Release of Arsenic from Volcanic Rocks through Interactions with Inorganic Anions and Organic Ligands

The effects of a number of inorganic anions (F⁻, HCO₃ ⁻, B(OH)₄⁻, Cl⁻, I⁻) and of the siderophore DFO-B on the release of As from volcanic rocks were investigated in batch experiments. While previously reported field and laboratory data support a role of inorganic anions on As mobilization into aquifers, the role of siderophores on As-induced mobilization was less investigated. Fluoride, bicarbonate and DFO-B have shown a significant influence on the release of As from the rocks. Lava was mostly affected among the investigated rocks at pH 6 and 20°C by releasing 4% of its initial As content in the presence of 0.01 M F⁻and 10% in the presence of 500 μM DFO-B. The effect of fluoride was larger at pH 6 than at pH 8.5 for all the rocks. In the case of DFO-B, there was also a larger effect at pH 6 compared to pH 8 for the various rocks except tuff. Bicarbonate played a role under alkaline conditions while its effect was negligible at pH 6. Anion exchange processes in the presence of fluoride and bicarbonate and complexation processes in the presence of the siderophore DFO-B appear to be the major processes responsible for the release of arsenic from the rocks. The siderophore DFO-B plays mainly an indirect role on the As release by complexing Al, Fe and Mn, thus favoring the dissolution of the rocks and the consequent release of As bound to surface Al, Fe and Mn oxy-hydroxides. These findings suggest that ionic interactions with fluoride, bicarbonate and siderophore may be a further triggering factor in the mobilization of As from aquifer rocks.     

Chlorine-rich metasomatic H2O-CO2 fluids in amphibole-bearing peridotites from Injibara (Lake Tana region, Ethiopian plateau): Nature and evolution of volatiles in the mantle of a region of continental flood basalts

Petrological and geochemical study of volatile bearing phases (fluid inclusions, amphibole, and nominally anhydrous minerals) in a spinel lherzolite xenolith suite from Quaternary lavas at Injibara (Lake Tana region, Ethiopian plateau) shows compelling evidence for metasomatism in the lithospheric mantle in a region of mantle upwelling and continental flood basalts. The xenolith suite consists of deformed (i.e., protogranular to porphyroclastic texture) Cl-rich pargasite lherzolites, metasomatized (LILE and Pb enrichment in clinopyroxene and amphibole) at T ? 1000 °C. Lherzolites contain chlorine-rich H₂O-CO₂ fluid inclusions, but no melt inclusions. Fluid inclusions are preserved only in orthopyroxene, while in olivine, they underwent extensive interaction with the host mineral. The metasomatic fluid composition is estimated: X_CO2 = 0.64, X_H2O = 0.33, X_Na = 0.006, X_Mg = 0.006, X_Cl = 0.018, (salinity = 14-10 NaCl eq. wt.%, a_H2O = 0.2, Cl = 4-5 mol.%). Fluid isochores correspond to trapping pressures of 1.4-1.5 GPa or 50-54 km depth (at T = 950 °C). Synchrotron sourced micro-infrared mapping (ELECTRA, Trieste) shows gradients for H₂O-distribution in nominally anhydrous minerals, with considerable enrichment at grain boundaries, along intragranular microfractures, and around fluid inclusions. Total water amounts in lherzolites are variable from about 150 up to 400 ppm. Calculated trace-element pattern of metasomatic fluid phases, combined with distribution and amount of H₂O in nominally anhydrous minerals, delineate a metasomatic Cl- and LILE-rich fluid phase heterogeneously distributed in the continental lithosphere. Present data suggest that Cl-rich aqueous fluids were important metasomatic agents beneath the Ethiopian plateau, locally forming a source of high water content in the peridotite, which may be easily melted. High Cl, LILE, and Pb in metasomatic fluid phases suggest the contribution of recycled altered oceanic lithosphere component in their source.     

A stratigraphic and geophysical approach to studying the deep-circulating groundwater and thermal springs, and their recharge areas, in Cimini Mountains–Viterbo area, central Italy

The stratigraphic and structural setting of the Cimini Mountains and Viterbo area of Italy has been reconstructed. The architecture of the tectonic edifice, below the Pleistocene Cimino and Vicano volcanic districts cover, is characterized by the Mesozoic–Cenozoic Tuscan Nappe and the similar Umbria-Marche Succession; both are capped by the overthrusted Ligurian Late Cretaceous–Eocene Tolfa Flysch. A shallow unconfined volcanic aquifer is separated, by a thick aquiclude, from the deep confined carbonate aquifer consisting of the Tuscan Nappe and the Umbria-Marche Succession. The volcanic aquifer hosts cold waters, whilst the carbonate aquifer hosts hot sulphate–alkaline earth waters that emerge in the thermal area of Viterbo with a temperature of 30–60°C. The recharge area of cold waters is located in the Cimini Mountains. Thermal waters of the Viterbo hot springs are derived from a circuit of waters that emerge along the River Nera near Narni (about 34 km ENE of Viterbo), with a high salinity, a temperature of 16–18°C, a sulphate–alkaline earth composition, and a discharge of 13 m³/sec, whose recharge area is located in the central pre-Apennines reliefs.     

