U?Pb and 40Ar?39Ar geochronology of Palaeozoic units in the northern Apennines: determining protolith age and alpine evolution using the Calamita Schist and Ortano Porphyroid

In the northern Apennines, the Palaeozoic basement involved in the Late Oligocene–Middle Miocene nappe stack contains metamorphic units for which hypothetical ages have been assigned on the basis of lithological correlations with the Palaeozoic formations of the Variscan chain in Sardinia. This uncertainty concerning the age poses limitations to reconstructing the Palaeozoic stratigraphy, defining the Alpine and pre‐Alpine histories and correlations with other domains of the Variscan chain. We present the U Pb age of detrital zircon and the ⁴⁰Ar ³⁹Ar age of metamorphic muscovite for the Calamita Schist and Ortano Porphyroid, two metamorphic units of undetermined Palaeozoic age cropping out in the eastern Elba Island. The radioisotopic data allows us to: (i) define the Early Carboniferous and Middle Ordovician ages for the Calamita Schist and Ortano Porphyroid, respectively, as well as their derivation (flysch deposit and magmatic rocks); (ii) pose some constraints concerning their alpine tectonic and metamorphic histories. These new data generate a more precise reconstruction of the Palaeozoic sequence in the northern Apennines, and they document that the Palaeozoic basement involved in the alpine deformation underwent internal stacking with an inversion of the original sequence. Copyright © 2010 John Wiley & Sons, Ltd.     

Sensitivity analysis of CDOM spectral slope in artificial and natural samples: an application in the central eastern Mediterranean Basin

In the past two decades, optical properties of chromophoric dissolved organic matter (CDOM) in marine environments have been extensively studied. Many of these studies report CDOM properties for the offshore environment where this complex mixture of optically active compounds is strongly diluted. Nevertheless, autochthonous and allochthonous sources have been identified and sinks related to photodegradation and bacterial activity have been demonstrated. The calculation of the spectral slope of the CDOM absorption curve has been proven to be useful and is often reported. However, a rigorous uncertainty analysis of the slope calculation is rarely reported. In this paper, we propose a method to evaluate the uncertainty of CDOM spectral slope calculated between 270 and 400 nm, using both naturally sampled and artificial solutions. We use these results to study the ultra-oligotrophic waters of the Mediterranean Sea (central eastern basin), where little is known about CDOM spatial distribution. We show that dilutions of both artificial and natural samples produce a Gaussian distribution of spectral slopes, indicating that consistent values may be determined, with a typical uncertainty of ±0.0004 nm⁻¹ when absorption at 300 nm was greater then 0.1 m⁻¹ (0.1 m pathlength). Comparing the distribution of spectral slopes from central eastern basin samples to a Gaussian distribution, we show differences between measurements that were significantly different. These values allow us to distinguish possible sources (algal derived CDOM), sinks (e.g. photo-bleaching) at different depths. We propose a subdivision of CDOM compounds into refractory and semilabile/refractory pools and evaluate the CDOM spectral slope of algal derived CDOM released at or near deep chlorophyll maximum.     

New insights on the origin of troctolites from the breakaway area of the Godzilla Megamullion (Parece Vela back‐arc basin): The role of melt‐mantle interaction on the composition of the lower crust

The troctolites and olivine‐gabbros from the Dive 6 K‐1147 represent the most primitive gabbroic rocks collected at the Godzilla Megamullion, a giant oceanic core complex formed at an extinct spreading segment of the Parece Vela back‐arc basin (Philippine Sea). Previous investigations have shown that these rocks have textural and major elements mineral compositions consistent with a formation through multistage interaction between mantle‐derived melts and a pre‐existing ultramafic matrix. New investigations on trace element mineral compositions basically agree with this hypothesis. Clinopyroxenes and plagioclase have incompatible element signatures similar to that of typical‐MORB. However, the clinopyroxenes show very high Cr contents (similar to those of mantle clinopyroxene) and rim having sharply higher Zr/REE ratios with respect to the core. These features are in contrast with an evolution constrained by fractional crystallization processes, and suggest that the clinopyroxene compositions are controlled by melt‐rock interaction processes. The plagioclase anorthite versus clinopyroxene Mg#[Mg/(Mg + Fe^Tot)] correlation of the Dive 6 K‐1147 rocks shows a trend much steeper than those depicted by other oceanic gabbroic sections. Using a thermodynamic model, we show that this trend is reproducible by fractionation of melts assimilating 1 g of mantle peridotite per 1 °C of cooling. This model predicts the early crystallization of high Mg# clinopyroxene, consistent with our petrological observation. The melt‐peridotite interaction process produces Na‐rich melts causing the crystallization of plagioclase with low anorthite component, typically characterizing the evolved gabbros from Godzilla Megamullion.     

