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Review

Research Progress in the Remediation of Arsenic- and Cadmium-Contaminated Groundwater Mediated by Iron and Manganese Biomineralization

by
Feixing Li
1,
Jixiang Cai
1,
Xinxin Zhao
2,*,
Hui Liu
2,
Fanfan Ju
3 and
Youwen Li
1,*
1
Xinjiang Biomass Solid Waste Resources Technology and Engineering Center, College of Chemistry and Environmental Science, Kashi University, Kashi 844000, China
2
State Key Laboratory of Qinba Bio-Resource and Ecological Environment, School of Chemical & Environmental Science, Shaanxi University of Technology, Hanzhong 723001, China
3
Technology Innovation Center for Groundwater Disaster Prevention and Control Engineering for Metal Mines, Ministry of Natural Resources, North China Engineering Investigation Institute Co., Ltd., Shijiazhuang 050021, China
*
Authors to whom correspondence should be addressed.
Catalysts 2025, 15(6), 570; https://doi.org/10.3390/catal15060570
Submission received: 2 April 2025 / Revised: 15 May 2025 / Accepted: 28 May 2025 / Published: 9 June 2025
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Abstract

:
Arsenic (As) and cadmium (Cd) contamination in groundwater poses significant risks to human health and environmental sustainability. Iron–manganese minerals and associated microorganisms in subsurface environments exhibit remarkable potential for immobilizing and transforming toxic metal(loid)s through adsorption, redox reactions, and co-precipitation. This study integrates bibliometric analysis with mechanistic review strategies to systematically evaluate the roles of iron–manganese biomineralization in As/Cd stabilization. Bibliometric insights identify emerging research trends, including the application of biogenic oxides and microbial redox cycles in groundwater remediation. Mechanistic analysis reveals how microbial–mineral interactions regulate As/Cd sequestration, emphasizing the influence of environmental factors such as pH, redox conditions, and microbial metabolic pathways. Case studies demonstrate the viability of in situ remediation technologies leveraging these biogeochemical processes, though challenges persist in achieving consistent field-scale performance and long-term stability. Future efforts should prioritize optimizing microbial consortia, advancing real-time monitoring systems, and integrating biogeochemical strategies with engineered barriers. By synthesizing quantitative trends and mechanistic principles, this work provides actionable frameworks for enhancing natural attenuation and designing sustainable remediation systems for metal-contaminated groundwater.

Graphical Abstract

1. Introduction

Heavy metal contaminants such as arsenic (As) and cadmium (Cd) represent critical environmental threats to groundwater systems due to their high toxicity, bioaccumulative potential, and environmental persistence [1]. These elements predominantly exist in inorganic forms, such as arsenate (As(V)), arsenite (As(III)), and divalent cadmium (Cd(II)), with elevated concentrations in aquifers resulting from both natural geogenic processes and human-induced anthropogenic activities [2,3]. Especially in high-risk areas, there are a high proportion of monitoring wells whose arsenic concentration exceeds the regulatory limit, showing a worrying pollution level. This contamination pattern shows transnational dimensions as groundwater arsenic pollution (exceeding the World Health Organization (WHO) 10 ppb guideline) currently affects 108 countries, endangering approximately 230 million people globally [4]. The coexistence of multiple heavy metal contaminants is exemplified by cadmium levels surpassing the WHO thresholds in 68% (88/129) of groundwater samples from Pakistan’s Vehari district, underscoring the complex nature of groundwater quality deterioration worldwide [5]. Chronic exposure to As- and Cd-contaminated water has been epidemiologically linked to severe damage to human urinary, cardiovascular, renal, and neurological systems, significantly elevating mortality risks [6,7,8]. Over recent decades, major environmental incidents such as cadmium-tainted rice crises and endemic arsenicosis outbreaks have starkly demonstrated the devastating human health impacts of groundwater As/Cd contamination [8,9].
Current remediation strategies for groundwater arsenic (As) and cadmium (Cd) contamination, including chemical precipitation, ion exchange, and membrane filtration, demonstrate effectiveness but suffer from high operational costs, technical complexity, and risks of secondary contamination [10,11,12]. In recent years, iron–manganese (Fe–Mn) biomineralization has emerged as a promising alternative due to its cost-efficiency, environmental compatibility, and high remediation potential. This process involves the microbially mediated formation of Fe–Mn oxides that immobilize As/Cd through adsorption, co-precipitation, and redox-driven transformations. The resultant biogenic Fe–Mn oxides exhibit exceptional adsorption capacity and oxidative activity, effectively sequestering As/Cd while oxidizing mobile As(III) to less toxic As(V), thereby enhancing immobilization efficiency. Zhao et al. systematically investigated the As immobilization performance of Fe–Mn oxides in groundwater systems, revealing that Fe–Mn synergistic interactions significantly improved the stability of arsenic fixation [13]. Bai et al. characterized the formation of biogenic Fe–Mn oxides in complex groundwater matrices containing Fe(II)-, Mn(II)-, As(III/V)-, and Mn-oxidizing bacteria (Pseudomonas sp. QJX-1), demonstrating concurrent removal of multiple contaminants through mineral precipitation [14]. Recent work by Zeng et al. elucidated the mechanisms underlying Cd(II) immobilization by biogenic Fe–Mn oxides (BFMO), identifying critical roles of mineralogical components (MnO2, Mn3O4, FeO(OH), Fe2O3, and Fe3O4) and reactive functional groups in Cd sequestration [15]. While existing studies primarily focus on the immobilization efficiency, structural characteristics, influencing factors, and long-term stability of Fe–Mn biomineralization systems, bibliometric analysis reveals a notable research gap in systematically understanding the biogeochemical mechanisms governing As/Cd remediation. Key challenges persist in developing strategies for synthesizing structurally stable Fe–Mn oxides and elucidating the complex microbial–mineral interaction networks that dictate sustained immobilization performance.
To advance understanding of cutting-edge developments in Fe–Mn biomineralization-mediated remediation of As/Cd-contaminated groundwater, this study aims to synthesize global research trends and knowledge frontiers through integrated bibliometric analysis and critical review, with the specific purpose of unraveling the scientific basis for contaminant sequestration, clarifying the interactive mechanisms among biogenic minerals, microbial communities, and target pollutants, and bridging the gap between fundamental research and practical groundwater restoration. We systematically characterize the immobilization mechanisms governing As/Cd sequestration by biogenic Fe–Mn minerals, with particular emphasis on the interfacial interactions between mineralogical components, microbial communities, and contaminant species. This work further evaluates practical applications of Fe–Mn biomineralization in groundwater restoration while proposing strategic directions for overcoming current technological limitations. These insights provide a conceptual framework for identifying emerging research priorities and optimizing science-based remediation strategies for heavy metal(loid)-contaminated aquifer systems.

