从苯酐生产废水中萃取富马酸

用三辛癸胺和三辛胺为萃取剂,在无稀释剂的条件下,对苯酐生产废水中的富马酸进行了络合萃取研究。研究结果表明,萃取剂的负荷量与相比呈递减的幂函数关系,三辛癸胺比三辛胺的络合酸度大;温度对萃取处理效果有明显影响,温度为10～40℃时,萃取剂的负荷量随着温度的升高而增加,但温度过高易造成乳化,最佳操作温度为30～40℃;用氢氧化钠溶液再生萃取剂,最佳反萃操作条件为:振荡时间60s、相比(水/油,体积比)2、温度60℃、碱液质量浓度12g/L;萃取剂9次循环萃取和再生使用过程中,萃取率稳定在71 8%±1 7%,再生效率稳定在94 3%±1 9%,9次循环后萃取剂的损失量为4%;从每吨废水中可回收富马酸4 8kg,可获益24元。     

Distribution of PAEs in the middle and lower reaches of the Yellow River, China

Samples of water, sediment and suspended particulates were collected from 13 sites in the middle and lower reaches of the Yellow River in China. Phthalic acid esters (PAEs) concentrations in different phases of each sample were determined by Gas Chromatogram GC-FID. The results are shown as follows: (1) In the Xiao Langdi–Dongming Bridge section, PAEs concentrations in water phase from the main river ranged from 3.99 × 10⁻³ to 45.45 × 10⁻³ mg/L, which were similar to those from other rivers in the world. The PAEs levels in the tributaries of the Yellow River were much higher than those of the main river. (2) In the studied branches, the concentration of PAEs in sediment for Luoyang Petrochemical Channel (331.70 mg/Kg) was the highest. The concentrations of PAEs in sediment phase of the main river were 30.52 to 85.16 mg/Kg, which were much higher than those from other rivers in the world. In the main river, the concentration level of PAEs on suspended solid phases reached 94.22 mg/Kg, and it reached 691.23 mg/Kg in the Yiluo River – one tributary of the Yellow River. (3) Whether in the sediment or on the suspended solid phases, there was no significant correlation between the contents of PAEs and TOC or particle size of the solid phase; and the calculated Koc of Di (2-Ethylhexyl) Phthalate (DEHP) in the river were much less than the theoretical value, which inferred that PAEs were not on the equilibrium between water and suspended solid phases/sediment. (4) Among the measured PAEs compounds, the proportions of DEHP and di-n-butyl phthalate (DBP) were much higher than the others. The concentrations of DEHP exceeded the Quality Standard in all the main river and tributary stations except those in the Mengjin and Jiaogong Bridge of the main river. This indicates that more attention should be paid to pollution control and further assessment in understanding risks associated with human health.     

寡营养条件下超微细菌对邻苯二甲酸酯的生物降解

从松花江干流下游的底泥中分离并筛选出能够在寡营养条件下降解邻苯二甲酸酯(PAEs)的超微细菌菌群,研究了该菌群对4种PAE——邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸(2-乙基己)酯(DEHP)的降解能力.结果表明,4种PAE均可作为菌群的唯一碳源,菌群对4种PAE有不同的比生长速率和最大降解速率,比生长速率从大到小为DMP(0.176h-1)、DBP(0.158 5 h-1)、DEP(0.1409 h-1)、DEHP(0.107 6 h-1),最大降解速率从大到小为DEP(0.098 mg/(L·h))、DBP(0.062 7 mg/(L·h))、DMP(0.061 mg/(L·h))、DEHP(0.051 5 mg/(L·h)).利用极度稀释法从该菌群中分离出1株典型寡营养超微细菌菌株,命名为PAE-UM,根据16S rDNA序列系统发育分析,鉴定为丛毛单胞菌属(Curvibacter sp.).     

