有机官能团对改性硅吸附微囊藻毒素的影响

考察了不同有机改性硅对微囊藻毒素LR(mLR)和LA(mLA)的等温吸附行为。结果表明,有机改性硅可有效吸附去除水体中<0.1×10-6(质量分数)的微囊藻毒素,并且吸附去除效果随表面改性官能团中碳原子数量的增加而增加;相同条件下,有机改性硅在微囊藻毒素异构体之间存在着一定的吸附选择性。     

微囊藻毒素测定中产生的干扰及排除

采用固相萃取-高效液相色谱法定性、定量测定水中微囊藻毒素,对水样富集管(观赏鱼用氧气塑料管、橡胶管、医用乳胶管和硅胶管)、塑料材质(聚丙烯离心管等)、针式过滤器(水系、有机系针式过滤器)产生的干扰和吸附现象进行了深入探索.结果表明,观赏鱼用氧气塑料管对微囊藻毒索测定会产生严重的正干扰,在流动相甲醇:磷酸盐缓冲溶液(体积比)为50:50时,干扰得以排除;聚丙烯离心管在微囊藻毒素投加量较低时,对微囊藻毒索吸附率较高,造成回收率偏低;不同的针式过滤器对溶解在不同体积分数的甲醇溶液中的微囊藻毒素有明显不同的吸附能力.     

微囊藻毒素-RR的提取和臭氧氧化降解

在对采自云南滇池水华蓝藻细胞中的微囊藻毒素-RR(microcystin-RR,MC-RR)提取并发现其含量达到0.19mg/g(干重)的基础上,重点研究了臭氧氧化降解所提取的MC-RR。结果表明,当反应体系中臭氧浓度为5.7 mg/L时,初始浓度1.9 mg/L的MC-RR在15 min内被完全降解。利用HPLC/ESI/MS对提取的MC-RR及其氧化降解产物质荷比测定发现,降解前MC-RR的质谱图中出现特征离子m/z=1 038.7、m/z=519.8以及m/z=135.0。而降解后的产物质谱图中只有Adda基团中带苯环结构化合物(C9H10O)的特征离子峰m/z=135.0存在,其他2个离子峰完全消失。由此推断反应体系中MC-RR(m/z=1 038.2)在大量臭氧及其.OH自由基全面攻击下,分子结构中Adda基团以及单环结构中的不饱和双键直接被氧化而发生断链,最终形成小分子的有机物。     

阳澄湖和滆湖微囊藻毒素分布及其与富营养化因子的关系

2013年6—10月进行了阳澄湖和滆湖的水样采集及分析,对水体中胞内和胞外3种微囊藻毒素(MC-LR,MCRR,MC-YR)和TN、TP、Chl-a等富营养化指标在两湖的分布情况及关系进行了研究。结果表明,阳澄湖的微囊藻毒素及富营养化因子浓度在不同点位的差异小,而滆湖从北部到南部呈下降趋势,两湖相比,滆湖的浓度远远高于阳澄湖;富营养化因子影响微囊藻毒素的浓度分布和变化;相关性分析表明MC-LR、MC-RR和MC-YR与CODMn、TN、TP、PO3-4-P、Chl-a分别呈极显著正相关性(P0.01),MC-LR、MC-YR与NH+4-N呈显著负相关(P0.05);逐步回归性分析显示Chl-a是影响3种微囊藻毒素浓度的关键因子,可以通过Chl-a对水体中MCs的浓度进行预测,为微囊藻水华和微囊藻毒素污染的预警提供重要的科学参考。     

火山石生物滤床对微囊藻毒素的去除

微囊藻水华爆发导致大量微囊藻毒素释放至地表水环境中,严重威胁着饮用水供水安全.通过不同条件火山石自然曝气生物滤床(活性挂膜、灭活挂膜、未挂膜和无填料滤床)对不同形态、构型(MC-LR、MC-RR)的微囊藻毒素的去除实验,探讨其去除效率、途径和机理.结果表明,火山石自然曝气生物滤床对微囊藻毒素的去除是微生物降解和基质吸附共同作用的结果.胞外毒素和胞内毒素的总去除率分别为58％和91％.其中,胞外毒素主要通过微生物降解作用途径去除,占胞外毒素总去除率的(41±4.2)％,胞内毒素则主要通过基质吸附途径去除,占胞内毒素总去除率的(64±5.1)％.生物膜吸附、光降解等其他途径无明显作用.另外,不同构型的微囊藻毒素在火山石自然曝气生物滤床中均能有效去除,MC-LR和MC-RR的去除率分别为68％和54％.     