2. Research Methods

This study investigates Fe–Mn biomineralization-mediated remediation of As/Cd-contaminated groundwater through bibliometric analysis of 1022 English publications (2005–2024) retrieved from the Web of Science Core Collection using VOSviewer visualization. The database was accessed on 26 October 2024. Irrelevant documents such as reviews, conference abstracts, and non-English records were excluded to ensure the articles analyzed were relevant research articles. The search query was as follows: TS = (“Fe–Mn oxyhydroxide “ or “iron-manganese oxide*” or “Fe–Mn oxides” or “iron and manganese oxides” or “ferromanganese minera” or “biomineralization” or “biomineral” or “biomineralisation” or “biomineralization synthesis” or “biomineral method” or “mineralization”) and TS = (“arsenic*”or “arsenical” or “arsenicum” or “cadmium” or “Cd”) and TS = (“water” or “groundwater” or “contaminated groundwater” or “underwater” or “plerotic water” or “the ground water” or “ free water” or “subsurface water” or “subsoil water”). The analysis of the total amount of literature shows that in the past two decades, the total number of publications in this field has been increasing year by year. Among them, the number of publications in China is the largest (309, 35.4%), followed by the United States (143, 16.4%), Germany (64, 7.3%), and India (61, 7.0%). Worldwide, China has close cooperative relations with countries such as the United States, Canada, and Russia. This indicates that this field has attracted the attention and emphasis of scholars in related fields internationally (Figure 1). Current research hotspots focus on: (1) The adsorption mechanisms and influencing factors of As/Cd immobilization by Fe–Mn minerals. The “arsenic” in the red clusters in the figure is closely related to the keywords such as “adsorption” and “mechanism” in the blue clusters, indicating that the adsorption mechanism of arsenic (As) is a research hotspot. The “cadmium” in the green cluster is also related to the adsorption-related keywords in the blue cluster, suggesting that the immobilization of cadmium (Cd) also involves the adsorption mechanism. (2) The synergistic effects of Mn-Fe biomineralization with engineered materials in complex environments. The “biomineralization” in the blue area of the figure, as well as the keywords that may be related to minerals (such as the “mineralization” in the red area) and the concepts related to engineering materials, show a synergistic research trend between Mn-Fe biomineralization and engineering materials in complex environments. (3) The performance optimization of remediation systems. The keywords such as “removal” and “bioremediation” in the blue clusters in the figure indicate that the performance optimization of the repair system is a research direction. The associations of these keywords with other clusters (such as the red area and the green area related to metal pollution) indicate that the repair system needs to comprehensively consider various factors and enhance the removal effect of pollutants such as As and Cd through optimization (Figure 2a). Emerging trends emphasize advanced mechanistic studies of As/Cd-mineral interactions, process intensification strategies, and the development of novel composite materials. Arsenic and cadmium are located in the transitional area towards light colors (2016–2018), indicating that people are increasingly concerned about their interaction with minerals. The keywords such as “adsorption” and “mechanism” are also in the yellow area (close to 2018), highlighting the latest progress in mechanism research. The “removal” and “bioremediation” in the yellow zone (2018) reflect the surge in process intensification strategies aimed at enhancing repair efficiency. Furthermore, the “biomineralization” near the color area in 2018 indicates the emerging development of new composite materials (Figure 2b). While natural Fe–Mn minerals demonstrate critical roles in stabilizing groundwater As/Cd through adsorption and co-precipitation [16], significant knowledge gaps persist regarding microbial–mineral interaction networks and biogeochemical controls under dynamic subsurface conditions. Future investigations should prioritize mechanistic elucidation of functional microbial consortia driving Fe–Mn biomineralization and their resilience in heterogeneous aquifer environments.

