Oxygen isotope fractionation of dissolved oxygen during reduction by ferrous iron

The oxygen isotope fractionation factor of dissolved oxygen gas has been measured during inorganic reduction by aqueous FeSO₄ at 10−54 °C under neutral (pH 7) and acidic (pH 2) conditions, with Fe(II) concentrations ranging up to 0.67 mol L⁻¹, in order to better understand the geochemical behavior of oxygen in ferrous iron-rich groundwater and acidic mine pit lakes. The rate of oxygen reduction increased with increasing temperature and increasing Fe(II) concentration, with the pseudo-first-order rate constant k ranging from 2.3 to 82.9 × 10⁻⁶ s⁻¹ under neutral conditions and 2.1 to 37.4 × 10⁻⁷ s⁻¹ under acidic conditions. The activation energy of oxygen reduction was 30.9 ± 6.6 kJ mol⁻¹ and 49.7 ± 13.0 kJ mol⁻¹ under neutral and acidic conditions, respectively. Oxygen isotope enrichment factors (ε) become smaller with increasing temperature, increasing ferrous iron concentration, and increasing reaction rate under acidic conditions, with ε values ranging from −4.5‰ to −11.6‰. Under neutral conditions, ε does not show any systematic trends vs. temperature or ferrous iron concentration, with ε values ranging from −7.3 to −10.3‰. Characterization of the oxygen isotope fractionation factor associated with O₂ reduction by Fe(II) will have application to elucidating the process or processes responsible for oxygen consumption in environments such as groundwater and acidic mine pit lakes, where a number of possible processes (e.g. biological respiration, reduction by reduced species) may have taken place.     

Scaling effects of proximate desertification drivers on soil nutrients in northeastern Tanzania

We tested the scaling effects of proximate desertification drivers (i.e. soil erosion, bush encroachment and grazing pressure) on soil nutrients in northeastern Tanzania. We analyzed nutrient concentrations in the desertified and non-degraded benchmark. For the desertified landscapes we analyzed nutrient concentrations at the coarse (landscape), medium (micro-landscape) and sampling unit (fine scale) levels. Further, for the desertified micro-landscapes, we used the differences in total nutrient concentrations to identify moderately dysfunctional and dysfunctional micro-landscapes. The desertified micro-landscapes had an overall lower soil organic matter, total nitrogen and exchangeable phosphorus, and soil water, but had elevated cation exchange capacity and soluble bases compared with the benchmark. Different intensities of desertification processes, mediated by the three proximate desertification drivers, produced varied amounts of nutrients corresponding with moderately dysfunctional and dysfunctional micro-landscapes. The dysfunctional micro-landscapes had the lowest nutrient availability. The effects of proximate desertification drivers on pooled nutrients were scale-independent. For individual nutrients only pH, soil water and Mg⁺⁺ showed scaling effects at the coarse or medium scales for soil erosion, while for grazing pressure pH, soil water, CEC, Na⁺, Mg²⁺⁺ and Ca²⁺⁺ showed scale dependence. The scaling effects were interlinked with landscape processes that operated simultaneously and interactively with different drivers.