Controls of δS and δO in dissolved sulphate: Learning from a detailed survey in the Llobregat River (Spain)

The S and O isotopic composition of dissolved SO₄, used as a tracer for SO₄ sources, was applied to the water of the Llobregat River system (NE Spain). The survey was carried out at 30 sites where surface water was sampled on a monthly basis over a period of 2a. The concentration of dissolved SO₄ varied from 20 to 1575 mg L⁻¹. Sulphur isotopic compositions clustered in two populations: one – 93% of the samples – had positive values with a mode of +9‰; the other had negative values and a mode of −5‰. Data for δ¹⁸O_SO4 showed a mean value of +11‰, with no bi-modal distribution, though lower values of δ¹⁸O corresponded to samples with negative δ³⁴S. These values can not be explained solely by the contribution of bedrock SO₄ sources: that is, sulphide oxidation and the weathering of outcrops of sulphates, though numerous chemical sediments exist in the basin. Even in a river with a high concentration of natural sources of dissolved SO₄, such as the Llobregat River, the δ³⁴S values suggest that dissolved SO₄ is controlled by a complex mix of both natural and anthropogenic sources. The main anthropogenic sources in this basin are fertilizers, sewage, potash mine effluent and power plant emissions. Detailed river water sampling, together with the chemical and isotopic characterisation of the main anthropogenic inputs, allowed determination of the influence of redox processes, as well as identification of the contribution of natural and anthropogenic SO₄ sources and detection of spatial variations and seasonal changes among these sources. For instance, in the Llobregat River the input of fertilisers is well marked seasonally. Minimum values of δ³⁴S are reported during fertilization periods – from January to March – indicating a higher contribution of this source. The dual isotope approach, δ³⁴S and δ¹⁸O, is useful to better constrain the sources of SO₄. Moreover, in small-scale studies, where the inputs are well known and limited, the mixing models can be enhanced and the contribution of the different sources can be quantified to some extent.     

Genetic Relationships Among One Non-Endemic and Two Endemic Mediterranean Triplefin Blennies (Pisces, Blennioidei)

Abstract. Three triplefin blennies occur sympatrically in the Mediterranean Sea; Tripterygion tripteronotus and T. melanurus are endemic, whereas T. delaisi is also found in the Eastern Atlantic. Although very similar in morphology, ecology and behaviour, some striking differences exist among reproductive strategies. Several authors proposed hypotheses on the evolution of these species. In order to enhance insight into the genetic structure of this genus, an enzyme electrophoretic survey was performed. Samples of 40 to 45 specimens of each species were collected near Calvi (Corsica, France). Twenty-four enzyme loci were analysed, of which 17 appeared polymorphic. T. delaisi showed a high level of average observed heterozygosity (H_o) of 0.140, as opposed to very low levels of 0.009 and 0.021 in T. tripteronotus and T. melanurus , respectively. Nei's genetic distance was 0.21 between T. delaisi and T. tripteronotus , 0.35 between T. delaisi and T. melanurus and 0.45 between T. tripteronotus and T. melanurus . We hypothesise that divergence of these species started before the Pleistocene and that the endemic species survived the Pleistocene glaciations in refugia within the Mediterranean. The possibility that T. tripteronotus and T. delaisi diverged through sympatric speciation is discussed.     

Southeastern U.S. Vegetation Response to ENSO Events (1989–1999)

El Niño/Southern Oscillation (ENSO) is considered one of the most powerful forces driving anomalous global weather patterns. Large-scale seasonal precipitation and temperature changes influenced by ENSO have been examined in many areas of the world. The southeastern United States is one of the regions affected by ENSO events. In this study, remote sensing detection of vegetation response to ENSO phases is demonstrated with one-kilometer biweekly Normalized Difference Vegetation Index (NDVI) data (1989–1999) derived from the Advanced Very High Resolution Radiometer(AVHRR). The impacts of three ENSO phases, cold, warm and neutral, on vegetation were analyzed with a focus on two vegetation cover types, two seasons and two geographic regions within the southeastern U.S. Significant ENSO effects on vegetation were found in cropland and forest vegetation cover types based on image and statistical analysis of the NDVI data. The results indicate that vegetation condition was optimal during the ENSO neutral phase for both agricultural and natural vegetation.     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Application of pyrolysis-GC/MS for rapid assessment of organic contamination in sediments from Barcelona harbor

Pyrolysis-GC/MS is advantageous as a tool for rapid sediment contamination assessment because of the small sample size required, minimal sample preparation and its ability to detect a wide variety of organic pollutants as well as naturally-occurring biological materials. Py-GC/MS was applied, together with determination of organic carbon, and major and minor element concentrations, to evaluate potentially contaminated sediments in the port of Barcelona (Spain) and the adjacent Llobregat River delta. Detected contaminant markers, most evident in the Old Port (Port Vell) area, included hopanes and alkylated PAHs (petroleum), sterenes (sewage), C₁₆–C₁₉ phenylalkanes (detergents) and parent PAHs (combusted fuels).     

Effect of suction on the mechanical behaviour of iron ore rock

The effect of suction on the behaviour of iron ore has been studied from both physical and mechanical points of view. The porosity and the suction phenomena have been analysed using different experimental techniques. Uniaxial compressive tests on partially saturated samples have shown that the suction is responsible for strength and cohesion improvement. Considering the theory of partially saturated porous soils of Coussy and Dangla (Mécanique des sols non saturés (2002 edn). Hermès Science: 2002; 390), we have proposed a constitutive law for partially saturated iron ore. The real increase in the apparent cohesion due to the capillary attraction forces is overestimated if the yield function is written in terms of effective stresses. The effect of the capillary cohesion has been modelled with a function in the expression of the apparent cohesion of the yield function. The effect of suction on the mechanical behaviour has been represented in the effective stresses space and in the total stresses space like the Alonso model (Géotechnique 1990; 40 :405–430). Copyright © 2005 John Wiley & Sons, Ltd.