Evolution of arsenic speciation during thermal treatment simulating wildfire heating in arsenic-rich sediments

Understanding arsenic transformations during wildfires can help better constrain the environmental impacts of increased wildfire intensity, frequency, and burned area. Previous studies have monitored the evolution of metal(loid) speciation at specific time/temperature endpoints, hampering the comprehension of the dynamic transformations of metal(loid)s during wildfires. Here, a novel approach, namely in situ time-resolved X-ray absorption near edge structure (TR-XANES) spectroscopy, was used for the first time to monitor the heat-induced redox transformations of arsenic (As) in two As-rich sediments with different characteristics. No arsenic transformations were observed in either sediment at room temperature or when the sediments were heated to a maximum temperature of 400 ºC. When heated to a maximum temperature of 600 or 700 ºC, As underwent complex, dynamic, and partially reversible redox transformations, the extent of which varied with sediment properties, initial As speciation, and heating temperature and duration. In the case of sediments initially containing As(V) and a low sulfide/sulfate ratio, the As(V) was reduced to As(III) over a short period of time, followed by immediate reoxidation of As(III) to As(V). The extent of the transient As reduction increased with increasing maximum temperature. The final As speciation at the end of the heating experiment was not substantially different from that at the beginning of the experiment. In contrast, in sediments that were best described by a more complex combination of reference compounds (As(V) coprecipitated with or adsorbed on iron oxide, arseniosiderite, arsenopyrite) with a high sulfide/sulfate ratio, As(V) phases were reduced to As(III) and As(III) was further reduced to As(-I) (at 700 ºC, only), followed by delayed reoxidation of As(-I) to As(III) (at 700 ºC, only) and reoxidation of As(III) to As(V). Approximately 9% and 26% of all As remained as As(III) (i.e., was not reoxidized to As(V)) at the end of the experiment when heated to a maximum temperature of 600 and 700 ºC, respectively, which is higher than the relative abundance of As(III) in the native sediment. These fire-induced As transformations can potentially enhance As mobilization to surface water and groundwater, posing risks to environmental and human health.