Oxidation of polycyclic aromatic hydrocarbons by horseradish peroxidase in water containing an organic cosolvent

Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants that are toxic, mutagenic, and carcinogenic. We investigated the horseradish peroxidase (HRP)-catalyzed oxidation of PAHs in water containing N,N-dimethylformamide. Four PAHs (anthracene, phenanthrene, pyrene, and fluoranthene) were investigated using single-PAH and mixed-PAH systems. The results provide useful information regarding the preferential oxidation of anthracene over other PAHs regardless of the reaction time, enzyme dosage, and hydrogen peroxide concentration. The removal of PAHs was found to be very strongly correlated with the ionization potential (IP), and much greater PAH oxidation was observed at a lower IP. The oxidation of anthracene was specifically pH- and temperature-dependent, with the optimal pH and temperature being 8.0 and 40 °C, respectively. The redox mediators 1-hydroxybenzotriazole and veratryl alcohol promoted the transformation of anthracene by HRP; 9,10-anthraquinone was the main product detected from the anthracene oxidation system. The results of this study not only provide a better understanding of the oxidation of PAHs by utilizing a plant biocatalyst, but also provide a theoretical basis for establishing the HRP-catalyzed treatment of PAH-contaminated wastewater.     

Understanding the patterns and mechanisms of urban water ecosystem degradation: phytoplankton community structure and water quality in the Qinhuai River, Nanjing City, China

The temporal and spatial distribution characteristics of environmental parameters and the phytoplankton community were investigated in October 2010 and January 2011 in the Qinhuai River, Nanjing, China. Results showed that the water quality in the study area was generally poor, and the main parameters exceeding standards (level V) were nitrogen and phosphorus. The observed average concentrations of the total nitrogen (TN) were 4.90 mg?L^?1 in autumn and 9.29 mg?L^?1 in winter, and those of the total phosphorus (TP) were 0.24 mg?L^?1 in autumn and 0.88 mg?L^?1 in winter, respectively. Thirty-seven species, 30 genera, and four phyla of phytoplankton were detected in the river. Cyanophyta and Bacillariophyta were the dominant phyla in autumn, with average abundance and biomass of 221.5?×?10⁴?cells?L^?1 and 4.41 mg?L^?1, respectively. The dominant population in winter was Bacillariophyta, and the average abundance and biomass were 153.4?×?10⁴?cells?L^?1 and 6.58 mg?L^?1, respectively. The results of canonical correspondence analysis (CCA) between environmental parameters and phytoplankton communities showed that Chlorophyta could tolerate the higher concentrations of the permanganate index, nitrogen, and phosphorus in eutrophic water; Bacillariophyta could adapt well to changing water environments; and the TN/TP ratio had obvious impacts on the distributions of Cyanophyta, Euglenophyta, and some species of Chlorophyta. CCA analyses for autumn and winter data revealed that the main environmental parameters influencing phytoplankton distribution were water temperature, conductivity, and total nitrogen, and the secondary factors were dissolved oxygen, NH₄ ⁺–N, NO₃–N, TN, COD_Mn, TN/TP ratio, and oxidation-reduction potential.     

水生态环境质量评价方法及在黄河流域的应用进展

开展水生态环境质量评价方法研究,建立合适的河流健康评价体系是解决河流健康问题的前提和实现河流健康管理的重要手段。黄河自上而下生态环境现状迥异,水生态环境脆弱,寻求一种或多种适合黄河流域水生态环境质量的评价方法具有重要意义。该文介绍了国内外水生态环境质量评价方法及在黄河流域的应用进展,总结了鱼类生物完整性指数(F-IBI)、底栖无脊椎动物完整指数(B-IBI)、着生藻类生物完整性指数(P-IBI)及水生态环境质量综合评价法的主要指标,以及黄河流域不同区域生物种类的评价指标,分析了各评价方法优缺点及应用范围,并根据目前研究基础评述了黄河流域水生态环境质量评价存在的问题,对黄河流域水生态环境质量评价方法、指示生物的选择及水生态环境质量综合评价法的研究等提出了具体建议。     

Removal of polycyclic aromatic hydrocarbons from aqueous solution on soybean stalk-based carbon

Soybean [ (L.) Merr.] stalk-based carbons were prepared by phosphoric acid activation at different carbonization temperatures. Characteristics of the prepared carbon, including specific surface area, iodine number, and amount of methylene blue sorption, were determined. Experiments on phenanthrene, naphthalene, and acenaphthene, as representatives of polycyclic aromatic hydrocarbons (PAHs), removal from aqueous solution by the prepared carbon were conducted at different levels of carbon addition. The results indicated that the specific surface area, iodine number, and amount of methylene blue sorption increased with an increase of carbonization temperature. The maximum values were observed at 700°C and were 287.63 m g, 508.99 mg g, and 90.14 mg g, respectively. The removal efficiencies of phenanthrene, naphthalene, and acenaphthene tended to increase with increasing carbon amounts and carbonization temperature. The optimal removal performance was obtained under the experimental conditions of carbon concentrations of 0.04 g 32 mL and carbonization temperature of 700°C, and the removal efficiencies of phenanthrene, naphthalene, and acenaphthene were 99.89, 100, and 95.64%, respectively. The performance of the prepared carbon was superior to that of commercial activated carbon. Additionally, for the same carbon concentrations, the removal efficiency of PAHs on prepared carbons followed the order: phenanthrene > naphthalene > acenaphthene. Results obtained from this work provide some insight into the reuse of an agricultural residue, and also provide a new application for the treatment of PAHs in contaminated water utilizing activated carbon prepared from agricultural residues.     

