Removal of substituted phenols onto iron‐treated Nostoc sp. biomass

This study explored the possibility of removing 4‐nitrophenol (4‐NP) and 2,4‐dichlorophenol (2,4‐DCP) from water by using a dead blue‐green algae, Nostoc sp., dried and untreated and dried and treated with iron (Fe‐treated with 0.1 M ferric chloride solution for 1 day). The Nostoc sp. untreated and Fe‐treated biomass were used to study the sorption and desorption of 4‐NP and 2,4‐DCP. The effects of solute concentration, ionic strength, and temperature on sorption and desorption in the presence of untreated and treated Nostoc sp. biomass were investigated. The Fe‐treated Nostoc sp. biomass sorbed higher amounts of both 4‐NP and 2,4‐DCP than the untreated biomass. The percent cumulative desorption decreased from 6.41% to 0.28% and 1.84% to 0.19%, respectively, for 4‐NP and 2,4‐DCP for the Fe‐treated biomass. Biosorption of 4‐NP and 2,4‐DCP onto untreated and Fe‐treated Nostoc sp. biomass conformed to Freundlich isotherms. Iron treatment of Nostoc sp. biomass increased the value of ln K from 8.07 to 8.59 for 4‐NP and from 8.04 to 8.51 for 2,4‐DCP but decreased their desorption. An increase in ionic strength (0.003–0.03) increased the biosorption of both substituted phenols and decreased their percent desorption. An increase in temperature in the range of 15–35°C decreased the sorption of 4‐NP and 2,4‐DCP onto both untreated and Fe‐treated Nostoc sp. biomass and increased their desorption, indicating that the biosorption of both substituted phenols onto untreated and Fe‐treated Nostoc sp. biomass was principally a physical process. The results of this study suggest that Fe‐treated dried Nostoc sp. biomass could be explored as an inexpensive and eco‐friendly material for the effective removal of these phenols and, potentially, other chemicals from industrial wastewater and contaminated groundwater.     

Formation of dioxins during exposure of pesticide formulations to sunlight

Chlorinated pesticides can contain impurities of dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and their precursors, as a result of various manufacturing processes and conditions. As precursor formation of PCDD/Fs can also be mediated by ultraviolet light (UV), this study investigated whether PCDD/Fs are formed when currently used pesticides are exposed to natural sunlight. Formulations containing pentachloronitrobenzene (PCNB; n = 2) and 2,4-dichlorophenoxyacetic acid (2,4-D; n = 1) were exposed to sunlight in quartz tubes, and the concentration of 93 PCDD/F congeners were monitored over time. Considerable formation of PCDD/Fs was observed in both PCNB formulations (by up to 5600%, to a maximum concentration of 57 000 μg ∑PCDD/F kg⁻¹) as well as the 2,4-D formulation (by 3000%, to 140 μg ∑PCDD/F kg⁻¹). TEQ also increased by up to 980%, to a maximum concentration of 28 μg kg⁻¹ in PCNB, but did not change in the 2,4-D formulation. Assuming similar yields as observed in the present study as a worst case scenario the use of PCNB in Australia may result in the formation of 155 g TEQ annum⁻¹, contributed primarily by OCDD formation. This warrants detailed evaluations on the contemporary release of PCDD/Fs to the environment after the use of pesticides. Changes in congener profiles (including the ratio of PCDDs to PCDFs (DF ratio)) suggest that pesticide sources of PCDD/Fs after sunlight exposure may not be recognized based on matching source fingerprints established from manufacturing impurities. These changes also provide preliminary insights into the possible formation routes and types of precursors involved.     

Determination of 2,4-Dichlorophenoxyacetic acid in food and water samples using a modified graphene oxide sorbent and high-performance liquid chromatography

Abstract

In the present work, dispersive micro-solid phase extraction (D-μ-SPE) method using magnetic graphene oxide tert-butylamine (GO/Fe₃O₄/TBA) nanocomposite, as an efficient sorbent, was applied for determining 2,4-dichlorophenoxyacetic acid (2,4-D) in water and food samples. Detection was carried out using high-performance liquid chromatography (HPLC) instrument. Influential parameters of D-μ-SPE such as sorbent and its amount, elution solvent and its volume, adsorption and desorption times and pH of sample solution were investigated and optimized. Under the optimized conditions, limit of detection and quantitation values were 0.007 and 0.02?μg/mL, respectively. Recovery data for several real samples were obtained within the range of 88.0–94.0% with a relative standard deviation (RSD) less than 7.5%. The proposed method was successfully applied to quantitative determination of 2,4-D in several vegetables and water samples.     

