Micromorphological analysis of sediments from the Middle Stone Age site of Sibudu Cave, KwaZulu-Natal, South Africa, provides a high-resolution sequence and evidence of site formation processes of predominantly anthropogenic deposits. This methodology allows for a detailed interpretation of individual anthropogenic activities, including the construction of hearths and bedding and the maintenance of occupational surfaces through the sweep out of hearths and the repeated burning of bedding. This analysis also provides a context for evaluating other studies at the site relating to magnetic susceptibility, paleobotany, paleozoology, anthracology, and studies of ochre.
The heterogeneous Fenton process has been widely applied though some aspects of this process are still poorly understood. In this study, we simultaneously quantify the adsorption and decomposition of formate and H2O2 at pH 4.0 in the presence of freshly formed ferrihydrite and provide new insights into the ferrihydrite-induced heterogeneous Fenton mechanism with the aid of kinetic and reactive-transport modeling. Our results show that the decomposition of H2O2 and formate is controlled by surface-initiated reactions. Adsorbed formate occupies the surface sites otherwise available for reaction with H2O2 and therefore hampers the surface Fenton reactions despite the negligible accumulation of H2O2 on the surface. The minimal impact of methanol (an effective HO• scavenger) on formate oxidation as well as the poor oxidation of fully adsorbed oxalate compared with the ready oxidation of partially adsorbed formate demonstrates that oxidation mainly occurs in the solid–liquid boundary layer, rather than in bulk or on the surface. This is suggested to be due to the diffusion of surface-generated HO•, rather than surface Fe(II), to the boundary layer with the results of kinetic and reactive-transport modeling supporting this conclusion. The new findings are critical to our understanding of the removal behavior of more complex organic target species and to the design of more effective heterogeneous Fenton technologies.
29 December 2021 in Environmental Science & Technology