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Efficacy of Mn-doped ZnO towards Removal of Congo Red Dye under UV Exposure: Isotherm, Kinetics, Thermodynamics and Optimization Study
2023
Roy, Tapas | Mondal, Naba Kumar | Mitra, Partha
Discharge of synthetic dyes from industries without treatment leads to major environmental problems. Present research highlighted the Mn-doped ZnO along with UV-induced photo degradation of Congo red (CR) dye through batch study. The synthesized Mn-doped ZnO (MDZO) was characterized by Transmission electron microscope (TEM) and Fourier transform infrared spectroscopy (FTIR). The results revealed that MDZO along with UV exposure degraded the CR dye up to 99.3% at concentration 4 mg/L, pH (7), adsorbent dose (0.6 g/L) and contact time (30 min). The degradation data nicely fitted with pseudo-secondary kinetics and the thermodynamic study suggest the said reaction is exothermic in nature. A statistical method, central composite design (CCD) was used to screen out the optimized condition of dye degradation. The interactions of main factors and optimal conditions were also evaluated by 3D surface plots. The statistical output clearly demonstrates that the dye degradation data is nicely fitted with very high goodness of fit and F value (86.19). Present research clearly suggested that Mn-doped ZnO along with UV could be an effective treatment towards degradation of Congo red dye.
Show more [+] Less [-]The adsorption mechanisms of oriental plane tree biochar toward bisphenol S: A combined thermodynamic evidence, spectroscopic analysis and theoretical calculations
2022
Fang, Zheng | Gao, Yurong | Zhang, Fangbin | Zhu, Kaipeng | Shen, Zihan | Liang, Haixia | Xie, Yue | Yu, Chenglong | Bao, Yanping | Feng, Bo | Bolan, Nanthi | Wang, Hailong
Garden pruning waste is becoming a problem that intensifies the garbage siege. It is of great significance to purify polluted water using biochar prepared from garden pruning waste. Herein, the interaction mechanism between BPS and oriental plane tree biochar (TBC) with different surface functional groups was investigated by adsorption experiments, spectroscopic analysis and theoretical calculations. Adsorption kinetics and isotherm of BPS on TBC can be satisfactorily fitted into pseudo-second-order kinetic and Langmuir models, respectively. A rapid adsorption kinetic toward BPS was achieved by TBC in 15 min. As compared with TBC prepared at low temperature (300 °C) (LTBC), the maximum adsorption capacity of TBC prepared at high temperature (600 °C) (HTBC) can be significantly improved from 46.7 mg g⁻¹ to 72.9 mg g⁻¹. Besides, the microstructure and surface functional groups of HTBC were characterized using SEM, BET-N₂, and XPS analysis. According to density functional theory (DFT) theoretical calculations, the higher adsorption energy of HTBC for BPS was mainly attributed to π-π interaction rather than hydrogen bonding, which was further supported by the analysis of FTIR and Raman spectra as well as the adsorption thermodynamic parameters. These findings suggested that by improving π-π interaction through high pyrolysis temperature, BPS could be removed and adsorbed by biochar with high efficacy, cost-efficiency, easy availability, and carbon-negative in nature, contributing to global carbon neutrality.
Show more [+] Less [-]Assessing the oxidative potential of PAHs in ambient PM2.5 using the DTT consumption assay
2021
Kramer, Amber L. | Dorn, Shelby | Perez, Allison | Roper, Courtney | Titaley, Ivan A. | Cayton, Kaylee | Cook, Ronald P. | Cheong, Paul H-Y | Massey Simonich, Staci L.
