Metabolism of metals in microalgae and adaptation to metal excess are of significant environmental importance. We report a three-step mechanism that the green microalga Chlorella sorokiniana activates during the acquisition of and adaptation to manganese (Mn), which is both an essential trace metal and a pollutant of waters. In the early stage, Mn2+ was mainly bound to membrane phospholipids and phosphates in released mucilage. The outer cell wall was reorganized and lipids were accumulated, with a relative increase in lipid saturation. Intracellular redox settings were rapidly altered in the presence of Mn excess, with increased production of reactive oxygen species that resulted in lipid peroxidation and a decrease in the concentration of thiols. In the later stage, Mn2+ was chelated by polyphosphates and accumulated in the cells. The structure of the inner cell wall was modified and the redox milieu established a new balance. Polyphosphates serve as a transient Mn2+ storage ligand, as proposed previously. In the final stage, Mn was stored in multivalent Mn clusters that resemble the structure of the tetramanganese-calcium core of the oxygen-evolving complex. The present findings elucidate the bioinorganic chemistry and metabolism of Mn in microalgae, and may shed new light on water-splitting Mn clusters.
A unidirectional flow solar photocatalytic fuel cell (PFC) was successfully developed for the first time to offer alternative for electricity generation and simultaneous wastewater treatment. This study was focused on the synthesis of α-, δ- and β-MnO2 by wet chemical hydrothermal method for application as the cathodic catalyst in PFC. The crystallographic evolution was performed by varying the ratios of KMnO4 to MnSO4. The mechanism of the PFC with the MnO2/C as cathode was also discussed. Results showed that the catalytic activity of MnO2/C cathode was mainly predominated by their crystallographic structures which included Mn-O bond strength and tunnel size, following order of α- > δ- > β-MnO2/C. Interestingly, it was discovered that the specific surface areas (SBET) of different crystal phases did not give an impact on the PFC performance. However, the Pmax could be significantly influenced by the micropore surface area (Smicro) in the comparison among α-MnO2. Furthermore, the morphological transformation carried out by altering the hydrothermal duration demonstrated that the nanowire α-M3(24 h)/C with 1:1 ratio of KMnO4 and MnSO4 yielded excellent PFC performance with a Pmax of 2.8680 μW cm-2 and the lowest Rint of 700 Ω.
The textile industry consumes a large volume of organic dyes and water. These organic dyes, which remained in the effluents, are usually persistent and difficult to degrade by conventional wastewater treatment techniques. If the wastewater is not treated properly and is discharged into water system, it will cause environmental pollution and risk to living organisms. To mitigate these impacts, the photo-driven catalysis process using semiconductor materials emerges as a promising approach. The semiconductor photocatalysts are able to remove the organic effluent through their mineralization and decolorization abilities. Besides the commonly used titanium dioxide (TiO2), manganese dioxide (MnO2) is a potential photocatalyst for wastewater treatment. MnO2 has a narrow bandgap energy of 1~2 eV. Thus, it possesses high possibility to be driven by visible light and infrared light for dye degradation. This paper reviews the MnO2-based photocatalysts in various aspects, including its fundamental and photocatalytic mechanisms, recent progress in the synthesis of MnO2 nanostructures in particle forms and on supporting systems, and regeneration of photocatalysts for repeated use. In addition, the effect of various factors that could affect the photocatalytic performance of MnO2 nanostructures are discussed, followed by the future prospects of the development of this semiconductor photocatalysts towards commercialization.
A systematic set of borotellurite glasses doped with manganese (1-x) [(B(2)O(3))(0.3)(TeO(2))(0.7)]-xMnO, with x = 0.1, 0.2, 0.3 and 0.4 mol%, were successfully synthesized by using a conventional melt and quench-casting technique. In this study, the remelting effect of the glass samples on their microstructure was investigated through density measurement and FT-IR spectra and evaluated by XRD techniques. Initial experimental results from XRD evaluation show that there are two distinct phases of glassy and crystallite microstructure due to the existence of peaks in the sample. The different physical behaviors of the studied glasses were closely related to the concentration of manganese in each phase. FTIR spectra revealed that the addition of manganese oxide contributes the transformation of TeO(4) trigonal bipyramids with bridging oxygen (BO) to TeO(3) trigonal pyramids with non-bridging oxygen (NBO).
