Laboratory measurements and modeling of metal-humic interactions under estuarine conditions

Equilibrium dialysis was used to measure Co- and Cu-binding by an isolated peat humic acid (PHA) in controlled laboratory experiments under simulated estuarine conditions: ionic strengths of 0.005 to 0.7 M in NaCl and mixed Na-Mg-Ca chloride solutions, with trace metal concentrations of ∼5 × 10⁻⁷ M, a PHA concentration of 10 mg/L, and at constant pH values of ∼7.8 (Co and Cu) and ∼4.6 (Cu only). Generally, Co- and Cu-humic binding decreased substantially with increasing ionic strength and, in the case of Cu, with decreasing pH. The presence of seawater concentrations of Ca and Mg had a relatively small effect on Co-humic binding and no measurable effect on that of Cu under the experimental conditions. The binding data were well-described by an equilibrium speciation code (the Windermere Humic Aqueous Model, WHAM) after optimising the fits by varying the metal-proton exchange constants for humic acid within justifiable limits (i.e., within 1 standard deviation of the mean exchange constants used in the WHAM database). The main factor producing the observed variations in metal-humic binding at constant pH was the electrostatic effect on the humic molecule. WHAM was used to predict Co- and Cu-humic binding in simulations of real estuaries. Co-humic binding is predicted to be relatively unimportant (generally <5% of total Co), whereas the Cu-humic complex is likely to be the dominant species throughout an estuary. The main factors producing changes in Co- and Cu-humic binding in the real-estuary simulations are the electrostatic effect on the humic molecule, ligand competition (mainly from carbonate species) for metals, and to a lesser extent Ca and Mg competition for humic binding sites. Variations in pH are significant only at the freshwater end of an estuary. WHAM simulations also indicated that competition effects between metals are more likely to occur in freshwaters than in seawater, due to enhanced electrostatic binding at low ionic strength.     

An experimental study of the stability of copper chloride complexes in water vapor at elevated temperatures and pressures

The solubility of copper chloride in liquid-undersaturated HCl-bearing water vapor was investigated experimentally at temperatures of 280 to 320°C and pressures up to 103 bars. Results of these experiments show that the solubility of copper in the vapor phase is significant and increases with increasing f_H2O, but is retrograde with respect to temperature. This solubility is attributed to the formation of hydrated copper-chloride gas species, interpreted to have a copper-chlorine ratio of 1:1 (e.g., CuCl, Cu₃Cl₃, etc.) and a hydration number varying from 7.6 at 320°C, to 6.0 at 300°C, and 6.1 at 280°C. Complex formation is proposed to have occurred through the reaction:

A1     

Crystallization conditions of Los Angeles, a basaltic Martian meteorite

The texture of Los Angeles (stone 1) is dominated by relatively large (0.5−2.0 mm) anhedral to subhedral grains of pyroxene, and generally subhedral to euhedral shocked plagioclase feldspar (maskelynite). Minor phases include subhedral titanomagnetite and ilmenite, Fe-rich olivine, olivine+augite-dominated symplectites [some of which include a Si-rich phase and some which do not], pyrrhotite, phosphate(s), and an impact shock-related alkali- and silica-rich glass closely associated with anhedral to euhedral silica grains. Observations and model calculations indicate that the initial crystallization of Mg-rich pigeonitic pyroxenes at ≤1150 °C, probably concomitantly with plagioclase, was followed by pigeonitic and augitic compositions between 1100 and 1050 °C whereas between 1050 and 920 to 905 °C pyroxene of single composition crystallized. Below 920 to 905 °C, single composition Fe-rich clinopyroxene exsolved to augite and pigeonite. Initial appearance of titanomagnetite probably occurred near 990 °C and FMQ-1.5 whereas at and below 990 °C and ≥FMQ-1.5 titanomagnetite and single composition Fe-rich clinopyroxene may have started to react, producing ilmenite and olivine. However, judging from the most common titanomagnetite compositions, we infer that most of this reaction likely occurred between 950 and 900 °C at FMQ-1.0±0.2 and nearly simultaneously with pyroxene exsolution, thus producing assemblages of pigeonite, titanomagnetite, olivine, ilmenite, and augite. We deem this reaction as the most plausible explanation for the formation of the olivine+augite-dominated symplectites in Los Angeles. But we cannot preclude possible contributions to the symplectites from the shock-related alkali- and silica-rich glass or shocked plagioclase, and the breakdown of Fe-rich pigeonite compositions to olivine+augite+silica below 900 °C. Reactions between Fe-Ti oxides and silicate minerals in Los Angeles and other similar basaltic Martian meteorites can control the T-fO₂ equilibration path during cooling, which may better explain the relative differences in fO₂ among the basaltic Martian meteorites.     

Mesoproterozoic (1.47–1.44 Ga) orogenic magmatism in Fennoscandia; Baddeleyite U–Pb dating of a suite of massif-type anorthosite in S. Sweden

The Jönköping Anorthositic Suite (JAS) in S. Sweden has characteristics typical for (Proterozoic) massif-type anorthosites. The interstitial liquid of these plagioclase-porphyritic rocks solidified at 1,455 ± 6 Ma, as determined by U–Pb isotope analysis of baddeleyite. The JAS developed during a regional 1.47–1.44 event in Fennoscandia that generated widespread mafic magmatism (basalts, and diabase dykes and sills) in the north and emplacement of felsic plutons in the south. The event of 1.47–1.44 Ga magmatism in Fennoscandia largely coincides in age with dynamic high-grade metamorphism in SW Sweden and was probably related to convergent active-margin processes during the Danopolonian orogeny.     