·OH自由基介导2,4-二氯酚光降解机理及产物毒性变化特征的理论研究

由于2,4-二氯酚(2,4-dichlorophenol,简称2,4-DCP)具有"三致"作用及潜在的生态风险,其光化学降解机理及产物的生态毒理效应目前成为人们关注的焦点。本研究采用理论化学计算手段,系统阐明了2,4-DCP在水环境中·OH介导的间接光化学转化机理、动力学和转化产物的生态毒性变化特征。结果表明2,4-DCP很容易被·OH氧化降解,其降解主要通过·OH-加成和H-迁移路径进行。在低温条件下·OH-加成路径将占主导,主要形成4,6-二氯苯-1,3-二酚;而当温度超过313 K时,·OH提取酚羟基上的氢原子为主要降解途径,主要形成2-氯苯-对苯醌。尤其在活性物种浓度较低的高温环境中,H-迁移路径有可能生成二噁英。计算毒理学结果表明:H-迁移产物的水生毒性超过·OH-加成产物,甚至超出母体2,4-DCP一个毒性等级。因此,我们建议在以后的环境监测以及风险评估过程中,关注2,4-DCP及其转化产物特别是H-迁移路径的转化产物的生态毒理学问题。     

2，4’-DDT对斑马鱼生长、繁殖力及卵黄蛋白原的影响

以斑马鱼体内卵黄蛋白原（Vtg）作为雌激素污染物的生物标志物,比较研究了不同浓度2,4。DDT对成年斑马鱼生长、发育、繁殖以及体内Vtg含量的影响。结果表明,当水环境中p（2,4。DDT）为2和10μg·L-1时,斑马鱼产卵量和受精率与空白和溶剂对照组相比均显著下降（P〈0．05）。当水环境中P（2,4。DDT）为0．2、2和10μg·L-1时,斑马鱼肝脏指数与空白和溶剂对照组相比显著升高（P〈0．05）;10μg·L。2,4。DDT处理组雄性斑马鱼体内Vtg含量显著高于空白和溶剂对照组（P〈0．05）,而0．2、2和10μg·L～2,4。DDT处理组雌性斑马鱼体内Vtg含量均显著高于空白和溶剂对照组（P〈0．05）,且随暴露浓度的增加而增大。SDS—PAGE检测及免疫印迹分析均显示雄鱼血液内出现Vtg特异条带,表明2,4。DDT对斑马鱼具有雌激素效应。     

苯酚存在对生物强化系统降解2,4-二氯酚的影响

研究了采用生物强化技术降解废水中2,4-二氯酚(简称2,4-DCP)时,不同浓度的苯酚存在对生物强化系统降解2,4-DCP的影响,并通过半连续流实验研究了苯酚长期存在下强化系统中2,4-DCP和苯酚生物降解速率的变化趋势.结果表明,苯酚浓度为10mg/L,50mg/L,100 mg/L及300mg/L时,都会对强化系统中2,4-DCP的降解速率产生一定的抑制作用,而且抑制作用随着苯酚浓度的增加而增强.不同浓度的苯酚与2,4-DCP长期共存时,2,4-DCP的降解速率表现出下降的趋势,而苯酚的降解速率则有所增强.     

Cd胁迫下不同外源植物激素对水稻幼苗抗氧化系统及Cd吸收积累的影响

为了探讨外源添加植物激素对Cd胁迫下水稻幼苗的抗氧化系统及Cd吸收积累情况的影响,减少Cd在植物体内的运输和积累,从而来缓解Cd对水稻的胁迫.以中嘉早17水稻幼苗为研究对象,进行水培试验,设置0、5和25 μmol·L^-1这3个Cd浓度处理,3种外源植物激素处理：不添加植物激素、100 μmol·L^-1褪黑素（MT）、0.2 μmol·L^-12,4-表油菜素内酯（EBL）和0.2 μmol·L^-1茉莉酸（JA）,共12个处理,每个处理重复3次.测定水稻幼苗体内Cd的含量,同时也对水稻幼苗地上部及根部丙二醛（MDA）、过氧化物酶（POD）、过氧化氢酶（CAT）和还原型谷胱甘肽（GSH）含量进行分析.结果表明,在5 μmol·L^-1和25 μmol·L^-1 Cd胁迫下,外源添加MT、EBL和JA使地上部MDA含量显著降低了11%~24%,但是根系与地上部情况恰好相反,添加3种外源物质均导致根系中MDA含量增加,其中MT和EBL现象明显,在5 μmol·L^-1 Cd胁迫下,与CK相比,分别提高了45.5%和20.0%;在25 μmol·L^-1 Cd胁迫下,分别提高了46.2%和19.8%.外源添加植物激素可显著增加水稻幼苗地上部和地下部POD、CAT的活性,降低GSH以及Cd的含量,在5 μmol·L^-1 Cd胁迫下,添加MT、EBL和JA导致水稻地上部Cd含量分别降低39.4%、40.1%和51.6%,根部分别降低38.9%、40.2%和7.0%;25 μmol·L^-1 Cd胁迫下,地上部Cd含量分别降低18.9%、14.5%和35.6%,根部分别降低85.3%、81.1%和56.5%.由此可见,通过外源添加低浓度植物激素MT、EBL和JA,可缓解Cd对水稻的胁迫,降低Cd对水稻的毒害作用.     

