金属离子对δ-MnO2 去除对叔辛基酚抑制作用的研究

研究了pH 4.0的水溶液中各种金属离子对合成的δ-MnO2去除对叔辛基酚(4-t-OP)的影响.实验表明反应150 min时,δ-MnO2对4-t-OP的去除率达到100%,但当反应体系中含有金属离子时,去除效果受到抑制.抑制效果随金属离子浓度的增加而增大,并随金属离子的不同表现出较大的差异.在pH 4.0条件下,Pb2+和Mn2+的抑制效果最强,其次为过渡金属离子,再次是碱土金属离子,而碱金属离子基本上不产生抑制作用.还比较了δ-MnO2对多种金属离子的吸附能力,其对Pb2+的吸附作用最强,在其余的金属离子中,对过渡金属离子的吸附量稍大于碱土金属离子.结果表明,金属离子所产生抑制作用的源于其占据了δ-MnO2表面反应位点并与4-t-OP形成竞争,而抑制作用大小的差异主要来源于δ-MnO2与金属离子间吸附作用强弱的差别,MnO2表面结构的变化,以及溶液中自由态金属离子的分布比例及其离子半径的不同.     

UV和H2 O2联合消毒灭活饮用水中大肠杆菌研究

以大肠杆菌为研究对象,对单独紫外线(UV)、H2O2及两者不同组合方式的灭活效果进行了分析.结果表明,单独H2O2对大肠杆菌基本无灭活效果,加入浓度为20 mg·L-1的H2O2接触时间为30 min时,灭活率仅为0.02个对数级;单独UV工艺可在一定程度上灭活大肠杆菌,紫外线剂量为10 mJ·cm-2时,灭活率可达到4.51个对数级.紫外线和H2O2联合消毒在一定程度上提高了消毒效果,且不同的组合方式对灭活效果有很大的影响.先UV后H2O2消毒效果优于先H2O2后UV,当紫外线剂量为5 mJ·cm-2时,加入H2O2分别反应2.5、5、10、20 min后,两者的灭活率分别较单独UV消毒增加0.09、0.35、0.38、0.68和0.01、0.07、0.14、0.53个对数级.而UV与H2O2同时消毒效果优于UV与H2O2顺序消毒,当紫外线剂量为5 mJ·cm-2时,加入H2O2反应20 min后,灭活率较UV-H2O2和H2O2-UV工艺分别增加了0.43和0.58个对数级.随着紫外线强度的增加,大肠杆菌的灭活效果不断提高.     

三峡库区大宁河枯水期藻细胞的时空分布

本研究旨在为三峡库区大宁河藻华预警提供基础数据,于2011年4～9月期间在大宁河流域选择4个取样点开展藻细胞时空变化研究.藻细胞在时间序列表现为:4～9月,藻种主要以蓝藻、绿藻和硅藻为主,藻密度呈逐步递增趋势;在此期间4个取样点的蓝藻比重均逐步增大,硅藻比重逐步降低,绿藻比重变化不显著.藻细胞在空间分布上表现为:藻密度与水温和叶绿素呈极显著相关,相关系数分别为0.97和0.95,与光照、溶解氧、pH值和可溶性磷盐呈显著相关,相关系数分别为0.87、0.83、0.82、0.82;菜子坝在整个试验期间0 m处藻密度比其他水层的藻密度高,白水河在6月和7月的2.0 m处藻密度最高,双龙在7、8和9月的0 m和2.0 m处藻密度较高,大昌在整个试验期间,藻密度变化不大;不同藻细胞在垂向水层中的比重也随时间的变化而改变,可能是不同藻细胞适合不同生态环境所致.     

Degradation of direct azo dye by Cucurbita pepo free and immobilized peroxidase

Enzymatic decolourization of the azo dye, Direct Yellow (DY106) by Cucurbita pepo (courgette) peroxidase (CP) is a complex process, which is greatly affected by pH, temperature, enzyme activity and the concentrations of H₂O₂ and dye. Courgette peroxidase was extracted and its performance was evaluated by using the free-CP (FCP) and immobilized-CP (ICP) forms in the decolourization of DY106. Immobilization of peroxidase in calcium alginate beads was performed according to a strategy aiming to minimize enzyme leakage and keep its activity at a maximum value by optimizing sodium alginate content, enzyme loading and calcium chloride concentration. The initial conditions at which the highest DY106 decolourization yield was obtained were found at pH 2, temperature 20℃, H₂O₂ dose 1 mmol/L (FCP) and 100 mmol/L (ICP). The highest decolourization rates were obtained for dye concentrations 50 mg/L (FCP) and 80 mg/L (ICP). Under optimal conditions, the FCP was able to decolorize more than 87% of the dye within 2 min. While with ICP, the decolourization yield was 75% within 15 min. The decolourization and removal of DY106 was proved by UV-Vis analysis. Fourier transform infrared (FT-IR) spectroscopy analysis was also performed on DY106 and enzymatic treatment precipitated byproduct.     

