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Enhanced Removal of Chromate from Aqueous Solution Using a Metal Oxide Nanocomposite Derived from Bimetallic Metal Organic Framework with Both Adsorption and Catalytic Properties
2024
Salari, Hadi | Zeraatkar Moghaddam, Ali
Removing environmental pollutants and preserving the environment is an important issue and many efforts have been made in this regard in recent years. In the present work, chromate ions were removed from aqueous solutions by ZnO/CuO acting as both adsorbent and catalyst. Metal oxide fabrication from metal organic framework is one of the most important and interesting scientific issues for the synthesis of high surface area materials. Here, we demonstrate ZnO/CuO synthesis from bimetallic Zn-Cu metal-organic framework (Zn(50)-Cu(50)-BTC) using temperature-programmed oxidation method. The adsorptive and catalytic removal procedure were optimized in terms of its batch efficiency using experimental designs. The effect of hole scavenger type was investigated, and the relationships between the effective important removal procedure parameters and chromate removal efficiency were analyzed through the response surface methodology (RSM) based on central composite design (CCD). The correlation coefficient (R2) and F values were 0.9883 and 74.81, respectively. Finally, simplex non-linear optimization was carried out and the optimal pH, ZnO/CuO amount and contact time were determined to be 2, 20 mg, and 17.5 min. Under these conditions, the predicted removal efficiency of 50 ppm chromate at a 95% confidence level was 98.1 ± 2.4%, which was very close to the recorded response (i.e. 99.4 ± 1.9%). The kinetic and isothermal profiles of the proposed ZnO/CuO, were thoroughly investigated under optimal conditions. The adsorption isotherm follow the Langmuir model and kinetics were found to be pseudo-second-order.
اظهر المزيد [+] اقل [-]Newly-synthesized iron-oxide nanoparticles showed synergetic effect with citric acid for alleviating arsenic phytotoxicity in soybean
2022
Bhat, Javaid Akhter | Bhat, Masroor Ahmad | Abdalmegeed, Dyaaaldin | Yu, Deyue | Chen, Jian | Bajguz, Andrzej | Ahmad, Ajaz | Ahmad, Parvaiz
In the current investigation, we presented the success of the modified hydrothermal method for synthesizing the iron-oxide nanoparticles (Fe₂O₃-NPs) efficiently. These NPs were further characterized by using different techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM) micrographs, energy-dispersive X-ray spectroscopy (EDAX)/Mapping pattern, Raman Spectroscopy Pattern, ultra violet (UV) and Photoluminescence (PL). All these analyses revealed highly pure nature of Fe₂O₃-NPs with no internal defects, and suggested its application for plant growth improvement. Therefore, we further investigated the separate as well as combined effects of the Fe₂O₃-NPs and citric acid (CA) in the alleviation of arsenic (As) toxicity in the soybean (Glycine max L.), by evaluating the different plant growth and metabolic attributes. Results of our study revealed that As-induced growth inhibition, reduction of photosynthesis, water use efficiency (WUE), and reactive oxygen species (ROS) accumulation whereas application of the Fe₂O₃-NPs and CA significantly reversed all these adverse effects in soybean plants. Moreover, the As-stress induced malondialdehyde (MDA) and hydrogen peroxide (H₂O₂) production were partially reversed by the Fe₂O₃-NPs and CA in the As-stressed plants by 16% and 10% (MDA) and 29% and 12% (H₂O₂). This might have resulted due to the Fe₂O₃-NPs and CA induced activities of the antioxidant defense in plants. Overall, the Fe₂O₃-NPs and CA supplementation separately and in combination positively regulated the As tolerance in soybean; however, the effect of the combined application on the As tolerance was more profound relative to the individual application. These results suggested the synergetic effect of the Fe₂O₃-NPs and CA on the As-tolerance in soybean. However, in-depth mechanism underlying the defense crosstalk between the Fe₂O₃-NPs and CA needs to be further explored.
