Benthic fluxes of copper,complexing ligands and thiol compounds in shallow lagoon waters

Benthic fluxes of copper, copper complexing ligands and thiol compounds in the shallow waters of Venice Lagoon (Italy) were determined using benthic chambers and compared to porewater concentrations to confirm their origin. Benthic copper fluxes were small due to small concentration differences between the porewaters and the overlying water, and the equilibrium concentration was the same at both sites, suggesting that the sediments acted to buffer the copper concentration. Thiol fluxes were ～10 × greater at 50–60 pmol cm^?2 h^?1, at the two sites. Porewater measurements demonstrated that the sediments were an important source of the thiols to the overlying waters. The overlying waters were found to contain at least two ligands, a strong one, L1 (log K′_CuL1 = 14.2) and a weaker one, L2 (log K′_CuL2 = 12.5). The concentration of L1 remained relatively constant during the incubation and similar to that of copper, whereas that of L2 was in great excess of copper, its concentration balanced by porewater releases and breakdown, probably due to uptake by microorganisms, similar to that of the thiol compounds. Similarity of the thiol and L2 concentrations and similar complex stability with copper suggest that L2 was dominated by the thiols. The free copper concentration ([Cu´]) in the Lagoon waters was lowered by a factor of 10⁵ as a result of the organic complexation.     

Modeling radar-rainfall estimation uncertainties using parametric and non-parametric approaches

There are large uncertainties associated with radar estimates of rainfall, including systematic errors as well as the random effects from several sources. This study focuses on the modeling of the systematic error component, which can be described mathematically in terms of a conditional expectation function. The authors present two different approaches: non-parametric (kernel-based) and parametric (copula-based). A large sample (more than six years) of rain gauge measurements from a dense network located in south-west England is used as an approximation of the true ground rainfall. These data are complemented with rainfall estimates by a C-band weather radar located at Wardon Hill, which is about 40 km from the catchment. The authors compare the results obtained using the parametric and non-parametric schemes for four temporal scales of hydrologic interest (5 and 15 min, hourly and three-hourly) by means of several different performance indices and discuss the strengths and weaknesses of each approach.     

Layered amphibolite sequence in NE Sardinia,Italy: remnant of a pre-Variscan mafic silicic layered intrusion?

A banded amphibolite sequence of alternating ultramafic, mafic (amphibolite) and silicic layers, tectonically enclosed within Variscan migmatites, outcrops at Monte Plebi (NE Sardinia) and shows similarities with leptyno-amphibolite complexes. The ultramafic layers consist of amphibole (75–98%), garnet (0–20%), opaque minerals (1–5%) and biotite (0–3%). The mafic rocks are made up of amphibole (65–80%), plagioclase (15–30%), quartz (0–15%), opaque minerals (2–3%) and biotite (0–2%). The silicic layers consist of plagioclase (60–75%), amphibole (15–30%) and quartz (10–15%). Alteration, metasomatic, metamorphic and hydrothermal processes did not significantly modify the original protolith chemistry, as proved by a lack of K₂O-enrichment, Rb-enrichment, CaO-depletion, MgO-depletion and by no shift in the rare earth element (REE) patterns. Field, geochemical and isotopic data suggest that ultramafic, mafic and silicic layers represent repeated sequences of cumulates, basic and acidic rocks similar to macrorhythmic units of mafic silicic layered intrusions. The ultramafic layers recall the evolved cumulates of Skaergaard and Pleasant Bay mafic silicic layered intrusions. Mafic layers resemble Thingmuli tholeiites and chilled Pleasant Bay mafic rocks. Silicic layers with Na₂O: 4–6 wt%, SiO₂: 67–71 wt% were likely oligoclase-rich adcumulates common in many mafic silicic layered intrusions. Some amphibolite showing a strong Ti-, P-depletion and REE-depletion are interpreted as early cumulates nearly devoid of ilmenite and phosphates. All Monte Plebi rocks have extremely low Nb, Ta, Zr, Hf content and high LILE/HFSE ratios, a feature inherited from the original mantle sources. The mafic and ultramafic layers show slight and strong LREE enrichment respectively. Most mafic layer samples plot in the field of continental tholeiites in the TiO₂–K₂O–P₂O₅ diagram and are completely different from N-MORB, E-MORB and T-MORB as regards REE patterns and Nd, Sr isotope ratios but show analogies with Siberian, Deccan and proto-Atlantic rift tholeiites. Comparisons with Thingmuli, Skaergaard and Kiglapait rocks and with experimental data suggest that the Monte Plebi intrusion was an open-to-oxygen system with fO₂ FMQ. Mafic and ultramafic samples yielded _Nd(460)=+0.79 /+3.06 and ⁸⁷Sr/⁸⁶Sr=0.702934–0.703426, and four silicic samples _Nd(460)=–0.53/–1.13; ⁸⁷Sr/⁸⁶Sr=0.703239–0.703653. Significant differences in Nd isotope ratios between mafic and silicic rocks prove that both groups evolved separately in deeper magma chambers, from different mantle sources, with negligible interaction with crustal material, and were later repeatedly injected within a shallower magma chamber. The spectrum of Sr and Nd isotope data is consistent with a slightly enriched mantle metasomatized during an event earlier than 460 Ma. The metasomatising component was represented by alkali-Th-rich fluids of crustal origin rather than by sedimentary materials, able to modify alkali and Sr–Nd isotope systematics. Monte Plebi layered amphibolites might represent the first example of a strongly metamorphosed fragment of an early Paleozoic mafic silicic layered intrusion emplaced in a thinning continental crust and then tectonically dismembered by Variscan orogeny.     

