精□唑禾草灵和1-氨基-2,4-二溴蒽醌光致毒性演变过程与机理

研究了除草剂精□唑禾草灵和染料中间体1-氨基-2,4-二溴蒽醌对大型□(Daphnia magna)的光致急性毒性作用机制. 精□唑禾草灵(EC₅₀ 95%置信区间为4.62～6.63 mg/L)光解生成光稳定性以及急性毒性更大的产物□唑酚(EC₅₀ 95%置信区间为1.49～1.64 mg/L),推测精□唑禾草灵通过光修饰作用机制对大型□发挥光致毒性作用. 1-氨基-2,4-二溴蒽醌通过光化学转化生成二聚体,光修饰作用降低了其母体化合物的光致毒性. 在1-氨基-2,4-二溴蒽醌和模拟日光单独存在的条件下,大型□体内的活性氧物种(ROS)没有明显变化;在1-氨基-2,4-二溴蒽醌和模拟日光共同存在的条件下,生物体内的ROS呈先增加后降低的趋势. 另外,添加抗氧化剂可以减弱1-氨基-2,4-二溴蒽醌对大型□的光致毒性. 结果表明,光敏化作用是1-氨基-2,4-二溴蒽醌对大型□产生光致毒性的主要作用机制. 含时-密度泛函理论(TD-DFT)的计算结果表明,1-氨基-2,4-二溴蒽醌在水溶液中能够通过能量传递和电子转移2种方式发生光敏化反应.      

零价铁PRB修复2,4-DNT污染地下水模拟研究

研究了零价铁(Fe0)作为PRB墙体介质材料去除地下水环境中2,4-二硝基甲苯(2,4-DNT)可行性.通过室内试验研究地下水环境中Fe0去除水相2,4-DNT效果以及降解动力学参数,并结合一假设地下水受2,4-DNT污染的场地,采用Visual Modflow模拟Fe0墙体材料PRB(Fe0-PRB)修复地下水中2,4-DNT降解效果并评价其可行性.结果表明:在模拟过程中,PRB能有效控制并减少污染羽面积,降低污染浓度;污染4a后,污染地下水的2,4-DNT总质量约1.46×104kg,可推知PRB修复达标耗用Fe0材料为8.76×104kg;渗透系数增大导致地下水速率增大,2,4-DNT与墙体Fe0材料接触时间不充分,污染物污染下游地下水,同时也加速PRB上游污染羽面积减少.因此,结合数值模拟是有效的评价PRB介质材料修复地下水污染效果及确定PRB参数的重要手段之一.     

Determination of glyoxal and methylglyoxal in atmospheric particulate matter by 2,4-dinitrophenylhydrazine derivatisation

A simple and rapid method has been optimised to determine glyoxal and methylglyoxal in atmospheric particulate matter by extraction and derivatisation with 2,4-dinitrophenylhydrazine solutions. Minimal sample preparation was required by mixing a portion of filter charged with atmospheric particulate matter with 5?mL of a saturated solution of 2,4-dinitrophenylhydrazine (1.6?g?L^?1) in acetonitrile and acidified by H₂SO₄ (50?µL?L^?1). Chromatographic analyses were carried out 1?h after derivatisation solution was mixed. Finally, the proposed method was applied to quantify these dicarbonyls in atmospheric particulate matter samples, which were obtained as part of a large field study to characterise atmospheric aerosol from a rural area of Madrid. Glyoxal concentrations averaged 0.24?ng?m^?3, whereas mean values of methyl glyoxal were around 0.95?ng?m^?3. Methyl glyoxal levels showed a clear relationship with the particulate matter levels, whereas glyoxal data did not show such a correlation. This could indicate that both dicarbonyls come from different sources.     

Formation of polychlorinated biphenyls and chlorinated benzenes by heating of bis(2,4‐dichlorobenzoyl) peroxide

The formation of di‐, tri‐, and tetrachlorobenzenes, and di‐ to hexachlorobiphenyls was demonstrated after thermal degradation of bis(2,4‐dichlorobenzoyl) peroxide alone or in various solvents at 250 °C with yields of up to several percent. Possible radical reactions between solvents and the solute are suggested. PCB congeners are also present in silicone rubber crosslinked by this peroxide.     

DISSIPATION OF 2,4-D DMA AND BEE FROM WATER,MUD, AND FISH AT LAKE SEMINOLE,GEORGIA1

ABSTRACT: Four 10-ha plots in dense watermilfoil beds of Lake Seminole, Georgia, were each treated with either 2,4-D DMA or 2,4-D BEE at rates of 22.5 and 45 kg a.e./ha. Both formulations were shown to be rapidly converted to the 2,4-D acid form, with no detection of 2,4-D DMA or 2,4-D BEE in the water within less than 24 hours after treatment. The maximum detected 2,4-D concentrations in the high rate 2,4-D DMA and 2,4-D BEE plots were 3.6 and 0.68 mg/, respectively. However, all but seven samples at a 2,4-D BEE plot showed nondetectable herbicide levels by day 7, with all water samples showing nondetectable levels by day 13. Dimethylnitrosamine and 2,4-dichlorophenol, potentially toxic transformation products of the herbicide formulations, were at nondetectable levels in all water samples. Sediment samples showed no significant net accumulation of 2,4-D, 2,4-D BEE, or 2,4-dichlorophenol during the summer monitoring; dimethylnitrosamine remained at nondetectable levels. There was no accumulation of 2,4-D in fish collected from the two plots treated with 2,4-D DMA. Four of 24 game fish from the 2,4-D BEE treatment plots contained low levels of 2,4-D in muscle tissue, with a maximum value of 0.29 μg/g. In contrast, 18 of 20 gizzard shad collected from these plots through day 13 contained detectable 2,4-D in the muscle, with a maximum concentration of 6.9 μg/g. All fish collected after day 13 contained nondetectable levels of 2,4-D. Small decreases in dissolved oxygen and pH, associated with the complete watermilfoil control in all plots, had returned to normal summer values by day 28.     