In vitro assessment of thyroid hormone receptor activity of four organophosphate esters

Previous animal experiments have implied that organophosphate esters(OPEs) have a disruption effect on the thyroid endocrine system. However, knowledge of the toxicological mechanism remains limited. In this study, the activities of four OPEs have been characterized against the thyroid hormone(TH) nuclear receptor(TR) using two in vitro models, with the aim of evaluating their toxicity mechanisms towards the TR. The results of a TH-dependent cell proliferation assay showed that tris(2-chloro-1-(chloromethyl)ethyl)phosphate(TDCPP) could induce cell growth, while the other three OPEs had no effect. The results of a luciferase reporter gene assay revealed that all four of the OPEs tested in the current study showed agonistic activity towards TRβ, with TDCPP being the most potent one. Moreover, molecular docking revealed that all the tested OPEs could fit into the ligand binding pocket of TRβ, with TDCPP binding more effectively than the other three OPEs. Taken together, these data suggest that OPEs might disrupt the thyroid endocrine system via a mechanism involving the activation of TR.     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg^?1) and DEHP (100 mg kg^?1) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1–0.45 μm to 500–2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

In-field variation in 2,4-D mineralization in relation to sorption and soil microbial communities

This study was undertaken to assess 2,4-D mineralization in an undulating cultivated field, along a sloping transect (458 m to 442 m above sea level), as a function of soil type, soil microbial communities and the sorption of 2,4-D to soil. The 2,4-D soil sorption coefficient (Kd) ranged from 1.81 to 4.28 L kg^?1, the 2,4-D first-order mineralization rate constant (k) ranged from 0.04 to 0.13 day^?1 and the total amount of 2,4-D mineralized at 130 days (M₁₃₀) ranged from 24 to 39%. Both k and M₁₃₀ were significantly negatively associated (or correlated) with soil organic carbon content (SOC) and Kd. Both k and M₁₃₀ were significantly associated with two fatty-acid methyl esters (FAME), i17:1 and a18, but not with twenty-two other individual FAME. Imperfectly drained soils (Gleyed Dark Grey Chernozems) in lower-slopes showed significantly lesser 2,4-D mineralization relative to well-drained soils (Orthic Dark Grey Chernozems) in mid- and upper-slopes. Well-drained soils had a greater potential for 2,4-D mineralization because of greater abundance and diversity of the microbial community in these soils. However, the reduced 2,4-D mineralization in imperfectly drained soils was predominantly because of their greater SOC and increased 2,4-D sorption, limiting the bioavailability of 2,4-D for degradation. The wide range of 2,4-D sorption and mineralization in this undulating cultivated field is comparable in magnitude and extent to the variability of 2,4-D sorption and mineralization observed at a regional scale in Manitoba. As such, in-field variations in SOC and the abundance and diversity of microbial communities are determining factors that require greater attention in assessing the risk of movement of 2,4-D by runoff, eroded soil and leaching.     

辽河干流河岸带土壤有机磷酸酯污染特征研究

本研究分析了辽河干流河岸带土壤中有机磷酸酯（OPEs）的含量水平,阐明了其空间分布特征,探讨了OPEs含量与土壤总有机碳（TOC）的关系,评估了OPEs造成的潜在生态风险.结果表明,13种OPEs在辽河干流河岸带土壤中的总浓度范围为19.6~89.4ng/g,平均浓度为44.2ng/g,处于国内外研究的较低水平;河岸带土壤中OPEs的含量总体上表现为上游较低、中下游较高,辽河上游主要由烷基OPEs和TPPO（Triphenylphosphine oxide）组成,辽河中下游主要是烷基OPEs;辽河干流河岸带土壤中OPEs的含量与土壤TOC含量没有相关性,这与OPEs的疏水特性有关;各OPEs单体的危害熵以及12种OPEs的总危害熵均低于1,表明辽河干流河岸带土壤中OPEs造成的生态风险较小.     

长江武汉段丰水期水体和沉积物中多环芳烃及邻苯二甲酸酯类有机污染物污染特征及来源分析

持久性有机污染物(POPs)在我国地表水和沉积物等环境介质中被广泛检出,对生态环境和人类健康具有潜在的风险.针对现阶段长江经济带核心区域(武汉段)POPs的污染状况信息严重缺乏的问题,本文以使用量较大且环境中检出高的PAHs和PAEs为研究对象,通过对2016年长江武汉段干流15个采样点丰水期水体和沉积物中16种PAHs和6种PAEs污染物含量水平、分布特征和污染来源的系统分析.结果表明,长江武汉段2016年丰水期水体和沉积物中ΣPAHs浓度分别为20.8~90.4 ng·L~(-1)(均值40.7 ng·L~(-1))和46.1~424.0 ng·g~(-1)(均值191.8 ng·g~(-1)),ΣPAEs浓度分别为280.9~779.0 ng·L~(-1)(均值538.6 ng·L~(-1))和1 346.2~7 641.1 ng·g~(-1)(均值3 699.5 ng·g~(-1)).PAHs和PAEs含量均低于国家地表水环境质量标准规定的限值,污染程度小.长江武汉段水体中PAHs以2~3环为主,沉积物中PAHs以2~3环和4环为主,水体和沉积物中PAEs以DEHP和DBP为主.基于比率及主成分分析,长江武汉段水体与沉积物中PAHs主要的来源为煤和生物质燃烧,以及石油来源;水体和沉积物中PAEs的主要来源于塑料和重化工工业,以及生活垃圾.水体及沉积物中两类典型POPs(PAHs和PAEs)对人类健康会产生潜在有害影响,需加强监控.研究成果可为长江(武汉段)环境保护提供基础数据和技术支撑.     

