The mechanism and kinetics of DTPA-promoted dissolution of barite

The dissolution rate of natural barite, BaSO₄, was measured in solutions of DTPA (diethylene triamine penta-acetic acid) to investigate the mechanism of ligand-promoted dissolution using a strong chelating agent. Experiments were carried out over a range of DTPA concentrations 0.5–0.0001 M solutions, at room temperature (22 °C), as well as a range of temperatures, 22–80 °C at 1 atm. The dissolution rate is inversely related to the DTPA concentration in solution. A more dilute DTPA solution is shown to be more efficient as a solvent in terms of the approach to the equilibrium saturation value for the dissolution of Ba²⁺. An analysis of the temperature dependence of the dissolution rate at high pH by the determination of activation energies indicates that the reaction is probably controlled by the pre-exponential term in the rate constant. This indicates that reaction frequency mostly controls differences in reactivity and suggests an explanation for the results in terms of stearic hindrance due to adsorbed DTPA molecules at the barite surface. The effect of DTPA on the solvation of the Ba²⁺ ion may also influence the dissolution rate.     

Fault slip analysis in the Koralm Massif (Eastern Alps) and consequences for the final uplift of “cold spots” in Miocene times

The Paleogene and Neogene evolution of Austroalpine basement units east of the Tauern Window is characterised by the formation of two major sets of faults: (1) ESE–WNW- to E–W-trending faults, associated with ENE- and NNW-trending conjugate structures and (2) N–S to NNE-SSW striking structures, mainly acting as high-angle normal faults, often associated with E-dipping low-angle normal faults along the western margin of the Styrian Basin.Together with the stratigraphic evolution of the Styrian and Lavanttal Basins and the related subsidence histories a tectonic evolution may be reconstructed for this part of the Eastern Alps. In the southern part of the Koralm Massif, WNW-trending fractures were activated as dextral strike-slip faults, associated with the evolution of WNW-trending troughs filled up with coarse block debris. W- to WNW-trending fractures were reactivated as normal faults, indicating N–S extension. It is assumed that these phases resulted in subsidence and block debris sedimentation in Karpatian and Badenian times (ca. 17–13 Ma).In the Western Styrian Basin no Sarmatian (13–11.5 Ma) sediments are observed; Pannonian (11.5 to 7.1 Ma) sediments are restricted to the Eastern Styrian Basin. This indicates, that the Koralm basement and the Western Styrian Basin were affected by post-Sarmatian uplift, coinciding with a re-activation of N-trending normal faults along the eastern margin of the Koralm Massif. Therefore, we suggest that the final uplift of the Koralm Complex, partly together with the Western Styrian Basin, occurred during the early Pannonian (at approximately 10 Ma). The elevation of clastic deposits indicates that the Koralm Complex was elevated by approximately 800 m during this phase, associated with an additional phase of E–W-directed extension accommodated by N–S striking normal faults.     

High-precision late Aptian Pb/U age for the Punta del Barco Formation (Baqueró Group), Santa Cruz Province,Argentina

The Baqueró Group holds a rich fossil flora including macrofloristic and palynological remains that characterize the Early Cretaceous vegetation of Argentina. The age of the upper part of the Group, known as Punta del Barco Formation, has been a topic of several discussions in the past. The type locality of this stratigraphic unit exposes fossiliferous tuffs together with muddy tuffs and tuffaceous sandstones beds. However, there have been no reliable age constraints for the fossil assemblages. ²⁰⁶Pb/²³⁸U analyses of zircon crystals yielded an age of 114.67 ± 0.18 Ma. This age control makes possible an improved analysis and comparison of the floras in the southern region.     

Microelectrona cladara gen.et sp.nov.:A New Protodikraneurini from the Eocene Baltic Amber(Hemiptera:Cicadomorpha:Cicadellidae:Typhlocybinae)

<正>A new genus Microelectrona gen.nov.and species Microelectrona cladara sp.nov.of the extinct tribe Protodikraneurini of the leafhoppers(Cicadeilidae:Typhlocybinae) from the Eocene Baltic amber is described. The piece of amber containing leafhopper inclusion is broken,unveiling some of the morphological structures,and enabling their studies using scanning electron microscopy.     

“Invisible” silver and gold in supergene digenite (Cu1.8S)

