几种农药对鲤鱼脑AchE的联合毒性效应

采用体内染毒的方法,以鲤鱼脑乙酰胆碱酯酶(AchE)活力为指标,研究了有机磷农药对硫磷与氯乐果、甲胺磷涕灭威之间的联合毒性效应.结果表明,这些农药之间均产生较强的协同作用,但是两种农药以不同比例加入,其产生的毒性效应有明显差别,涕灭威/对硫磷之间的协同作用要强于同类农药间的作用.     

一种有机磷农药单克隆抗体的制备及其特性研究

合成与有机磷农药化学结构相近似的一类半抗原,制备该类半抗原的特异性单克隆抗体,建立酶免疫分析方法,并对4种有机磷农药(毒死蜱、甲基对硫磷、辛硫磷及三唑磷)进行检测.结果显示,此方法对部分有机磷农药灵敏度高,可以简便、快速地检测具有特定结构的有机磷农药,检测灵敏度与被检有机磷农药的化学结构相关.     

不同种植方式蔬菜中农药残留的差异及污染控制研究

采集了陕西地区不同种植方式的瓜果类、叶菜类蔬菜样品,研究了其中各种农药的残留情况,并分析了农药残留对环境的污染及其控制措施。结果表明:露地种植蔬菜与设施种植蔬菜相比,无论是农药残留检出率还是超标率都略高,两者的农药残留检出率分别为42.0%、36.5%,超标率分别为12.0%、8.2%;叶菜类蔬菜与瓜果类蔬菜相比,无论是农药残留检出率还是超标率都较高,两者的农药残留检出率分别为52.6%、29.6%,超标率分别为17.3%、5.4%;设施种植的瓜果类蔬菜和叶菜类蔬菜的农药残留检出率基本接近,而叶菜类蔬菜的农药残留超标率明显高于瓜果类蔬菜,露地种植的叶菜类蔬菜的农药残留检出率和超标率都远高于瓜果类蔬菜;设施种植蔬菜与露地种植蔬菜相比,甲胺磷、对硫磷、甲基对硫磷、毒死蜱、三氟氯氰菊酯和氰戊菊酯的残留检出率更高;瓜果类蔬菜与叶菜类蔬菜相比,毒死蜱、甲氰菊酯、三氟氯氰菊酯、氰戊菊酯的残留检出率更高;叶菜类蔬菜的农药施用浓度较高,施用农药后要间隔一定时间后再上市销售,并应采用更科学的施药方式,以减少农药在蔬菜中的残留和降低对环境的危害;一方面要开发并积极倡导使用高效、低毒、低残留的无公害农药,另一方面则要开发能够高效、快速降解残留农药的物质,同时还要进行农产品的清洁生产,以提高农产品的安全性,并降低环境中农药的残留危害。     

微生物燃料电池型生物毒性传感器对5种典型农药的毒性检测

目前,微生物燃料电池(microbialfuelcell,MFC)型生物毒性传感器被广泛用于检测重金属、氰化物和抗生素等污染物,但将其应用于检测农药的研究极少.为此,探究了MFC型生物毒性传感器对溴氰菊酯、敌百虫、百菌清、莠去津和烟嘧磺隆5种典型农药的检测性能.实验结果表明:这5种典型农药的响应(产电抑制率)均与其浓度的对数呈良好的线性关系,且溴氰菊酯、敌百虫、百菌清、莠去津和烟嘧磺隆使MFC型生物毒性传感器产电抑制率达到10％的质量浓度分别低至0.016、0.070、0.013、0.005和0.033 mg·L-1;中毒后,MFC型生物毒性传感器的恢复时间随农药浓度的增加而延长,但240 min内均可快速恢复稳定;另外,这5种典型农药所配制的不同混合农药的生物毒性均高于单一农药.以上结果表明,MFC型生物毒性传感器对这5种典型农药的响应灵敏,检出限较低且中毒后恢复速度快,具有快速检测和预警水体农药污染的应用潜力.     

几种农药对发光菌毒性的测定和构效关系研究

测定了10种农药对发光菌的毒性数据(-lgEC50);采用密度泛涵理论(DFT)中的B3LYP方法,在B3LYP/6-31G*水平上全优化计算了17种农药的结构参数和热力学参数,将这些参数作为理论描述符,依据修正的线性溶解能理论,利用半致死浓度(EC50)实验数据,建立了用于预测农药毒性的模型,其相关方程(相关系数r=0.945 5)包含2个变量,即分子的最正氢原子电荷(qH )和熵(Sθ),并用留一交叉验证法对模型的稳定性进行了验证.此外,还利用该模型预测了17种农药对发光菌的一IgEC50.     