3. Iron and Manganese Biomineralization

3.1. The Role of Functional Microorganisms

Iron–manganese biomineralization refers to microbially mediated chemical processes involving oxidation, reduction, and precipitation reactions that generate Fe–Mn mineral phases. Microbial participation occurs through two distinct pathways: biologically controlled mineralization (BCM) and biologically induced mineralization (BIM) [17]. Table 1 summarizes the key differences between these two routes. BCM involves direct cellular regulation where microbes adsorb metal ions onto cell surfaces and template mineral nucleation either intracellularly or extracellularly [18,19]. In contrast, BIM operates through microbial modification of local geochemical conditions via enzymatic activities, organic/inorganic acid secretion, or redox transformations, thereby altering pH, dissolved oxygen, and ionic concentrations to influence mineral solubility and precipitation kinetics [20,21]. Research demonstrates that microbial communities actively catalyze the oxidation of dissolved Fe(II) and Mn(II) species into stable Fe–Mn (oxyhydr) oxide precipitates. Experimental studies consistently reveal microbial mediation as a critical driver of iron–manganese biogeochemical cycling, with substantial impacts on metal(loid) sequestration through mineral formation and surface complexation mechanisms [20].
Microorganisms play pivotal roles in iron–manganese (Fe–Mn) biomineralization through diverse biogeochemical processes, including redox transformations that govern mineral nucleation, phase transitions, and dissolution dynamics [22]. A broad spectrum of metal(loid)-mineralizing microbes—spanning carbonate-precipitating bacteria, sulfate-reducing species, Bacillus spp., Fe/Mn-oxidizing bacteria, and fungal/algal communities—actively participate in these processes [23]. For instance, the marine bacterium Paenisporosarcina quisquiliarum generates alkaline microenvironments with elevated Fe2+ concentrations under aerobic conditions, creating favorable conditions for Fe-hydroxide precipitation while providing nucleation templates for mineral formation on cell surfaces [24]. Mn-oxidizing bacteria exhibit catalytic efficiency in metal oxidation–precipitation cascades, preferentially oxidizing Fe2+ to Fe3+ hydroxides that subsequently adsorb Mn2+ through colloidal interactions, thereby facilitating sequential Mn-oxide deposition and Fe–Mn mineral accumulation [25].
Fungal and algal systems enhance biomineralization efficiency through distinct mechanisms. Fungal hyphae immobilize metal ions via extracellular polymeric substances (EPS), enabling nanoparticle synthesis and mineral precipitation through surface-mediated redox reactions [26]. Similarly, chlorophyte algae achieve metal sequestration through cell wall adsorption and secretory biomineralization processes [27]. Microbial communities also drive non-enzymatic Fe–Mn precipitation pathways, as evidenced by metagenomic analyses of deep-sea Fe–Mn nodules revealing microbially enhanced metal enrichment through metabolic byproducts and EPS-mediated mineralization. These collective mechanisms underscore the sophistication of microbial strategies in governing Fe–Mn biogeochemical cycles and contaminant immobilization.

