Groundwater-Gossan interaction and the genesis of the secondarysiderite rock at Las Cruces ore deposit (SW Spain)

Part of the Las Cruces secondary siderite deposit has sparked an interest in the scientific communitybecause of its unique mineralogy. The original gossan formed by goethite and hematite has been replacedby a siderite and galena rock. We postulate that this rock can be formed by the interaction of iron oxideswith groundwater similar in composition to that of the present day. Hydrochemical and isotopic charac-teristics of groundwater support this hypothesis. The negative Eh values, the existence of H2S and the ten-dency toward high sulfate isotope values indicate a reducing groundwater condition. The highammonium, boron and iodine concentrations as well as the low d13C values of dissolved inorganic carbon(DIC) confirm the organic matter oxidation. The reductive dissolution of Pb-bearing goethite at theexpense of Dissolved Organic Carbon (DOC) leads to the precipitation of Fe-sulfides, galena and siderite.The formation of siderite from this process is confirmed by the low amount of dissolved Fe in groundwa-ter (<10 ppb), its low d13C values and thermodynamic calculations. One-dimensional reactive transportmodeling demonstrated that the present-day groundwater flux and chemical composition could formthe siderite rock in less than 1 Ma with no external supply of reactants. Sensitivity analyses revealed thatthe time of formation depends on the structure of the groundwater flux (spaced fractures or pervasive),the flow rate and especially the DOC concentration. In fact, calculations with the highest DOC measuredconcentration resulted in a mineral zonation: one zone formed by Fe-sulfides and other zone formed bysiderite, with galena in both zones. Reactive transport calculations and the similarity of its high d34S val-ues indicate that the sulfur of galena came from the current groundwater. Reactive transport calculationsand the similarity of its high d34S values indicate that the sulfur of galena came from the currentgroundwater

Recent and old groundwater in the Niebla-Posadas regional aquifer (southern Spain): Implications for its management

The Niebla-Posadas (NP) aquifer in southern Spain is one of the main groundwater sources for the lower Guadalquivir Valley, a semiarid region supporting an important population, agriculture and industry. To contribute to the understanding of this aquifer the assessment of sustainable use of groundwater, the residence time of groundwater in the NP aquifer has been estimated using 3H, 14C and 36Cl. Along the flow paths, recharged groundwater mixes with NaCl-type waters and undergoes calcite dissolution and is further modified by cation exchange (Ca Na). Consequently, the water loses most of its calcium and the residual d13CDIC in the groundwater is isotopically enriched. Further modifications take place along the flow path in deeper zones, where depleted d13CDIC values are overprinted due to SO42 and iron oxide reduction, triggered by the presence of organic matter. Dating with 3H, 14C and 36Cl has allowed the differentiation of several zones: recharge zone (30 ky). An apparent link between the tectonic structure and the groundwater residence time zonation can be established. Regional faults clearly separates deep zone 1 from the distinctly older age (>30 ky) deep zone 2. From the estimated residence times, two groundwater areas of different behavior can be differentiated within the aquifer

Phosphonate Chelators for Medicinal Metal Ions

A family of phosphonate-bearing chelators was synthesized to study their potential in metal-based (radio)- pharmaceuticals. Three ligands (H6phospa, H6dipedpa, H6eppy; structures illustrated in manuscript) were fully characterized, including X-ray crystallographic structures of H6phospa and H6dipedpa. NMR spectroscopy techniques were used to confirm the complexation of each ligand with selected trivalent metal ions. These methods were particularly useful in discerning structural information for Sc3+ and La3+ complexes. Solution studies were conducted to evaluate the complex stability of 15 metal complexes. As a general trend, H6phospa was noted to form the most stable complexes, and H6eppy associated with the least stable complexes. Moreover, In3+ complexes were determined to be the most stable, and complexes with La3+ were the least stable, across all metals. Density functional theory (DFT) was employed to calculate structures of H6phospa and H6dipedpa complexes with La3+ and Sc3+. A comparison of experimental 1 H NMR spectra with calculated 1 H NMR spectra using DFT-optimized structures was used as a method of structure validation. It was noted that theoretical NMR spectra were very sensitive to a number of variables, such as ligand configuration, protonation state, and the number/orientation of explicit water molecules. In general, the inclusion of an explicit second shell of water molecules qualitatively improved the agreement between theoretical and experimental NMR spectra versus a polarizable continuum solvent model alone. Formation constants were also calculated from DFT results using potential-energy optimized structures. Strong dependence of molecular free energies on explicit water molecule number, water molecule configuration, and protonation state was observed, highlighting the need for dynamic data in accurate first-principles calculations of metal−ligand stability constants

Stress assessment in captive greylag geese (<em>Anser anser</em>)

Chronic stress—or, more appropriately, “allostatic overload”—may be physiologically harmful and can cause death in the most severe cases. Animals in captivity are thought to be particularly vulnerable to allostatic overload due to artificial housing and group makeup. Here we attempted to determine if captive greylag geese (Anser anser), housed lifelong in captivity, showed elevated levels of immunoreactive corticosterone metabolites (CORT) and ectoparasites in dropping samples as well as some hematological parameters (hematocrit, packed cell volume, total white blood cell count [TWBC], and heterophil:lymphocyte ratio [H:L]). All of these have been measured as indicators of chronic stress. Furthermore, we correlated the various stress parameters within individuals. Captive geese showed elevated values of CORT and ectoparasites relative to a wild population sampled in the vicinity of the area where the captive flock is held. The elevated levels, however, were by no means at a pathological level and fall well into the range of other published values in wild greylag geese. We found no correlations between any of the variables measured from droppings with any of the ones collected from blood. Among the blood parameters, only the H:L negatively correlated with TWBC. We examine the problem of inferring allostatic overload when measuring only 1 stress parameter, as there is no consistency between various measurements taken. We discuss the different aspects of each of the parameters measured and the extensive individual variation in response to stress as well as the timing at which different systems respond to a stressor and what is actually measured at the time of data collection. We conclude that measuring only 1 stress parameter often is insufficient to evaluate the well-being of both wild and captively housed animals and that collecting behavioral data on stress might be a suitable addition