Biodegradation of 3,5-dimethyl-2,4-dichlorophenol in saline wastewater by newly isolated Penicillium sp. yz11-22N2

In this study,the performance of 3,5-dimethyl-2,4-dichlorophenol(DCMX) degradation by a screened strain was investigated.18 S r DNA and the neighbor-joining method were used for identification of the isolated strain.The results of phylogenetic analysis and scanning electron micrographs showed that the most probable identity of the screened strain should be Penicillium sp.Growth characteristics of Penicillium sp.and degradation processes of DCMX were examined.Fourier transform infrared spectroscopy of the inoculated DCMX solution was recorded,which supported the capacity of DCMX degradation by the screened Penicillium sp.Under different salinity conditions,the highest growth rate and removal efficiency for DCMX were obtained at p H 6.0.The removal efficiency decreased from 100%to 66% when the DCMX concentration increased from 5 to 60 mg/L,respectively.Using a Box–Behnken design,the maximum DCMX removal efficiency was determined to be 98.4%.With acclimation to salinity,higher removal efficiency could be achieved.The results demonstrate that the screened Penicillium sp.has the capability for degradation of DCMX.     

碳纳米管对水中4-氯酚和2,4-二氯酚的吸附性能研究

碳纳米管是一种具有独特结构和优异性能的新型纳米材料。文章利用碳纳米管对水溶液中的4-氯酚和2,4-二氯酚进行了吸附研究,考察了吸附时间、pH值、温度等对吸附效果的影响,并采用Langmuir和Freundlich方程进行拟合,探讨了其可能的吸附机理。研究结果表明,碳纳米管对4-氯酚和2,4-二氯酚的最佳吸附酸度在pH=2～6。碳纳米管对2,4-二氯酚吸附量大于对4-氯酚的吸附量,二者动力学特征均符合准二级动力学方程。研究了4-氯酚和2,4-二氯酚在碳纳米管上的吸附等温线。研究结果表明:4-氯酚和2,4-二氯酚在碳纳米管上的吸附量随着温度的升高而下降。吸附过程是一个放热的过程,Langmuir和Freundlich等温吸附方程均能较好地拟合吸附等温线。碳纳米管能较好地用于除去水溶液中的4-氯酚和2,4-二氯酚。     

水/载O_3有机溶剂两相臭氧氧化法降解水体中2,4-二氯苯氧乙酸

以水/载O3有机溶剂(全氟萘烷)为新型两相臭氧氧化体系,研究了臭氧在全氟萘烷中的溶解度和稳定性,并以水体中2,4-二氯苯氧乙酸(2,4-D)为研究对象,考察了初始pH值、臭氧投加量、自由基抑制剂对两相臭氧氧化体系降解2,4-D效果的影响.结果表明:臭氧在全氟萘烷中有很高的溶解度和很好的稳定性;碱性pH环境有利于2,4-D的降解,随着水相初始pH的增加,2,4-D在水/载饱和O3全氟萘烷两相体系中的去除率明显增加;随着初始全氟萘烷载O3量与2,4-D物质的量比的增加,2,4-D总去除率明显增加;叔丁醇(20mg·mL-1)对两相体系中2,4-D降解影响不显著.     

钛基氧化物阳极氧化降解水中2,4-二氯酚

采用热氧化法制备了具有TiO2、RuO2和IrO2涂层的钛基氧化物电极(Ti/TiO2/RuO2/IrO2),并以其为工作电极考察了:①水中2,4-二氯酚(DCP)的循环伏安特性;②pH值、阳极电位和反应时间对阳极氧化降解DCP的影响;③阳极氧化对DCP水溶液可生化性的影响.结果表明,电极的氧化物负载量显著影响DCP的循环伏安特性.较高的介质pH值利于DCP的电化学氧化降解,而低pH值更易导致DCP挥发.低阳极电位下,DCP主要通过阳极直接氧化降解,因受电流密度过低的限制其降解效果较差;高阳极电位下,DCP主要通过阳极间接氧化降解,当阳极电位为1.8V,反应时间为360min时,DCP去除率可达100%,COD的去除超过50%,但能耗较高.COD的检测与紫外-可视光谱曲线表明,DCP的电化学氧化降解过程产生了有机中间体.Ti/TiO2/RuO2/IrO2阳极氧化可显著提高DCP水溶液的可生化性,表明其在氯酚废水预处理或脱毒领域有一定应用潜力.