The oxidative potential (OP) of atmospheric fine particulate matter (PM₂.₅) has been linked to organic content, which includes polycyclic aromatic hydrocarbons (PAHs). The OP of 135 individual PAHs (including six subclasses) was measured using the dithiolthreitol (DTT) consumption assay. The DTT assay results were used to compute the concentration of each PAH needed to consume 50% of the DTT concentration in the assay (DTT₅₀), and the reduction potential of the PAHs (ΔGᵣₓₙ). Computed reduction potential results were found to match literature reduction potential values (r² = 0.97), while DTT₅₀ results had no correlations with the computed ΔGᵣₓₙ values (r² < 0.1). The GINI equality index was used to assess the electron distribution across the surface of unreacted and reacted PAHs. GINI values correlated with ΔGᵣₓₙ in UPAH, HPAH, and OHPAH subclasses, as well as with all 135 PAHs in this study but did not correlate with DTT₅₀, indicating that electron dispersion is linked to thermodynamic reactions and structural differences in PAHs, but not linked to the OP of PAHs. Three ambient PM₂.₅ filters extracts were measured in the DTT assay, alongside mixtures of analytical standards prepared to match PAH concentrations in the filter extracts to test if the OP follows an additive model of toxicity. The additive prediction model did not accurately predict the DTT consumption in the assay for any of the prepared standard mixtures or ambient PM₂.₅ filter extracts, indicating a much more complex model of toxicity for the OP of PAHs in ambient PM₂.₅. This study combined computed molecular properties with toxicologically relevant assay results to probe the OP of anthropogenically driven portions of ambient PM₂.₅, and results in a better understanding of the complexity of ambient PM₂.₅ OP.
Show more [+] Less [-]Effective removal of excessive fluoride from aqueous environment using activated pods of Bauhinia variegata: Batch and dynamic analysis
2021
Jayashree, D Eunice | Kumar, P Senthil | Ngueagni, P Tsopbou | Vo, Dai-VietN. | Chew, Kit Wayne
In this study, a novel biosorbent is prepared from the pods of Bauhinia variegata is used for defluoridation of the fluoride contaminated water. It is an eco-friendly and economically feasible material. Comparison of adsorption capacity of Physically Treated Bauhinia (PTB) and Chemically Treated Bauhinia (CTB) are carried in this work. Characterization studies like SEM, EDS, FTIR, and XRD are executed to analyze surface morphology and functional groups in PTB and CTB. The experimental procedure was implemented in a batch process where the operating constraints such as dosage, pH, initial fluoride concentration, time, and temperature are varied to attain optimized efficiency. PTB and CTB yield an adsorption capacities of 10.90 mg/g and 15.45 mg/g respectively in the batch process. PTB adheres fluoride in monolayer formation whereas CTB forms multilayer adsorption. The adsorption process was described by the Pseudo first-order model to state the mechanism of physisorption. The negative values of thermodynamic parameters indicate spontaneity and favorable conditions for adsorption process. As CTB has a higher adsorption capacity than PTB, the batch study has been extended to column adsorption. Bed depth, initial fluoride concentration, and flow rate are the experimental variables used to acquire breakthrough curves. Simplified column models like Adam-Bohart, Thomas, and Yoon-Nelson models were analyzed. In column studies, Yoon-Nelson model fitted well in describing the process of adsorption. The maximum adsorption capacity acquired during the column process was found to be 1.176 mg/g with a bed depth of 5 cm and a flow rate of 5 ml/min. Thus, the innocuous and sustainable adsorbent is developed and serves as an excellent defluoridation agent.
Show more [+] Less [-]Sustainable functionalized metal-organic framework NH2-MIL-101(Al) for CO2 separation under cryogenic conditions
2021
Bābar, Muḥammad | Mubashir, Muhammad | Mukhtar, Ahmad | Saqib, Sidra | Ullah, Sami | Bustam, Mohamad Azmi | Show, Pau Loke
In this study, a sustainable NH₂-MIL-101(Al) is synthesized and subjected to characterization for cryogenic CO₂ adsorption, isotherms, and thermodynamic study. The morphology revealed a highly porous surface. The XRD showed that NH₂-MIL-101(Al) was crystalline. The NH₂-MIL-101(Al) decomposes at a temperature (>500 °C) indicating excellent thermal stability. The BET investigation revealed the specific surface area of 2530 m²/g and the pore volume of 1.32 cm³/g. The CO₂ adsorption capacity was found to be 9.55 wt% to 2.31 wt% within the investigated temperature range. The isotherms revealed the availability of adsorption sites with favorable adsorption at lower temperatures indicating the thermodynamically controlled process. The thermodynamics showed that the process is non-spontaneous, endothermic, with fewer disorders, chemisorption. Finally, the breakthrough time of NH₂-MIL-101(Al) is 31.25% more than spherical glass beads. The CO₂ captured by the particles was 2.29 kg m⁻³. The CO₂ capture using glass packing was 121% less than NH₂-MIL-101(Al) under similar conditions of temperature and pressure.