Aerobic oxidation of 5-Hydroxymethylfurfural (HMF) to 2,5-Diformylfuran (DFF) using O2 gas represents a sustainable approach for valorization of lignocellulosic compounds. As manganese dioxide (MnO2) is validated as a useful oxidation catalyst and many crystalline forms of MnO2 exist, it is critical to explore how the crystalline structures of MnO2 influence their physical/chemical properties, which, in turn, determine catalytic activities of MnO2 crystals for HMF oxidation to DFF. In particular, six MnO2 crystals, α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, ε-MnO2, and λ-MnO2 are prepared and investigated for their catalytic activities for HMF oxidation to DFF. With different morphologies and crystalline structures, these MnO2 crystals possess very distinct surficial chemistry, redox capabilities, and textural properties, making these MnO2 exhibit different catalytic activities towards HMF conversion. Especially, β-MnO2 can produce much higher DFF per surface area than other MnO2 crystals. β-MnO2 could achieve the highest CHMF = 99% and YDFF = 97%, which are much higher than the reported values in literature, possibly because the surficial reactivity of β-MnO2 appears to be highest in comparison to other MnO2 crystals. Especially, β-MnO2 could exhibit YDFF > 90% over 5 cycles of reusability test, and maintain its crystalline structure, revealing its advantageous feature for aerobic oxidation of HMF to DFF. Through this study, the relationship between morphology, surface chemistry, and catalytic activity of MnO2 with different crystal forms is elucidated for providing scientific insights into design, application and development of MnO2-based materials for aerobic oxidation of bio-derived molecules to value-added products.
The present study was carried out to determine the concentrations of selected metal elements (lead, copper, manganese, zinc and iron) in 51 samples of commercial drinking water and tap water available in Malaysia. The results indicated that low metal elements were found in the studied water samples. Lead, manganese, zinc and iron were not detected in some of the studied samples, except copper. The concentrations of the metal elements in the studied samples were well below the maximum permitted concentrations as recommended. Therefore these drinking water are safe for consumption and do not pose adverse effect to the health of consumers due to metal toxicity.
Groundwater is one of the alternatives to surface water that can be used for drinking water; however, it normally exists with high iron and manganese content. In this study, a column study was conducted to observe the elimination of iron (Fe) and manganese (Mn) in the groundwater under different retention times by using zeolite immobilized with iron-oxidizing bacteria (IOB). Rossellomorea sp., representing an IOB, was found from the isolation process and was further cultured in the laboratory for immobilization into the natural zeolite as replacement materials for the sand filter. When the zeolite assisted with the Rossellomorea sp. was used, the elimination of Fe and Mn were 99.34% and 88.92%, respectively, compared to the removal of Fe and Mn, which were 93.62% and 93.73%, respectively, for media without immobilization. The presence of Rossellomorea sp. enhances the Fe oxidation, resulting in high removal of Fe. The Thomas and Yoon-Nelson models were performed in both raw zeolite and zeolite with IOB. The total coliform (most probable number [MPN]) increased from 70.8 to 307.6 MPN/100 mL because of the Rossellomorea sp. present that promotes the growth of coliform bacteria. In conclusion, the immobilization of zeolite with IOB is a potential technique to extract the Fe and Mn in the groundwater. PRACTITIONER POINTS: Zeolite incorporated with Rossellomorea sp. has higher removal performance of Fe, whereas the removal of Mn reduced compared to the raw zeolite. The presence of Rossellomorea sp. enhances the oxidation of ferrous iron and improves the removal of Fe in the groundwater because the ferric iron is the priority ion to be exchanged. The removal of UV254 increase when Rossellomorea sp. present in the zeolite because the Rossellomorea sp. consume the natural organic matter as carbon source.
