Geochemical processes controlling the spatial distribution of selenium in soil and water,west central South Dakota,USA

Selenium (Se) is essential in the human diet, but has a low threshold for toxic concentration. It is recommended that nutrients such as Se should be consumed through foods as part of a normal diet. Se concentrations in crops and meat depend on the amount of labile Se in the soil where crops and forage are grown. Therefore, managing agriculture for optimal Se in grain crops and forage requires an understanding of the distribution and mobility of Se. Elevated concentrations of Se occur in waters, soils, and forage 120 km west of Pierre in west central South Dakota, USA. The research site lies in an elevated, dissected plain where soils developed on gently dipping Pierre Shale. Soils were sampled along catena transects and waters collected from soil, ponds, and shallow borings in areas of known elevated forage and crop Se. Soil extracts from saturated-paste extraction and acid (aqua regia and hydrofluoric acid) extraction were analyzed. Selenate was the dominant Se species in both acid and saturated-paste extracts; selenite and organic Se were below detection (<0.2 ppb) in the same soil extracts. On average, 98% of soil Se was not water-soluble. The distribution of total Se shows much less spatial variation than water-soluble Se in the areas sampled. Se shows correlation with organic carbon in soils and waters, suggesting its association with organic carbon. Ca shows some correlation to Se in acid extracts, but not in saturated-paste extracts or in waters. Total Se shows no significant correlation to Na, Mg, and total S in the soils. Se in saturated-paste extracts and water samples shows good correlations with Na, Mg, and SO₄, suggesting that evaporitic Na–Mg–sulfate minerals may temporarily concentrate water-soluble Se in shallow soils. The dissolution and precipitation of these Na–Mg–sulfate salts together with pH and oxidation–reduction conditions apparently control water-soluble Se distribution and mobilization in shallow subsurface environments.     

Mineralogy and geochemistry of sediments from Simbock Lake,Yaoundé area (southern Cameroon): provenance and environmental implications

Two cores of sediments, named NR and EB, were collected in the Simbock Lake (Mefou watershed, Yaoundé) to assess their provenance and the degree of heavy metal pollution based on mineralogical and geochemical data. The sediments are sandy, sand-clayey to clayey, and yellowish brown to greenish brown, and with high amounts of organic matter (average value of TOC is 1.95%). The sediments are mainly composed of quartz, kaolinite, accessory goethite, smectite, rutile, feldspars, illite, gibbsite, and interstratified illite-vermiculite. Fourier transform infrared (FT-IR) spectroscopy shows that kaolinite is less crystallized in the NR core than in the EB core. The Index of Compositional Variability (ICV), Chemical Index of Alteration (CIA), Plagioclase Index of Alteration (PIA), and the Rb/Sr and K₂O/Rb ratios indicate a high weathering intensity in the source area. These sediments have low contents in Al₂O₃, Fe₂O₃, Na₂O, K₂O, MgO, and CaO as well as high values in SiO₂, P₂O₅, TiO₂, and MnO relative to the upper continental crust. The concentrations of Cr, V, Ba, and Zr are higher in the NR core than those in EB. The total rare earth element (REE) content varies between 78 and 405 ppm. The light REE are abundant (LREE/HREE ~?18–59; avg.?=?25.61). The chondrite-normalized REE patterns exhibit (i) negative Eu anomaly (Eu/Eu^* ~?0.38–0.62; avg.?=?0.5), (ii) slight positive Ce anomaly (Ce/Ce^* ~?1.11–1.34; avg.?=?1.11), and (iii) high REE fractionation ((La/Yb)_N ~?12.3–51.75; avg.?=?25.61). The enrichment factor (EF) shows that the Mefou watershed through the Simbock Lake sediments is slightly polluted by the agricultural and urban activities.     

STRESS-METAMORPHISM AND ISOTOPIC AGE OF SHEAR ZONE GRANITOID TECTONITES OF IRTYSH SHEAR ZONE (ALTAI REGION)

The Irtysh shear zone (ISZ) of Altai region is the lineament structure of the collision-suture type, where granites of Kalba complex and granodiorites of Zmeinogorsk complex are exposed to regional gneiss-formation and stress-metamorphic alterations. This study is based on detailed structural observations at special grounds using optical and electron microscopy, and on the behavior analysis of isotopic systems from altered granitoids.Within the ISZ area we have established the continuous rows of granitoid stress-metamorphism from initial recrystallization of protolite, its cataclasis and mechanical flaring up to complete recrystallization with alteration of mineral composition and formation of the streaky complexes of granite tectonites of blastomylonite and blastocataclasite types. The directed alteration of rocks has several impulse and is expressed by a change in morphology of mineral grains and their relations, magnification of deformation component in the rock structure, and formation of new mineral phases on the basis of initial ones without surface fluidization. At transformation of isotopic systems from granitoid, their feldspars,biotite and hornblende, we can observe “rejuvenation“ of the rock substrate from 270- 290 Ma for Kalba granitoids to 220-235 Ma for their tectonites, and for Rudny Altai granodiorites, their ages changes from 285-317 Ma to 232-257 Ma for their tectonites.     

Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

Algal and fungal diversity on various dimension stone substrata in the Saale/Unstrut region

Physical, chemical and biogenic weathering considerably threatens all historic stone monuments. Microorganisms, though inconspicuous, are key players of stone surface colonization and penetration. This study highlights eukaryotic microbial communities on dimension stone surfaces from two representative monuments of the “cultural landscape corridor” in the Saale–Unstrut area. The historical buildings were erected from local Triassic limestone and sandstone and are prone to various deteriorative mechanisms. Generally, trebouxiophyceaen algae and ascomycete fungi dominate among the latter dematiaceous fungi and lichen fungi are abundant. Inside the stone substratum, ascomycetes, mosses and even large soil organisms (tardigrades) are present. This may be taken as a hint for the formation of pores with large radii, which are “risk indicators” for progressive weathering and degradation of the rock matrix.     