Show more [+] Less [-]Remediation of artificially contaminated soil and groundwater with copper using hydroxyapatite/calcium silicate hydrate recovered from phosphorus-rich wastewater
2021
Liu, Yiyang | Zhang, Rongbin | Sun, Zhenjie | Shen, Qin | Li, Yuan | Wang, Yuan | Xia, Siqing | Zhao, Jianfu | Wang, Xuejiang
Excessive copper (Cu) in contaminated soil and groundwater has attracted continuous attentions due to the bioaccumulation and durability. In this study, the feasibility of remediation of heavy metal pollution in soil and groundwater was investigated using hydroxyapatite/calcium silicate hydrate (HAP/C–S–H) recovered from phosphorus-rich wastewater in farmland. The results show that the pH has a strong effect on copper removal from Cu-contaminated groundwater but the impact of ion strength on the removal is weak. In general, high pH and low ion strength give better results in copper removal. Kinetic and isotherm data from the study fit well with Pseudo-second-order kinetic model and Langmuir isotherm model, respectively. The maximum adsorption capacity of HAP/C–S–H (138 mg/g) was higher than that of C–S–H (90.3 mg/g) when pH value, temperature, and ionic strength were 5, 308 K, and 0.01 M, respectively. Thermodynamics results indicate that Cu removal is a spontaneous and endothermic process. X-ray diffraction (XRD) results show that the mechanism of copper removal involves physical adsorption, chemical precipitation and ion exchange. For the remediation of Cu-contaminated soil, 76.3% of leachable copper was immobilized by HAP/C–S–H after 28 d. Acid soluble Cu, the main contributor to biotoxicity, decreased significantly while reducible and residual Cu increased. After immobilization, the acid neutralization capacity of the soil increased and the dissolution of copper was substantially reduced in near-neutral pH. It can be concluded that HAP/C–S–H is an effective, low-cost and eco-friendly reagent for in-situ remediation of heavy metal polluted soil and groundwater.
Show more [+] Less [-]Strong temporal and spatial variation of dissolved Cu isotope composition in acid mine drainage under contrasted hydrological conditions
2020
Masbou, J. | Viers, J. | Grande, J.-A. | Freydier, R. | Zouiten, C. | Seyler, P. | Pokrovsky, O.S. | Behra, P. | Dubreuil, B. | de la Torre, M.-L.
Copper export and mobility in acid mine drainage are difficult to understand with conventional approaches. Within this context, Cu isotopes could be a powerful tool and here we have examined the relative abundance of dissolved (<0.22 μm) Cu isotopes (δ⁶⁵Cu) in the Meca River which is an outlet of the Tharsis mine, one of the largest abandoned mines of the Iberian Pyrite Belt, Spain. We followed the chemical and isotopic composition of the upstream and downstream points of the catchment during a 24-h diel cycle. Additional δ⁶⁵Cu values were obtained from the tributary stream, suspended matter (>0.22 μm) and bed sediments samples. Our goals were to 1) assess Cu sources variability at the upstream point under contrasted hydrological conditions and 2) investigate the conservative vs. non conservative Cu behavior along a stream. Average δ⁶⁵Cu values varied from −0.47 to −0.08‰ (n = 9) upstream and from −0.63 to −0.31‰ downstream (n = 7) demonstrating that Cu isotopes are heterogeneous over the diel cycle and along the Meca River. During dry conditions, at the upstream point of the Meca River the Cu isotopic composition was heavier which is in agreement with the preferential release of heavy isotopes during the oxidative dissolution of primary sulfides. The more negative values obtained during high water flow are explained by the contribution of soil and waste deposit weathering. Finally, a comparison of upstream vs. downstream Cu isotope composition is consistent with a conservative behavior of Cu, and isotope mass balance calculations estimate that 87% of dissolved Cu detected downstream originate from the Tharsis mine outlet. These interpretations were supported by thermodynamic modelling and sediment characterization data (X-ray diffraction, Raman Spectroscopy). Overall, based on contrasted hydrological conditions (dry vs flooded), and taking the advantage of isotope insensitivity to dilution, the present work demonstrates the efficiency of using the Cu isotopes approach for tracing sources and processes in the AMD regions.