Compositionally zoned crystals and real-time degassing data reveal changes in magma transfer dynamics during the 2006 summit eruptive episodes of Mt. Etna

One of the major objectives of volcanology remains relating variations in surface monitoring signals to the magmatic processes at depth that cause these variations. We present a method that enables compositional and temporal information stored in zoning of minerals (olivine in this case) to be linked to observations of real-time degassing data. The integrated record may reveal details of the dynamics of gradual evolution of a plumbing system during eruption. We illustrate our approach using the 2006 summit eruptive episodes of Mt. Etna. We find that the history tracked by olivine crystals, and hence, most likely the magma pathways within the shallow plumbing system of Mt. Etna, differed considerably between the July and October eruptions. The compositional and temporal record preserved in the olivine zoning patterns reveal two mafic recharge events within months of each other (June and September 2006), and each of these magma supplies may have triggered the initiation of different eruptive cycles (July 14–24 and August 31–December 14). Correlation of these observations with gas monitoring data shows that the systematic rise of the CO₂/SO₂ gas values is associated with the gradual (pre- and syn-eruptive) supply of batches of gas-rich mafic magma into segments of Etna’s shallow plumbing system, where mixing with pre-existing and more evolved magma occurred.     

Volcanic ash detection by GPS signal

We investigate the ability of GPS to detect volcanic plumes at Mt. Etna, Italy. We use a robust statistical approach to highlight whether the presence of a volcanic plume in the atmosphere may really affect the GPS undifferenced post-fit phase residuals. The proposed method has been tested for the September 4–5, 2007 activity of Mt. Etna. This eruption produced powerful lava fountains forming a weak, a few kilometers high plume for several hours, representing typical activity at Etna over the last 5 years. We analyzed data from nineteen Etna permanent GPS stations located on the volcano flanks at different heights and applied a statistical test based on four main steps: (a) realization of a simplified model representing the volcanic plume in atmosphere; (b) evaluation of the GPS satellite and station couples intersecting the plume; (c) calculation of the volcanic plume region crossed by the GPS signal; (d) application of a robust statistical test in order to see whether the volcanic plume affected the GPS signals. Results show that during the September 4–5, 2007 explosive activity, the GPS residuals definitely include the contribution of the volcanic plume. Our analysis shows that values of the GPS residuals are ten times smaller than those found for the Miyakejima eruption (Japan), highlighting a likely relationship between residuals and eruption intensity. In the future, data derived from the GPS stations located on Etna’s flanks could be used to improve the alerting system of volcanic ash, already operating at the Istituto Nazionale di Geofisica e Vulcanologia, Osservatorio Etneo.     

ESEEM of industrial quartz powders: insights into crystal chemistry of Al defects

A set of raw industrial materials, that is, pure quartz and quartz-rich mixtures, were investigated through electron paramagnetic resonance and electron spin echo-envelope modulation spectroscopies, with the aim of evaluating the effective role played by defect centres and of assessing whether they can be used to monitor changes in the physical properties of quartz powders with reference to their health effects. The obtained results point to two interactions of the Al defect centres with H⁺, hosted in sites within the channels parallel and perpendicular to the c axis of quartz, respectively. These two Al/H⁺ (h_Al) centres exhibit a weak chemical bond, and their relative amounts appear to be modified/controlled by the thermo-mechanical processes underwent by powders. Indeed, a mechanically promoted inter-conversion between the two kinds of site is suggested. As a consequence, the h_Al centres are effective in monitoring even modest activations of powders, through thermal or mechanical processes, and they are also supposed to play a specific, relevant role in quartz reactivity during the considered industrial processes.     

Geochemistry and zircon U-Pb geochronology of Aligoodarz granitoid complex, Sanandaj-Sirjan Zone, Iran