2,4-二叔丁基苯酚对斑马鱼早期发育阶段的神经毒性

2,4-二叔丁基苯酚（2,4-di-tert-butylphenol,2,4-DTBP）作为一种合成酚类抗氧化剂（Synthetic Phenolic Antioxidants,SPAs）被广泛应用于塑料、橡胶、食品等工业产品中,近年来在水体、空气、生物体中被不同程度检出.然而目前有关2,4-DTBP的毒理学研究十分有限,尤其是对鱼类早期发育阶段的神经毒性效应尚未可知.因此,本文以斑马鱼为研究对象,在涵盖环境相关浓度水平上（0.01、0.1和1 μmol·L^-1,即2.06、20.6和206 μg·L^-1）,从运动活性、焦虑行为及多巴胺和5-羟色胺神经信号通路的基因转录水平探讨2,4-DTBP对斑马鱼早期发育阶段的神经毒性效应及其作用机制.结果发现,0.01和0.1 μmol·L^-1 2,4-DTBP暴露引起仔鱼在暗周期过度活跃,1 μmol·L^-1 2,4-DTBP暴露引起仔鱼在光周期异常平静及焦虑行为,斑马鱼的行为异常可能与5ht1ab 和drd1的过度表达有关.研究表明,2,4-DTBP可能对斑马鱼早期发育阶段具有神经毒性,且不同剂量下的作用机制不同.     

ACUTE TOXICITY OF PICRIC ACID AND PICRAMIC ACID TO RAINBOW TROUT,SALMO GAIRDNERI,AND AMERICAN OYSTER,CRASSOSTREA VIRGINICA1

ABSTRACT Picric acid (2,4,6-trinitrophenol) and picramic acid (2-amino-4,6-dinitrophenol) are potential water pollutents due to a variety of industrial and munition uses. The possible impacts of picric and picramic acid to two recreationally and commercially important species, rainbow trout, Salmo gairdneri, and American oysters, Crassostrea virginica, were evaluated. Picramic acid was more toxic than picric acid to both species tested. The 96-h LC50s for picric and picramic acids for rainbow trout were 109.6 and 46.2 mg/1, respectively. The 144-h LC50s for picric and picramic acid for American oysters were 254.9 and 69.8 mg/1, respectively. Sublethal no growth EC50s and shell deposition EC50s for oysters showed that both compounds caused adverse effects at much lower concentrations than indicated by the LC50s. For example, the 144-h shell deposition EC50s were 27.9 mg/1 for picric acid and 5.6 mg/1 for picramic acid. Sediment adsorbtion studies in estuarine water indicated that both compounds are not readily adsorbed which suggests that sediment would not play a major role as a sink in contaminated systems. Oysters, which filter large quantities of particulate matter, would more likely be affected by picric and picramic acids in the water column than by exposure to contaminated sediment.     

pH和盐对活性炭纤维吸附2,4-二硝基酚的影响

采用静态吸附的方法,研究了pH和盐对活性炭纤维ST-8和ST-13吸附水中2,4-二硝基酚的影响。结果表明,在pH0～14范围内,吸附量先随着pH的增大而增大,然后吸附量随着pH的增大而减小;在pH11时,吸附量最小但不为零;在pH11～14范围内,吸附量随着pH增大而增大;ST-8和ST-13吸附2,4-二硝基酚的最佳pH分别为2和3。pH对吸附的影响主要是改变2,4-二硝基酚的存在形态、活性炭纤维表面的电荷和溶液的物理化学性质。盐的存在对吸附2,4-二硝基酚有利;低pH时,氯化钠的作用是盐析效应;在pH较大时,氯化钠的作用是屏蔽效应。在pH为11的条件下,氯化钠浓度为5.0mol/L时,ST-13可以完全消除静电斥力,而ST-8只能克服大部分的静电斥力。