The oxygen isotopic composition as an indicator of the genesis of “Basaltic” corundum

This paper reports an oxygen isotopic study of corundums and associated minerals from the Yogo lamprophyres (Montana, US), plagioclase-corundum inclusions in alkali basalt (Tunkin depression, Russia), and from modern alluvium of Podgelbanochnyi alkaline basaltic volcano (Primorye, Russia). It is shown that all sapphires genetically related to mafic magmatic rocks have a similar oxygen isotopic composition (the variations of δ¹⁸O are within 2.5‰) with most values plotting between +4.5 and +7.0‰ SMOW. The oxygen isotopic ratios in the associated minerals (olivines, pyroxenes, mica, and others) and host rocks are plotted in the same interval. This indicates that the sapphire crystallized during evolution of the parental mafic magma. However, there are xenogenic corundums, which were only transported by basaltic magma to the Earth’s surface. They have a sharply distinct oxygen isotopic composition, which suggests their disequilibrium with the host lavas, and, correspondingly, a different genetic nature.     

Depths of the Sea of Okhotsk sedimentary basin in the Cenozoic

The biofacies analysis of benthic foraminifers in sediments of the Sea of Okhotsk paleobasin revealed the presence of typical abyssal species in their Oligocene-Miocene assemblages that are missing in the Pliocene and Pleistocene section. The development of the abyssal fauna in the Sea of Okhotsk was determined by its relatively large depths (>2000 m) and intense water exchange with the Pacific Ocean. The Sakhalin folding phase at the Neogene-Quaternary transition resulted in the uplifting of the Japan-Kurile cordillera and separation of deep basins of the Japan and Okhotsk seas from the ocean, which was responsible for the formation of unfavorable conditions for migration and existence of the Pacific abyssal fauna. The taxonomic similarity and general tendencies in the development of the Neogene benthic foraminifers common for the Japan and Okhotsk seas imply the lack of narrow and shallow thresholds between these basins similar to the present-day Nevel’skoi, La Pérouse, and Sangar straits. Such bottom topography stimulated the intense northward water flow, which determined the similarity between the benthic foraminiferal assemblages of the Japanese and Okhotsk paleobasins.     

Geochemistry and potential use of groundwater in the Rocca Busambra area (Sicily, Italy)

In the Rocca Busambra area (mid-west Sicily, Italy), from November 1999 to July 2002, 23 water points including wells and springs were sampled and studied for their chemical and isotopic compositions. Two rain gauges were also installed at different altitudes, and rainwater was collected monthly to determine the isotopic composition. The obtained results revealed the Rocca Busambra carbonate complex as being the main recharge area on account of its high permeability value. From a chemical view point, two main groups of water can be distinguished: calcium–magnesium–bicarbonate-type and calcium–magnesium–chloride–sulphate-type waters. The first group reflects the dissolution of the carbonate rocks; the second group probably originates from circulation within flyschoid sediments. Three water wells differ from the other samples due to their relatively high Na and K content, which probably is to be referred to a marked interaction with the “Calcareniti di Corleone” formation, which is rich in glauconite [(K, Na)(Fe³⁺, Al, Mg)₂(Si, Al)₄O₁₀(OH)₂]. In accordance with WHO guidelines for drinking water (2004), almost all the samples collected can be considered drinkable, with the exception of four of them, whose NO₃ ⁻, F⁻ and Na⁺ contents exceed the limits. On the contrary, the sampled groundwater studied is basically suitable for irrigation.     

Crustal seismic velocity in the Marche region (Central Italy): computation of a minimum 1-D model with seismic station corrections

A 1-D velocity model for the Marche region (Central Italy) was computed by inverting P- and S-wave arrival times of local earthquakes. A total of 160 seismic events with a minimum of ten observations, a travel time residual ≤0.8 s and an azimuthal gap lower than 180° have been selected. This “minimum 1-D velocity model” is complemented by station corrections, which can be used to take into account possible near-surface velocity heterogeneities beneath each station. Using this new P-wave velocity model and the program HYPOELLIPSE (Lahr 1999), the selected local events were relocated. Earthquake locations in this study are of higher quality with respect to the original ones. The obtained minimum 1-D velocity model can be used to improve the routine earthquake locations and represents a further step towards more detailed seismotectonic studies of the area.     

Different magneto-rotational supernovae

We present the results of two-dimensional calculations of a magneto-rotational (MR) supernova explosion with a collapsing core for various core masses, rotational angular momenta, and magnetic-field configurations. It is shown that the MR mechanism produces an explosion energy that corresponds to observed values. The form of the explosion depends substantially on the initial configuration of the magnetic field. MR instability develops during the evolution of the magnetic field in an MR supernova explosion, resulting in an exponential increase of all components of the magnetic field, thereby substantially decreasing the time scale of the MR explosion. The energy of the supernova increases with the core’s mass and initial rotational energy.     

Evaluation of distributed recharge in an upland semi-arid karst system: the West Bank Mountain Aquifer,Middle East

Assessment of recharge in a structurally complex upland karst limestone aquifer situated in a semi-arid environment is difficult. Resort to surrogate indicators such as measurement of spring outflow and borehole discharge, is a common alternative, and attempts to apply conventional soil moisture deficit analysis may not adequately account for the intermittent spate conditions that arise in such environments. A modelling approach has been made using the West Bank Mountain Aquifer system in the Middle East as a trial. The model uses object oriented software which allows various objects to be switched on and off. Each of the main recharge processes identified in the West Bank is incorporated. The model allows either conventional soil moisture deficit analysis calculations or wetting threshold calculations to be made as appropriate, and accommodates both direct recharge and secondary recharge. Daily time steps enable recharge and runoff routing to be calculated for each node. Model runs have enabled a series of simulations for each of the three aquifer basins in the West Bank and for the whole of the West Bank. These provide recharge estimates comparable to those prepared by earlier workers by conventional means. The model is adaptable and has been successfully used in other environments.