Development and testing of a physically based,three-dimensional model of surface and subsurface hydrology

We present a numerical, catchment-scale model that solves flow equations of surface and subsurface flow in a three-dimensional domain. Surface flow is described by the two-dimensional parabolic approximation of the St. Venant equation, using Manning’s equation of motion; subsurface flow is described by the three-dimensional Richards’ equation for the unsaturated zone and by three-dimensional Darcy’s law for the saturated zone, using an integrated finite difference formulation. The hydrological component is a dynamic link library implemented within a comprehensive model which simulates surface energy, radiation budget, snow melt, potential evapotranspiration, plant development and plant water uptake. We tested the model by comparing distributed and integrated three-dimensional simulated and observed perched water depth (PWD), stream flow data, and soil water contents for a small catchment. Additional tests were performed for the snow melting algorithm as well as the different hydrological processes involved. The model successfully described the water balance and its components as evidenced by good agreement between measured and modelled data.     

Optimal experimental design for reservoir property estimates in geothermal exploration

During geothermal reservoir development, drilling deep boreholes turns out to be extremely expensive and risky. Thus, it is of great importance to work out the details of suitable borehole locations in advance. Here, given a set of existing boreholes, we demonstrate how a sophisticated numerical technique called optimal experimental design helps to find a location of an additional exploratory borehole that reduces risk and, ultimately, saves cost. More precisely, the approach minimizes the uncertainty when deducing the effective permeability of a buried reservoir layer from a temperature profile measured in this exploratory borehole. In this paper, we (1) outline the mathematical formulation in terms of an optimization problem, (2) describe the numerical implementation involving various software components, and (3) apply the method to a 3D numerical simulation model representing a real geothermal reservoir in northern Italy. Our results show that optimal experimental design is conceptually and computationally feasible for industrial-scale applications. For the particular reservoir and the estimation of permeability from temperature, the optimal location of the additional borehole coincides with regions of high flow rates and large deviations from the mean temperature of the reservoir layer in question. Finally, the presentation shows that, methodologically, the optimization method can be generalized from estimating permeability to finding any other reservoir properties.     