含氯消毒剂与多类农药的反应活性研究

为了研究农药在饮用水消毒过程中的降解情况,选择了8类使用广泛或者在水源中已检测出有残留的农药,研究其与普遍使用的3种含氯消毒剂(自由氯、氯胺和二氧化氯)的反应活性.实验结果表明,在农药浓度为5μmol/L(少数除外),消毒剂与农药摩尔比为200:1,pH 6.58-6.84,温度25±3℃的条件下,自由氯与除草定、乐果、涕灭威、涕灭威亚砜和灭虫威这5种农药反应很快,在2 min内就将其完全降解,杀线威在60 min内降解了98%;一氯胺只与涕灭威、灭虫威有很高的反应活性,分别在1 min和4 min内将2种农药降解完毕;二氧化氯可以在10 min内完全降解除草定,反应120 min后对涕灭威和灭虫威的降解率分别为75%和81%.3种消毒剂与其他种类农药的反应活性都很低.因此,在使用这3种消毒剂进行饮用水消毒处理时,只能有效降解(或转化)少数种类的农药,而大多数种类的农药将可能维持其化学结构,进入供水管网.     

活性焦吸附处理一硝基甲苯(MNT)废水

一硝基甲苯(MNT)废水是一种具有高毒性、难降解的火炸药废水。以活性焦为吸附剂,研究了活性焦对MNT废水中COD的吸附性能及pH、时间、温度和活性焦用量对吸附效果的影响,并分析了吸附前后MNT废水水质和急性毒性的变化。实验结果表明,pH、时间和活性焦用量是影响吸附效果的主要因素,吸附过程符合拟二级动力学,吸附速率常数为1.01×10-2g/(mg·min),可以用Freundlich吸附等温线来描述,等温线常数为Kf=1.14×10-4,n=0.58;在pH为3,温度为20℃,活性焦用量为80g/L的条件下吸附MNT废水3 h,COD的去除率达到72.0%,急性毒性下降了98.6%,表明活性焦能有效地吸附处理MNT废水。     

高铁酸盐与过硫酸钠联合降解水中滴滴涕和六六六

针对滴滴涕(DDTs)和六六六(HCHs)等有机氯农药(OCPs)难以同步降解的问题,采用高铁酸钾(K_2FeO_4)和过硫酸钠(Na_2S_2O_8)联合降解水溶液中的7种OCPs;分别考察了K_2FeO_4投加量、Na_2S_2O_8投加量和溶液初始pH因素的单独作用及交互作用对OCPs降解率的影响;采用气相色谱-质谱联用仪分析鉴定了降解产物,并探讨了K_2FeO_4/Na_2S_2O_8体系对各OCPs的降解机理。结果表明:K_2FeO_4/Na_2S_2O_8体系处理的OCPs降解率大于K_2FeO_4单独处理下的降解率;碱性环境(pH=9～11)有利于α-HCH和γ-HCH的降解,弱碱性环境(pH=7～9)有利于DDTs的降解,中性环境(pH=7)有利于β-HCH的降解。采用二次多项式和逐步回归法可以较好地拟合和预测OCPs降解率与反应条件的关系,当K_2FeO_4投加量8 g·L~(-1)、Na_2S_2O_8投加量2 g·L~(-1)、pH=11时,总环境风险削减率可达79.16%,与验证实验结果相近。这表明模型具有较好的预测能力。K_2FeO_4/Na_2S_2O_8联合处理对OCPs的降解途径主要为脱氯脱氢,但仍有不完全脱氯产物残留。与K_2FeO_4单独处理相比,K_2FeO_4/Na_2S_2O_8双氧化体系实现了对DDTs和HCHs的高效同步降解。     

Meta-analysis of time-series studies of air pollution and mortality: effects of gases and particles and the influence of cause of death,age, and season

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 microg/m3 particulate matter (PM) of median diameter < or = 10 microm (PM10); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO2; 1.6% (1.1-2.0%) per 31.2 ppb O3; and 0.9% (0.7-1.2%) per 9.4 ppb SO2 (daily maximum concentration for O3, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM10 and SO2. Larger effect sizes were observed for respiratory mortality for all pollutants except O3. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

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.     

Meta-Analysis of Time-Series Studies of Air Pollution and Mortality: Effects of Gases and Particles and the Influence of Cause of Death,Age, and Season

Abstract

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 μg/m³ particulate matter (PM) of median diameter <10 μm (PM₁₀); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO₂; 1.6% (1.1-2.0%) per 31.2 ppb O₃; and 0.9% (0.7-1.2%) per 9.4 ppb SO₂ (daily maximum concentration for O₃, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM₁₀ and SO₂. Larger effect sizes were observed for respiratory mortality for all pollutants except O₃. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

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。     

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。     

Experimental and statistical validation of SPME-GC-MS analysis of phenol and chlorophenols in raw and treated water

A procedure based on solid-phase microextraction (SPME) and gas chromatography coupled with mass spectrometry (GC-MS) was developed and validated in order to analyse 10 phenols in water samples. The optimised conditions were obtained using polyacrylate fibre (PA), 20ml of sample volume, 10% NaCl, pH 4.0 and direct extraction at 35 degrees C and 1000rpm, for 40min. The linear range and quantification limits for these compounds by SPME-GC-MS were defined. An evaluation of the main uncertainty sources of this method is included, which allows expanded uncertainties in the 9.4-35% range for the majority of the compounds. The main source of uncertainty is associated with matrix effects. The validated method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from water supply system of a large area (Lisbon and neighbour municipalities).     

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.