3.2. Mineralization Mechanism

The principal mechanisms governing Fe and Mn biomineralization encompass microbial adsorption, enzymatic catalysis, redox transformations, organic matrix mediation, and surface/cellular-regulated mineralization pathways, as systematically illustrated in Figure 3. Bacteria can adsorb iron and manganese ions extracellularly through their cell surface functional groups. Intracellularly there are proteins and nucleic acids that may participate in the biomineralization process. Additionally, enzymes secreted by bacteria can catalyze the oxidation of iron and manganese ions, and the presence of organic material can also influence the mineralization process. These processes involve microbial regulation of mineral nucleation through biomacromolecules and metabolic byproducts under physicochemical controls (temperature, pH, and metal concentration) and biological constraints [28].
Microbial adsorption predominates as a critical mechanism [29], where cell surface functional groups sequester Fe2+ and Mn2+ ions via electrostatic interactions and ligand complexation. This ion enrichment facilitates subsequent mineral precipitation while modulating crystal growth kinetics [30]. Enzymatic processes further drive metal oxidation cascades—neutrophilic Leptothrix species exemplify this through Mn2+ oxidase-mediated generation of Mn oxide precipitates in aerobic environments [31]. Catalytic oxidation pathways enable microbes to utilize Fe/Mn as electron donors, generating insoluble Fe3+/Mn4+ (oxyhydr)oxides. Iron-oxidizing bacteria transform Fe2+ into hematite or goethite through enzymatic oxidation [32], while Mn-oxidizers employ multicopper oxidases to precipitate MnO2 phases [33]. Organic matrices critically regulate mineralization through template-directed nucleation, where biomolecules organize metal ions into proto-crystalline structures that mature into stable minerals under favorable conditions [34].
Surface-mediated mineralization exploits bacterial exopolysaccharides and charged functional groups to adsorb metal ions, with subsequent pH modulation and redox activity controlling precipitation patterns [35,36]. In parallel, intracellular mechanisms involve metal–protein interactions and compartmentalized biomineral synthesis. Cyanobacterial ferritin-mediated iron storage exemplifies this process, where Fe3+ supersaturation triggers intracellular mineral deposition [37]. Yan et al. demonstrated synergistic extracellular and intracellular mineralization in Bacillus subtilis Daniel-1, revealing spatial coordination between membrane-associated nucleation and cytoplasmic precursor synthesis [38]. These interconnected mechanisms highlight the hierarchical control of Fe–Mn biomineralization through microbial physiological adaptation and environmental responsiveness.

4. Immobilization of As and Cd by Iron and Manganese Biomineralization

4.1. Immobilization Mechanism

Immobilization refers to physicochemical and biological processes that reduce contaminant mobility and bioavailability by decreasing the environmental transport capacity of pollutants such as arsenic (As) and cadmium (Cd). The Fe and Mn biomineralization-mediated immobilization of As/Cd is governed by the following three principal mechanisms (Figure 4): (1) mineral-specific binding through surface complexation, isomorphic substitution, and co-precipitation; (2) auxiliary immobilization mediated by microbial extracellular polymeric substances (EPSs), whose abundant functional groups (e.g., carboxyl and hydroxyl groups) form stable complexes with heavy metals through chelation; (3) microbial–metabolic coordination involving redox transformations, enzymatic catalysis, and synergistic interactions between biogenic minerals and metal(loid) species.

4.1.1. Mineral-Specific Binding

The mineral-specific binding mechanism arises from the distinctive crystallographic features of biogenic Fe–Mn minerals that enable selective As/Cd sequestration through structural coordination. Metastable amorphous Fe–Mn phases exhibit tetrahedrally coordinated surface sites and octahedral-dominated core regions, creating reactive domains for contaminant complexation. Goethite (α-FeOOH), characterized by double chains of edge-sharing octahedra, immobilizes arsenic through sequential adsorption–precipitation processes: initial rapid surface complexation followed by inner-sphere coordination and secondary mineral formation [39,40]. Similarly, microbially synthesized birnessite (δ-MnO2) possesses a 2.31 Å interlayer spacing that facilitates Cd2+ incorporation via size-selective intercalation within its phyllomanganate structure, achieving structural stabilization through Jahn–Teller distortion effects [41]. This mechanism is of primary importance as it directly utilizes the structural characteristics of minerals to sequester As/Cd. For example, in many groundwater systems, goethite-mediated arsenic immobilization accounts for a significant portion (up to 60–70% in some cases) of total arsenic sequestration, as shown in field studies where mineral-specific binding dominates the immobilization process [42,43].

4.1.2. EPS-Mediated Chelation

Extracellular polymeric substances (EPSs), as high-molecular-weight polymer composites secreted by microorganisms, exhibit pronounced synergistic effects in heavy metal immobilization mechanisms [44]. Composed primarily of polysaccharides, proteins, nucleic acids, and uronic acids, EPS forms a three-dimensional network matrix enriched with functional groups (-COOH, -OH, and -NH2) that coordinate with As(III)/As(V) and Cd2+ to form stable complexes [45]. Spanò et al. demonstrated that EPS functional groups (O–H, C=O, C–O, and C=C bonds, as well as N–O groups) participate in arsenic adsorption, showing stronger interactions with arsenite (As-III) than arsenate (As-V) [46]. Furthermore, Irshad et al. investigated how EPS production by Bacillus XZM enhances the arsenic adsorption capacity of biochar–Bacillus XZM (BCXZM) composites. The BCXZM system achieved a maximum adsorption capacity of 42.3 mg/g, outperforming standalone biochar [47]. Lei et al. quantitatively established EPSs’ Cd2+ immobilization efficacy, reporting a maximum adsorption capacity of 45 mg/g in aqueous solutions. Fourier-transform infrared (FTIR) spectroscopy confirmed the involvement of key functional groups (C–O–C, amide I, -CH2, -COOH, and -OH) in Cd2+ coordination [48]. Notably, Kuang et al. revealed that kaolinite–EPS composites exhibit superior Cd(II) adsorption compared to pristine kaolinite, with hydroxyl groups (-OH) identified as critical binding sites through spectroscopic analyses [49]. These findings collectively highlight EPSs’ dual role in enhancing contaminant sequestration through both direct coordination and synergistic interactions with mineral substrates. EPS-mediated chelation is crucial as it can enhance the overall immobilization efficiency by 30–50% compared to mineral-only systems, as evidenced by laboratory experiments where EPS-containing systems show higher adsorption capacities and faster immobilization rates [50,51].

