Immobilization of iodide on copper(I) sulfide minerals

In the goal of finding efficient scavengers for radioiodide in conditions (pH, pE) close to those encountered in deep geological sites, sorption of iodide ions on cuprous sulfide minerals (especially roxbyite, Cu(1.75)S) has been studied. Surface analysis by X-ray photoelectron spectroscopy has shown that commercial cuprous sulfides are covered by an oxidized overlayer (mainly in the form of CuSO(4)). Therefore, a synthetic procedure to get roxbyite (typically by mixing Na(2)S with an aqueous suspension of commercial Cu(2)O) was applied to produce pure samples with clean surfaces. Batch equilibration of cuprous sulfide particles suspended in aqueous solutions containing iodide species has revealed significant consumption of iodide. The sorption mechanism involves the formation of a surface complex via the exchange of surface hydroxyl groups by iodide anions, as highlighted by a transient pH increase during the immobilization process. Other copper and mixed copper-iron sulfides (e.g. CuS, CuFeS(2)), which are stable over wide pH and potential ranges are also likely to accumulate iodide species. Because of the specific interaction between iodide and copper(I) centers on the minerals, high distribution coefficients (>1000 ml/g) were observed.     

Stable carbon isotope reconstructions of diet and paleoenvironment from the late Middle Pleistocene Snake Cave in Northeastern Thailand

Thailand’s geographical location in the tropics and almost complete, relatively uninterrupted forest cover makes it valuable for paleodiet and paleoclimate research. We present the first dietary and environmental reconstructions in Northeastern Thailand, using stable isotope abundances in mammalian tooth enamel from the late Middle Pleistocene locality, Tham Wiman Nakin (Snake Cave), which reflect a much higher (over 70%) than modern (13%) occurrence of C4 plants. Bovids and cervids appear to have had almost entirely a C4 plant diet. Carnivores consumed a mixture of C3 (suids) and C4 (bovids, cervids) consumers. Rhinoceroses and orangutan appear to have maintained their preference through time for forested or open C3 environment, respectively. ¹³C/¹²C from bone bioapatite, horn and hair of modern Southeast Asian mammals almost exclusively demonstrate C3 vegetation dominance. C4 consumption is rare in analysed modern species and it could be related to anthropogenic influences such as ingestion of domestic crops or livestock. Interesting implications emerge in the C4 vegetation distribution in southern Eurasian ecosystems, indicating that Southeast Asia, south of the Tibet, could be part of the global C4 vegetation spread, which occurred around 7 Ma. However, the C4 percentage in ecosystems varied geographically. Despite modern reversal towards C3 habitats due to factors such as increasing CO₂, we think that anthropological influences may be responsible for habitat and dietary changes in extant species. Bovids demonstrate the most significant shift in diet and habitat through time, from C4-dominated open habitats to C3-dominated habitats indicative of dense forest understory.     

Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process "electro-Fenton"

Diuron (N'-[3,4-dichlorophenyl]-N,N-dimethylurea) is a herbicide belonging to the phenylurea family, widely used to destroy weeds on uncultivated surfaces. Because of its toxicity for aquatic organisms and suspicion of being carcinogenic for humans, diuron is the object of growing environmental concern. Therefore, we have developed the electro-Fenton method, an electrochemical advanced oxidation process (EAOP), to degrade diuron in aqueous medium, and we have studied the evolution of the toxicity of treated solution during the process. Indeed, the EAOPs catalytically generate hydroxyl radicals that oxidize the persistent organic pollutants, and can ultimately destroy and mineralize them. But, sometimes, relatively toxic organic metabolites are formed during the oxidation reaction. In this work, the evolution of toxicity of diuron aqueous solutions was studied at different initial concentrations, during treatment by the electro-Fenton method. Samples were collected at various electrolysis times and mineralization degrees during the treatment. The toxicity of the samples was measured using the bacteria Vibrio fischeri (Microtox) and the green alga Scenedesmus obliquus. Our results demonstrated that the toxicity of diuron aqueous solutions (concentrations=3.0-27.6 mg L(-1)) varied considerably with time. The formation and disappearance of several metabolites, having toxicity often stronger than that of the initial herbicide, were observed. To improve the efficiency of water decontamination, the electro-Fenton method should be applied during a time long enough (several hours) and at relatively high electrolysis current (I=250 mA) to reach a nearly complete mineralization of the herbicide in the aqueous medium.     

Dietary characterization of the hominoid Khoratpithecus (Miocene of Thailand): evidence from dental topographic and microwear texture analyses

The genus Khoratpithecus, a hominoid thought to be related to the orangutan lineage, is represented by two known fossil species K. chiangmuanensis and K. piriyai. Both were discovered in Southeast Asia (Thailand) and are dated to the Middle and Late Miocene, respectively. In this study, dental topographic and microwear texture analyses were used to examine molars from both of these species, with the goal of understanding their dietary preferences. Although sample sizes are small for Khoratpithecus, available data are compared to that collected for extant apes. Environmental evidence, such as botanical remains and sedimentological data, is also considered for comparisons with dietary reconstruction. Results from dental topographic analysis suggest that the two fossil species were better adapted to a diet of fruits than to one of leaves, much like the living orangutan or chimpanzee. Results from microwear texture analysis further support this, suggesting that Khoratpithecus preferred soft fruits to hard fruits or seeds. And finally, the botanical and sedimentological evidence point to environments for Khoratpithecus that would have been compatible with a fruit-eating species. Given the small sample sizes available for analysis, however, definitive judgments are not yet possible at this time.     

