Temperature-dependent oxide removal from manganese- and iron oxide-coated soil redox bars

Purpose

Soil temperature is a fundamental parameter affecting not only microbial activity but also manganese (Mn^III,IV) and iron (Fe^III) oxide reduction rates. The relationship between Mn^III,IV oxide removal from oxide-coated redox bars is missing at present. This study investigated the effect of variable soil temperatures on oxide removal by Mn^III,IV and Fe^III oxide-coated redox bars in water-saturated soil columns in the laboratory.

Materials and methods

The Mn coatings contained the mineral birnessite, whereas the Fe coatings contained a mixture of ferrihydrite and goethite. Additionally, platinum (Pt) electrodes designed to measure the redox potential (E_H) were installed in the soil columns, which were filled with either a humic topsoil with an organic carbon (C_org) content of 85 g kg^?1 (pH 5.8) or a subsoil containing 2 g C_org kg^?1 (pH 7.5). Experiments were performed at 5, 15, and 25 °C.

Results and discussion

Although elevated soil temperatures accelerated the decrease in E_H after water saturation in the topsoil, no E_H decreases regardless of soil temperature occurred in the subsoil. Besides soil temperature, the importance of soil organic matter as an electron donor is highlighted in this case. Complete removal of the Mn^III,IV oxide coating was observed after 28, 14, and 7 days in the soil columns filled with topsoil at 5, 15, and 25 °C, respectively. Along the Fe redox bars, Fe^III reducing conditions first appeared at 15 °C and oxide removal was enhanced at 25 °C because of lower E_H, with the preferential dissolution of ferrihydrite over goethite as revealed by visual differences in the Fe^III oxide coating. Oxide removal along redox bars followed the thermodynamics of the applied minerals in the order birnessite > ferrihydrite > goethite.

Conclusions

In line with Van’t Hoff’s rule, turnover rates of Mn^III,IV and Fe^III oxide reduction increased as a result of increased soil temperatures. Taking into account the stability lines of the designated minerals, E_H-pH conditions were in accordance with oxide removal. Soil temperature must therefore be considered a master variable when evaluating the oxide removal of redox bars employed for the monitoring of soil redox status.