The artificial neural network (ANN) modeling of m-cresol photodegradation was carried out for determination of the optimum and importance values of the effective variables to achieve the maximum efficiency. The photodegradation was carried out in the suspension of synthesized manganese doped ZnO nanoparticles under visible-light irradiation. The input considered effective variables of the photodegradation were irradiation time, pH, photocatalyst amount, and concentration of m-cresol while the efficiency was the only response as output. The performed experiments were designed into three data sets such as training, testing, and validation that were randomly splitted by the software's option. To obtain the optimum topologies, ANN was trained by quick propagation (QP), Incremental Back Propagation (IBP), Batch Back Propagation (BBP), and Levenberg-Marquardt (LM) algorithms for testing data set. The topologies were determined by the indicator of minimized root mean squared error (RMSE) for each algorithm. According to the indicator, the QP-4-8-1, IBP-4-15-1, BBP-4-6-1, and LM-4-10-1 were selected as the optimized topologies. Among the topologies, QP-4-8-1 has presented the minimum RMSE and absolute average deviation as well as maximum R-squared. Therefore, QP-4-8-1 was selected as final model for validation test and navigation of the process. The model was used for determination of the optimum values of the effective variables by a few three-dimensional plots. The optimum points of the variables were confirmed by further validated experiments. Moreover, the model predicted the relative importance of the variables which showed none of them was neglectable in this work.
Manganese (Mn(2+)) is one of the inorganic contaminant that causes problem to water treatment and water distribution due to the accumulation on water piping systems. In this study, Bacillus sp. and sewage activated sludge (SAS) were investigated as biosorbents in laboratory-scale experiments. The study showed that Bacillus sp. was a more effective biosorbent than SAS. The experimental data were fitted to the Langmuir (Langmuir-1 & Langmuir-2), Freundlich, Temkin, Dubinin-Radushkevich (D-R) and Redlich-Peterson (R-P) isotherms to obtain the characteristic parameters of each model. Mn(2+) biosorption by Bacillus sp. was found to be significantly better fitted to the Langmuir-1 isotherm than the other isotherms, while the D-R isotherm was the best fit for SAS; i.e., the χ(2) value was smaller than that for the Freundlich, Temkin, and R-P isotherms. According to the evaluation using the Langmuir-1 isotherm, the maximum biosorption capacities of Mn(2+) onto Bacillus sp. and SAS were 43.5 mg Mn(2+)/g biomass and 12.7 mg Mn(2+)/g biomass, respectively. The data fitted using the D-R isotherm showed that the Mn(2+) biosorption processes by both Bacillus sp. and SAS occurred via the chemical ion-exchange mechanism between the functional groups and Mn(2+) ion.
Photopyroelectric (PPE) spectroscopy is a nondestructive tool that is used to study the optical properties of the ceramics (ZnO + 0.4MnO(2) + 0.4Co(3)O(4) + xV(2)O(5)), x = 0-1 mol%. Wavelength of incident light, modulated at 10 Hz, was in the range of 300-800 nm. PPE spectrum with reference to the doping level and sintering temperature is discussed. Optical energy band-gap (E(g)) was 2.11 eV for 0.3 mol% V(2)O(5) at a sintering temperature of 1025 °C as determined from the plot (ρhυ)(2)versushυ. With a further increase in V(2)O(5), the value of E(g) was found to be 2.59 eV. Steepness factor 'σ(A)' and 'σ(B)', which characterize the slope of exponential optical absorption, is discussed with reference to the variation of E(g). XRD, SEM and EDAX are also used for characterization of the ceramic. For this ceramic, the maximum relative density and grain size was observed to be 91.8% and 9.5 μm, respectively.
Environmental monitoring was carried out at Upper Layang Reservoir situated in Masai, Johor, Malaysia. The study shows that thermal stratification and natural mixing of the water column do exist in the reservoir and the level of stratification varies at different times of the year. Artificial destratification via diffused air aeration techniques was employed at the reservoir for two months. The results show that thermal stratification was eliminated after a week of continuous aeration. The concentrations of iron and to a lesser extent manganese in the water column was also reduced during the aeration period.
