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Removal of fluoroquinolone from aqueous solution using graphene oxide: experimental and computational elucidation Full text
2018
Yadav, Sarita | Goel, Neetu | Kumar, Vinod | Tikoo, Kulbhushan | Singhal, Sonal
The environmental risks of antibiotics have attracted increasing research attention due to their prevalence and persistence in the aquatic environment. In this study, oxygen functionalized graphene, namely, graphene oxide (GO), was synthesized by modified Hummer’s and Offeman’s method and used as potential effective absorbent for the removal of fluoroquinolones (FQs), i.e., ciprofloxacin (CIP), norfloxacin (NOR), and ofloxacin (OFL), from aqueous solution. The as-synthesized GO was characterized by Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), and high-resolution transmission electron microscopy (HRTEM). Out of various factors that were taken to consideration while studying the adsorption process, it was found that pH of antibiotic solution is more crucial than the other experimental parameters such as initial antibiotic concentration, contact time, and adsorbent dosage and has significant impact on FQ adsorption via the GO adsorbent. The maximum removal of FQ was observed at pH 7 for CIP and NOR, while adsorption was maximum at pH 4 for OFL. Experimental data best fitted to the pseudo-second-order model as compared to the pseudo-first-order kinetic adsorption model. Best fitting of the equilibrium experimental data to Langmuir isotherm compared to Freundlich isotherm models established that FQ adsorbs over the GO in monolayer manner. Density functional theory (DFT) calculations performed at B3LYP/6-31G(d) level of theory in order to elucidate the thermodynamic feasibility of adsorption process and nature of interactions of antibiotic molecules with the GO adsorbent. Graphical abstract ᅟ
Show more [+] Less [-]Microscopy in addition to chemical analyses and ecotoxicological assays for the environmental hazard assessment of coal tar-polluted soils Full text
2018
Lors, Christine | Ponge, Jean-François | Damidot, Denis
Chemical analysis of soils contaminated with coal tar indicated that most organic compounds, and particularly PAHs, were contained in coarser particles (> 200 μm). Microscopic observations of this fraction, carried out on polished sections, reported the presence of organic particles in addition to mineral particles. Some organic particles had a very low porosity, and their microstructure did not evolve during biotreatment. Alternatively, other organic particles had a large porosity composed of an interconnected pore network that was open to coal tar surface and thus in contact with soil water. Interconnected porosity seemed to increase during biotreatment in relation to a decrease in the amount of organic compounds. The amount of open porosity in contact with soil water was expected to increase the desorption rate of PAHs. Consequently, the environmental hazard could depend on the amount of open porosity in addition to chemical properties of organic particles, such as their concentration in PAHs. Thus, microscopy can be complementary to chemical analysis and ecotoxicological assays to assess the best strategy for remediation but also to follow the advancement of a biotreatment.
Show more [+] Less [-]Effect of water constituents on the degradation of sulfaclozine in the three systems: UV/TiO2, UV/K2S2O8, and UV/TiO2/K2S2O8 Full text
2018
Ismail, Liliane | Ferronato, Corinne | Fine, Ludovic | Jaber, Farouk | Chovelon, Jean-Marc
Bicarbonate, phosphate, chloride ions, and humic substances are among the constituents most widely present in natural waters. These non-target constituents can greatly affect the efficiency of advanced oxidation processes used for water decontamination due to their capacity to interfere with the adsorption of the target compounds on the surface of TiO₂, absorb photons, scavenge hydroxyl radicals (·OH), and generate photochemical reactive intermediates. In this work, the effect of these constituents on the degradation of sulfaclozine (SCL) was monitored in three different AOPs systems: UV/TiO₂, UV/K₂S₂O₈, and UV/TiO₂/K₂S₂O₈. It was shown that bicarbonate (HCO₃⁻) and phosphate (HPO₄²⁻) ions enhanced the degradation of SCL in UV/TiO₂ and UV/TiO₂/K₂S₂O₈ systems whereas the addition of humic substances influenced these rates with a much smaller extent. On the other hand, the degradation rate of SCL in the UV/K₂S₂O₈ system was not affected by the presence of HCO₃⁻ and HPO₄²⁻ but was inhibited in the presence of humic substances. In addition, the different mechanisms that can take place in the presence of these constituents were discussed and the degradation rate enhancement in presence of HCO₃⁻ and HPO₄²⁻ was attributed to the formation of new reactive species such as carbonate (CO₃·–) and hydroxyl (·OH) radicals activated by TiO₂ holes (h⁺). In the presence of chloride (Cl⁻) and nitrate (NO₃⁻) ions, an enhancement of SCL adsorption on the surface of TiO₂ was observed. Finally, a comparative study of the degradation of SCL in river water and ultrapure water was reported.
