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.     

Effects of suburban land use on phosphorus fractions and speciation in the Upper Peruque Creek, Eastern Missouri

This field study was conducted to explore the spatial and seasonal changes in total phosphorus and fraction distribution in relation to land uses. Water samples were collected biweekly at four sampling locations, which represented different potential phosphorus sources along the Upper Peruque Creek in Eastern Missouri. Total phosphorus concentrations of > 0.8 mg/L appeared sporadically at site 2, downstream of a small community, with an average of 0.82 +/- 0.14 mg/L in fall. Particulate phosphorus accounted for approximately 80% of total phosphorus at all sampling sites, except for site 2, where approximately 50 to 75% of dissolved phosphorus was often observed. Approximately 71 and 85% of total phosphorus in the sediment was in the form of iron (III) phosphate at the headwaters and downstream sites, respectively; 29 and 15% was in the form of phytic acid at the two sites. Land uses affect the total phosphorus concentration and alternate phosphorus fraction and speciation in the creek.     

Temperature-associated dynamics of songbird winter distributions and abundances

Using Christmas Bird Count data, we analyze the annual spatio-temporal abundances of six passerine species in the upper Great Plains, US (1960-1990). This study provides new insight into how global warming could cause separation of species within present-day communities. We find that winter relative abundances of similarly-sized songbirds are differentially affected by ambient winter temperature. As such, average annual winter temperature fluctuations (i.e., severity of winter) are significantly (P < 0.05) correlated with the relative abundances of three species while the other three are not. Our conditional probability-of-occurrence analysis indicates that the abundances of the three temperature-associated species declined markedly below -4 degrees C while the abundances of the other three species fluctuated little from 8 degrees C to -16 degrees C. We conclude that even in colder climates i) the winter distributions of some, but not all, songbirds are directly or indirectly limited by temperature; and ii) these birds have dynamic abundances that can quickly respond to temperature changes.     

A new generic approach for estimating the concentrations of down-the-drain chemicals at catchment and national scale

A new generic approach for estimating chemical concentrations in rivers at catchment and national scales is presented. Domestic chemical loads in waste water are estimated using gridded population data. River flows are estimated by combining predicted runoff with topographically derived flow direction. Regional scale exposure is characterised by two summary statistics: PEC(works), the average concentration immediately downstream of emission points, and, PEC(area), the catchment-average chemical concentration. The method was applied to boron at national (England and Wales) and catchment (Aire-Calder) scales. Predicted concentrations were within 50% of measured mean values in the Aire-Calder catchment and in agreement with results from the GREAT-ER model. The concentration grids generated provide a picture of the spatial distribution of expected chemical concentrations at various scales, and can be used to identify areas of potentially high risk.