Rice brown spot (BS) exerts devastating agronomic effects on grain quality and overall productivity. In Peninsular Malaysia, BS disease incidence is fairly prevalent and little is known about the diversity of BS pathogens in the local granaries. Fifteen isolates from BS symptomatic rice plants were identified at five different rice granaries across Peninsular Malaysia. Based on the morphological and molecular analyses, two isolates were confirmed as Bipolaris oryzae while the rest were identified as Exserohilum rostratum. Phylogenetic tree analysis revealed that BS incidence in rice granaries in Peninsular Malaysia is caused by a pair of closely related fungal pathogens, E. rostratum and B. oryzae, with the former being more predominant. Cultural characterization of E. rostratum isolate KT831962 showed the best growth and sporulation activity on corn meal agar plates incubated in complete darkness. The effects of calcium silicate (CaSiO3) and rice husk ash (RHA) soil amendment against MR219 and MR253 rice varieties were evaluated during rice-E. rostratum interaction. Results showed that soil amelioration using CaSiO3 and RHA singly and in combination with manganese (Mn) significantly reduced rice BS disease severity. The BS disease index was reduced significantly to less than 31.6% in the silicon-treated rice plants relative to the control plants at 41.2%. Likewise, the grain yield at the harvest stage showed significantly higher yield in the Si-treated rice plants in comparison to the control, non-Si treated rice plants. The findings highlight the potential of RHA agro-waste as Si fertilizer in a sustainable rice production system.
Availability of quality-certified water is pertinent to the production of food and pharmaceutical products. Adverse effects of manganese content of water on the corrosion of vessels and reactors necessitate that process water is scrutinized for allowable concentration levels before being applied in the production processes. In this research, optimization of the adsorption process conditions germane to the removal of manganese from biotreated palm oil mill effluent (BPOME) using zeolite 3A subsequent to a comparative adsorption with clinoptilolite was studied. A face-centered central composite design (FCCCD) of the response surface methodology (RSM) was adopted for the study. Analysis of variance (ANOVA) for response surface quadratic model revealed that the model was significant with dosage and agitation speed connoting the main significant process factors for the optimization. R(2) of 0.9478 yielded by the model was in agreement with predicted R(2). Langmuir and pseudo-second-order suggest the adsorption mechanism involved monolayer adsorption and cation exchanging.
In this study, the selenium enriched peanuts and the different solubility proteins extracted from them were investigated. The dried defatted selenium enriched peanuts (SeP) powder (0.3147 μg/g) had a 2.5-fold higher mean total selenium concentration than general peanuts (GP) power (0.1233 μg/g). The SeP had higher concentration of selenium, manganese and zinc than that of GP, but less calcium. The rate of extraction of protein was 23.39% for peanuts and alkali soluble protein was the main component of protein in SeP, which accounted for 92.82% of total soluble protein and combined selenium was 77.33% of total selenium protein. In different forms of proteins from SeP, the WSePr due to higher concentration of selenium had higher DPPH free-radical scavenging activity, higher reducing activity and longer induction time than other proteins.
Asymmetric supercapacitors (ASC) have shown a great potential candidate for high-performance supercapacitor due to their wide operating potential which can remarkably enhance the capacitive behaviour. In present work, a novel positive electrode derived from functionalised carbon nanofibers/poly(3,4-ethylenedioxythiophene)/manganese oxide (f-CNFs/PEDOT/MnO2) was prepared using a multi-step route and activated carbon (AC) was fabricated as a negative electrode for ASC. A uniform distribution of PEDOT and MnO2 on f-CNFs as well as porous granular of AC are well-observed in FESEM. The assembled f-CNFs/PEDOT/MnO2//AC with an operating potential of 1.6 V can achieve a maximum specific capacitance of 537 F/g at a scan rate of 5 mV/s and good cycling stability (81.06% after cycling 8000 times). Furthermore, the as-prepared ASC exhibited reasonably high specific energy of 49.4 Wh/kg and low charge transfer resistance (Rct) of 2.27 Ω, thus, confirming f-CNFs/PEDOT/MnO2//AC as a promising electrode material for the future energy storage system.