Effects of Methoxyisoflavone, Ecdysterone, and Sulfo-Polysaccharide Supplementation on Training Adaptations in Resistance-Trained Males

PURPOSE: Methoxyisoflavone (M), 20-hydroxyecdysone (E), and sulfo-polysaccharide (CSP3) have been marketed to athletes as dietary supplements that can increase strength and muscle mass during resistancetraining. However, little is known about their potential ergogenic value. The purpose of this study was to determine whether these supplements affect training adaptations and/or markers of muscle anabolism/catabolism in resistance-trained athletes. METHODS: Forty-five resistance-trained males (20.5±3 yrs; 179±7 cm, 84±16 kg, 17.3±9 % body fat) were matched according to FFM and randomly assigned to ingest in a double blind manner supplements containing either a placebo (P); 800 mg/day of M; 200 mg of E; or, 1,000 mg/day of CSP3 for 8-weeks during training. At 0, 4, and 8-weeks, subjects donated fasting blood samples and completed comprehensive muscular strength, muscular endurance, anaerobic capacity, and body composition analysis. Data were analyzed by repeated measures ANOVA. RESULTS: No significant differences (p&gt;0.05) were observed in training adaptations among groups in the variables FFM, percent body fat, bench press 1RM, leg press 1RM or sprint peak power. Anabolic/catabolic analysis revealed no significant differences among groups in active testosterone (AT), free testosterone (FT), cortisol, the AT to cortisol ratio, urea nitrogen, creatinine, the blood urea nitrogen to creatinine ratio. In addition, no significant differences were seen from pr

Seasonal differences of corticosterone metabolite concentrations and parasite burden in northern bald ibis (Geronticus eremita): The role of affiliative interactions

The reproductive season is energetically costly as revealed by elevated glucocorticoid concentrations, constrained immune functions and an increased risk of infections. Social allies and affiliative interactions may buffer physiological stress responses and thereby alleviate associated effects. In the present study, we investigated the seasonal differences of immune reactive corticosterone metabolite concentrations, endoparasite burden (nematode eggs and coccidian oocysts) and affiliative interactions in northern bald ibis (Geronticus eremita), a critically endangered bird. In total, 43 individually marked focal animals from a freeranging colony were investigated. The analyses included a description of initiated and received affiliative interactions, pair bond status as well as seasonal patterns of hormone and endoparasite levels. During the reproductive season, droppings contained parasite eggs more often and corticosterone metabolite levels were higher as compared to the period after reproduction. The excretion rate of endoparasite products was lower in paired individuals than in unpaired ones, but paired animals exhibited higher corticosterone metabolite concentrations than unpaired individuals. Furthermore, paired individuals initiated affiliative behaviour more frequently than unpaired ones. This suggests that the reproductive season influences the excretion patterns of endoparasite products and corticosterone metabolites and that affiliative interactions between pair partners may positively affect endoparasite burden during periods of elevated glucocorticoid levels. Being embedded in a pair bond may have a positive impact on individual immune system and parasite resistance

Excretion patterns of coccidian oocysts and nematode eggs during the reproductive season in Northern Bald Ibis (Geronticus eremita)

Individual reproductive success largely depends on the ability to optimize behaviour, immune function and the physiological stress response. We have investigated correlations between behaviour, faecal steroid metabolites, immune parameters, parasite excretion patterns and reproductive output in a critically endangered avian species, the Northern Bald Ibis (Geronticus eremita). In particular, we related haematocrit, heterophil/lymphocyte ratio, excreted immune-reactive corticosterone metabolites and social behaviour with parasite excretion and two individual fitness parameters, namely, number of eggs laid and number of fledglings. We found that the frequency of excretion of parasites’ oocysts and eggs tended to increase with ambient temperature. Paired individuals excreted significantly more samples containing nematode eggs than unpaired ones. The excretion of nematode eggs was also significantly more frequent in females than in males. Individuals with a high proportion of droppings containing coccidian oocysts were more often preened by their partners than individuals with lower excretion rates. We observed that the more eggs an individual incubated and the fewer offspring fledged, the higher the rates of excreted samples containing coccidian oocysts. Our results confirm that social behaviour, physiology and parasite burden are linked in a complex and context-dependent manner. They also contribute background information supporting future conservation programmes dealing with this critically endangered species

Law, Environment, and the “Nondismal” Social Sciences

Over the past 30 years, the influence of economics over the study of environmental law and policy has expanded considerably, becoming in the process the predominant framework for analyzing regulations that address pollution, natural resource use, and other environmental issues. This review seeks to complement the expansion of economic reasoning and methodology within the field of environmental law and policy by identifying insights to be gleaned from various “nondismal” social sciences. In particular, three areas of inquiry are highlighted as illustrative of interdisciplinary work that might help to complement law and economics and, in some cases, compensate for it: the study of how human individuals perceive, judge, and decide; the observation and interpretation of how knowledge schemes are created, used, and regulated; and the analysis of how states and other actors coordinate through international and global regulatory regimes. The hope is to provide some examples of how environmental law and policy research can be improved by deeper and more diverse engagement with social science