Kinetic Modeling and Mechanisms of Manganese Removal from Alkaline Mine Water Using a Pilot Scale Column Reactor

Manganese (Mn) is a major element in various aqueous and soil environments that is sometimes highly concentrated in mine water and other mineral processing wastewater. In this study, we investigated Mn removal from alkaline mine water (pH > 9) with an Mn-coated silica sand packed into a pilot-scale column reactor and examined the specific reaction mechanism using X-ray absorption near-edge structure (XANES) analysis and geochemical kinetic modeling. The kinetic effect of dissolved Mn(II) removal by birnessite (δ-Mn(IV)O2) at pH 6 and 8 was evaluated at different Mn(II)/Mn(IV) molar ratios of 0.1–10. Our results confirmed the positive effect of the presence of δ-MnO2 on the short-term removal (60 min) of dissolved Mn. XANES analysis results revealed that δ-MnO2 was more abundant than Mn(III)OOH in the reactor, which may have accumulated during a long-term reaction (4 months) after the reactor was turned on. A gradual decrease in dissolved Mn(II) concentration with depth was observed in the reactor, and comparison with the kinetic modeling result confirmed that δ-MnO2 interaction was the dominant Mn removal mechanism. Our results show that δ-MnO2 contents could play a significant role in controlling Mn removability from mine water in the reactor.

Effect of Cu(II) and Conserved Copper Binding Sites on Multicopper Oxidase CopA and Characterization of the BioMnOx

The microbial manganese removal process is believed to be the catalytic oxidation of Mn(II) by manganese oxidase. In this study, the multicopper oxidase CopA was purified and found to have high manganese oxidation activity in vitro and Cu(II) can significantly enhance its manganese oxidation activity. The gene site-directed mutagenesis was used to mutate four conserved copper binding sites of CopA and then obtain four mutant strains. The manganese removal efficiency of the four strains was determined to find that H120 is the catalytic active site of the CopA. Protein modification analysis of CopA obtained under different conditions by mass spectrometry revealed that the loss of Cu(Ⅱ) and the mutation of the conserved copper binding site H120 resulted in the loss of modification of ethoxyformyl and quinone, the number of modifications was reduced and the position of modification was changed, eventually causing a decrease in protein activity. It reveals that Cu(II) and H120 play an indispensable role in the manganese oxidation of the multicopper oxidase CopA. The Mn valence state of BioMnOx was analyzed by XPS, finding that both the strain-mediated product and the CopA-mediated product were composed of MnO2 and Mn3O4 and the average valence of Mn is 3.2.

The performance of calcined serpentine to simultaneously remove fluoride, iron and manganese

To solve the problem of high fluoride, iron and manganese concentrations in groundwater, serpentine (Srp) was modified by metal salt impregnation, acid-base activation and calcination, and the effects of these three modifications on removal performance of Srp were compared. Specifically, the effects of the calcined serpentine (Csrp) dose, reaction time, pH, and temperature on the removal performance of F−, Fe2+ and Mn2+ on Csrp were analysed. An isothermal adsorption model and adsorption kinetic equation were established and confirmed through SEM, EDS, XRD and FTIR spectroscopy to analyse the mechanism of removing F−, Fe2+ and Mn2+ by Csrp. The results show that when 3 g/L Csrp was used to treat water samples with 5 mg/L F−, 20 mg/L Fe2+, and 5 mg/L Mn2+ (pH of 6, reaction temperature of 35 °C, and time of 150 min), the removal rates of F−, Fe2+, and Mn2+ were 94.3%, 99.0%, 98.9%, respectively. The adsorption of F−, Fe2+ and Mn2+ on Csrp follows the quasi-second-order kinetic equation and Langmuir isotherm adsorption model. After 5 cycles of regeneration of Csrp, Csrp can still maintain good properties of fluoride,iron and manganese removal.

