University of Wisconsin-Madison, Department of Civil and Environmental Engineering, 660 N. Park St., Madison, WI, USA.
Environ Sci Process Impacts. 2014 May;16(6):1247-66. doi: 10.1039/c3em00703k.
Naturally occurring manganese (Mn(iii/iv)) oxides are ubiquitous in a wide range of environmental settings and play a key role in numerous biogeochemical cycles. In addition, Mn(iii/iv) oxides are powerful oxidants that are capable of oxidizing a wide range of compounds. This review critically assesses the reactivity of Mn oxides with organic contaminants. Initial work with organic reductants employed high concentrations of model compounds (e.g., substituted phenols and anilines) and emphasized the reductive dissolution of the Mn oxides. Studies with lower concentrations of organic contaminants demonstrate that Mn oxides are capable of oxidizing a wide range of compounds (e.g., antibacterial agents, endocrine disruptors, and pesticides). Both model compounds and organic contaminants undergo similar reaction mechanisms on the oxide surface. The oxidation rates of organic compounds by manganese oxides are dependent upon solution conditions, such as pH and the presence of cations, anions, or dissolved organic matter. Similarly, physicochemical properties of the minerals used affect the rates of organic compound oxidation, which increase with the average oxidation state, redox potential, and specific surface area of the Mn oxides. Due to their reactivity with contaminants under environmentally relevant conditions, Mn oxides may oxidize contaminants in soils and/or be applied in water treatment applications.
天然存在的锰(Mn(iii/iv))氧化物广泛存在于各种环境中,在许多生物地球化学循环中起着关键作用。此外,Mn(iii/iv)氧化物是一种强大的氧化剂,能够氧化多种化合物。本综述批判性地评估了 Mn 氧化物与有机污染物的反应性。最初使用有机还原剂的工作采用了高浓度的模型化合物(例如取代酚和苯胺),并强调了 Mn 氧化物的还原溶解。用较低浓度的有机污染物进行的研究表明,Mn 氧化物能够氧化多种化合物(例如,抗菌剂、内分泌干扰物和杀虫剂)。在氧化物表面上,模型化合物和有机污染物经历相似的反应机制。有机化合物被锰氧化物氧化的速率取决于溶液条件,如 pH 值以及阳离子、阴离子或溶解有机物的存在。类似地,所用矿物的物理化学性质也会影响有机化合物氧化的速率,这一速率随 Mn 氧化物的平均氧化态、氧化还原电位和比表面积的增加而增加。由于 Mn 氧化物在环境相关条件下与污染物的反应性,Mn 氧化物可能会氧化土壤中的污染物和/或应用于水处理应用中。