Geochemistry of trace elements in surface waters of the Arno River Basin,northern Tuscany,Italy

Trace element geochemistry of the Arno River and its main tributaries was investigated on the basis of two sampling campaigns carried out in November 1996 and June 1997. By analyzing filtered and unfiltered water samples, Fe and Al are found in solution mainly as colloidal particles of size lower than 0.45 μm. In June (lower flow rate), Fe and Al are enriched in the filtered waters from the main river, and this feature was interpreted in terms of higher water temperature promoting the formation of smaller particles, thus reducing their aggregation properties. Iron and Al show perfectly synchronous downstream profiles along the Arno River, correlate quite well each to other, and display abrupt concentration increases near to Florence, where the lithology of the catchment changes from siliciclastic dominated to clay-sand (lacustrine-marine)-dominated. The same behaviour is shown by most of the other trace elements in the river, thus supporting a general lithological control. Trace elements in the final part of the Arno River are influenced by flocculation processes in addition to mixing. Adsorption phenomena on oxy-hydroxides are denoted by good elemental correlations with Fe (and Al). Sporadic anomalous concentration values, possibly related to anthropogenic contributions, may prevent such correlations. Referring to the quality of waters for potable use and fish life, toxic elements are below the acceptable limits of current European regulations, with few exceptions for Hg exceeding guideline values. Multivariate analysis groups trace elements according to geochemical affinities and natural or anthropogenic sources, thus distinguishing contaminated from uncontaminated samples. The results achieved in this work will help regional and national Authorities for compliance with the EU water policy, especially in assessing the water quality at the river basin scale and its vulnerability to human activities.     

Geology and petrology of a deep crustal zone from the Famatinian paleo-arc, Sierras de Valle Fértil and La Huerta, San Juan, Argentina

The ranges of the Sierras Valle Fértil-La Huerta expose natural cross sections through a paleo-arc crust that formed in the Late Cambrian - Early Ordovician Famatinian magmatic arc, northwestern Argentina. Thick mafic sequences of amphibole gabbronorites to orthopyroxene-amphibole-biotite diorites form the lower levels of the exposed paleo-arc section. This mafic unit includes lens-shaped bodies of olivine-bearing cumulate rocks and tabular-shaped sill/dike intrusions of fine-grained chilled amphibole gabbro. The mafic magmas were emplaced into regional metasedimentary sequences at lower crustal levels, corresponding to pressure from 5 to 7 kbar. Gabbronorites likely representing the parental magmas that fluxed into the exposed paleo-arc crust differ from primitive magmatic arc rocks in having somewhat lower Mg-number (ca. 0.60) and compatible (Cr and Ni) trace element contents, and slightly higher Al₂O₃ contents. This difference is taken to indicate that a pyroxene-rich olivine-bearing assemblage with a bulk high Mg/Fe ratio and low Al₂O₃ content crystallized from mantle-derived melts before mafic magmas reached the crustal levels currently exhumed. However, some gabbronorites have incompatible trace element signatures typical of primitive mafic arc magmatism. Igneous rocks to some extent more evolved than those of the mafic unit make up a tonalite-dominated intermediate unit. The intermediate unit consists of a heterogeneous suite that ranges from orthopyroxene-bearing amphibole-rich diorites to biotite-rich amphibole-poor tonalites. Within the intermediate unit, chilled mafic rocks are found as a network of dikes, whereas metasedimentary migmatites appear interlayered as m-wide septa and km-long strips. The tonalite-dominated intermediate unit passes into a granodiorite batholith through a transitional zone that is up to 2-km wide. The boundary zone separating the tonalite-dominated and granodiorite-dominated units is characterized by mingling of tonalitic and leucogranitic magmas, which together appear multiply-intruded by mafic sill/dike bodies. Within the tonalite- and granodiorite-dominated units, the less evolved mafic rocks occur as: (1) bodies tens of meters long, (2) chilled dikes and sills, and (3) microgranular inclusions (enclaves), supporting the inference that mafic magmatism was the main source for generating a vast volume of intermediate and silicic igneous rocks. Mass balance calculations and trace element systematics are combined to demonstrate that tonalites and granodiorites formed by concurrent closed-system fractional crystallization and open-system incorporation of paragneissic migmatites and/or anatectic leucogranites into the evolving igneous sequence. This study argues that the sequence of igneous rocks from Valle Fértil-La Huerta was formed as the result of complementary petrogenetic processes that operated concurrently at different levels of the Famatinian arc crust.     

Nutrient dynamics in water and sediment of Mediterranean ponds across a wide hydroperiod gradient