城市典型不透水下垫面径流中邻苯二甲酸酯的污染特征

在我国属于优先控制污染物的邻苯二甲酸酯(PAEs)应用依然广泛,径流中的PAEs对受纳水体的污染值得高度关注.对上海典型的城市不透水下垫面路面及屋面降雨径流中6种优先控制PAEs的质量浓度进行监测,评价城市不透水下垫面径流中PAEs的污染特征.结果表明,上海市路面及屋面径流中Σ_6PAEs的EMC平均值分别为170. 64μg·L~(-1)和40. 92μg·L~(-1),与国外城市相比污染严重,DEHP为主要PAEs污染物.对不同类型水样中PAEs含量差异的显著性分析发现,不同下垫面径流中低分子量(LMW) PAEs浓度不存在显著性差异,路面径流中高分子量(HMW) PAEs浓度显著高于屋面径流及雨水(P 0. 01),道路交通是造成下垫面径流PAEs污染的重要因素.路面径流中PAEs、TSS及COD浓度随降雨历时的变化特征表明,PAEs的变化趋势与TSS及COD相同,初期径流浓度较高,存在初期冲刷效应.不透水下垫面径流中PAEs浓度及其影响因素的相关分析表明,屋面径流中Σ_6PAEs浓度与降雨强度呈负相关,与TSS呈正相关.路面径流中Σ_6PAEs浓度与降雨量、降雨强度呈负相关,与前期晴天数、TSS、COD呈正相关.下垫面径流中Σ_6PAEs浓度与表面累积的颗粒物含量有关. DEHP、DBP为我国《地表水环境质量标准》控制污染物,路面及屋面径流中DEHP的浓度超过8μg·L~(-1)的标准值分别达到32、7倍,路面径流中DBP浓度在多数降雨事件中超过标准值3μg·L~(-1),屋面径流中DBP浓度在多数降雨事件中低于标准值,下垫面径流直接排放对受纳水体,特别是饮用水水源地存在威胁.     

Distribution and sources of polycyclic aromatic hydrocarbons and phthalic acid esters in water and surface sediment from the Three Gorges Reservoir

After the impoundment of the Three Gorges Reservoir(TGR), the hydrological situation of the reservoir has changed greatly. The concentration and distribution of typical persistent organic pollutants in water and sediment have also changed accordingly. In this study, the concentration, distribution and potential sources of 16 polycyclic aromatic hydrocarbons(PAHs) and 6 phthalic acid esters(PAEs) during the water drawdown and impoundment periods were investigated in water and sediment from the TGR. According to our results, PAHs and PAEs showed temporal and spatial variations. The mean ΣPAH and ΣPAE concentrations in water and sediment were both higher during the water impoundment period than during the water drawdown period. The water samples from the main stream showed larger ΣPAH concentration fluctuations than those from tributaries. Both the PAH and PAE concentrations meet the Chinese national water environmental quality standard(GB 3838-2002). PAH monomers with 2–3 rings and 4 rings were dominant in water, and 4-ring and 5–6-ring PAHs were dominant in sediment. Di-n-butyl phthalate(DBP) and di-2-ethylhexyl phthalate(DEHP)were the dominant PAE pollutants in the TGR. DBP and DEHP had the highest concentrations in water and sediment, respectively. The main source of PAHs in water from the TGR was petroleum and emissions from coal and biomass combustion, whereas the main sources of PAHs in sediments included coal and biomass combustion, petroleum, and petroleum combustion. The main source of PAEs in water was domestic waste, and the plastics and heavy chemical industries were the main sources of PAEs in sediment.