Impact of Redox Cycles on Manganese, Iron, Cobalt, and Lead in Nodules

International audienceRedox processes are responsible for Fe and Mn segregation as Fe–Mn oxide coatings or nodules. These nodules are also trace element scavengers in soils. Redox processes are of particular importance in seasonally saturated soil containing naturally high concentrations of trace metals. We investigated the dynamics of Fe–Mn nodules and two associated trace elements, Co and Pb, under controlled redox conditions in a column experiment, including five columns fed with mimicked topsoil solution that was elevated in Fe and Mn. The results show that the redox conditions reached 100 mV, which was sufficient to dissolve Mn oxides and release the associated Co, while Pb was readsorbed onto nodule surfaces. The amounts of Mn and Co released into the water were small compared with the quantities stored in the nodules (<0.1% of the initial stock stored in the nodules). The redox conditions were insufficient, however, to allow Fe oxide dissolution. On the contrary, 70 to 90% of the Fe entering the column was fixed onto the nodules. In terms of an environmental threat, these results showed that Pb would not be released from soil during nodule dissolution, whereas Co, which is less toxic, would be released

Mass balance of zinc redistribution during the pedogenesis of a soil developed on a natural geochemical anomaly

Pedogenetic processes that redistribute soil elements over time have been considerably investigated and clearly identified. Nevertheless, the quantification of their respective influences on element redistribution is still poorly known, while soil protection requires extensive knowledge of their long-time depending evolution. The quantitative redistribution of elements is of prime importance in polluted soils, since the long-term environmental hazards depend on their potential mobility and biodisponibility, thus speciation. Among the elements frequently encountered in polluted soils and exhibiting a well-established phytotoxic nature, zinc is of great concern. Nevertheless, pollutions are too recent to observe or even predict the long-term behavior of zinc in polluted soils. An alternative approach is to study paleosoil developed on natural geochemical anomalies. Indeed, such paleosoils display zinc concentrations equivalent to those of polluted soils with the advantage to involve long pedological time of contact between the elements and the different soil phases. Our study aims at quantifying the long-term redistribution of zinc during the pedogenesis of a soil developed upon a natural geochemical anomaly. We first determined zinc speciation both in the parental material and in the solum, then quantified redistribution by mass balance calculations. This approach permits to estimate Zn outputs or inputs in the solum and to quantify its redistribution along the profile and among the different mineral phases

Zinc Redistribution in a Soil Developed from Limestone During Pedogenesis

International audienceThe long-term redistribution of Zn in a naturally Zn-enriched soil during pedogenesis was quantified based on mass balance calculations. According to their fate, parent limestones comprised three Zn pools: bound to calcite and pyritesphalerite grains, bound to phyllosilicates and bound to goethite in the inherited phosphate nodules. Four pedological processes, i.e., carbonate dissolution, two stages of redox processes and eluviation, redistributed Zn during pedogenesis. The carbonate dissolution of limestones released Zn bound to calcite into soil solution. Due to residual enrichment, Zn concentrations in the soil are higher than those in parent limestones. Birnessite, ferrihydrite and goethite dispersed in soil horizon trapped high quantities of Zn during their formation. Afterwards, primary redox conditions induced the release of Zn and Fe into soil solution, and the subsequent individualization of Fe and Mn into Zn-rich concretions. Both processes and subsequent aging of the concretions formed induced significant exportation of Zn through the bottom water table. Secondary redox conditions promoted the weathering of Fe and Mn oxides in cements and concretions. This process caused other losses of Zn through lateral exportation in an upper water table. Concomitantly, eluviation occurred at the top of the solum. The lateral exportation of eluviated minerals through the upper water table limited illuviation. Eluviation was also responsible for Zn loss, but this Zn bound to phyllosilicates was not bioavailabl