氯酚类化合物对紫背浮萍生长及叶绿素含量的影响

以我国本土水生植物紫背浮萍为受试物种,利用其生长抑制和叶绿素含量的变化评价了3种氯酚类化合物的毒性效应.结果显示:2,4-二氯酚(2,4-DCP), 2,4,6-三氯酚(2,4,6-TCP)和五氯酚(PCP)对紫背浮萍的96h IC50值分别为12.73,8.49,1.12mg/L.根据化学物质对水生生物毒性分级标准,3种物质均为高毒.2,4-DCP,2,4,6-TCP和PCP对紫背浮萍基于叶绿素含量变化的最大可接受浓度(MATC)分别为2.24,1.58, 0.35mg/L,对应的急慢性毒性比(ACR)分别为5.68,5.37和3.20.     

A review on environmental distributions and risk management of phenols pertaining to the endocrine disrupting chemicals in Taiwan

Some phenols, including pentachlorophenol, dichlorophenol, alkylphenols (nonylphenol & octylphenol) and bisphenol-A, have been identified as endocrine disrupting chemicals (EDCs). These phenolic EDCs are extensively used in a wide range of household products, thus posing potential health risks for humans exposed to them. From the viewpoints of ecotoxicology, human health and regulations, it is urgent to restrict the emissions and releases of these estrogenic chemicals from the industrial processes and commercial products. This review article first focused on the physicochemical properties of phenolic EDCs and their industrial/commercial uses. Furthermore, their environmental distributions and regulatory frameworks for integrated risk management of these chemicals in Taiwan were conducted as a case study. Emphasis was thus put on the cross-ministerial joint venture (i.e., environment, health, agriculture, labor, and industry authorities), and the government policy on the risk management of EDCs. Finally, some recommendations for pollution prevention and toxicity reduction of phenolic EDCs were also addressed and analyzed to progress towards a sustainable society in Taiwan.     

Regression models for some solute distribution equilibria in the terrestrial environment

Sorption coefficients (K_p) of several organochlorine insecticides (OCs) in volcanic ash silt from Central Java are presented.

Selected experimental and estimated octanol‐water partition coefficient (P) values are used to study log‐log regressions with K_p data collected from the literature (PAHs, chlorophenols, phenylureas, chloro‐s‐triazines, carbamates and organophosphorus insecticides) and those of the OCs determined in the present study. Leaching distances and bioactivities in soil are correlated with the K_p values of the pesticides, and with the organic matter and the water content of the soil.     

三种氯代酚的水生态毒理和水质基准

氯酚化合物主要包括2,4-二氯酚、2,4,6-三氯酚和五氯酚等, 是一类重要的化工产品, 在环境中分布广泛. 氯酚在水体中的生态毒理行为一直是人们关注的焦点. 本文概述了2,4-二氯酚、2,4,6-三氯酚和五氯酚在水环境中的迁移归趋, 在水生生物体内的吸收代谢及其生态毒性和毒理特性. 在此基础上, 对3种氯代酚的水生态基准进行推导讨论, 以期为氯酚类污染物的环境管理、安全评价和污染防治提供基础资料.     

Probabilistic ecological risk assessment for three chlorophenols in surface waters of China

Individual and combined assessment of risks of adverse effects to aquatic ecosystems of three chlorophenols (CPs), including 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), were conducted. A probabilistic approach based on the concentrations of CPs in surface waters of China was used to determine the likelihood of adverse effects. The potential risk of CPs in surface waters of China was determined to be of concern, especially PCP and mixtures of CPs. The risks of adverse effects were examined as the joint probabilities of exposure and response. The joint probability for PCP was 0.271 in the worst case and 0.111 in the median case, respectively. Based on the cumulative probability, 5% of aquatic organisms included in the assessment would be affected 21.36% of the time in the worst case and 5.99% of the time in median case, respectively. For the mixtures of CPs, the joint probability were 0.171 in the worst case and 0.503 in median case, respectively and 5% of species would be affected 49.83% of the time for the worst case and 12.72% in the median case, respectively. Risks of effects of the individual CPs, 2,4-DCP and 2,4,6-TCP were deemed to be acceptable with a overlapping probability of < 0.1 with 5% of species being affected less than 4% of the time.     

Effect of chlorine content of chlorophenols on their adsorption by mesoporous SBA-15

Studies on the effect of the chlorine content of chlorophenols (CPs) on their adsorption from aqueous solution by mesoporous SBA-15 are important in understanding the mechanisms of CP adsorption. In this study, three CPs with different degrees of chlorine content (i.e., 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol) were investigated. The effects of parameters such as temperature and solution pH were studied. The results showed that CP adsorption by SBA-15 increased with increasing number of chlorine substituents and depended strongly on the temperature and solution pH. Thermodynamic parameters such as Gibbs free energy change (ΔG⁰), enthalpy change (ΔH⁰) and entropy change (ΔS⁰) were also calculated. By comparison of the adsorption coefficient of CPs with varying physical-chemical properties (size, hydrophobicity and electron density), we propose that hydrophobic interactions between CPs and the SBA-15 surface, as well as electron donor-acceptor (EDA) complexes between oxygen of the siloxane surface of SBA-15 (e^--donor) and the πup-system of the CPs (e^--acceptor), were dominant adsorption mechanisms.     