Investigation of low-molecular weight organic acids and their spatiotemporal variation characteristics in Hongfeng Lake, China

The identities and concentrations of low-molecular-weight organic acids (LMWOAs) were determined by ion chromatography throughout a 20-m water column in Hongfeng Lake, China. The spatiotemporal variations of LMWOAs and their contributions to dissolved organic matter (DOM) in a research period of 24 hr were also investigated. The results demonstrated that five LMWOAs (lactic, acetic, pyruvic, sorbic, oxalic acid) were detected, and their total concentration and proportion in DOC were 6.55 μmol/L and 7.47%. Their average levels were 2.50, 0.65, 2.35, 0.96 and 0.09 μmol/L, respectively. LMWOAs were higher during daytime (10:00-18:00 on Jun 13, 2008) than nighttime (21:00-6:00 the next morning), in particular 4.99 μmol/L high in the epilimnion ( 1 m water depth), reflecting the fact that direct import from terrigenous sources and photochemical production from humic materials were dominant during LMWOAs’ origin and accumulation. The same factors caused LMWOAs to be 0.63 μmol/L in the epilimnion higher than in the hypolimnion. The rapid decrease of total organic acid (TOA) up until 18:00 mainly resulted from bio-uptake and mineralization in the hypolimnion (>1 m water depth). Pyruvic acid increased with time in the epilimnion and decreased in the hypolimnion, largely related to the two contrary processes of continuous degradation and synthesis of macromolecular organic matter during life materials’ cycle mediated by organisms. Simultaneously, plankton behavior and thermal stratification played a pivotal role in LMWOAs’ behavior in the water column, causing decreasing and increasing profiles. The distribution of LMWOAs represents an interesting resource for biogeochemical research of DOM in aquatic ecosystems.     

Electrochemical treatment of olive mill wastewater: Treatment extent and effluent phenolic compounds monitoring using some uncommon analytical tools

Problems related with industrials effluents can be divided in two parts: (1) their toxicity associated to their chemical content which should be removed before discharging the wastewater into the receptor media; (2) and the second part is linked to the difficulties of pollution characterisation and monitoring caused by the complexity of these matrixes. This investigation deals with these two aspects, an electrochemical treatment method of an olive mill wastewater (OMW) under platinized expanded titanium electrodes using a modified Grignard reactor for toxicity removal as well as the exploration of the use of some specific analytical tools to monitor effluent phenolic compounds elimination. The results showed that electrochemical oxidation is able to remove/mitigate the OMW pollution. Indeed, 87% of OMW color was removed and all aromatic compounds were disappeared from the solution by anodic oxidation. Moreover, 55% of the chemical oxygen demand (COD) and the total organic carbon (TOC) were reduced. On the other hand, UV- Visible spectrophotometry, Gaz chromatography/mass spectrometry, cyclic voltammetry and 13 C Nuclear Magnetic Resonance (NMR) showed that the used treatment seems efficaciously to eliminate phenolic compounds from OMW. It was concluded that electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of all phenolic compounds present in OMW. Among the monitoring analytical tools applied, cyclic voltammetry and 13 C NMR are among the techniques that are introduced for the first time to control the advancement of the OMW treatment and gave a close insight on polyphenols disappearance.     

Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GC×GC- TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of μg/L in wastewater.     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

Phytoremediation potential of charophytes: Bioaccumulation and toxicity studies of cadmium, lead and zinc

The ability for usage of common freshwater charophytes,Chara aculeolata and Nitella opaca in removal of cadmium (Cd),lead (Pb) and zinc (Zn) from wastewater was examined.C.aculeolata and N.opaca were exposed to various concentrations of Cd (0.25 and 0.5 mg/L),Pb (5 and 10 mg/L) and Zn (5 and 10 mg/L) solutions under hydroponic conditions for 6 days.C.aculeolata was more tolerant of Cd and Pb than N.opaca.The relative growth rate of N.opaca was drastically reduced at high concentrations of Cd and Pb although both were tolerant of Zn.Both macroalgae showed a reduction in chloroplast,chlorophyll and carotenoid content after Cd and Pb exposure,while Zn exposure had little effects.The bioaccumulation of both Cd and Pb was higher in N.opaca (1544.3 μg/g at 0.5 mg/L Cd,21657.0 μg/g at 10 mg/L Pb) whereas higher Zn accumulation was observed in C.aculeolata (6703.5 μg/g at 10 mg/L Zn).In addition,high bioconcentration factor values (> 1000) for Cd and Pb were observed in both species.C.aculeolata showed higher percentage of Cd and Pb removal (> 95%) than N.opaca and seemed to be a better choice for Cd and Pb removal from wastewater due to its tolerance to these metals.     

Occurrence and distribution of hexabromocyclododecane in sediments from seven major river drainage basins in China

The concentrations and geographical distribution of hexabromocyclododecane (HBCD) were investigated in 37 composite surface sediments from seven major river drainage basins in China, including Yangtze River, Yellow River, Pearl River, Liaohe River, Haihe River, Tarim River and Ertix River. The detection frequency of HBCD was 54%, with the concentrations ranged from below limit of detection (LOD) to 206 ng/g dry weight. In general, the geographical distribution showed increasing trends from the upper reaches to the lower reaches of the rivers and from North China to Southeast China. Compared to other regions in the world, the average concentration of HBCD in sediments from Yangtze River drainage basin was at relatively high level, whereas those from other six river drainage basins were at lower or similar level. The highest HBCD concentration in sediment from Yangtze River Delta and the highest detection frequency of HBCD in Pearl River drainage basins suggested that the industrial and urban activities could evidently affect the HBCD distribution. HBCD diastereoisomer profiles showed that γ-HBCD dominated in most of the sediment samples, followed by α- and β-HBCD, which was consistent with those in the commercial HBCD mixtures. Further risk assessment reflected that the average inventories of HBCD were 18.3, 5.87, 3.92, 2.50, 1.77 ng/cm 2 in sediments from Pearl River, Haihe River, Tarim River, Yellow River and Yangtze River, respectively.