碳源对铜绿微囊藻生理特性及微囊藻毒素产率的影响

为研究水体中不同碳源对铜绿微囊藻生理特性的影响,以Na2CO3与葡萄糖分别作为铜绿微囊藻生长的无机碳源与有机碳源,将铜绿微囊藻于光照下进行培养,并对其一系列的生理特性与微囊藻毒素产率进行检测。实验结果表明,同等碳浓度下,有机碳源更能促进铜绿微囊藻的生长,经过30 d的培养,铜绿微囊藻在有机碳源中的产量为187.55 g,比其在无机碳源中的产量提高了6.06%;微囊藻毒素在有机碳源中的产量为969.00μg/g,而在无机碳源中的产量却升高至1 193.60μg/g。参与藻毒素合成的3种氨基酸在无机碳源中的浓度要比有机碳源中的浓度高,但是其余几种氨基酸的含量与之情况相反。而有机碳源培养的铜绿微囊藻总可溶性蛋白含量为387.00μg/g,比无机碳源培养的铜绿微囊藻的蛋白含量提高了93.60%。     

包埋水华鱼腥藻和活性炭对污水中氮磷的净化

采用聚乙烯醇-海藻酸钠（PVA—SA）凝胶包埋水华鱼腥藻与活性炭混合物，对比水华鱼腥藻在包埋、吸附以及悬浮状态下对高浓度模拟废水中氨氮的去除效果，实验结果表明，水华鱼腥藻在包埋状态下对氨氮有更好的去除效果。通过正交实验研究SA、粉末活性炭（PAC）、水华鱼腥藻之间不同质量比的包埋混合物对去除污水中NH4＋-N、TP以及处理后废水中微囊藻毒素（MC）残留量的影响，结果表明，当PVA量为8％时，SA、PAC和藻含量分别在0．5％、0．5％和0．2％为NH4＋-N、TP的最佳去除组合，同时处理后污水中MC的含量也低于联合国标准1Iμg／L，避免了二次污染的同时为产毒素藻类的利用创造了条件。     

孔结构和表面化学性质对活性炭吸附性能的影响

测定了室温下3种活性炭(GAC-C、GAC-P和GAC-T)对CO2、CH4和N2的吸附性能,并对颗粒活性炭孔结构和表面化学性质进行了表征,探讨了孔结构和表面化学性质对活性炭吸附性能的影响。结果表明:由于吸附机理、孔结构、表面含氧官能团和分子极性的差异,CO2、CH4和N2在活性炭上的饱和吸附量和吸附常数的关系为CO2>CH4>N2;CH4和N2的饱和吸附量主要受活性炭微孔孔容的影响,N2和CO2饱和吸附量的差异分别是由0.572～2.0 nm的微孔和0.4～6 nm的孔引起的;CH4吸附常数主要受较大中孔和大孔影响,N2吸附常数与微孔密切相关,大孔对CO2的吸附常数影响最大。     