4.1.3. Microbial-Metabolic Coordination

Synergistic microbial–metabolic immobilization mechanisms involve tripartite interactions between microorganisms, Fe–Mn minerals, and metal(loid)s. Metal stress induces microbial physiological adaptations that enhance Fe/Mn biomineralization capacity, including biofilm formation, extracellular polymeric substance secretion, and redox homeostasis regulation [52]. Microorganisms mediate contaminant immobilization through dual biosorption–biotransformation pathways: (1) intracellular Cd2+ sequestration via ion exchange and metallothionein complexation [53] and (2) enzymatic oxidation of mobile As(III) to less-soluble As(V) species through multicopper oxidase-mediated redox cycling [54]. These coupled processes establish self-reinforcing immobilization networks where microbial metabolic activity drives mineral formation while biogenic minerals serve as reactive substrates for subsequent contaminant sequestration. This mechanism is essential for long-term and dynamic immobilization, especially in complex environments. For instance, in situ field studies show that microbial–metabolic coordination can maintain As/Cd immobilization stability over months, with microbial activity ensuring continuous mineralization and contaminant sequestration, contributing about 20–30% to the overall immobilization efficiency in some dynamic systems [55].

4.2. Influencing Factors

The immobilization of arsenic (As) and cadmium (Cd) through Fe and Mn biomineralization is governed by interdependent microbial, geochemical, and mineralogical factors (Figure 5), exhibiting complex synergistic, competitive, and antagonistic interactions. Table 2 summarizes the specific influences of these factors.
(1) Microbial Determinants
Microbial species specificity dictates mineralization pathways via unique enzymatic systems and metabolic strategies. Fe/Mn-oxidizing bacteria employ cytochrome-based electron transport chains and multicopper oxidases to catalyze metal oxidation, driving Fe–Mn (oxyhydr) oxide precipitation [56]. Extracellular polymeric substances (EPSs) secreted by these microbes serve as nucleation scaffolds, enhancing mineral deposition kinetics and contaminant sequestration efficiency [57]. Microbial activity is tightly regulated by environmental parameters as optimal temperature ranges (20–40 °C) maintain enzymatic reaction rates [58], whilst circumneutral pH preserves membrane potential and metalloenzyme functionality [59]. Aerobic conditions sustain oxidative metabolism, with dissolved oxygen acting as the terminal electron acceptor for Fe2+/Mn2+ oxidation [60].
(2) Geochemical Controls
Solution pH critically regulates mineral stability and contaminant speciation. Acidic conditions (pH < 5) promote Fe/Mn mineral dissolution, releasing immobilized As/Cd, whereas alkaline environments (pH > 8) favor crystalline-phase transformations that alter adsorption capacities. Redox potential (Eh) governs metal oxidation states, and oxidation conditions (high Eh) help stabilize Fe3+/Mn⁴+ oxides with high As/Cd affinity, while reductive dissolution under low Eh risks secondary contaminant release [61]. Competitive ions (Ca2+, Mg2+, CO32−, and PO43−) impair immobilization through site competition and ternary complex formation [62]. Studies show that when the environmental pH value is acidic (pH < 5), the dissolution of Fe–Mn minerals leads to a 50% increase in As/Cd mobility. Similarly, the presence of PO43− can reduce the adsorption capacity of Fe–Mn minerals for As by up to 40% due to competitive binding [63,64,65].
(3) Mineralogical Properties
Crystalline structure and surface reactivity determine contaminant retention mechanisms. Well-ordered phases like goethite (α-FeOOH) and pyrolusite (β-MnO2) exhibit high As/Cd affinity through inner-sphere complexation, while amorphous ferrihydrite shows greater initial reactivity but lower stability [66]. Surface area and defect density further influence adsorption capacity, with nanoparticulate minerals providing enhanced reactive sites. A comparative study showed that goethite has an adsorption capacity for As up to 50 mg/g, whilst amorphous ferrihydrite, though initially adsorbing faster, has a lower long-term stability with capacity dropping by 30% after one month under certain conditions [67,68,69].