اظهر المزيد [+] اقل [-]Co-exposure to priority-controlled metals mixture and blood pressure in Chinese children from two panel studies
2022
Liu, Miao | Li, Meng | Guo, Wenting | Zhao, Lei | Yang, Huihua | Yu, Jie | Liu, Linlin | Fang, Qin | Lai, Xuefeng | Yang, Liangle | Zhu, Kejing | Dai, Wencan | Mei, Wenhua | Zhang, Xiaomin
Metals may affect adversely cardiovascular system, but epidemiological evidence on the associations of priority-controlled metals including antimony (Sb), arsenic (As), cadmium, lead, and thallium with children's blood pressure (BP) was scarce and inconsistent. We conducted two panel studies with 3 surveys across 3 seasons among 144 and 142 children aged 4–12 years in Guangzhou and Weinan, respectively. During each seasonal survey, urine samples were collected for 4 consecutive days and BP was measured on the 4th day. We obtained 786 BP values and urinary metals measurements at least once within 4 days, while 773, 596, 612, and 754 urinary metals measurements were effective on the health examination day (Lag 0), and the 1ˢᵗ, 2ⁿᵈ, and 3ʳᵈ day preceding BP measurement (Lag 1, lag 2 and lag 3), respectively. We used linear mixed-effect models, generalized estimating equations and multiple informant models to assess the associations of individual metal at each lag day and accumulated lag day (4 days averaged, lag 0–3) with BP and hypertension, and Bayesian Kernel Machine Regression to evaluate the relations of metals mixture at lag 0–3 and BP outcomes. We found Sb was positively and consistently related to systolic BP (SBP), mean arterial pressure (MAP), and odds of having hypertension within 4 days, which were the strongest at lag 0 and declined over time. And such relationships at lag 0–3 showed in a dose-response manner. Meanwhile, Sb was the only contributor to the relations of mixture with SBP, MAP, and odds of having hypertension. Also, synergistic interaction between Sb and As was significant. In addition, modification effect of passive smoking status on the association of Sb and SBP was more evident in passive smokers. Accordingly, urinary Sb was consistently and dose-responsively associated with increased BP and hypertension, of which Sb was the major contributor among children.
اظهر المزيد [+] اقل [-]Biochar composite derived from cellulase hydrolysis apple branch for quinolone antibiotics enhanced removal: Precursor pyrolysis performance, functional group introduction and adsorption mechanisms
2022
Zou, Mengyuan | Tian, Weijun | Chu, Meile | Gao, Huizi | Zhang, Dantong
In this study, magnetic biochar (MAB) and humic acid (HA)-coated magnetic biochar produced from apple branches without and after cellulase hydrolysis (HMAB and CHMAB, respectively) were prepared and tested as adsorbents of enrofloxacin (ENR) and moxifloxacin (MFX) in aqueous solution. Compared with MAB and HMAB, novel adsorbent CHMAB possessed a superior mesoporous structure, greater graphitization degree and abundant functional groups. When antibiotic solutions ranged from 2 to 20 mg L⁻¹, the theoretical maximum adsorption capacities of CHMAB for ENR and MFX were 48.3 and 61.5 mg g⁻¹ at 35 °C with adsorbent dosage of 0.4 g L⁻¹, respectively, while those of MAB and HMAB were 39.6 and 54.4 mg g⁻¹, and 44.7 and 59.0 mg g⁻¹, respectively. The pseudo-second-order kinetic model and Langmuir model presented a better fitting to the spontaneous and endothermic adsorption process. The maximum adsorption capacity of ENR and MFX onto CHMAB was achieved at initial pH values of 5 and 8, respectively. Additionally, the adsorption capacity of ENR and MFX decreased with increasing concentrations of K⁺ and Ca²⁺ (0.02–0.1 mol L⁻¹). Synergism between the pore-filling effect, π-π electron-donor-acceptor interactions, regular and negative charge-assisted H-bonding, surface complexation, electrostatic interactions and hydrophobic interactions may dominate the adsorption process. This study demonstrated that a novel magnetic biochar composite prepared through pyrolysis of agricultural waste lignocellulose hydrolyzed by cellulase in combination with HA coating was a promising adsorbent for eliminating quinolone antibiotics from aqueous media.
اظهر المزيد [+] اقل [-]The role of nanoplastics on the toxicity of the herbicide phenmedipham, using Danio rerio embryos as model organisms
2022
Santos, Joana | Barreto, Angela | Sousa, Érika M.L. | Calisto, Vânia | Amorim, Mónica J.B. | Maria, Vera L.
Once in the aquatic ecosystems, nanoplastics (NPls) can interact with other contaminants acting as vectors of transport and altering their toxicological effects towards organisms. Thus, the present study aims to investigate how polystyrene NPls (44 nm) interact with the herbicide phenmedipham (PHE) and affect its toxicity to zebrafish embryos. Single exposures to 0, 0.015, 0.15, 1.5, 15 and 150 mg/L NPls and 0.02, 0.2, 2 and 20 mg/L PHE were performed. Embryos were also exposed to the binominal combinations: 0.015 mg/L NPls + 2 mg/L PHE, 0.015 mg/L NPls + 20 mg/L PHE, 1.5 mg/L NPls + 2 mg/L PHE and 1.5 mg/L NPls + 20 mg/L PHE. Due to the low solubility of PHE in water, a solvent control was performed (0.01% acetone). PHE was quantified. Mortality, heartbeat and hatching rate, malformations appearance, locomotor behavior and biomarkers related to oxidative stress, neurotransmission and energy budgets were analyzed. During 96 h, NPls and PHE single and combined exposures did not affect embryos development. After 120 h, NPls induced hyperactivity and PHE induced hypoactivity. After 96 h, NPls increased catalase activity and PHE increased glutathione S-transferases activity. On the combination 0.015 mg/L NPls + 20 mg/L PHE, hyperactivity behavior was found, similar to 0.015 mg/L NPls, and cholinesterase activity was inhibited. Additionally, the combination 1.5 mg/L NPls + 20 mg/L PHE increased both catalase and glutathione S-transferases activities. The combination NPls with PHE affected more biochemical endpoints than the single exposures, showing the higher effect of the binominal combinations. Dissimilar interactions effects – no interaction, synergism and antagonism – between NPls and PHE were found. The current study shows that the effects of NPls on bioavailability and toxicity of other contaminants (e.g. PHE) cannot be ignored during the assessment of NPls environmental behavior and risks.