Despite its potential economic and environmental importance, the study of trace metals in supergene (secondary) Cu-sulfides has been seriously overlooked in the past decades. In this study, the concentration and mineralogical form of “invisible” precious metals (Ag, Au) and metalloids (As, Sb, Se, Te) in supergene digenite (Cu_1.8S) from various Cu deposits in the Atacama Desert of northern Chile, the world’s premier Cu province, were determined in detail using a combination of microanalytical techniques. Secondary ion mass spectrometry (SIMS) and electron microprobe analyzer (EMPA) measurements reveal that, apart from hosting up to ∼11,000 ppm Ag, supergene digenite can incorporate up to part-per-million contents of Au (∼6 ppm) and associated metalloids such as As (∼300 ppm), Sb (∼60 ppm), Se (∼96 ppm) and Te (∼18 ppm). SIMS analyses of trace metals show that Ag and Au concentrations strongly correlate with As in supergene digenite, defining wedge-shaped zones in Ag-As and Au-As log-log spaces. SIMS depth profiling and high-resolution transmission electron microscopy (HRTEM) observations reveal that samples with anomalously high Ag/As (>∼30) and Au/As (>∼0.03) ratios plot above the wedge zones and contain nanoparticles of metallic Ag and Au, while samples with lower ratios contain Ag and Au that is structurally bound to the Cu-sulfide matrix. The Ag-Au-As relations reported in this study strongly suggest that the incorporation of precious metals in Cu-sulfides formed under supergene, low-temperature conditions respond to the incorporation of a minor component, in this case As. Therefore, As might play a significant role by increasing the solubility of Ag and Au in supergene digenite and controlling the formation and occurrence of Ag and Au nanoparticles. Considering the fact that processes of supergene enrichment in Cu deposits can be active from tens of millions of years (e.g. Atacama Desert), we conclude that supergene digenite may play a previously unforeseen role in scavenging precious metals from undersaturated (or locally slightly supersaturated) solutions in near-surface environments.     

Fe(III) Reduction in the Presence of Catechol in Seawater

Fe(II)-Fe(III) redox behavior has been studied in the presence of catechol under different pH, ionic media, and organic compound concentrations. Catechol undergoes oxidation in oxic conditions producing semiquinone and quinone and reduces Fe(III) in natural solutions including seawater (SW). It is a pH-dependent process. Under darkness, the amount of Fe(II) generated is smaller and is related to less oxidation of catechol. The Fe(II) regeneration is higher at lower pH values both in SW with log k = 1.86 (M⁻¹ s⁻¹) at pH 7.3 and 0.26 (M⁻¹ s⁻¹) at pH 8.0, and in NaCl solutions with log k of 1.54 (M⁻¹ s⁻¹) at pH 7.3 and 0.57 (M⁻¹ s⁻¹) at pH 8.0. At higher pH values, rate constants are higher in NaCl solutions than in SW. This is due to the complexation of Mg(II) present in the media with the semiquinone that inhibits the formation of a second Fe(II) through the reaction of this intermediate with other center Fe(Cat)⁺.     

Numerical simulation of atmospheric bore waves on Mars

The Viking Orbiters imaged early morning, long, linear wave clouds along the flanks of the Tharsis volcanoes during late northern spring and early summer. These clouds are believed to be a product of either an atmospheric bore wave or a hydraulic jump generated by nightly katabatic winds. The Mars Regional Atmospheric Modeling System was used to study the interaction of the katabatic flows with the surrounding atmosphere to determine what mechanism is responsible for the clouds. Simulations at Ls=90°, 100°, 142°, 180°, 270°, and 358° were conducted focusing on the eastern flank of Olympus Mons. Model results compare well with Viking observations and closely approximate theoretical treatments of atmospheric bores. Strong downslope flows are simulated during the night, with a bore wave forming on and behind a well-defined katabatic front. The observed seasonality of the clouds was reproduced in the simulations; the bore was deeper and faster during northern summer and weakest during the winter. When the bore was strong, it was undular in form, and generated vertically propagating gravity waves in the atmosphere above. During the winter, the atmospheric structure was such that any gravity waves generated damped with height. Less atmospheric water vapor abundance during northern winter, as compared to the summer, is also a factor in the seasonality of the wave clouds. This study concludes that bore waves are the most likely mechanism for the generation of the observed linear wave clouds.     

Results of statistical analysis of primary components concentrations in bulk chemical composition of ordinary chondrite groups

We used two different methods of statistical analysis—cluster analysis and principal component analysis—to analyze the concentrations of principal chemical components (Si, Mg, Ca, Fe, Ni) and Co in ordinary chondrites. The analysis is based predominantly on published data (metadata). In total, chemical composition data from 646 ordinary chondrites were used in the statistical analysis. The aim of this analysis was to establish whether it would be possible or not to distinguish H, L, and LL chondrites based on the concentrations of major elements and Co in their bulk chemical compositions. It was also important to determine what conclusions such an analysis could enable to draw about matter differentiation in the formation environments of primordial parent bodies of particular ordinary chondrite groups (H, L, and LL). Another aim of the statistical analysis was to determine whether the distribution of Fe and Ni (with Co admixtures) is independent of petrographic types within particular groups of chondrites. This is of crucial importance for determining the distribution of FeNi(Co) ore occurrences in potential extraterrestrial deposits on modern asteroids—the sources of ordinary chondrites. The obtained results of statistical analyses confirmed that a clear-cut distinction between particular groups of ordinary chondrites is only possible for group H, while distinguishing L chondrites from LL chondrites is not always obvious. The results of the statistical analyses relating to the question of the possible existence of several primordial parent bodies (formation environments) of each group of ordinary chondrites are consistent with the results of contemporary astronomical spectroscopy research. What is particularly interesting is obtaining indications of the existence of common formation environments of the matter of L and LL chondrites, possibly on a few primordial parent bodies. The statistical analyses indicate that there is no correlation between the concentration of principal chemical components and the petrographic type of ordinary chondrites. This proves homogenous distributions of these elements within the parent bodies of each group of ordinary chondrites. Hence, the distribution of these elements in individual present-day asteroids is also homogenous.