Monitoring desertification by remote sensing using the Tasselled Cap transform for long-term change detection

Sensitive areas like oases are threatened by climatic variations and human activities that can catalyze desertification processes. Remote sensing the Earth surface from satellites is a good tool to monitor such types of change through several techniques. In this paper a remote sensing method that has been widely used for vegetated areas is adapted to study dry regions. The method consists of a combination of the Change Vector Analysis and the Tasselled Cap (TC) transform. To adapt it to dryland conditions a new set of parameters for the TC transform is hereby calculated for the Landsat 8 OLI system. The new TC parameters are tested in the analysis of the surface change in Azraq Oasis, Jordan, over a time span of 30 years (1984–2013) for Landsat satellites images. Azraq is considered a good testing site since in the early 1990s it has been subject to a complete drying up of the superficial springs, mainly due to over-exploitation of the groundwater basin. Results show that the chosen technique is able to detect the expected change on the surface, consistent with photo-interpretation and historical information available.     

Geodynamic significance of the Raspas Metamorphic Complex (SW Ecuador): geochemical and isotopic constraints

The Raspas Metamorphic Complex of southwestern Ecuador is regarded as the southernmost remnant of oceanic and continental terranes accreted in the latest Jurassic–Early Cretaceous. It consists of variably metamorphosed rock types. (1) Mafic and ultramafic rocks metamorphosed under high-pressure (HP) conditions (eclogite facies) show oceanic plateau affinities with flat REE chondrite-normalized patterns, Nd_{150 Ma} ranging from +4.6 to 9.8 and initial Pb isotopic ratios intermediate between MORB and OIB. (2) Sedimentary rocks metamorphosed under eclogitic conditions exhibit LREE enriched patterns, strong negative Eu anomalies, Rb, Nb, U, Th, Pb enrichments, low Nd_{150 Ma} values (from −6.4 to −9.5), and high initial ⁸⁷Sr/⁸⁶Sr and ^206,207,208Pb/²⁰⁴Pb isotopic ratios suggesting they were originally sediments derived from the erosion of an old continental crust. (3) Epidote-bearing amphibolites show N-MORB affinities with LREE depleted patterns, LILE, Zr, Hf and Th depletion, high Nd_{150 Ma} (>+10) and low initial Pb isotopic ratios.The present-day well defined internal structure of the Raspas Metamorphic Complex seems to be inconsistent with the formerly proposed interpretation of a “tectonic mélange”. The association of oceanic plateau rocks and continent-derived sediments both metamorphosed in HP conditions suggests that the thin edge of the oceanic plateau first entered the subduction zone and dragged sediments downward of the accretionary wedge along the Wadatti–Benioff zone. Subsequently, when its thickest part arrived into the subduction zone, the oceanic plateau jammed the subduction processes, due to its high buoyancy.In Ecuador and Colombia, the latest Jurassic–Early Cretaceous suture involves HP oceanic plateau rocks and N-MORB rocks metamorphosed under lower grades, suggesting a composite or polyphase nature for the latest Jurassic–Early Cretaceous accretionary event.     

Mineralogy,chemistry, and grain size composition of recent sediments in the northern Tyrrhenian Sea: Contribution to the study of sediment transport and distribution

As a contribution to an environmental study on Tuscany's marine shelf, textural, mineralogical, and chemical characteristics of recent sediments in the northern Tyrrhenian Sea between Elba Island and Livorno have been analyzed. The data provide clear information on sediment sources and movement patterns. The main sediment source appears to be the Cecina River; very subordinate is the contribution of the Fine River. As to sediment movement patterns, the surveyed basin appears to be divided into two subbasins: (1) a greater, southern subbasin, bounded by Tuscany mainland, Elba Island and Elba Ridge, and Capraia Isle, and Vada Shoals; and (2) a smaller, northern subbasin, enclosed between Vada Shoals and Meloria Shoals (off Livorno port).In the former the coarse-grade Cecina River sediments are transported southward along most of the mainland coast by littoral drift and coastal current; a northward flowing countercurrent seems to be active only in the southernmost part. Silts and clays are distributed in concentric belts around basin's central part, being transported mainly by slow circular water movements. In the marginal western zone, very little terrigenous influx is coupled with a high biologic productivity, and biogenic debris sedimentation prevails there.In the northern subbasin the sediment contribution from Fine River is more appreciable. Here the environmental energies are very low and the coarse sediments are restricted to a few small pocket beaches where they are deposited by local creeks. Most of the subbasin area is occupied by sapropelitic muds, again distributed by slow small-scale gyres.