اظهر المزيد [+] اقل [-]Impacts of combined exposure to formaldehyde and PM2.5 at ambient concentrations on airway inflammation in mice
2022
Lu, Xianxian | Gong, Cunyi | Lv, Ke | Zheng, Lifang | Li, Beibei | Zhao, Yuanteng | Lu, Haonan | Wei, Tingting | Huang, Jiawei | Li, Rui
Asthma is a respiratory disease that can be exacerbated by certain environmental factors. Both formaldehyde (FA) and PM₂.₅, the most common indoor and outdoor air pollutants in mainland China, are closely associated with the onset and development of asthma. To date, however, there is very little report available on whether there is an exacerbating effect of combined exposure to FA and PM₂.₅ at ambient concentrations. In this study, asthmatic mice were exposed to 1 mg/m³ FA, 1 mg/kg PM₂.₅, or a combination of 0.5 mg/m³ FA and 0.5 mg/kg PM₂.₅, respectively. Results demonstrated that both levels of oxidative stress and inflammation were significantly increased, accompanied by an obvious decline in lung function. Further, the initial activation of p38 MAPK and NF-κB that intensified the immune imbalance of asthmatic mice were found to be visibly mitigated following the administration of SB203580, a p38 MAPK inhibitor. Noteworthily, it was found that combined exposure to the two at ambient concentrations could significantly worsen asthma than exposure to each of the two alone at twice the ambient concentration. This suggests that combined exposure to formaldehyde and PM₂.₅ at ambient concentrations may have a synergistic effect, thus causing more severe damage in asthmatic mice. In general, this work has revealed that the combined exposure to FA and PM₂.₅ at ambient concentrations can synergistically aggravate asthma via the p38 MAPK pathway in mice.
اظهر المزيد [+] اقل [-]Decrypting the synergistic action of the Fenton process and biochar addition for sustainable remediation of real technogenic soil from PAHs and heavy metals
2022
Mazarji, Mahmoud | Minkina, Tatiana | Sushkova, Svetlana | Mandzhieva, Saglara | Barakhov, Anatoly | Barbashev, Andrey | Dudnikova, Tamara | Lobzenko, Iliya | Giannakis, Stefanos
The objective of this study was to demonstrate the feasibility and the relevance of combining biochar with the Fenton process for the simultaneous improvement of polycyclic aromatic hydrocarbons (PAHs) degradation and immobilization of heavy metals (HMs) in real soil remediation processes at circumneutral pH. The evaluation of PAHs degradation results was performed through multivariate statistical tools, including principal component analysis (PCA) and partial least squares (PLS). PCA showed that the level of biochar amendment decisively affected the degree of degradation of total PAHs, highlighting the role of biochar in catalyzing the Fenton reaction. Moreover, the PLS model was used to interpret the important features of each PAH's physico-chemical properties and its correlation to degradation efficiency. The electron affinity of PAHs correlated positively with the degradation efficiency only if the level of biochar amendment sat at 5%, explained by the ability of biochar to transfer the electrons to PAHs, improving the Fenton-like degradation. Moreover, the addition of biochar reduced the mobilization of HMs by their fixation on their surface, reducing the Fenton-induced metal leaching from the destruction of metal-organic complexes. In overall, these results on the high immobilization rate of HMs accompanied with additional moderate PAHs degradation highlighted the advantages of using a biochar-assisted Fenton-like reaction for sustainable remediation of technogenic soil.
