X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by FeII-bearing minerals

The long-lived radionuclide 79Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (SeVIO4(2-)) and selenite (SeIVO3(2-)). Previous investigations have demonstrated, however, that SeIV and SeVI are reduced by surface-associated FeII, thereby forming insoluble Se0 and Fe selenides. Here we show that the mixed FeII/III (hydr)oxides green rust and magnetite, and the FeII sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the FeII carbonate siderite produces elemental Se. In the case of mackinawite, both S(-II) and FeII surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these FeII systems is controlled by the concentration of HSe(-); Se0 forms only at lower HSe(-) concentrations related to slower HSeO3(-) reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe2+-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 x 10(-8) M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since FeII phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product 79Se may be much lower than previously assumed.     

Phytotoxic effects of phenolic acids from <Emphasis Type="Italic">Merostachys riedeliana,</Emphasis> a native and overabundant Brazilian bamboo

Merostachys riedeliana Rupr. is a native and overabundant bamboo species in the Brazilian Atlantic Forest. Moderate to strong allelopathic activity may be one mechanism that explains this super-dominance and the changes in structure and composition of forest areas occupied by bamboo. This study evaluated the phytotoxic effect of M. riedeliana extracts and fractions and identified their putative allelochemicals. We investigated the presence of allelochemicals in soil collected from stands occupied by M. riedeliana. Furthermore, we evaluated the putative effect of tree allelochemicals, individually and combined, on germination and growth. The aqueous extract of leaves and its ethyl acetate fraction presented the highest inhibitory effects on seed germination and seedling growth. The effect of the extracts and fractions on the target species was species-specific. Neither the individual nor the combined phenolic acids significantly inhibited seed germination; however, a pronounced growth inhibition was observed in M. bimucronata seedlings treated with vanillic acid and in E. verna and M. bimucronata seedlings treated with combined phenolic acids. Isovitexin, vitexin, isoorientin, orientin, and their O-glycoside derivatives, the lactonic dimer of the p-hydroxybenzoic acid and 3,4-methylenedioxymandelic acid were identified in the aqueous extracts and ethyl acetate fraction by Liquid Chromatography-Diode Array Dectector/Electrospray Ionization/Mass Spectrometry (LC-DAD/ESI–MS/MS). The Gas Chromatography-Mass Spectrometer (GC–MS) profile of the same extract and fraction showed the presence of benzoic, benzeneacetic, salicylic, p-hydroxybenzoic, p-hydroxyphenylacetic, vanillic, p-coumaric, protocatechuic, syringic, gallic, m-coumaric vanillylmandelic, 4-methylmandelic, 3,4-methylenedioxymandelic and trans-ferulic acids. The p-benzoic acid and the apigenin 6-C-glucoside (isovitexin) were identified in the soil extract collected from under bamboo-growing areas. Even though laboratory bioassays are not completely predictive of the allelopathic effects that occur in nature, the results of this study provide preliminary evidence of allelopathy as a possible species-specific inhibition mechanism of native species that explain the impoverishment of floristic richness and the functional groups in areas where M. riedeliana is overabundant.     

Environmental risk assessment in five rivers of Parana River basin,Southern Brazil,through biomarkers in Astyanax spp.

Environmental Science and Pollution Research - In the current study, water quality of five river sites in Parana River basin (Brazil), utilized for public water supply, was assessed through a set...     

Chemical composition and hygroscopic properties of size-segregated aerosol particles collected at the Adriatic coast of Slovenia

The chemical composition as well as the water uptake characteristics of aerosols was determined in size-segregated samples collected during November 2002 on the Slovenian coast. Major ions, water-soluble organic compounds (WSOC), short-chain carboxylic acids and trace elements were determined in the water-soluble fraction of the aerosol. Total aerosol black carbon (BC) was measured from filter samples. Our results showed that the origin of air masses is an important factor that controls the variation in the size distribution of the main components. Very high concentrations of WSOC as well as higher concentrations of BC were found under mostly continental influence. Besides the main ionic species (SO4(2-), NH4(+), K+) in the finest size fraction (0.17-0.53 microm), the concentration of NO3(-) was also high. The difference between the two different air mass origins is particularly expressed for Cl-, Na+, Mg2+ and Ca2+ determined in particles larger than 1.6 microm. As expected, a very good correlation was found between Na+ and Cl-. A good correlation was found between sea salt elements and elements of crustal origin (Na+, Cl-, Mg2+, Ca2+, Sr). A good relationship between typical anthropogenic tracers (K, V and Pb) was also observed. The mass growth factors, for all size fractions of aerosols collected under continental influence were very low (maximum 2.23 at 94%, 1.6-5.1 microm), while under marine influence the mass growth factors increased significantly with the particle size. At 97% humidity, the mass growth factors were 6.95 for the size fraction 0.53-1.6 microm and 9.78 for larger particles (1.6-5.1 microm).