ZnO催化剂对苯胺光降解的研究

以太阳光，氙灯为光源，ＺｎＯ为光催化剂，对苯胺光降解行为进行研究，考察了溶液的初始浓度催化剂量，溶液ｐＨ值对苯胺光降解速率的影响。实验结果证实苯胺光降解符合准 级动力学规律，氧不足的条件下苯胺降妥的速率减慢。     

Direct and indirect photolysis of cyhalofop in aqueous systems

The photodegradation of the aryloxyphenoxy propionic herbicide cyhalofop-butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), and of its primary metabolite (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA) was studied in water at different irradiation wavelengths. The sunlight irradiation was investigated also in the presence of humic acid (HA), Fe oxide, titanium dioxide (TiO₂) and zinc oxide (ZnO) as photocatalysts.CyB and CyA were rapidly degraded by UV irradiation. CyB afforded the butyl ester of 2-[3-(4-cyano-2-fluorophenyl)-4-hydroxy-phenoxy]propanoic acid (CyI), a metabolite arising from a photo-Fries rearrangement. Instead, CyA yielded (R)-2-4-(4-carboxyl-2-fluorophenoxy)phenoxypropanoic acid (CyD), a dicarboxylic acid arising from the photo-hydrolysis of cyano group via amide. CyB was stable in simulated sunlight also in the presence of the catalysts tested.The irradiation of a CyA solution, in the presence of HA or Fe oxide, with simulated sunlight did not produce any significant degradation. In the same experimental conditions, CyA was totally mineralized in the presence of TiO₂ and ZnO.     

Impact of biosolids, ZnO, ZnO/biosolids on bacterial community and enantioselective transformation of racemic–quizalofop–ethyl in agricultural soil

The effects of biosolids,ZnO,and ZnO/biosolids on soil microorganism and the environmental fate of coexisting racemic–quizalofop–ethyl(rac-QE) were investigated.Microbial biomass carbon in native soil,soil/biosolids decreased by 62% and 52% in the presence of ZnO(2‰,weight ratio).The soil bacterial community structure differed significantly among native soil,soil/biosolids,soil/ZnO,and soil/biosolids/ZnO based on a principal co-ordinate analysis(PCo A) of OTUs and one-way ANOVA test of bacterial genera.Chemical transformation caused by ZnO only contributed 4% and 3% of the overall transformation of R-quizalofop-ethyl(R-QE) and S-quizalofop-ethyl(S-QE) in soil/ZnO.The inhibition effect of ZnO on the initial transformation rate of R-QE(rR-QE) and S-QE(rR-QE) in soil only observed when enantiomer concentration was larger than 10 mg/kg.Biosolids embedded with ZnO(biosolids/ZnO) caused a 17%–42% and 22%–38% decrease of rR-QEand rS-QE,although rR-QEand rS-QEincreased by 0%–17% and 22%–58% by the addition of biosolids.The results also demonstrated that the effects of biosolids on agricultural soil microorganism and enantioselective transformation of chiral pesticide was altered by the embedded nanoparticles.     

恶臭假单胞菌原位还原Pd(0) NPs对微生物电子传递性能及活性的影响

微生物原位合成零价金属纳米颗粒在材料合成和环境应用领域引起了广泛关注和研究.本研究利用Pseudomonas putida(P.putida)合成Pd(0)纳米颗粒(NPs),通过FESEM、TEM、XPS等对合成的纳米颗粒进行形貌、价态表征,并对其电化学性能及微生物抑制作用进行分析.结果表明,在厌氧条件下,P.putida在胞外及细胞周质空间可原位合成粒径约10 nm的Pd(0)NPs.CV实验表明,相比P.putida,含Pd(0)NPs的P.putida有更高的氧化还原电流;随着初始反应Pd(Ⅱ)浓度增加至0.07和0.1 mmol·L~(-1),恒电位实验中的乳酸氧化电流分别升至(10.6±5.2)和(22.5±9.7)nA,分别为P.putida((5.7±2.8)nA)的1.85和3.95倍;TTC-ETS和INT-ETS分别提升至89.02和209.09μg·mg~(-1)·h~(-1),分别是P.putida的1.64和1.34倍.以上结果证明了Pd(0)NPs对微生物胞外电子传递(Extracellular Electron Transfer,EET)的正面影响.抑菌圈实验和激光共聚焦图像表明,低量Pd(0)NPs具有较好的生物相容性,过多Pd(Ⅱ)和Pd(0)NPs对微生物有一定的毒性.     