4.3. Application Status

Figure 6 illustrates the sources and migration-transformation dynamics of arsenic (As) and cadmium (Cd) in groundwater systems. Natural As contamination primarily originates from weathering of arsenic-bearing minerals such as arsenopyrite (FeAsS) and orpiment (As2S3), which release soluble As species through leaching processes [70,71]. Anthropogenic contributions arise from mining activities, industrial effluents, agricultural chemicals, and improper waste disposal [4]. Biogenic Fe–Mn minerals formed during biomineralization processes exhibit high-surface-area and redox-active Mn phases, demonstrating exceptional As sequestration capabilities (Table 3) [72,73,74]. Previous studies have shown that enhanced As removal efficiencies under anaerobic conditions with Fe–Mn-reducing bacteria (FMR), achieving 17% and 16% improvements in As(III) and As(V) removal, respectively, compared to abiotic controls [13]. In parallel, Si et al. investigated arsenic removal using a novel manganese-oxidizing bacterium, Morganella morganii MnOx−1, to synthesize biogenic Fe–Mn oxides (BFMO) [75]. Their results revealed that BFMO achieved an As(III) oxidation rate of 74.1%, representing a 1.43-fold enhancement over biogenic Mn oxides (BMO) alone. In co-treatment systems combining BFMO and MnOx−1, simultaneous removal efficiencies reached 87.05% for As(III) and 94.23% for As(V) (100 mg/L each) within 7 days, with sustained performance of 80.26% and 99.32%, respectively, after 28 days. Bai et al. elucidated sequential As detoxification mechanisms involving initial FeOOH-mediated As(III) adsorption followed by Mn-oxide-catalyzed oxidation to less mobile As(V) [14].
The main sources of Cd in groundwater are similar to those of As and can be classified into natural and anthropogenic pollution sources. Natural pollution sources include rock weathering, volcanic activities, migration and deposition of cadmium dust in the atmosphere, and erosion of the ground by rainwater, etc.; whereas anthropogenic pollution sources include mining of cadmium ores, smelting of non-ferrous metals, electroplating, glass, ceramics, paints and other industrial emissions, etc. [76]. In the groundwater environment, the biomineralization process of iron and manganese has significant environmental significance. The formation of minerals by this process plays an important role in the research on groundwater pollution control and remediation. Zeng et al. characterized Cd immobilization by in situ formed BFMO, identifying surface complexation and redox-mediated precipitation as dominant mechanisms [15]. Liu et al. achieved 22.09–35.33% removal efficiencies for As, Pb, and Cd in multi-contaminant systems, demonstrating Mn/Fe ratio optimization as critical for As removal enhancement [77]. Huang et al. quantified microbial contributions to Cd stabilization, reporting a 36.84% reduction in bioavailable Cd through biogenic goethite and todorokite formation, coupled with Fe/Mn oxidation rates exceeding 63–70% [78]. Notably, these findings are primarily derived from laboratory-scale studies under controlled conditions, with limited data available for pilot or full-scale applications. For instance, while Si et al. achieved high As removal efficiencies in batch reactors [75], scaling up to complex aquifers may encounter challenges, such as variable pH, redox fluctuations, and competitive ion interference, which could reduce mineral stability and contaminant sequestration efficiency.
Pilot-scale trials have begun to address these gaps, but they reveal new constraints. A one-month in situ biological-mineralization As/Cd-remediation field experiment demonstrated that the initial removal rates of low-concentration soil exchangeable cadmium (3.504 mg/kg) and high-concentration soil exchangeable cadmium (9.324 mg/kg) were 76.96% and 66.43%, respectively. Over time, due to the gradual clogging of the reaction zone by secondary mineral precipitation, the exchangeable cadmium removal rate decreased to 14% [79,80]. This observation aligns with the geochemical controls discussed in Section 4.2, where acidic conditions (pH < 5) and competitive ions (e.g., Ca2+, PO43−) were shown to destabilize Fe–Mn minerals and impair immobilization efficiency [70,77]. Long-term monitoring is essential to track mineral stability and contaminant speciation changes—critical for distinguishing temporary immobilization from permanent sequestration. Technological advancements, such as integrating biosensors to monitor real-time redox potential and As/Cd speciation or using microbial tracers to assess in situ biomineralization activity, could enable adaptive management of remediation systems [81]. These findings collectively validate Fe–Mn biomineralization as a viable strategy for in-situ groundwater remediation, offering dual advantages of contaminant immobilization and natural attenuation process enhancement.
Table 3. The fixation effects of different systems/materials on arsenic and cadmium.
Table 3. The fixation effects of different systems/materials on arsenic and cadmium.
System/MaterialPerformance IndexDataReferences
Biochar–Bacillus XZM (BCXZM)Maximum adsorption capacity of As42.3 mg/g[47]
EPS (Aqueous solution)Maximum adsorption capacity of Cd45 mg/g[48]
Biogenic Fe–Mn oxides (BFMO)Oxidation rate of As(III)74.1%[75]
BFMO + Morganella morganii MnOx−1The 7-day removal efficiency of As(III)87.05%[75]
BFMO + Morganella morganii MnOx−1The 7-day removal efficiency of As(V)94.23%[75]
BFMO + Morganella morganii MnOx−1The 28-day removal efficiency of As(III)80.26%[75]
BFMO + Morganella morganii MnOx−1The 28-day removal efficiency of As(V)99.32%[75]
Multi-pollutant system (As/Pb/Cd)As/Pb/Cd removal efficiency22.09–35.33%[77]
Biogoethite and calcium-manganese ore systemsBioavailable Cd reduction rate36.84%[78]
Fe–Mn-reducing bacteria (FMR)As (III) removal efficiencyIncreased by 17%[13]
Fe–Mn-reducing bacteria (FMR)As (V) removal efficiencyIncreased by 16%[13]

