Eawag, Swiss Federal Institute of Aquatic Science and Technology, CH-6047 Kastanienbaum, Switzerland.
Environ Sci Process Impacts. 2014 Apr;16(4):879-89. doi: 10.1039/c3em00676j.
Distinct layers of iron(III) and manganese(IV) (Fe/Mn) oxides are found buried within the reducing part of the sediments in Lake Baikal and cause considerable complexity and steep vertical gradients with respect to the redox sequence. For the on-site investigation of the responsible biogeochemical processes, we applied filter tube samplers for the extraction of sediment porewater combined with a portable capillary electrophoresis instrument for the analyses of inorganic cations and anions. On the basis of the new results, the sequence of diagenetic processes leading to the formation, transformation, and dissolution of the Fe/Mn layers was investigated. With two exemplary cores we demonstrate that the dissolution of particulate Fe and Mn is coupled to the anaerobic oxidation of CH₄ (AOM) either via the reduction of sulphate (SO₄(2-)) and the subsequent generation of Fe(II) by S(-II) oxidation, or directly coupled to Fe reduction. Dissolved Fe(II) diffuses upwards to reduce particulate Mn(IV) thus forming a sharp mineral boundary. An alternative dissolution pathway is indicated by the occurrence of anaerobic nitrification of NH₄(+) observed at locations with Mn(IV). Furthermore, the reasons and consequences of the non-steady-state sediment pattern and the resulting redox discontinuities are discussed and a suggestion for the burial of active Fe/Mn layers is presented.
在贝加尔湖沉积物的还原部分发现了具有明显层次的铁(III)和锰(IV)(Fe/Mn)氧化物,这导致了其在氧化还原序列方面具有相当大的复杂性和陡峭的垂直梯度。为了现场研究负责的生物地球化学过程,我们应用了过滤管采样器来提取沉积物孔隙水,并结合便携式毛细管电泳仪来分析无机阳离子和阴离子。基于新的结果,研究了导致 Fe/Mn 层形成、转化和溶解的成岩过程序列。通过两个典型的岩芯,我们证明了颗粒态 Fe 和 Mn 的溶解与 CH₄(AOM)的厌氧氧化有关,要么是通过硫酸盐(SO₄(2-)的还原和随后由 S(-II)氧化产生的 Fe(II),要么直接与 Fe 还原有关。溶解的 Fe(II)向上扩散以还原颗粒态 Mn(IV),从而形成一个明显的矿物边界。在 Mn(IV)存在的地方观察到的 NH₄(+)的厌氧硝化表明存在另一种溶解途径。此外,还讨论了非稳态沉积物模式的原因和后果,以及导致的氧化还原不连续性,并提出了一种活性 Fe/Mn 层埋藏的建议。