Effective and selective separation of perrhenate from acidic wastewater by super-stable,superhydrophobic, and recyclable biosorbent

• A ZnO-biochar hybrid composite was prepared by solvothermal-pyrolysis synthesis. • The superhydrophobic composite is suitable for selective recovery of Re(VII). • The adsorption mechanism is elucidated by experiments and material characterization. The recovery of scattered metal ions such as perrhenate (Re(VII)) from industrial effluents has enormous economic benefits and promotes resource reuse. Nanoscale-metal/biochar hybrid biosorbents are attractive for recovery but are limited by their insufficient stability and low selectivity in harsh environments. Herein, a superstable biochar-based biosorbent composed of ZnO nanoparticles with remarkable superhydrophobic features is fabricated, and its adsorption/desorption capabilities toward Re(VII) in strongly acidic aqueous solutions are investigated. The ZnO nanoparticle/biochar hybrid composite (ZBC) exhibits strong acid resistance and high chemical stability, which are attributable to strong C-O-Zn interactions between the biochar and ZnO nanoparticles. Due to the advantages of its hydrolytic stability, superhydrophobicity, and abundance of Zn-O sites, the ZBC proves suitable for the effective and selective separation of Re(VII) from single, binary and multiple ion systems (pH= 1), with a maximum sorption capacity of 29.41 mg/g. More importantly, this material also shows good recyclability and reusability, with high adsorption efficiency after six adsorption-desorption cycles. The findings in this work demonstrate that a metal/biochar hybrid composite is a promising sorbent for Re(VII) separation.     

纳米氧化铜(CuO NPs)对紫花苜蓿幼苗根系活性氧(ROS)、抗氧化酶活性和根系活力的影响

根系通常是植物直接受到外界环境物质(如重金属离子和纳米金属氧化物)毒害的主要器官。本研究以紫花苜蓿的幼苗为实验材料,探讨了CuO NPs胁迫对紫花苜蓿幼苗根系的活性氧(ROS)积累、抗氧化酶活性和根系活力的影响。研究结果表明:(1)不同浓度的CuO NPs对紫花苜蓿幼苗根系H_2O_2和O-2·含量具有显著影响。随CuO NPs浓度增大,紫花苜蓿幼苗根系中H_2O_2和O-2·整体上呈现先增大后减少的趋势,除了0.00125 mol·L~(-1)CuO NPs浓度下紫花苜蓿幼苗根系中H_2O_2含量比对照减少外,其他浓度下的H_2O_2和O-2·的含量都比对照有所增加,并且H_2O_2和O-2·的含量都是在0.0125 mol·L~(-1)CuO NPs浓度下达到最大值。(2)不同浓度的CuO NPs对紫花苜蓿幼苗根系抗氧化酶活性具有显著影响。随CuO NPs浓度增大,紫花苜蓿幼苗根系中SOD、POD、APX和CAT酶的活性都呈现先增大后减少的趋势,其中,SOD和POD、APX、CAT酶的活性分别是在0.00625、0.0125、0.0625 mol·L~(-1)CuO NPs处理下达到最大,表明这些抗氧化酶在清除根系中的活性氧方面表现出较强的协同性和补偿性。(3)不同浓度的CuO NPs对紫花苜蓿幼苗根系活力具有显著的影响。随着CuO NPs浓度的增加,紫花苜蓿幼苗根系活力逐步升高,这是一种生物适应性应激响应的体现。     

Comparative phytotoxicity of ZnO nanoparticles,ZnO microparticles,and Zn2+ on rapeseed (Brassica napus L.): investigating a wide range of concentrations

The effects of ZnO nanoparticles (NPs), ZnO microparticles (MPs), and zinc ions (Zn²⁺) on some growth parameters of rapeseed (Brassica napus) seedlings have been studied. The growth inhibition by ZnO NPs was not stronger than that by ZnO MPs while treatment with Zn²⁺ inhibition was clearly stronger.     