5. Conclusions and Future Directions

Groundwater contamination by As and Cd presents critical environmental challenges, with 1022 peer-reviewed studies (2005–2024) indexed in Web of Science demonstrating exponential growth in research addressing these issues. While substantial progress has been made in elucidating Fe–Mn biomineralization mechanisms—including mineral-specific metal(loid) sequestration and microbial–metabolic coordination—along with influencing factors and material synergies, critical knowledge gaps persist regarding long-term performance under field-relevant conditions. Current investigations predominantly focus on laboratory-scale simulations, yet practical applications face multifaceted challenges such as complex interactions between microbial consortia, dynamic geochemical parameters, and mineral phase stability, compounded by regulatory ambiguities in technology approval, high economic costs associated with large-scale implementation, and scalability hurdles in translating lab-scale efficiencies to heterogeneous aquifer systems. These challenges are further exacerbated by risks of secondary contamination from mobilized remediation byproducts. To address these limitations, three strategic directions emerge as priorities.
(1) Optimization of microbial metabolic regulation
Deciphering metabolic networks governing Fe–Mn biomineralization under multi-contaminant stress and environmental fluctuations. Developing targeted induction protocols (e.g., bio-stimulants, environmental preconditioning) to enhance microbial metal(loid) transformation efficiency through pathway engineering.
(2) Advanced in situ monitoring systems
Implementing nanotechnology-enabled biosensors for real-time tracking of microbial activity, mineralogical evolution, and contaminant flux. Integrating machine learning-driven analytics to enable adaptive remediation strategies through predictive modeling of system responses.
(3) Hybrid remediation technologies
Based on the characteristics of groundwater contamination, physical, chemical, and biological remediation technologies should be strategically integrated. For instance, ion exchange techniques can efficiently remove specific ions to optimize the groundwater chemical environment, thereby enhancing the adsorption capacity of Fe–Mn biominerals for As and Cd. Alternatively, chemical precipitation methods may rapidly reduce the concentrations of As and Cd ions in groundwater, shortening remediation cycles and achieving efficient, stable remediation of complex contaminated groundwater systems.
These scientific advancements are pivotal for advancing sustainable groundwater management in developing regions where contaminated aquifers often serve as the primary water source for vulnerable communities. Prioritizing cost-effective, locally scalable solutions—such as hybrid-technologies leveraging indigenous microbes and accessible materials, paired with decentralized monitoring systems adapted to resource-constrained settings—can bridge the gap between lab research and on-the-ground impact. Integrating these innovations into regional water security strategies while building capacity for local stakeholders will ensure durable, context-specific solutions that address the complex challenges of heterogeneous aquifers.

Author Contributions

F.L.: Conceptualization, methodology, software, investigation, and writing—original draft. J.C.: investigation. X.Z.: writing—review and editing and funding acquisition. H.L.: investigation. F.J.: investigation. Y.L.: writing—review and editing and funding acquisition. All authors have read and agreed to the published version of the manuscript.

Funding

This work was jointly supported by the Basic Scientific Research Operating Funds for Higher Education Institutions in Xinjiang Uygur Autonomous Region (KJEDU2022P092), the Xinjiang Biomass Solid Waste Resources Technology and Engineering Center Project, Kashi University of China (KSUGCZX202305), the Funds for Central Guide Local Science and Technology Development of Xinjiang Uygur Autonomous Region (ZYYD2024CG10), the Shaanxi Provincial Natural Science Foundation (2024JC-YBQN-0255), and the Shijiazhuang Major Science and Technology Special Project (246241567A).

Data Availability Statement

No new data were created or analyzed in this study. Data sharing is not applicable to this article.