Show more [+] Less [-]Preparation of 2D nitrogen-doped magnetic Fe3C/C by in-situ self-assembled double-template method for enhanced removal of Cr(VI)
2020
Su, Qiaohong | Su, Zhi | Xie, Wenyu | Tian, Chen | Su, Xintai | Lin, Zhang
Porous carbon, which can be functionalized, is considered as a potential carbon material. Herein, two-dimensional (2D) nitrogen-doped magnetic Fe₃C/C (NMC) was prepared by a simple carbonization method using potassium humate (HA-K) as raw material. Remarkably, two templates, g-C₃N₄ and KCl, were formed in situ during the carbonization process, which provide the necessary conditions for the formation of 2D NMC. The NMC was comprehensively studied by different characterization methods. The results show that NMC has a large surface area and mesoporous structure. The prepared NMC-0.50 was used to test the removal performance of Cr(VI). The effects of pH value, coexisting ions and time on Cr(VI) removal performance were investigated, and the adsorption kinetics, isotherm and thermodynamics were studied. The results showed that the adsorption isotherm model of NMC-50 accorded with the Langmuir model, and the maximum adsorption capacity was 423.73 mg g⁻¹. The reaction mechanism of Cr(VI) is adsorption and redox reaction. In addition, NMC-0.50 exhibit high selectivity, separability and regeneration performance. A convenient means for the synthesis of NMC was designed in this work, and demonstrate that NMC has practical value as an adsorbent.
Show more [+] Less [-]Phosphorus transport in riverbed sediments and related adsorption and desorption characteristics in the Beiyun River, China
2020
Liao, Renkuan | Hu, Jieyun | Li, Yunkai | Li, Shuqin
Riverbed sediments are the interface layer in riverine ecosystems connecting the overlying medium of water and the vadose zone. The transport behavior of phosphorus (P), which has been recognized as the primary cause of freshwater eutrophication, in riverbed sediments remains unclear. Understanding the impact of riverbed sediments on P transport is a necessary prerequisite for the development of appropriate strategies to reduce potential groundwater pollution. In this study, riverbed sediments were collected from the upstream, midstream, and downstream sections of the Beiyun River, China, and packed into vertical soil columns to perform leaching experiments to quantify P transport characteristics. In addition, the impact mechanisms were further explored by conducting laboratory batch tests of P adsorption and desorption. The results demonstrated that approximately 80% of P can be adsorbed by riverbed sediments in soil column leaching experiment, and a tailing phenomenon was observed in its desorption. The hydraulic conductivity properties of riverbed sediments were evaluated by the advection-dispersion equation, showing a gradually decreasing adsorption capacity for P from upstream to downstream sections, which was supported by the results obtained from adsorption–desorption thermodynamic and kinetic batch tests. The estimated annual leaching masses of P increased from 60.72 g/(m² a) in the upstream section to 132.31 g/(m² a) in the downstream section. The role of riverbed sediments as a source or sink of P is possibly determined by their coarse sand particles content, and the mean equilibrium P concentration (EPC0). The competitive relationship between P and other forms of nutrients also has an important influence on its source-sink role. These findings suggest that the prevention of the potential P leaching is most needed in the downstream sections of Beiyun River, and corresponding control strategies should be developed to avoid groundwater pollution.
Show more [+] Less [-]Synthesis of nano-magnetic MnFe2O4 to remove Cr(III) and Cr(VI) from aqueous solution: A comprehensive study
2020
Eyvazi, Behzad | Jamshidi-Zanjani, Ahmad | Darban, Ahmad Khodadadi
The co-precipitation method was used to synthesize nano-magnetic adsorbent MnFe₂O₄ (nMFO), characterized through XRD, SEM, EDS, and BET techniques. The synthesized nMFO was used for hexavalent and trivalent chromium ions elimination from the aqueous phase. The optimum pH for the adsorption of Cr (VI) and Cr (III) was determined as 2 and 5, respectively. The chromium ions adsorption behavior was well interpreted through the pseudo-second order kinetics model. Furthermore, isotherm studies were conducted, and the obtained results indicated that Langmuir isotherm model could well justify the chromium ions adsorption process. Quick removal (less than 10 min) of both chromium ions and high removal efficiency were occurred using nMFO. The utmost adsorption capacity of trivalent and hexavalent chromium ions were determined as 39.6 and 34.84 mg g⁻¹, respectively. Thermodynamic studies on chromium adsorption revealed positive value for ΔH and negative value for ΔG, representing that chromium ions adsorption was an endothermic and spontaneous process. The multilinearity in the graphs of chromium ions adsorption was observed using intra-particle diffusion model. In this regard, the external mass transfer of chromium ions on synthesized nanoparticles was the important and controlling step in the adsorption process.
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