Molecular identification and nanoremediation of microbial contaminants in algal systems using untreated wastewater

Wastewater-algal biomass is a promising option to biofuel production. However, microbial contaminants constitute a substantial barrier to algal biofuel yield. A series of algal strains, Nannochloris oculata and Chlorella vulgaris samples (n = 30), were purchased from the University of Texas, and were used for both stock flask cultures and flat-panel vertical bioreactors. A number of media were used for isolation and differentiation of potential contaminants according to laboratory standards (CLSI). Conventional PCR amplification was performed followed by 16S rDNA sequencing to identify isolates at the species level. Nanotherapeutics involving a nanomicellar combination of natural chitosan and zinc oxide (CZNPs) were tested against the microbial lytic groups through Minimum Inhibitory Concentration (MIC) tests and Transmission Electronic Microscopy (TEM). Results indicated the presence of Pseudomonas spp., Bacillus pumilus/ safensis, Cellulosimicrobium cellulans, Micrococcus luteus and Staphylococcus epidermidis strains at a substantial level in the wastewater-fed algal reactors. TEM confirmed the effectiveness of CZNPs on the lytic group while the average MICs (mg/mL) detected for the strains, Pseudomonas spp, Micrococcus luteus, and Bacillus pumilus were 0.417, 3.33, and 1.458, respectively. Conclusively, CZNP antimicrobials proved to be effective as inhibitory agents against currently identified lytic microbial group, did not impact algae cells, and shows promise for in situ interventions.     

Polymer coating of copper oxide nanoparticles increases nanoparticles uptake and toxicity in the green alga Chlamydomonas reinhardtii

Copper oxide nanoparticles (CuO NPs) are frequently used in a polymer-coated form, to be included in paints or fabrics for antimicrobial properties. Their application in antifouling paints may lead to the contamination of aquatic ecosystems. However, the toxicological risk of NPs in the environment is hard to evaluate due to a lack of knowledge on the mechanisms of NP interaction with biological systems. In this study, we investigated the effect of polymer coating on CuO NP toxicity in the green alga Chlamydomonas reinhardtii by comparing bare and polymer-coated CuO NPs prepared from the same CuO nanopowder. Both CuO NP suspensions were toxic to C. reinhardtii after 6 h treatment to concentrations of 0.005-0.04 g L⁻¹. Bare and polymer-coated CuO NPs induced a decrease of Photosystem II activity and the formation of reactive oxygen species. Polymer-coated CuO NP was found to be more toxic than the uncoated CuO NP. The higher toxicity of CS-CuO NP was mainly associated with the increased capacity of polymer-coated CuO NP to penetrate the cell compared to bare CuO NPs. These results indicates that the high toxicity of polymer-coated CuO NPs in algal cells results of intracellular interactions between NPs and the cellular system.     

Biochemical and histopathological ultrastructural changes caused by ZnO nanoparticles in mice

Five week-old mice were divided into a vehicle control group, and groups exposed to ZnO nanoparticles at low (0.5 g/kg), middle (1 g/kg), high (3 g/kg), and exceptionally high-dose (5 g/kg). After the first, second, third, and fourth weeks’ of exposure, blood biochemistry, histopathology, and electron microscopic ultrastructural changes in liver, kidney and spleen were investigated. Increased alkaline phosphatase activities were observed in all treated mice being statistically significant at higher dose. No changes were observed in the serum glutamic pyruvic transaminase, serum glutamic oxaloacetic transaminase, creatinine, blood urea nitrogen, and lipid levels. During the first and second weeks of the treatment, effects on the cytoarchitecture of liver, kidney, and spleen were not perceived while during the third and fouth weeks of treatment sporadic mild effects were seen. Ultrastructural electron microscopic changes in liver, kidney, and spleen were not observed for the low-dose group on the first, second, third, and fourth weeks, suggesting that exposure to ZnO nanoparticles at low dose is safe. Long-term (i.e., more than 28 days) exposure to the exceptionally high-dose resulted in sporadic changes in nuclear chromatin condensation, irregular nuclear membrane, polymorphic mitochondria, mitochondrial swelling, and vacuolation. ZnO nanoparticles could be well tolerated and no death occurred in any group of treated mice.