Show more [+] Less [-]How important is woody tissue photosynthesis in EuCahetus dunnii Maiden and Osmanthus fragrans (Thunb.) Lour. under O3 stress? Full text
2018
Yu, Hao | Shang, He | Cao, Jixin | Chen, Zhan
Numerous studies have demonstrated the negative effects of elevated O₃ on leaf photosynthesis. Within trees, a portion of respired CO₂ is assimilated by woody tissue photosynthesis, but its response to elevated O₃ remains unclear. Saplings of two evergreen tree species, EuCahetus dunnii Maiden (E. dunnii) and Osmanthus fragrans (Thunb.) Lour. (O. fragrans), were exposed to non-filtered air (NF), 100 nmol mol⁻¹ O₃ air (E1) and 150 nmol mol⁻¹ O₃ air (E2) in open-top chambers from May 5 to September 5, 2016 (8 h a day; 7 days a week) in subtropical China. In this study, O₃ fumigation significantly reduced leaf net photosynthesis rate in both two tree species on most measurements. However, compared with leaf net photosynthesis rate, woody tissue gross photosynthesis rate showed less negative response to O₃ fumigation and was even stimulated to increase. Refixation rate reflects the utilization efficiency of the respired CO₂ by woody tissue photosynthesis. During the experiment period, E1 and E2 both increased refixation rate in O. fragrans compared with NF. Whereas for E. dunnii, E1 increased refixation rate until 81 days after starting of fumigation and then decreased it, and E2 decreased it all the time. Refixation rate had a significant positive correlation with woody tissue chlorophyll contents, indicating that the response of refixation rate to elevated O₃ may relate to chlorophyll contents. All these suggested that under O₃ fumigation, when atmospheric CO₂ uptake and fixation by leaf is limited, woody tissue photosynthesis can contribute more to the total carbon assimilation in trees. The findings help to understand the significance of woody tissue photosynthesis under elevated O₃ conditions.
Show more [+] Less [-]Assessment of heavy metal in coal gangue: distribution, leaching characteristic and potential ecological risk Full text
2018
Hua, Chunyu | Zhou, Guangzhu | Yin, Xin | Wang, Cuizhen | Chi, Baorong | Cao, Yiyun | Wang, Yue | Zheng, Yin | Cheng, Zirui | Li, Ruyue
In the process of excavation and utilization of the coal gangue hill, gangue at different weathering degree was exposed to the environment, which can be harmful to the surroundings. In order to find the law of heavy metal release and to evaluate the potential ecological risk, five kinds of coal gangue at different weathering degrees were collected from a coal mine named Suncun, an over 100-year-old mine of Xinwen coal mining field located in Tai’an city, Shandong Province of China. Samples were processed with microwave digestion for total content determination of heavy metals, and another part of samples was processed by Tessier sequential extraction for chemical forms analysis. Leaching tests at various pH were carried out to investigate the release of heavy metal. The laws of transformation and release of heavy metals were discussed and potential ecological risk was evaluated. The results indicated that the weathering degree had a significant impact on the content of heavy metal. Exchangeable and carbonate fractions of Cr and Pb were a large proportion of the total and should attract great attention. Potential ecological risk was at strong level (light black) and was up to very strong level (deep black) because of Cd. But Cr had contributed the most for gray gangue, which was 71% of the total. The species of heavy metal in gangue changed due to weathering and lead to the difference of the leaching characteristic and risk.