In Mediterranean ponds, summer drought enhances seasonality whose intensity varies along topographic and climatic gradients. The alternation of wet and dry periods in rain dependent ponds affects their biogeochemistry and differentiates them from ponds fed by more stable water sources, such as groundwater springs. Superimposed onto this, land use is also a very strong factor of variability. In this study we compared nutrients and organic matter concentrations, in water and in sediment, among different types of Mediterranean ponds based on the source of water, hydroperiod and land use. Forty-three ponds were sampled in Eastern Spain corresponding to five pond types: (1) permanent spring ponds in lowlands, (2) permanent spring ponds in mountains, (3) semi-permanent rain ponds, (4) temporary rain ponds with long hydroperiod and (5) temporary rain ponds with short hydroperiod.The results of this study indicate relevant differences among these pond types. The temporary rain ponds with short hydroperiod are characterized by high turbidity due to suspension of sediment particles rich in phosphorous adsorbed onto them (argillotrophic aquatic systems). They are used for watering domestic sheep that enhance sediment suspension by trampling. Total phosphorous (TP) concentrations in the water are high (like those of hypertrophic lakes), but planktonic chlorophyll a is very low and not correlated with TP, because of the low P-bioavailavility in the water. At the other extreme, we have permanent ponds in lowlands fed by groundwater springs. They are heavily loaded with nitrates due to the surrounding intensive agriculture. In these and other permanent/semipermanent ponds chlorophyll is highly correlated with TP. Sediment characteristics provide a good indication of the hydroperiod, since desiccation has important effects on biogeochemical transformations. A threshold of 5% organic matter (OM) in the sediment separates temporary ponds with a short hydroperiod from those with a long hydroperiod, and a threshold of 8% separates the later from the semi-permanent and permanent ponds. Besides OM reduction, important loss of N occurs during desiccation through mineralization, ammonia volatization and the sequential nitrification/denitrification pathway. On the other hand, the increase of organic P mineralization in dry sediments does not represent a loss of P from the system, since o-P remains adsorbed or bound onto the soil. This leads to a low TN/TP ratio in sediments in temporary ponds with short hydroperiod. These characteristics have to be taken into account when establishing pond typologies and ecological thresholds to assess water quality in these unique aquatic habitats.     

Implications of Arctic industrial growth and strategies to mitigate future vessel and fishing gear impacts on bowhead whales

The objective of this paper was to investigate and illustrate how insights gained from experience managing human activities in order to protect North Atlantic right whales (Eubalaena glacialis) along the heavily industrialized east coast of North America might be applied in the Arctic, where bowhead whales (Balaena mysticetus) face some of the same risks as right whales. The reduced extent and thickness of sea ice and the resultant longer open-water season have major, complex implications for the Arctic marine ecosystem. Increased maritime ship traffic and commercial fishing in the Arctic are bound to affect bowheads and Native (indigenous) hunting communities who depend on whales for subsistence and cultural identity. Bowheads and right whales were greatly depleted by commercial whaling in the 19th and early 20th centuries. While the Western Arctic bowhead population has been recovering steadily in recent decades, North Atlantic right whales remain highly endangered because of persistent lethal and sublethal vessel strikes and frequent entanglement in commercial fishing gear. Entanglement can be transitory or persistent, with debilitation lasting for months before the animal finally succumbs. Vessel strike and fishing gear trauma has been documented in bowheads, but at a much lower rate than in right whales. Initiatives intended to mitigate the impacts of ship traffic on North Atlantic right whales have included speed limits and routing changes. Those meant to reduce the incidence and severity of entanglements include the modification of gear design and gear deployment practices. Management measures need to be considered in advance in the Arctic in order to minimize the risks to bowhead whales as shipping and industrial fishing expand in the Arctic with ice retreat.     

A test for directional-linear independence,with applications to wildfire orientation and size

A nonparametric test for assessing the independence between a directional random variable (circular or spherical, as particular cases) and a linear one is proposed in this paper. The statistic is based on the squared distance between nonparametric kernel density estimates and its calibration is done by a permutation approach. The size and power characteristics of various variants of the test are investigated and compared with those for classical correlation-based tests of independence in an extensive simulation study. Finally, the best-performing variant of the new test is applied in the analysis of the relation between the orientation and size of Portuguese wildfires.     

Goodness-of-fit tests for the spatial spectral density

Detection and modeling the spatial correlation is an important issue in spatial data analysis. We extend in this work two different goodness-of-fit testing techniques for the spatial spectral density. The first approach is based on a smoothed version of the ratio between the periodogram and a parametric estimator of the spectral density. The second one is a generalized likelihood ratio test statistic, based on the log-periodogram representation as the response variable in a regression model. As a particular case, we provide tests for independence. Asymptotic normal distribution of both statistics is obtained, under the null hypothesis. For the application in practice, a resampling procedure for calibrating these tests is also given. The performance of the method is checked by a simulation study. Application to real data is also provided.     

Determination of confined phreatic aquifer anisotropy

The determination of anisotropy in a phreatic aquifer by means of a pumping test can be carried out, under given conditions, with common analysis methods. This paper develops and applies an amended method based on a technique proposed by Boulton (1970). This new method enables a quick, simple determination of vertical hydraulic conductivity, given drawdown data from a pumping well and at least one observation well, that is applicable to confined phreatic aquifers.     

Enhancement of ionizing radiation during a solar flare

Measurements of electron concentrations in the ionosphere, between 100 and 250 km altitude, were used to compute the increase in solar ionizing radiation during two flares on 21 and 23 May 1967. Since the altitude of maximum absorption of the solar energy (approximately unit optical depth) depends on the wavelength of the radiation, it is possible to estimate separately the energy enhancement in different portions of the spectrum. An ionizing energy flux increase of nearly 5 erg cm^–2 sec^–1 was observed on 21 May, while on the 23rd, the increase was over 7 erg cm^–2 sec^–1. In both flares, most of the absolute increase occurred in the 20–205 Å region of the spectrum, although the relative increase was much larger at the shorter wavelengths.