Despite the widespread presence of hydrogen peroxide (H₂O₂) in surface water and groundwater systems, little is known about the impact of environmental levels of H₂O₂ on the redox activity of minerals. Here we demonstrate that environmental concentrations of H₂O₂ can alter the reactivity of birnessite-type manganese oxide, an earth-abundant functional material, and decrease its oxidative activity in natural systems across a wide range of pH values (4–8). The H₂O₂-induced reductive dissolution generates Mn(II) that will re-bind to MnO₂ surfaces, thereby affecting the surface charge of MnO₂. Competition of Bisphenol A (BPA), used as a target compound here, and Mn(II) to interact with reactive surface sites may cause suppression of the oxidative ability of MnO₂. This suppressive effect becomes more effective in the presence of oxyanions such as phosphate or silicate at concentrations comparable to those encountered in natural waters. Unlike nitrate, adsorption of phosphate or silicate onto birnessite increased in the presence of Mn(II) added or generated through H₂O₂-induced reduction of MnO₂. This suggests that naturally occurring anions and H₂O₂ may have synergetic effects on the reactivity of birnessite-type manganese oxide at a range of environmentally relevant H₂O₂ amounts. As layered structure manganese oxides play a key role in the global carbon cycle as well as pollutant dynamics, the impact of environmental levels of hydrogen peroxide (H₂O₂/MnO₂ molar ratio ≤ 0.3) should be considered in environmental fate and transport models.

中文翻译：

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过氧化氢和氧阴离子的环境水平对二氧化锰颗粒氧化还原活性的影响

尽管过氧化氢 (H ₂ O ₂ ) 在地表水和地下水系统中广泛存在，但人们对环境水平的 H ₂ O ₂对矿物质氧化还原活性的影响知之甚少。在这里，我们证明 H ₂ O _{2 的}环境浓度可以改变水钠锰矿型氧化锰（一种地球上丰富的功能材料）的反应性，并降低其在各种 pH 值范围内的自然系统中的氧化活性 (4-8)。H ₂ O ₂诱导的还原溶解生成 Mn( II )，它会重新与 MnO ₂结合表面，从而影响 MnO ₂的表面电荷。此处用作目标化合物的双酚 A (BPA)与与反应性表面位点相互作用的Mn( II ) 的竞争可能会抑制 MnO ₂的氧化能力。这种抑制作用在含氧阴离子（如磷酸盐或硅酸盐）与天然水中遇到的浓度相当的情况下变得更加有效。与硝酸盐不同，磷酸盐或硅酸盐在水钠锰矿上的吸附在通过 H ₂ O ₂诱导的 MnO ₂还原添加或生成的 Mn( II )的存在下增加。这表明天然存在的阴离子和 H ₂ O ₂在环境相关的 H ₂ O ₂量范围内，可能对水钠锰矿型锰氧化物的反应性具有协同作用。由于层状结构锰氧化物在全球碳循环和污染物动力学中起着关键作用，因此在环境归宿和传输模型中应考虑过氧化氢的环境水平（H ₂ O ₂ /MnO ₂摩尔比≤ 0.3）的影响.