The OH-induced degradation mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA) with two forms in the water: a DFT comparison

The initial degradation mechanisms of OH and 4-chloro-2-methylphenoxyacetic acid (MCPA) including molecular form and anionic form are studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. Possible reaction pathways of H-atom abstraction and OH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for OH and two forms of MCPA are different, and most reactions for anionic MCPA are easier than those for molecular MCPA. For H-atom abstraction reactions, the calculated energies show that OH abstracting H-atom from -CH₃ group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in -CH₂ group is slightly easier to be abstracted than that in -CH₃ group. For OH addition reactions, the addition of OH to the C1 site is the initial step for molecular MCPA and the predominant product is 4-chloro-2-methylphenol (denoted P3), while the C4 site is the most reactive site for anionic MCPA and the primary product results from the hydroxylation of the aromatic ring, which is in good agreement with the experimental observation. In additional, results from PCM calculations show that most reactions in water phase are more kinetically favorable than those in gas phase, though the mechanisms discussed above will not be changed.     

Thioarsenate formation upon dissolution of orpiment and arsenopyrite

Thioarsenates were previously determined as dominant species in geothermal and mineral waters with excess sulfide. Here, we used batch leaching experiments to determine their formation upon weathering or industrial leaching of the arsenic-sulfide minerals orpiment (As₂S₃) and arsenopyrite (FeAsS) under different pH and oxygen conditions. Under acidic conditions, as expected based on their known kinetic instability at low pH, no thioarsenates formed in either of the two mineral systems. Under neutral to alkaline conditions, orpiment dissolution yielded mono-, di- and trithioarsenate which accounted for up to 43-55% of total arsenic. Thioarsenate formation upon arsenopyrite dissolution was low at neutral (4%) but significant at alkaline pH, especially under suboxic to sulfidic conditions (20-43%, mainly as monothioarsenate). In contrast to orpiment, we postulate that recombination of arsenite and sulfide in solution is of minor importance for monothioarsenate formation during alkaline arsenopyrite dissolution. We propose instead that hydroxyl physisorption lead to formation of As-OH-S surface complexes by transposition of hydroxyl anions to arsenic or iron sites. Concurrently formed ironhydroxides could provide re-sorption sites for the freshly released monothioarsenate. However, sorption experiments with goethite showed slower sorption kinetics of monothioarsenate compared to arsenite, but comparable with arsenate. The discovery that thioarsenates are released by natural weathering and industrial leaching processes and that, once they are released, have a higher mobility than the commonly-investigated species arsenite and arsenate requires future studies to consider them when assessing arsenic release in sulfidic natural or mining-impacted environments.     

Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO₂ and CuO/TiO₂/Al₂O₃ by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO₂/RVC, 90% degradation was achieved in 2 h while with CuO/TiO₂/Al₂O₃/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO₂/RVC/UV and 99% with CuO/TiO₂/Al₂O₃/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.     

超声辐射浸渍法制备Fe-Ni-Mn/Al_2O_3催化剂及性能研究

以Al2O3为载体,分别采用超声辐射浸渍法和普通浸渍方法制备Fe-Ni-Mn/Al2O3催化剂。采用BET、XRD和SEM对催化剂的理化性质和孔结构进行了分析,以模拟酸性绿B废水为研究对象考察催化剂的催化性能。实验结果表明,浸渍溶液pH值和焙烧温度显著影响催化剂的性能。与普通浸渍法相比,超声浸渍法制备的Fe-Ni-Mn/Al2O3催化剂对酸性绿B脱色反应表现出较高的催化活性。     

Fe3O4/SDS磁性纳米颗粒吸附水体中的Cd2+和Zn2+

一种新型纳米固相萃取吸附剂,由阴离子表面活性剂十二烷基磺酸钠(SDS)包裹在Fe3O4磁性纳米颗粒表面形成,用于吸附水溶液中的重金属离子。研究了吸附过程的主要影响因素(如SDS浓度、溶液pH等)以及解吸过程的最佳条件,并对其机理进行了初步的探讨。研究结果表明,共沉淀法制备的Fe3O4颗粒粒径分布均匀,平均粒径约为54 nm;SDS浓度为300 mg/L时,Fe3O4/SDS磁性纳米颗粒吸附Cd2+和Zn2+的能力最强;在一定浓度范围内,Fe3O4/SDS体系对Cd2+和Zn2+的吸附平衡数据符合Langmuir吸附等温方程,饱和吸附量分别为22.42 mg/g和13.95 mg/g。最终结果表明,Fe3O4/SDS磁性纳米颗粒具有较强磁分离能力和较好的吸附效果。     

高效氨氧化菌群富集、驯化及其动态变化规律分析

利用选择性培养基对氨氧化菌群进行了连续驯化,得到了氨氮去除效率稳定的氨氧化菌群。采用平板菌落计数法结合聚合酶链式反应-变性梯度凝胶电泳(PCR-DGGE)技术考察了氨氧化菌群在连续传代过程中数量及群落结构的动态变化,并考察了pH值、碳源(HCO3-)浓度和氨氮浓度等因素对氨氧化菌群去除氨氮效率的影响。结果表明,通过连续驯化,氨氧化菌的比例由最初的1.8%提高到了31.3%。在碳源浓度为1.5 mg/L,NH4+-N初始浓度为200 mg/L,pH值为8的条件下,菌群对氨氮的去除率达99%以上。     

不同填料载体生物膜对微囊藻毒素的去除效果

利用自行设计的生物膜培养装置,通过对4种不同填料载体进行连续曝气循环培养生物膜,对湖水中的溶解态微囊藻毒素(MCs)的去除作用进行了研究。结果表明,填料载体上生物膜从形成到稳定大约需要3周;生物膜形成后对MCs的去除效率由高到低的顺序是:颗粒活性炭柱>多密孔球型滤料柱>塑料悬浮填料柱>陶瓷滤球柱。在实验水质条件下,当水力停留时间(HRT)=5 h,进水MCs浓度为21.5～47.25μg/L时,颗粒活性炭、多密孔球型滤料柱对MCs的去除率最高可达100%,塑料悬浮填料柱对MC-LR和MC-RR的去除率分别为70%和88%。当HRT=2.5 h时,塑料悬浮填料柱对MC-RR的去除率为MC-LR的2倍。生物膜对MCs的降解效果随温度(5～20℃)和溶解氧的升高而增加。塑料悬浮填料作为合适的生物膜挂膜填料载体对水源水的生物预处理具有良好的应用前景。