First Castorid (Mammalia,Rodentia) from the Middle Miocene of Southeast Asia

Today and in the Tertiary, the geographical distribution of castorids is limited throughout all of the northern continents. Fossils of the Castoridae genus Steneofiber are abundant in many localities of Eurasia from the late Oligocene to Pliocene period. Recently, Steneofiber fossils were discovered in two localities of northern Thailand, Mae Moh and Chiang Muan coal mines, in layers of late middle Miocene age. These discoveries represent the first records of castorids from Southeast Asia and correspond to their southernmost known range. The focus of this study is to describe this new Thai species of Steneofiber and to define its wear stages from the molar occlusal surfaces by using micro-CT scan analysis. The CT scan technique permits the analysis of the virtual occlusal surface changes from wear, allowing easier comparison to related species of Steneofiber cheek teeth without destroying the teeth. The new species, Steneofiber siamensis n. sp., can be distinguished from the other species of Steneofiber by several distinct characters, longer mesostriid on p4, presence of premesostria and metastria on P4, which are smaller than most of the other known species. The occurrence of this new castorid also supports a subtropical to tropical paleoclimate for these two localities of northern Thailand.     

Non-linear regression model for spatial variation in precipitation chemistry for South India

Chemical composition of rainwater changes from sea to inland under the influence of several major factors – topographic location of area, its distance from sea, annual rainfall. A model is developed here to quantify the variation in precipitation chemistry under the influence of inland distance and rainfall amount. Various sites in India categorized as ‘urban’, ‘suburban’ and ‘rural’ have been considered for model development. pH, HCO₃, NO₃ and Mg do not change much from coast to inland while, SO₄ and Ca change is subjected to local emissions. Cl and Na originate solely from sea salinity and are the chemistry parameters in the model.Non-linear multiple regressions performed for the various categories revealed that both rainfall amount and precipitation chemistry obeyed a power law reduction with distance from sea. Cl and Na decrease rapidly for the first 100 km distance from sea, then decrease marginally for the next 100 km, and later stabilize. Regression parameters estimated for different cases were found to be consistent (R² ～ 0.8). Variation in one of the parameters accounted for urbanization. Model was validated using data points from the southern peninsular region of the country. Estimates are found to be within 99.9% confidence interval.Finally, this relationship between the three parameters – rainfall amount, coastline distance, and concentration (in terms of Cl and Na) was validated with experiments conducted in a small experimental watershed in the south-west India. Chemistry estimated using the model was in good correlation with observed values with a relative error of ～5%. Monthly variation in the chemistry is predicted from a downscaling model and then compared with the observed data. Hence, the model developed for rain chemistry is useful in estimating the concentrations at different spatio-temporal scales and is especially applicable for south-west region of India.     

Spatial connectivity in a large river system: resolving the sources and fate of dissolved organic matter

Large rivers are generally heterogeneous and productive systems that receive important inputs of dissolved organic matter (DOM) from terrestrial and in situ sources. Thus, they are likely to play a significant role in the biogeochemical cycling of the DOM flowing to the oceans. The asymmetric spatial gradient driven by directional flow and environmental heterogeneity contributes to the fate of DOM flowing downstream. Yet, the relative effects of spatial connectivity and environmental heterogeneity on DOM dynamics are poorly understood. For example, since environmental variables show spatial heterogeneity, the variation explained by environmental and spatial variables may be redundant. We used the St. Lawrence River (SLR) as a representative large river to resolve the unique influences of environmental heterogeneity and spatial connectivity on DOM dynamics. We used three-dimensional fluorescence matrices combined with parallel factor analysis (PARAFAC) to characterize the DOM pool in the SLR. Seven fluorophores were modeled, of which two were identified to be of terrestrial origin and three from algal exudates. We measured a set of environmental variables that are known to drive the fate of DOM in aquatic systems. Additionally, we used asymmetric eigenvector map (AEM) modeling to take spatial connectivity into account. The combination of spatial and environmental models explained 85% of the DOM variation. We show that spatial connectivity is an important driver of DOM dynamics, as a large fraction of environmental heterogeneity was attributable to the asymmetric spatial gradient. Along the longitudinal axis, we noted a rapid increase in dissolved organic carbon (DOC), mostly controlled by terrestrial input of DOM originating from the tributaries. Variance partitioning demonstrated that freshly produced protein-like DOM was found to be the preferential substrate for heterotrophic bacteria undergoing rapid proliferation, while humic-like DOM was more correlated to the diffuse attenuation coefficient of UVA radiation.     

Removal of Cr(VI) from aqueous solution using electrosynthesized 4-amino-3-hydroxynaphthalene-1-sulfonic acid doped polypyrrole as adsorbent

Environmental Science and Pollution Research - Polypyrrole (PPy) conducting films, doped with 4-amino-3-hydroxynaphthalene sulfonic acid (AHNSA), were electrosynthesized by anodic oxidation of...