Elimination of diclofenac from water using irradiation technology

The effluents of wastewater treatment plants, usually directly emitted to the environment, often contain the anti-inflammatory drug diclofenac (DCF). The paper investigates DCF elimination using irradiation technology. Hydroxyl radical and hydrated electron reactive intermediates resulting from water radiolysis effectively degrade DCF and strongly reduce the toxicity of the solutions. OH attaches to one of the rings of DCF, and hydroxylated molecules, 2,6-dichloroaniline and quinoid type compounds are the products. Hydrated electron adds to the chlorine atom containing ring, in the reaction quinoid type compounds and 4-chloroacridine form. At a 0.1 mM DCF concentration, a ∼1 kGy absorbed dose is needed for the degradation of DCF molecules, but for mineralization of the products (in presence of O₂) an order of magnitude higher dose is required.For irradiation of wastewater after biological treatment a ∼1 kGy dose is suggested. At this dose DCF and other drugs or metabolites present at μg L⁻¹ level are eliminated together with microorganism deactivation.     

Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

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.     

光催化过程中羟基自由基的产生与效能

采用异丙醇淬灭的方法考察了羟基自由基在光催化氧化酸性橙II过程中的产生和效能,研究了TiO2(P-25)的浓度、异丙醇的用量、酸性橙II的初始浓度、初始pH条件和天然共存离子对羟基自由基贡献率的影响。结果表明,在TiO2(P-25)浓度提高时羟基自由基的贡献率逐步提高并稳定在77.6%,异丙醇的投加量对羟基自由基的贡献率影响不大,酸性橙II初始浓度的提高则使羟基自由基的贡献率降低。在中性pH条件下羟基自由基的贡献率最高,酸性或碱性条件下较低。天然共存离子中HCO3-对羟基自由基的淬灭效应最强,F-的淬灭效应最弱。     

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.     

气浮-·OH强氧化组合工艺处理高藻水的研究

以库区天然水培养的二形栅藻(Scenedesmus dimorphus)为研究对象,利用大气压强电场电离放电产生羟基自由基(·OH),结合压力溶气气浮前处理工艺处理高藻水.实验结果表明,对于藻密度为65.6×10~4 cells/mL,浊度为10.8NTU,COD_(Mn)为6.74mg/L的高藻水,在总氧化剂TRO浓度为1.03 mg/L时,藻类去除效率达到100%;总细菌,总大肠菌群和大肠埃希氏菌均未检出;出水COD_(Mn)由1.43 mg/L降至1.25mg/L,降低了10%;浊度由0.66NTU降至0.54NTU,降低了12.59在排放高藻水的主管路中·OH杀藻的接触反应时间仅为6s.因此汽浮-·OH强氧化组合工艺可高效快速地处理高藻水,为保障水源水的供水安全探索了一种新的思路.     

新型锰氧化菌株Pseudoxanthomonas mexicana S5-3-5X的分离及锰氧化机理研究

锰氧化微生物能催化氧化Mn^II生成锰氧化物（Mn^IV&III）,而生成的锰氧化物可强化水处理体系（如锰砂滤池、湿地）中的微量有机污染物降解及底泥中甲烷的厌氧氧化,因而受到广泛研究.从环境中分离出更多种属和生态位的锰氧化菌是生物强化环境中锰氧化过程的重要基础.依据锰氧化菌株对低浓度营养物的潜在偏好,本研究梯度稀释常用的锰氧化菌培养基（PYG培养基）,配置出5级营养物梯度浓度的培养基.相对于原培养基,从较低浓度的4级培养基中多分离出6个菌属的锰氧化菌株,提高了锰氧化菌株的分离效率.分离出的Pseudoxanthomonas（假黄色单胞菌属）菌属的锰氧化菌株（Pseudoxanthomonas mexicana S5-3_-5X）,属中文文献首次报道.研究发现该菌株能在环境常见条件（pH 6.0~7.8、低营养物浓度（如稀释5~625倍PYG培养基）、50 μmol·L^-1 ~1.6 mmol·L^-1的Mn^II浓度）生长并产生锰氧化活性;可以产生胞外超氧化物和锰氧化蛋白等锰氧化活性物质;基因组具有编码锰氧化模式菌株Pseudomonas putida GB-1的3个Mn^II氧化蛋白的同源基因,并且具有降解一些有机污染物的代谢通路.因此,该菌株具有较好的工程应用潜力.     

The Effect of Hydroxyl Radical Generation on Free-Radical Activation of TMP Fibers

The purpose of this work was to study the mechanisms involved in free radical activation of thermal mechanical pulp (TMP) fibers with the ultimate goal of developing methods for bonding wood fiber without the use of traditional adhesives. The generation of hydroxyl radicals in a mediated Fenton system was studied using electron spin resonance (ESR) spin-trapping techniques and indirectly through chemiluminescence measurement. The activation of TMP fibers was also evaluated by ESR measurement of free phenoxy radical generation on solid fibers. The results indicate that low molecular weight chelators can improve Fenton reactions, thus in turn stimulating the free radical activation of TMP fibers. However, it was also shown that excessive and prolonged free radical treatment may cause the destruction of fiber phenoxy radicals. In conclusion, this study demonstrates the potential for application, but also the complexity of free radical chemistry in biological materials, especially with regard to the chelation of transition metals and the interaction between free radicals.