اظهر المزيد [+] اقل [-]ZIF-8 templated assembly of La3+-anchored ZnO distorted nano-hexagons as an efficient active photocatalyst for the detoxification of rhodamine B in water
2021
Karuppasamy, K. | Rabani, Iqra | Vikraman, Dhanasekaran | Bathula, Chinna | Theerthagiri, J. | Bose, Ranjith | Yim, Chang-Joo | Kathalingam, A. | Seo, Young-Soo | Kim, Hyun-Seok
The use of lanthanum-anchored zinc oxide distorted hexagon (La@ZnO DH) nanoclusters as an active material for the photodegradation of rhodamine B (Rh–B) dye via hydrogen bonding, electrostatic, and π-π interactions is examined herein. The active photocatalyst is derived from porous zeolite imidazole frameworks (ZIF-8) via a combined ultrasonication and calcination process. The distorted hexagon nanocluster morphology with controlled surface area is shown to provide excellent catalytic activity, chemical stability and demarcated pore volume. In addition, the low bandgap (3.57 eV) of La@ZnO DH is shown to expand the degradation of Rh–B under irradiation of UV light as compared to the pristine ZIF-8-derived ZnO photocatalyst due to inhibited recombination of electrons and holes. The outstanding physicochemical stability and enhanced performance of La@ZnO DH could be ascribed to the synergistic interaction among La3+ particles and the ZnO nanoclusters and provide a route for their utilization as a promising catalyst for the detoxification of Rh–B.
اظهر المزيد [+] اقل [-]Bio-based dispersants for fuel oil spill remediation based on the Hydrophilic-Lipophilic Deviation (HLD) concept and Box-Behnken design
2021
Nawavimarn, Parisarin | Rongsayamanont, Witchaya | Subsanguan, Tipsuda | Luepromchai, Ekawan
The high density and viscosity of fuel oil leads to its prolonged persistence in the environment and causes widespread contamination. Dispersants with a low environmental impact are necessary for fuel oil spill remediation. This study aimed to formulate bio-based dispersants by mixing anionic biosurfactant (lipopeptides from Bacillus subtilis GY19) with nonionic oleochemical surfactant (Dehydol LS7TH). The synergistic effect of the anionic-nonionic surfactant mixture produced a Winsor Type III microemulsion, which promoted petroleum mobilization. The hydrophilic-lipophilic deviation (HLD) equations for ionic and nonionic surfactant mixtures were compared, and it was found that the ionic equation was applicable for the calculation of lipopeptides and Dehydol LS7TH concentrations. The best formula contained 6.6% w/v lipopeptides and 11.9% w/v Dehydol LS7TH in seawater, and its dispersion effectiveness for bunker fuels A and C was 92% and 78%, respectively. The application of bio-based dispersants in water sources was optimized by Box-Behnken design. The efficiency of the bio-based dispersant was affected by the dispersant-to-oil ratios (DORs) but not by the water salinity. A suitable range of DORs for different oil contamination levels could be identified from the response surface plot. The dispersed fuel oil was further degraded by adding an oil-degrading bacterial consortium to the chemically enhanced water accommodated fractions (CEWAFs). After 7 days of incubation, the concentration of fuel oil was reduced from 3692 mg/L to 356 mg/L (88% removal efficiency). On the other hand, the abiotic control removed less than 40% fuel oil from the CEWAFs. This bio-based dispersant had an efficiency comparable to that of a commercial dispersant. The process of dispersant formulation and optimization could be applied to other surfactant mixtures.
اظهر المزيد [+] اقل [-]Co-pyrolysis of food waste and wood bark to produce hydrogen with minimizing pollutant emissions
2021
In this study, the co-pyrolysis of food waste with lignocellulosic biomass (wood bark) in a continuous-flow pyrolysis reactor was considered as an effective strategy for the clean disposal and value-added utilization of the biowaste. To achieve this aim, the effects of major co-pyrolysis parameters such as pyrolysis temperature, the flow rate of the pyrolysis medium (nitrogen (N₂) gas), and the blending ratio of food waste/wood bark on the yields, compositions, and properties of three-phase pyrolytic products (i.e., non-condensable gases, condensable compounds, and char) were investigated. The temperature and the food waste/wood bark ratio were found to affect the pyrolytic product yields, while the N₂ flow rate did not. More non-condensable gases and less char were produced at higher temperatures. For example, as the temperature was increased from 300 °C to 700 °C, the yield of non-condensable gases increased from 6.3 to 17.5 wt%, while the yield of char decreased from 63.6 to 30.6 wt% for the co-pyrolysis of food waste and wood bark at a weight ratio of 1:1. Both the highest yield of hydrogen (H₂) gas and the most significant suppression of the formation of phenolic and polycyclic aromatic hydrocarbon (PAH) compounds were achieved with a combination of food waste and wood bark at a weight ratio of 1:1 at 700 °C. The results suggest that the synergetic effect of food waste and lignocellulosic biomass during co-pyrolysis can be exploited to increase the H₂ yield while limiting the formation of phenolic compounds and PAH derivatives. This study has also proven the effectiveness of co-pyrolysis as a process for the valorization of biowaste that is produced by agriculture, forestry, and the food industry, while reducing the formation of harmful chemicals.
اظهر المزيد [+] اقل [-]