Show more [+] Less [-]Screening of candidate gene responses to cadmium stress by RNA sequencing in oilseed rape (Brassica napus L.) Full text
2018
Ding, Yiran | Jian, Hongju | Wang, Tengyue | Di, Feifei | Wang, Jia | Li, Jiana | Liu, Liezhao
Cadmium (Cd) stress is one of the most serious threats to agriculture in the world. Oilseed rape (Brassica napus L.) is an important oil crop; however, Cd can easily accumulate in rapeseed and thus harm human health through the food chain. In the first experiment, our purpose was to measure the Cd accumulation in mature B. napus plants and its influences on fatty acid composition. The results showed that most Cd was accumulated in the root, and the seed fatty acid content was considerably different at different Cd toxicity levels. In the second experiment, 7-day-old B. napus seedlings stressed by Cd (1 mM) for 0 h (CK-0h), 24 h (T-24h), or 72 h (T-72h) were submitted to physiological and biological analyses, RNA-Seq and qRT-PCR. In total, 5469 and 6769 differentially expressed genes (DEGs) were identified in the comparisons of “CK-0h vs T-24h” and “CK-0h vs T-72h”, respectively. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analyses showed that the photosynthetic and glutathione (GSH) pathways were significantly enriched in response to Cd stress. Key factors in the response to Cd stress included BnPCS1, BnGSTU12, BnGSTU5, and BnHMAs. The transcription factors BnWRKY11 (BnaA03g51590D), BnWRKY28 (BnaA03g43640D), BnWRKY33 (BnaA03g17820D), and BnWRKY75 (BnaA03g04160D) were upregulated after Cd exposure. The present study revealed that upregulation of the genes encoding GST and PCS under Cd stress promoted the formation of low-molecular weight complexes (PC-Cd), and upregulation of heavy metal ATPase genes induced PC-Cd transfer to vacuoles. These findings may provide the basis for the molecular mechanism of the response of B. napus to Cd.
Show more [+] Less [-]Preparation and application of magnetic nitrogen-doped rGO for persulfate activation Full text
2018
Pang, Ya | Luo, Kun | Tang, Lin | Li, Xue | Song, Yong | Li, Cheng-yong | Wang, Li-ping
A heterogeneous catalyst (M-N-rGO) composed of stability enhanced magnetic iron oxide nanoparticles and nitrogen-doped reduced graphene oxide was synthesized and characterized by SEM, XRD, BET, and XPS. It showed excellent catalytic degradation properties in advanced oxidation technology. In the presence of 200 mg/L catalyst and 135 mg/L persulfate at pH 5, 95% of 10–20 mg/L methylene blue could be degraded in 90 min with the TOC removal efficiency of 50%. The rate constant based on pseudo-first-order kinetics ranged from 0.0227 to 0.0488/min in the temperature range of 15 to 32 °C, and the activation energy was 32.5 kJ/mol. Under the optimal operation conditions, 20 mg/L of 2,4-dichlorophneol (2,4-DCP) could be removed almost completely. EPR analysis showed that sulfate and hydroxyl radicals were responsible for degradation of pollutants, and radical quenching experiments indicated that nonradical pathway also played a role in pollutant removal. And a mechanism for M-N-rGO and persulfate system was elucidated. This catalyst was easy for preparation, low-cost, highly effective, convenient for separation, and could be used effectively for four times through 0.1 mol/L H₂SO₄ regeneration. It provided a choice for wastewater treatment in practice.
Show more [+] Less [-]Exposure of marine mussels to diclofenac: modulation of prostaglandin biosynthesis Full text
2018
Courant, Frédérique | Arpin-Pont, Lauren | Bonnefille, Bénilde | Vacher, Sébastien | Picot-Groz, Marina | Gomez, Elena | Fenet, Hélène
Human pharmaceuticals, such as nonsteroidal anti-inflammatory drugs (NSAIDs), are an emerging threat to marine organisms. NSAIDs act through inhibition of cyclooxygenase (COX) conversion of arachidonic acid into prostaglandins. One experiment was carried out whereby marine mussels were exposed for 72 h to 1 and 100 μg/L diclofenac (DCF). A specific and sensitive method using liquid chromatography high-resolution tandem mass spectrometry was developed to quantify DCF in mussel tissues. The developed method could also clearly identify and quantify COX products, i.e., prostaglandin levels, and be used to assess their modulation following DCF exposure. Prostaglandin-D₂ (PGD₂) was always found below the detection limit (20 μg/kg dry weight (dw)). Basal prostaglandin-E₂ (PGE₂) concentrations ranged from below the detection limit to 202 μg/kg dw. Exposure of 100 μg/L resulted in a significant reduction in PGE₂ levels, whereas a downward trend was observed at 1 μg/L exposure. No difference was observed for prostaglandin-F₂α (PGF₂α) levels between controls and exposed organisms.
