Cretaceous deposits of the Ust-Yenisei region are presented. The established facies confinement and indicative features of separate palynomorph groups are used, along with identified dinocyst morphotypes and taxa, in paleogeographic reconstructions. Seven palynomorph associations characterizing continental, coastal-marine, shallow-and deep-water facies are distinguished based on quantitative proportions between morphological groupings and individual taxa. As boundaries between distinguishable biostratigraphic and facies subdivisions do not coincide, dinocysts were likely insignificantly dependent in distribution on facies in the West Siberian epicontinental basin at least. On the other hand, distribution trends of particular dinocyst morphotypes and other microphytofossils are correlative with transgressive-regressive cycles and can be used for reconstruction of paleoenvironments.     

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.     

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.