Development of Tide–Surge Interaction Model for the Coastal Region of Bangladesh

In this paper, a two-dimensional, vertically integrated hydrodynamic model is developed taking into account entrained air bubbles during storm surges as well as incorporating inverted barometer, and river and land dynamics. The model is specifically designed for the coastal region of Bangladesh. A nested scheme method with a fine mesh scheme (FMS), capable of incorporating the complex coastline and all major offshore islands accurately, nested into a coarse mesh scheme (CMS) covering up to 15° N latitude in the Bay of Bengal is used. To incorporate the small and big offshore islands in the Meghna estuarine region with its complex coastline accurately, a very fine mesh scheme (VFMS) is again nested into the FMS. Along the northeast corner of the VFMS, the Meghna river discharge is taken into account. The coastal and island boundaries are approximated through proper stair steps. The model equations are solved by a semi-implicit finite difference technique using a staggered C-grid. A stable appropriate tidal condition over the model domain is generated by applying tidal forcing with the four major tidal constituents M ₂, S ₂, K ₁, and O ₁ along the southern open boundary of the CMS. This tidal regime is introduced as the initial state of the sea for nonlinear interaction of tide and surge. The model is applied to simulate water levels due to the interaction of tide and surge associated with the cyclones April 1991 and Aila at different coastal and island locations along the coast of Bangladesh. The results are found to be quite satisfactory with root mean square error of ～0.50 m as calculated for both the storm events. Tests of sensitivities on water levels are carried out for air bubbles, offshore islands, river discharge, inverse barometer, and grid resolution. The presence of air bubbles increases simulated water levels a little bit in our model, and the contribution of air bubbles in increasing water level is found around 2 %. Further, water levels are found to be influenced by offshore islands, river discharge, inverse barometer as well as grid resolution.     

The Catoca kimberlite pipe, Republic of Angola: A paleovolcanological model

The Catoca kimberlite pipe is among the world’s largest primary diamond deposits. The Catoca volcanic edifice is only slightly eroded. Kimberlitic rocks of various facies compose a crater of about 1 km in diameter and a diatreme. The structure of the pipe and mining conditions of the deposit are complicated by intense intrapipe tectonic processes related to large-amplitude subsidence. Based on geological data, we propose a structural model of the deposit and a paleovolcanological model of the Catoca pipe formed during a full cycle beginning with a stage of active volcanism and completed by stages of gradually waning volcanic activity and sedimentation. It is suggested that the banded tuffisitic kimberlite of the crater zone was deposited at the stage of active volcanic eruption from specific pyroclastic suspension as a low-viscosity mixture of crystals and aqueous sol rich in serpentine.     

Removal of dyes by adsorption on magnetically modified activated sludge

The ability of magnetically modified activated sludge affected by thermal treatment to remove water-soluble organic dyes was examined. Twelve different dyes were tested. Based on the results of the initial sorption study, four dyes (namely aniline blue, Nile blue, Bismarck brown Y and safranin O) were chosen for further experiments due to their promising binding onto magnetic activated sludge. Significant factors influencing adsorption efficiency such as dependence of contact time, initial pH or temperature were studied in detail. The adsorption process was very fast; more than 88 % of dye content (55 mg/L) was adsorbed within 15 min under experimental conditions used. The equilibrium adsorption data were analyzed by Freundlich, Langmuir and Sips adsorption isotherm models, and the fitting of each isotherm model to experimental data was assessed on the basis of error functions. The maximum adsorption capacities of magnetic activated sludge were 768.2, 246.9, 515.1 and 326.8 mg/g for aniline blue, Bismarck brown Y, Nile blue and safranin O, respectively. The kinetic studies indicated that adsorption of all selected dyes could be well described by the pseudo-second-order kinetic model, and the thermodynamic data suggested the spontaneous and endothermic process.     

Hydrogeology and sustainable future groundwater abstraction from the Agua Verde aquifer in the Atacama Desert,northern Chile

The hyper-arid conditions prevailing in Agua Verde aquifer in northern Chile make this system the most important water source for nearby towns and mining industries. Due to the growing demand for water in this region, recharge is investigated along with the impact of intense pumping activity in this aquifer. A conceptual model of the hydrogeological system is developed and implemented into a two-dimensional groundwater-flow numerical model. To assess the impact of climate change and groundwater extraction, several scenarios are simulated considering variations in both aquifer recharge and withdrawals. The estimated average groundwater lateral recharge from Precordillera (pre-mountain range) is about 4,482 m³/day. The scenarios that consider an increase of water withdrawal show a non-sustainable groundwater consumption leading to an over-exploitation of the resource, because the outflows surpasses inflows, causing storage depletion. The greater the depletion, the larger the impact of recharge reduction caused by the considered future climate change. This result indicates that the combined effects of such factors may have a severe impact on groundwater availability as found in other groundwater-dependent regions located in arid environments. Furthermore, the scenarios that consider a reduction of the extraction flow rate show that it may be possible to partially alleviate the damage already caused to the aquifer by the continuous extractions since 1974, and it can partially counteract climate change impacts on future groundwater availability caused by a decrease in precipitation (and so in recharge), if the desalination plant in Taltal increases its capacity.