Show more [+] Less [-]Equilibrium adsorption study of the adsorptive removal of Cd2+ and Cr6+ using activated carbon Full text
2018
Wang, Weiliang | Liu, Ying | Liu, Xiaohui | Deng, Baojun | Lu, Shaoyong | Zhang, Yaru | Bi, Bin | Ren, Zongming
The performance of activated carbon (AC) with respect to characterization, adsorption kinetics, thermodynamics, and isotherms was addressed in this study. The effects of initial concentration, pH, contact time, ion strength, and temperature on removal efficiency were also studied. The adsorption isotherms of Cd²⁺ and Cr⁶⁺ on activated carbon can fit the Langmuir model well, and correlation coefficients were above 0.99, all higher than the Freundlich and Temkin models. The maximum adsorption quantities of Cd²⁺ and Cr⁶⁺ were 19.380 and 19.305 mg g⁻¹ at 25 °C, respectively. The adsorption capacities of Cd²⁺ and Cr⁶⁺ are clearly pH dependent. The kinetics of the removal of Cd²⁺ and Cr⁶⁺ was in agreement with a pseudo-second-order model, and the adsorption efficiency of Cd²⁺ is higher than that of Cr⁶⁺. The thermodynamic results showed that increased temperature is favorable to adsorption. The speciation on activated carbon was mainly residual Cd²⁺ and Cr⁶⁺, and the potential ecological risk of Cd²⁺ is higher than that of Cr⁶⁺. The adsorptions of Cd²⁺ and Cr⁶⁺ on activated carbon were dominated by chelation and ion exchange, respectively.
Show more [+] Less [-]Degradation of the earthy and musty odorant 2,4,6-tricholoroanisole by persulfate activated with iron of different valences Full text
2018
Zhang, Kejia | Zhou, Xinyan | Zhang, Tuqiao | Yu, Lang | Qian, Zheming | Liao, Wenchao | Li, Cong
2,4,6-Trichloroanisole (TCA) is an odorous compound that is often detected in tap water and is difficult to be removed via water treatment. In this study, the transformation efficiency of TCA in the presence of persulfate (PS) activated by iron (Fe²⁺, Fe⁰, and Fe³⁺) was investigated for the first time. The effects of the activator dosage, oxidant dosage, pH, dosing method, chelating agents, humic acid, and temperature were evaluated. The degradation rate of TCA increased with increasing PS dosages (0.12–0.48 mM) and initial Fe²⁺ concentrations (0.12–0.96 mM), while it decreased with higher Fe²⁺ concentrations. Fe²⁺/PS and Fe⁰/PS systems achieved their best TCA removal efficiency at pH 7 and 2.5, respectively. According to the results of electron paramagnetic resonance (EPR), the contribution of SO₄⁻• to TCA degradation was much higher than that of •OH. Gradual addition of Fe²⁺ improved TCA degradation compared to single addition. Citric acid (CA) promoted TCA degradation under Fe²⁺/PS at the beginning of the reaction, but inhibited it after 10 min. Ethylenediaminetetraacetic acid (EDTA) improved the TCA removal rate with an EDTA/Fe²⁺ molar ratio of 0.5:1, while it decreased it at higher EDTA/Fe²⁺ molar ratios. Oxalic acid (OA) negatively affected TCA degradation with increasing OA/Fe²⁺ molar ratios. Among all of the chelating agents, only CA increased TCA degradation by Fe⁰/PS. Humic acid promoted TCA degradation by Fe²⁺/PS at the proper dosage (1 mg/L). Under our specific conditions and over the temperature ranging from 10 to 25 °C, no change was observed in the reaction kinetics. It was found that 2,4,6-trichlorophenol (TCP) was the only detected oxidation product. The presence of an Fe²⁺-Fe³⁺ redox cycle in iron-activated PS systems was confirmed by TCA degradation under the Fe³⁺/PS system.
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