超声波／纳米铁协同降解氯代苯酚的试验

通过间歇试验对超声波／纳米铁协同降解氯代苯酚（CPs）废水进行了研究，结果表明，超声波／纳米铁协同对CPs的降解率明显高于单纯超声波和单纯纳米铁的降解率；协同体系、单纯超声波和单纯纳米铁降解CPs均符合准一级反应动力学，协同体系的降解速率较单纯超声波提高了5．1-5．6倍，较单纯纳米铁提高了17．7～21倍，并且比它们的几何迭加值高4倍以上；氯代苯酚降解的准一级速率常数和降解率满足以下规律：PEP〉2，4，5-TCP〉2，4-DCP〉3-CP；探讨了混合废水的降解：在混合废水体系中，结构易裂解的优先降解，然后为浓度高的优先降解。     

双信号细胞电化学法检测氯酚类的毒性

以多壁碳纳米管和离子液体复合修饰电极(MWCNTs-IL/GCE)为工作电极,运用线性扫描伏安法(LSV)研究了人乳腺癌(MCF-7)细胞的电化学行为,检测到了2个明显的氧化峰,其氧化峰电位分别为0.725 V和1.038 V.结合4种嘌呤碱基与模型细胞的电化学行为比较与高效液相色谱分析,确定细胞的电化学响应来源分别为细胞质中黄嘌呤与鸟嘌呤、次黄嘌呤与腺嘌呤的电化学氧化.基于2个响应信号峰电流的变化,研究了五氯酚(PCP)、2,4,6-三氯酚(TCP)和2,4-二氯酚(DCP)对MCF-7细胞的毒性效应,根据剂量-效应关系曲线计算半数抑制效应浓度(IC50)值,并与四甲基偶氮唑盐(MTT)比色法进行比较.结果发现,氯酚类污染物对MCF-7细胞活性有明显抑制作用,细胞电化学法与MTT法测得细胞毒性顺序均为:PCPTCPDCP,表明细胞电化学法可以快速、准确地评价氯酚类污染物的细胞毒性.该研究结果可从核苷酸代谢角度为危害化学品的安全无标记、准确客观的毒性评价方法建立提供新思路.     

Formation of aromatic chlorinated compounds catalyzed by copper and iron

This study shows the catalyzing effects of iron and copper on the formation of chlorinated compounds such as chlorobenzenes (ClBzs), chlorophenols (CIPhs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Both total concentrations and congener distributions have been studied. The parameters and conditions varied during the combustion tests were the complete and incomplete combustion and the metal and chlorine addition. The incomplete combustion promoted the formation of organic chlorinated compounds in flue gas particles. Highly chlorinated congeners of PCDD/F were dominant in the flue gas particles, whereas the importance of lower chlorinated congener were increased in the gas phase. In the complete combustion conditions the concentrations of PCDD/Fs increased when the degree of chlorination were high, nevertheless the concentrations of tetra and penta PCDD/Fs were higher in the gas phase than the concentrations in the fly ash particles. Organic chlorine promoted the formation of chlorinated compounds more effectively than inorganic chlorine, which instead promoted the formation of PCDD/Fs in the gas phase, especially with copper catalyst. Different concentration levels of chlorinated compounds were observed in the gas phase and in particles when the chlorine source and combustion conditions were varied from incomplete to optimum conditions. Both copper and iron seem to have a catalytic effect on PCDD/F formation.     

Dechlorination of chlorophenols by zero valent iron impregnated silica

Laboratory studies were conducted to find out the efficacy of uniquely prepared zero valent iron impregnated silica in transforming xenobiotic chlorophenols namely 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol. Continuous mode column experiments were performed to investigate the transformation of chlorophenols by varying pH, column height, flow rate and initial chlorophenol concentration. Reusability study of the zero valent iron impregnated silica was studied as well as the morphological changes and the chemical composition of the catalyst medium were also investigated. Dechlorination kinetic studies were conducted and the order of dechlorination of chlorophenols was found to be 2,4,6-trichlorophenol > 2,4-dichlorophenol > 4-chlorophenol. The optimum pH, column height and flow rate were found to be 7, 20 cm and 0.75 L/hr respectively for all chlorophenols in the reaction duration of 4 hr. Intermediates formed during dechlorination study were identified by gas chromatography-mass spectroscopy analysis. This method was applied to real pulp and paper wastewater and was found satisfactory.