Manganese promotes stability of natural arsenic sinks in a groundwater system with arsenic-immobilization minerals: Natural remediation mechanism and environmental implications

Arsenic (As)-immobilizing iron (Fe)–manganese (Mn) minerals (AFMM) represent potential As sinks in As-enriched groundwater environments. The process and mechanisms governing As bio-leaching from AFMM through interaction with reducing bacteria, however, remain poorly delineated. This study examined the transformation and release of As from AFMM with varying Mn/Fe molar ratios (0:1, 1:5, 1:3, and 1:1) in the presence of As(V)-reducing bacteria specifically Shewanella putrefaciens CN32. Notably, strain CN32 significantly facilitated the bio-reduction of As(V), Fe(III), and Mn(IV) in AFMM. In systems with Mn/Fe molar ratios of 1:5, 1:3, and 1:1, As bio-reduction decreased by 28%, 34%, and 47%, respectively, compared to the system with a 0:1 ratio. This Mn-induced inhibition of Fe/As bio-reduction was linked to several concurrent factors: preferential Mn bio-reduction, reoxidation of resultant Fe(II)/As(III) due to Mn components, and As adsorption onto emergent Fe precipitates. Both the reductive dissolution of AFMM and the bio-reduction of As(V) predominantly controlled As bio-release. Structural equation models indicated that reducing bacteria destabilize natural As sinks more through As reduction than through Mn(II) release, Fe reduction, or Fe(II) release. Systems with Mn/Fe molar ratios of 1:5, 1:3, and 1:1 showed a decrease in As bio-release by 24%, 41%, and 59%, respectively, relative to the 0:1 system. The observed suppression of As bioleaching was ascribed to both the inhibition of As/Fe bio-reduction by Mn components and the immobilization of As by freshly generated Fe precipitates. These insights into the constraining effect of Mn on the biotransformation and bioleaching of As from AFMM are crucial for grasping the long-term stability of natural As sinks in groundwater, and enhance strategies for in-situ As stabilization in As-afflicted aquifers through Nature-Based Solutions. [Display omitted] •Mn components inhibited As bioleaching from As-immobilizing Fe–Mn minerals (AFMM).•AFMM was a vital natural As sink in groundwater with As-reducing bacteria.•As Bio-release was mainly due to reductive dissolution of AFMM and As bio-reduction.•Reducing bacteria affect the stability of natural As sinks more by As re-duction.