Manganese Stress Adaptation Mechanisms of Bacillus safensis Strain ST7 From Mine Soil

The mechanism of bacterial adaption to manganese-polluted environments was explored using 50 manganese-tolerant strains of bacteria isolated from soil of the largest manganese mine in China. Efficiency of manganese removal by the isolated strains was investigated using atomic absorption spectrophotometry. Bacillus safensis strain ST7 was the most effective manganese-oxidizing bacteria among the tested isolates, achieving up to 82% removal at a Mn(II) concentration of 2,200 mg/L. Bacteria-mediated manganese oxide precipitates and high motility were observed, and the growth of strain ST7 was inhibited while its biofilm formation was promoted by the presence of Mn(II). In addition, strain ST7 could grow in the presence of high concentrations of Al(III), Cr(VI), and Fe(III). Genome-wide analysis of the gene expression profile of strain ST7 using the RNA-seq method revealed that 2,580 genes were differently expressed under Mn(II) exposure, and there were more downregulated genes (n = 2,021) than upregulated genes (n = 559) induced by Mn stress. KAAS analysis indicated that these differently expressed genes were mainly enriched in material metabolisms, cellular processes, organism systems, and genetic and environmental information processing pathways. A total of twenty-six genes from the transcriptome of strain ST7 were involved in lignocellulosic degradation. Furthermore, after 15 genes were knocked out by homologous recombination technology, it was observed that the transporters, multicopper oxidase, and proteins involved in sporulation and flagellogenesis contributed to the removal of Mn(II) in strain ST7. In summary, B. safensis ST7 adapted to Mn exposure by changing its metabolism, upregulating cation transporters, inhibiting sporulation and flagellogenesis, and activating an alternative stress-related sigB pathway. This bacterial strain could potentially be used to restore soil polluted by multiple heavy metals and is a candidate to support the consolidated bioprocessing community.

Simultaneous removal of fluoride, manganese and iron by manganese oxide supported activated alumina: characterization and optimization via response surface methodology

Fluoride, iron and manganese simultaneous exceedance of standard can be observed in groundwater in northeastern China. This work aims to apply a highly efficient method combining adsorption and oxidation for the synchronous removal of the inorganic ions. An innovative adsorbent (manganese-supported activated alumina) was synthesized by the impregnation method and showed a significant adsorption capacity better than that of fresh activated alumina. The characterization (scanning electron microscope; Brunauer, Emmett and Teller; X-ray diffraction and fourier transform infrared spectroscopy) results verified the successful introduction of MnOOH and MnO2, and the improvement of surface microstructure enhanced the removal ability. The effect of single factors, such as pH value, reaction time or dosage on the removal performance has been verified. The maximum removal efficiencies of fluoride, iron and manganese were optimized via Response surface methodology considering the independent factors in the range of MO@AA dosage (5–9 g/L), pH (4–6) and contact time (4–12 h). Noted that compared with control, MO@AA exhibited 59.4% of improved fluoride performance. At pH of 5.79, contacting time of 12 h and 8.21 g/L of MO@AA, fluoride, iron and manganese removal were found to be 91, 100 and 23%, respectively. Herein, MO@AA was distinguished good applicability for the treatment of fluoride, iron and manganese containing groundwater.

Efficient Removal of Aqueous Manganese (II) Cations by Activated Opuntia Ficus Indica Powder: Adsorption Performance and Mechanism

The adsorption of manganese ions from aqueous solutions by pure and acid-treated Opuntia ficus indica as natural low-cost and eco-friendly adsorbents was investigated. The adsorbents’ structures were characterized by powder X-ray diffraction and infrared spectroscopy. Specific surface areas were determined using the Brunauer-Emmett-Tell equation. The study was carried out under various parameters influencing the manganese removal efficiency such as pH, temperature, contact time, adsorbent dose and initial concentration of manganese ion. The maximum adsorption capacity reached 42.02 mg/g for acid-treated Opuntia ficus indica, and only 20.8 mg /g for pure Opuntia ficus indica. The Langmuir, Freundlich and Temkin isotherms equations were tested, and the best fit was obtained by the Langmuir model for both adsorbents. The thermodynamic study shows that chemisorption is the main adsorption mechanism for the activated adsorbent while physisorption is the main adsorption mechanism for the pure adsorbent. The kinetics of the adsorption have been studied using four kinetics models of pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion. Structural analyses indicate the appearance of MnOx oxides on the cellulose fibers. The adsorption mechanisms consist of an electrostatic interaction followed by oxidation of the Mn (II) to higher degrees, then probably by binding to the surface of the adsorbent by different C-O-MnOx bonds.