Keratose-dominated sponge grounds from temperate mesophotic ecosystems (NW Mediterranean Sea)

Differently from the North Atlantic Ocean, only few examples of sponge grounds are known from the Mediterranean Sea, mainly thriving in the deep sea. In this study, a novel temperate mesophotic ecosystem dominated by massive keratose sponges is reported from the Ligurian deep continental shelf. An extensive Remotely Operated Vehicle (ROV) survey allowed to study the structure and large-scale distribution of this biocoenosis. The sponge grounds here described are highly fragmented, being formed by a large number of dense, discrete aggregations of Sarcotragus foetidus (up to 7.7 specimens/m²) and other sponges, including Spongia lamella and Axinella polypoides. They mainly occur on flat, patchy and highly silted hardgrounds between 40 and 70 m depth. These sponge-dominated ecosystems have an exceptionally wide spatial distribution, estimated to cover up to nearly 200 hectares, with the largest sponge grounds occurring along the westernmost part of the Ligurian coast, probably in relation to more suitable oceanographic conditions. The dominant sponge species reach considerable heights (up to 65 cm), greatly increasing the habitat three-dimensionality and acting as poles of attraction for a diverse sessile and vagile fauna. In addition, the high abundance of the keratose sponge grounds at mesophotic depths might represent a larval source for shallow-water populations that in the last decades have been stricken by several mass mortality events.     

The effect of organic compounds in the oxidation kinetics of Cr(III) by H2O2

The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 °C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant (k₁) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min⁻¹) for the pseudo first order rate constant k_1CrAha²⁺ and values approaching zero for and k_1CrAha3. These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H₂O₂ by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100.The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H₂O₂. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H₂O₂ appear to be lowered probably because of steric hindrance of the chelated Cr(III).     

Zeolitization of Oligo-Miocene volcaniclastic rocks from Logudoro (northern Sardinia, Italy)

The present study reports the results of research on volcaniclastic products from Logudoro (northern Sardinia), a reconstructed stratigraphic succession some hundreds of meters thick, comprising two different ignimbritic units separated by an epiclastic layer (generally ˜10 m thick). Clinoptilolite is the most widely distributed authigenic phase in epiclastite and unwelded units, always associated with opal-CT and sometimes with smectite. An adularia-like feldspar, cristobalite and epigenetic quartz are typical phases of welded units. Within the zeolitized units (unwelded ignimbrite and epiclastic units) clinoptilolite and opal-CT constitute the cement deriving from the transformation of the precursor rhyolitic glass, in agreement with a single zeolitization process that developed after the deposition of the entire succession. Silica increases in zeolitized rocks with respect to the precursor material, leading to hypothesize that the secondary mineralization process was favored by mineralized hydrothermal fluids preferentially circulating through the fault system of the area. Quartz veins in welded subunit and K-feldspar (adularia-like) preferentially located near the faults are in agreement with this hypothesis. The interaction of these fluids with the glassy fraction favored its dissolution and the consequent crystallization of clinoptilolite. Furthermore, the pH increase and the silica supersaturation enhanced the contemporary or subsequent precipitation of opal-CT. Received: 5 June 2000 / Accepted: 14 August 2000     

Occurrence of phlogopite in the Finero Mafic layered complex

Phlogopite-bearing lithologies are the main constituent of the Phlogopite-Peridotite unit of the Finero sequence and the result of pervasive migration of metasomatizing melts/fluids. Conversely, the presence of phlogopite within the associated Finero Mafic Complex, a mafic-ultramafic pluton intruded into the metamorphic basement of the Adria plate, is mentioned in literature as rare. Recent detailed fieldwork has evidenced the presence of two distinct phlogopite-rich ultramafic lithologies within the Amphibole-Peridotite unit of the Finero Mafic Complex, where phlogopite is always associated with amphibole. Field and petrographic features of these occurrences, as well as major- and trace-element mineral chemistry, are here presented to i) place constraints on the nature of the parent melt from which they have been generated and ii) to address their relationship with the other lithologies of the Finero Complex. We find that these rocks were formed by late melt migrations along shear zones under high-T conditions. The geochemical affinity of these lithologies is different to the tholeiitic-transitional affinity reported in literature for the Finero Mafic Complex. The enrichment in LREE, Th, U and Sr of the associated amphibole possibly suggests that these phlogopite-bearing lithologies are genetically related to the metasomatic events that have affected the Finero mantle massif.     

The old calcium plages differential rotation latitudinal profile: Its gross and fine structure evolution with the solar cycle

This work is a study of the rotational properties of the solar calcium plages, during the time interval 1967–1977; only plages older than 4 days have been the object of this research. We have looked systematically for any significant change occurring during the course of the solar cycle, and any kind of ‘anomaly’ or fine structure in the differential rotation latitudinal profile. We find that such a profile undergoes a cyclic transformation, making it assume the highest steepness at the solar maximum; a sudden flattening then occurs in the first years of declining activity; the last years of the cycle, as the first years of the next one, are characterized by intermediate steepness values. Moreover, we find that, in spite of the general belief that the angular rotation rate is continuously decreasing with increasing heliographic latitude, at least two inversions do exist of such an overall tendency:

1. A narrow, minimal angular-rotation-rate strip lies very close to the equatorward margin of the plage production band; this feature shifts continuously, in a wave-like manner, throughout the solar cycle, from 15/18° to 3/6° latitude.
2. A narrow, maximal angular-rotation-rate strip has been observed lying in the neighbourhood of the poleward margin of the activity band; a process of continuous transformation of the rotation rate profile is always active, in a narrow latitude strip on the equatorward side of such a feature, generating new features of the same kind, which replace the older ones, that disappeared due to the equatorward shift of the plage zone. All that simulates an equatorward shift of the observed ‘anomalies’; we observed them until the minimum activity epoch (1976), at 15/18° latitude. Some relations of these features with both torsionai waves (Howard and LaBonte, 1980) and magnetic activity are briefly discussed.