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Peatlands perform important ecosystem functions, such as carbon storage and nutrient retention, which are affected, among other factors, by vegetation and peat decomposition. The availability of silicon (Si) in peatlands differs strongly, ranging from 25 mg L−1. Since decomposition of organic material was recently shown to be accelerated by Si, the aim of this study was to examine how Si influences decomposition of carbon and nutrient and toxicant mobilization in peatlands. We selected a fen site in Northern Bavaria with naturally bioavailable Si pore water concentrations of 5 mg/L and conducted a Si addition experiment. At a fourfold higher Si availability, dissolved organic carbon, carbon dioxide, and methane concentrations increased significantly. Furthermore, dissolved nitrogen, phosphorus, iron, manganese, cobalt, zinc, and arsenic concentrations were significantly higher under high Si availability. This enhanced mobilization may result from Si competing for binding sites but also from stronger reducing conditions, caused by accelerated respiration. The stronger reducing conditions also increased reduction of arsenate to arsenite and thus the mobility of this toxicant. Hence, higher Si availability is suggested to decrease carbon storage and increase nutrient and toxicant mobility in peatland ecosystems.