The Aligoodarz granitoid complex (AGC) is located in the Sanandaj-Sirjan Zone (SSZ), western Iran and consists of quartz-diorites, granodiorites and subordinate granites. Whole rock major and trace element data mostly define linear trends on Harker diagrams suggesting a cogenetic origin of the different rock types. (⁸⁷Sr/⁸⁶Sr)_i and εNd_t ratios are in the ranges 0.7074-0.7110 and −3.56 to −5.50, respectively. The trace elements and Sr-Nd isotopic composition suggest that the granitoids from the AGC are similar to crustal derived I-type granitoids of continental arcs. The whole rock suite was produced by assimilation and fractional crystallization starting from a melt with intermediate composition likely possessing a mantle component. In situ zircon U-Pb data on the granites with LA-ICP-MS yield a crystallization age of ∼165 Ma. Inherited grains spanning in age from ∼180 Ma up to 2027 Ma were also found and confirm that assimilation of country rock has occurred.Chemical and chronological data on the AGC were compared with those available for other granitoid complexes of the central SSZ (e.g., Dehno, Boroujerd and Alvand). The comparison reveals that in spite of the different origins that have been proposed, all these granitoid complexes are likely genetically related. They share many chemical features and are derived from crustal melts with minor differences. Alvand granites have the most peculiar compositions most likely related to the presence of abundant pelitic component. All these intrusions are coeval and reveal the presence of an extensive magmatic activity in the central sector of the SSZ during middle Jurassic.     

Turbulent Transfer Between Street Canyons and the Overlying Atmospheric Boundary Layer

The turbulent exchange of momentum between a two-dimensional cavity and the overlying boundary layer has been studied experimentally, using hot-wire anemometry and particle image velocimetry (PIV). Conditions within the boundary layer were varied by changing the width of the canyons upstream of the test canyon, whilst maintaining the square geometry of the test canyon. The results show that turbulent transfer is due to the coupling between the instabilities generated in the shear layer above the canyons and the turbulent structures in the oncoming boundary layer. As a result, there is no single, unique velocity scale that correctly characterizes all the processes involved in the turbulent exchange of momentum across the boundary layer. Similarly, there is no single velocity scale that can characterize the different properties of the turbulent flow within the canyon, which depends strongly on the way in which turbulence from the outer flow is entrained into the cavity and carried round by the mean flow. The results from this study will be useful in developing simple parametrizations for momentum exchange in the urban canopy, in situations where the street geometry consists principally of relatively long, uniform streets arranged in grid-like patterns; they are unlikely to be applicable to sparse geometries composed of isolated three-dimensional obstacles.     

High-temperature emplacement of the Cerro Galán and Toconquis Group ignimbrites (Puna plateau,NW Argentina) determined by TRM analyses

Estimates of pyroclastic flow emplacement temperatures in the Cerro Galán ignimbrite and Toconquis Group ignimbrites were determined using thermal remanent magnetization of lithic clasts embedded within the deposits. These ignimbrites belong to the Cerro Galán volcanic system, one of the largest calderas in the world, in the Puna plateau, NW Argentina. Temperature estimates for the 2.08-Ma Cerro Galán ignimbrite are retrieved from 40 sites in 14 localities (176 measured clasts), distributed at different distances from the caldera and different stratigraphic heights. Additionally, temperature estimates were obtained from 27 sample sites (125 measured clasts) from seven ignimbrite units forming the older Toconquis Group (5.60–4.51 Ma), mainly outcropping along a type section at Rio Las Pitas, Vega Real Grande. The paleomagnetic data obtained by progressive thermal demagnetization show that the clasts of the Cerro Galán ignimbrite have one single magnetic component, oriented close to the expected geomagnetic field at the time of emplacement. Results show therefore that most of the clasts acquired a new magnetization oriented parallel to the magnetic field at the moment of the ignimbrite deposition, suggesting that the clasts were heated up to or above the highest blocking temperature (T _b) of the magnetic minerals (T _b = 580°C for magnetite; T _b = 600–630°C for hematite). We obtained similar emplacement temperature estimations for six out of the seven volcanic units belonging to the Toconquis Group, with the exception of one unit (Lower Merihuaca), where we found two distinct magnetic components. The estimation of emplacement temperatures in this latter case is constrained at 580–610°C, which are lower than the other ignimbrites. These estimations are also in agreement with the lowest pre-eruptive magma temperatures calculated for the same unit (i.e., 790°C; hornblende–plagioclase thermometer; Folkes et al. 2011b). We conclude that the Cerro Galán ignimbrite and Toconquis Group ignimbrites were emplaced at temperatures equal to or higher than 620°C, except for Lower Merihuaca unit emplaced at lower temperatures. The homogeneity of high temperatures from proximal to distal facies in the Cerro Galán ignimbrite provides constraints for the emplacement model, marked by a relatively low eruption column, low levels of turbulence, air entrainment, surface–water interaction, and a high level of topographic confinement, all ensuring minimal heat loss.     

Magnetic properties and cation ordering of nanopowders of the synthetic analogue of kuramite, Cu3SnS4

An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu₃SnS₄, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu₃SnS₄ crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)₂Cu(II)SnS₄ and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.