In Malaysia, the use of groundwater can help to meet the increasing water demand. The utilization of the aquifers is currently contributing in water supplies, particularly for the northern states. In this study, quantitative and qualitative assessments were carried out for the groundwater exploitation in the states of Kelantan, Melaka, Terengganu and Perak. The relevant data was acquired from the Department of Mineral and Geoscience, Malaysia. The quantitative assessment mainly included the determination of the use to yield ratio (UTY). The formula was proposed to determine the UTY ratio for aquifers in Malaysia. The proposed formula was applied to determine the maximum UTY ratios for the aquifers located in the states of Kelantan, Melaka, and Terengganu, and were found to be 4.2, 5.2 and 0.6, respectively. This indicated that exploitation of groundwater was beyond the safe limit in the states of Kelantan and Melaka. The qualitative assessment showed that the groundwater is slightly acidic. In addition, the concentrations of iron and manganese were found to be higher than the allowable limits, but the chloride concentration was found within the allowable limit.
This study was conducted to determine the effects of rice husk ash (RHA) and Fe-coated rice husk ash (Fe-RHA) on the bioavailability and mobility of As, Cd, and Mn in mine tailings. The amendments were added to the tailings at 0, 5, 10, or 20% (w/w) and the mixtures were incubated for 0, 7, 15, 30, 45, and 60 days. The CaCl2 extractable As, Cd, and Mn in the amended tailings were determined at each interval of incubation period. In addition, the tailings mixture was leached with simulated rain water (SRW) every week from 0 day (D 0) until day 60 (D 60). The results showed that both RHA and Fe-RHA application significantly decreased the CaCl2-extractable Cd and Mn but increased that of As in the tailings throughout the incubation period. Consequently, addition of both RHA and Fe-RHA leached out higher amount of As from the tailings but decreased Cd and Mn concentration compared to the controls. The amount of As leached from the Fe-RHA-amended tailings was less than that from RHA-amended tailings. Application of both RHA and Fe-RHA could be an effective way in decreasing the availability of cationic heavy metals (Cd and Mn) in the tailings but these amendments could result in increasing the availability of anionic metalloid (As). Therefore, selection of organic amendments to remediate metal-contaminated tailings must be done with great care because the outcomes might be different among the elements.
Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm(-2), in contrast to MnO2, which produced a maximum power density of 9.2 mW cm(-2). The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.
This paper presents the preparation of in situ electrodeposited rGO/MnO2 nanocomposite as a binder-free electrode for supercapacitor application. The work describes and evaluates the performance of prepared electrode via green and facile electrodeposition technique of in situ rGO/MnO2-glucose carbon nanocomposites. The carbon content in the composite electrode increased after GO and D (+) glucose solution has been added in the deposition electrolyte. This study found that a suitable concentration of D (+) glucose in the deposition electrolyte can slow down the nucleation process of MnO2 particles and lead to uniform and ultrathin nanoflakes structure. The optimize electrode exhibited low transfer resistance and resulted on excellent electrochemical performance in three electrolyte systems viz. Na2SO4, KOH and KOH/K3Fe(CN)6 redox electrolytes. The optimum energy density and power density were 1851 Whkg(-1) and 68 kWkg(-1) at current density of 20 Ag(-1) in mixed KOH/K3Fe(CN)6 electrolyte.
Manganese has recently been a topic of interest among researchers, particularly when 1,752 million tonnes of manganese are expected to be produced by the steel industry in 2020. Manganese discharges from industrial effluents have increased manganese contamination in water sources. Its concentrations of more than 0.2 mg/L in the water sources could have negative impacts on human health and the aquatic ecosystem. Thereby, the available water treatment processes face challenges in effectively removing manganese at low cost. In response to these challenges, adsorption has emerged as one of the most practical water treatment processes for manganese removal. In particular, agricultural waste adsorbents received a lot of attention owing to their low cost and high efficiency (99%) in the removal of manganese. Therefore, this paper reviews the removal of manganese by adsorption process using agricultural waste adsorbents. The factors affecting the adsorption process, the mechanisms, and the performances of the adsorbents are elucidated in detail.