Conflicts of Interest

Author Fanfan Ju was employed by the company North China Engineering Investigation Institute Co., Ltd., Shijiazhuang, China. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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Catalysts 15 00570 g001
Figure 1. Bibliometric methods were used to explore the research trend of iron and manganese biomineralization in the remediation of arsenic- and cadmium-contaminated groundwater. (a) Thesis data collection flow chart. (b) National cooperation network. (c) Annual and cumulative publications.
Figure 1. Bibliometric methods were used to explore the research trend of iron and manganese biomineralization in the remediation of arsenic- and cadmium-contaminated groundwater. (a) Thesis data collection flow chart. (b) National cooperation network. (c) Annual and cumulative publications.
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Figure 2. Based on VOS viewer retrieval, the research trend of keywords is obtained. (a) Co-occurrence diagram of research hotspots. (b) Research hotspot trend change chart.
Figure 2. Based on VOS viewer retrieval, the research trend of keywords is obtained. (a) Co-occurrence diagram of research hotspots. (b) Research hotspot trend change chart.
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Figure 3. Biomineralization mechanism and microbial action of iron and manganese.
Figure 3. Biomineralization mechanism and microbial action of iron and manganese.
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Figure 4. The immobilization mechanism of arsenic and cadmium by iron and manganese biomineralization.
Figure 4. The immobilization mechanism of arsenic and cadmium by iron and manganese biomineralization.
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Figure 5. The influence factors of immobilization.
Figure 5. The influence factors of immobilization.
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Figure 6. Sources, migration, and transformation of arsenic and cadmium pollutants in groundwater.
Figure 6. Sources, migration, and transformation of arsenic and cadmium pollutants in groundwater.
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Table 1. Key differences between BCM and BIM.
Table 1. Key differences between BCM and BIM.
CharacteristicBCMBIM
Regulation MechanismDirect cellular templating of mineral nucleation (intracellular/extracellular).Indirect induction via microbial modification of microenvironmental conditions (pH, redox potential).
Mineral CrystallinityHighly ordered crystals (e.g., intracellular magnetite).Amorphous or low-ordered oxyhydroxides (e.g., Fe/Mn precipitates formed via pH/redox changes).
Driving ForceActive cell-surface adsorption and enzyme-mediated direct nucleation.Indirect stimulation through enzymatic secretion, acid/base production, or redox shifts.
Representative MicrobesMagnetotactic bacteria and fungal hyphae (EPS-mediated templating).Fe/Mn-oxidizing bacteria and sulfate-reducing bacteria.
Role in GroundwaterRapid metal ion sequestration via surface adsorption or intracellular storage.Long-term regulation of mineral cycling and contaminant fate through solubility/precipitation dynamics.
Table 2. The influence of different influencing factors on arsenic and cadmium fixation.
Table 2. The influence of different influencing factors on arsenic and cadmium fixation.
Factor CategoryPerformance IndexData
Microbial DeterminantsTemperature (20–40 °C)Appropriate temperature maintains the activity of enzymes and promotes mineralization.
pH (6–8)Extreme pH (<5 or >8) significantly inhibits microbial activity, resulting in a decrease in fixation efficiency.
Aerobic conditionThe hypoxic environment slows down the oxidation of Fe2+/Mn2+ and hinders the formation of minerals.
Geochemical ControlspH (<5 or >8)Acidic conditions promote the dissolution of minerals, whilst alkaline conditions change the structure of minerals.
REDOX potentialLow Eh leads to mineral dissolution, while high Eh enhances the adsorption capacity of minerals.
Competing ionCompeting with arsenic and cadmium for binding sites reduces the fixation efficiency.
Mineralogical PropertiesCrystalline mineralsIt has a stable structure, high adsorption capacity, and good long-term fixation effect.
Amorphous mineralsThe initial response is fast but the stability is low, and the long-term fixation effect is relatively poor.
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Li, F.; Cai, J.; Zhao, X.; Liu, H.; Ju, F.; Li, Y. Research Progress in the Remediation of Arsenic- and Cadmium-Contaminated Groundwater Mediated by Iron and Manganese Biomineralization. Catalysts 2025, 15, 570. https://doi.org/10.3390/catal15060570

AMA Style

Li F, Cai J, Zhao X, Liu H, Ju F, Li Y. Research Progress in the Remediation of Arsenic- and Cadmium-Contaminated Groundwater Mediated by Iron and Manganese Biomineralization. Catalysts. 2025; 15(6):570. https://doi.org/10.3390/catal15060570

Chicago/Turabian Style

Li, Feixing, Jixiang Cai, Xinxin Zhao, Hui Liu, Fanfan Ju, and Youwen Li. 2025. "Research Progress in the Remediation of Arsenic- and Cadmium-Contaminated Groundwater Mediated by Iron and Manganese Biomineralization" Catalysts 15, no. 6: 570. https://doi.org/10.3390/catal15060570

APA Style

Li, F., Cai, J., Zhao, X., Liu, H., Ju, F., & Li, Y. (2025). Research Progress in the Remediation of Arsenic- and Cadmium-Contaminated Groundwater Mediated by Iron and Manganese Biomineralization. Catalysts, 15(6), 570. https://doi.org/10.3390/catal15060570

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