Magnetite drives self-dechlorination of 4-chlorophenol in anoxic aquatic sediments

The lack of available electron donors is well known as a major factor limiting the efficiency of microbial dechlorination of 4-chlorophenol (4-CP) in anoxic aquatic sediments. Considering that Fe(III) minerals largely contained in sediments can especially enrich Fe(III)-reducing bacteria and unlock the ring-like intermediates produced by dechlorination of 4-CP via dissimilatory Fe(III) reduction, a strategy of self-dechlorination of 4-CP utilizing its metabolism intermediates such as short-fatty acids (SCFAs) as the endogenous electron donors with magnetite was proposed in this study. The results showed that the removal efficiency of 4-CP increased by 156-203% in magnetite-supplemented biotic groups compared with the magnetite-free biotic group. Liquid chromatography-mass spectrometer (LC-MS) and gas chromatography (GC) revealed the possible metabolic pathway of anoxic 4-CP degradation with magnetite: 4-CP→phenol→cyclohexene-1-carboxylic acid→2-hydroxycyclohexanecarboxylic acid→hexanoic acid/valeric acid→butyric/propionic acids→CO₂. High-throughput sequencing analysis showed that the abundance of functional bacteria, Desulfuromonas, Pseudomonas and Bacillus species, were increased by 1.38-1.97, 1.50-2.04, and 11.60-17.18 folds in magnetite-supplemented biotic groups, compared with the magnetite-free biotic groups. Analysis of Fe²⁺ concentration and cyclic voltammetry (CV) suggested that the potential Fe(III)/Fe(II) transformation occurred and proceeded the anoxic 4-CP degradation continuously.