滇池铜绿微囊藻(Microcystis aeruginosa Küitz)毒素及其在水体中的变化

本文研究了昆明市滇池富营养化所形成水华的主要藻类———铜绿微囊藻 (MicrocystisaeruginosaK櫣ｉｔｚ)的毒素及其在水体的变化。经研究 ,滇池铜绿微囊藻的提取液有一个毒峰出现 ,用双波长紫外分光光度计测定 ,发现于 2 4 0nm出现一个毒峰。用色质谱联用扫描得出 ,其分子离子峰为1 0 4 0 M/Z。用小白鼠注入藻类提取液进行试验 ,发现其肝脏肿大 ,并呈紫褐色。再将肝脏匀浆提取液用高压液相色谱测定 ,发现有毒峰出现。在不同季节、不同地点 ,采取湖水 ,经过滤后 (去除藻类和碎屑 )进行测定 ,结果得出 :在藻类生长旺季及生长繁茂的地点 ,水体中藻毒素的含量较高。而在藻类生长淡季及分布较少的地点 ,水中藻毒素含量则较少。但总的看来 ,经过过滤后的湖水 ,其中藻毒素含量少     

微囊藻毒素-RR对反硝化细菌生长及生理特性的影响

用0.01、5.00 mg/L微囊藻毒素-RR(MC-RR)处理反硝化细菌,研究了MC-RR对反硝化细菌的生长、培养液中NO3--N和NO2--N含量以及细胞内硝酸还原酶活性的影响.结果表明,高浓度MC-RR能显著抑制反硝化细菌的生长,延缓其细胞增殖,抑制培养液中硝酸盐含量的降低和亚硝酸盐含量的升高以及细胞内硝酸还原酶的活性,因而可能抑制或减缓生态系统中氮循环的进程.这表明,微囊藻毒素在一定程度上可能调节水体细菌群落.     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

骆马湖富营养化和生态状况调查与评价

为了了解骆马湖水质状况，在2005年对骆马湖富营养化状态和生态特性进行了调查，并结合“十五”期间的监测资料进行了分析。2005年骆马湖水体中总氮和总磷的平均值超《地表水环境质量标准》（GB3838-2002）中Ⅲ类，超标情况分别为0．78倍和0．54倍，达到湖库特定项目Ⅳ类水标准，骆马湖处于轻度富营养化状态。对骆马湖生态特征分析表明，由于该湖泊的形态以及“藻型浊水状态”和“泥沙型浊水状态”交替出现，遏制了湖水从高营养盐含量向全面富营养化状态演变，保障了底栖动物的良好生长环境，从而形成了骆马湖独特的环境生态平衡。     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.     

剩余污泥浓缩脱水投药量优化和模型建立

应用高分子阳离子絮凝剂（CPF-100）和聚丙烯酰胺（PAM）对污水厂剩余污泥进行浓缩脱水实验，研究表明：CPF-100的浓缩脱水效果优于PAM；当CPF-00投加量为1．16‰时，污泥沉降性能改善程度为37．51％；且在CPF-100投加量逐渐增大的初始阶段，污泥沉降性能改善程度随投加量的增加而增大，但CPF-100投加量也不宜过大，当CPF-100投加量超过1．16‰后，反而会使浓缩脱水效果变差。同时，建立了污泥沉降性能改善程度与絮凝剂CPF-100投加量、沉降时间之间的数学模型，其能较好地反映污水厂剩余污泥的浓缩脱水效果。     

Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

Effects of compositional heterogeneity and nanoporosity of raw and treated biomass-generated soot on adsorption and absorption of organic contaminants

A biomass-generated soot was sequentially treated by HCl-HF solution, organic solvent, and oxidative acid to remove ash, extractable native organic matter (EOM), and amorphous carbon. The compositional heterogeneity and nano-structure of the untreated and treated soot samples were characterized by elemental analysis, thermal gravimetric analysis, BET-N₂ surface area, and electron microscopic analysis. Sorption properties of polar and nonpolar organic pollutants onto the soot samples were compared, and individual contributions of adsorption and absorption were quantified. The sorption isotherms for raw sample were practically linear, while were nonlinear for the pretreated-soot. The removal of EOM enhanced adsorption and reduced absorption, indicating that EOM served as a partitioning phase and simultaneously masked the adsorptive sites. By drastic-oxidation, the outer amorphous carbon and the inner disordered core of the soot particles were completely removed, and a fullerene-like nanoporous structure (aromatic shell) was created, which promoted additional π-π interaction between phenanthrene and the soot.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.