Effects of organic acids on copper and cadmium desorption from contaminated soils

A study was conducted to investigate the effect of organic acids on Cd and Cu desorption from natural contaminated soils (NCS) with permanent contamination by metal smelters and from artificial contaminated soils (ACS) derived from an artificial amendment of Cd to three representative zonal soils in Central China. Results showed that the desorption of Cd in either NCS or ACS, with the increment of tartrate or citrate concentration in desorption solution, can be characterized as a valley-like curve. The presence of tartrate or citrate at a low concentration (< or =0.5 mmol/l) inhibited Cd desorption from these two types of soils, whereas the presence of organic acids at high concentrations (> or =2 mmol/l for citrate and about > or =15 mmol/l for tartrate) apparently promoted Cd desorption. The desorption curve of Cu by tartrate solution with different tartrate concentrations can also be characterized as a valley-like curve, while the desorption of Cu in the presence of citrate was directly enhanced with the increment of citrate concentration. With the enhancement of initial pH value from 2 to 8 in the presence of citrate, Cu desorption ratio decreased at the first stage, then increased, and then decreased again. A valley and a peak sequentially appeared in the Cd or Cu desorption curve with initial pH value increment. Compared with citrate, the desorption ratio of Cd or Cu from NCS or ACS was directly decreased in the presence of tartrate, with the enhancement of the pH value from 2 to 8. Cd or Cu desorption was clearly enhanced when the electrolyte concentration of KNO3 or KCl increased in the presence of 2 mmol/l tartrate. Moreover, a higher desorption ratio of Cd or Cu was shown with KCl electrolyte than with KNO3 electrolyte with the same concentration. Based on these observations, we suggest that bioavailabilities of heavy metal can be promoted with selected suitable types and concentrations of organic acid amendment and reasonable field condition.     

Uptake of polycyclic aromatic hydrocarbons by Trifolium pretense L. from water in the presence of a nonionic surfactant

A greenhouse study examined plant uptake of phenanthrene and pyrene, as representatives of polycyclic aromatic hydrocarbons (PAHs), from an aqueous solution containing a nonionic surfactant Tween 80. The uptake was conducted with 1.0 mg l(-1) phenanthrene and 0.12 mg l(-1) pyrene under a wide range of Tween 80 concentrations (0-105.6 mg l(-1)). Tween 80 at the test concentrations did not show any apparent phytotoxity toward the growth of red clover (Trifolium pretense L.). At concentrations generally lower than 13.2 mg l(-1), Tween 80 enhanced the plant uptake based on the concentrations and PCFs (plant concentration factors) of these two PAHs. When present at higher concentrations, Tween 80 inhibited the uptake of both PAH compounds by the tested plant. The maximal plant uptake was observed at 6.6 mg l(-1) Tween 80, in which PAH concentrations and PCFs were 18-115% higher than those in Tween 80-free controls. The total mass removal (off-take) of phenanthrene and pyrene by root or shoot increased initially and decreased thereafter with the increase in Tween 80 concentrations. Although shoot biomass was evidently larger than root, the off-take was much higher in root than shoot because of the larger root concentrations of these chemicals. Results from this study show promises for the potential efficacy of enhanced phytoremediation in PAH contaminated sites using surfactant amendment.     

接种混合功能细菌降低黑麦草体内菲和芘污染的机理初探

本研究通过批量降解试验,探讨了功能菌株Massilia sp. Pn2和Mycobacterium flavescens 033降解菲和芘的基本动力学过程和规律;重点采用温室盆栽试验,研究了接种混合菌株对黑麦草体内PAHs含量及多酚氧化酶(PPO)和过氧化物酶(POD)活性的影响.结果表明,菌株Pn2和033可以分别利用菲和芘作为碳源和能源进行生长;在30℃、pH=7.0条件下,菌株Pn2和033对100 mg·L~(-1)菲和50 mg·L~(-1)芘的降解率分别高达99.7%和98.3%,降解半衰期分别为0.34 d和0.95 d(R~20.98).与接种灭活混合菌株对比,接种混合菌株Pn2和033显著地降低了黑麦草体内菲和芘的含量和积累量(p0.05),并阻控菲和芘由黑麦草根向茎叶转移.同时,接种混合菌株Pn2和033显著地提高了黑麦草根和茎叶中POD(p0.05)活性,该酶能够促进黑麦草体内超氧自由基的清除,并保护细胞免受PAHs损伤,进而影响PAHs在黑麦草体内的代谢过程.研究结果为阐明接种混合功能菌降低植物体内PAHs污染的作用机理提供了一定的参考价值.     

PAHs pass through the cell wall and partition into organelles of arbuscular mycorrhizal roots of ryegrass

The subcellular process and distribution of polycyclic aromatic hydrocarbons (PAHs) in arbuscular mycorrhizal plants remains to be elucidated. This work used a greenhouse experiment to show that, accompanied by the apoplastic and symplastic water movement through the root, acenaphthene (ACE) as a representative PAH passed through the cell-wall boundary, dissolved in the cell solution, and partition organelles in arbuscular mycorrhizal roots of ryegrass (Lolium multiflorum Lam.). The observed concentrations of ACE in organelles were 0.6 to 4.4 times higher than in the cell walls. The cell wall and organelles were the dominant storage domains for ACE in the root, and the distribution of ACE in cells of mycorrhizal ryegrass roots was, in descending order, cell organelles (40.8-70.8%) > cell wall (19.7-3.8%) cell solution (9.6-20.5%).     

芳香烃菲与基因碱基的非共价结合及驱动机制

疏水芳香烃类化合物能够导致基因遗传性的变化,理解这些化合物对基因污染的前提是必须首先阐明污染物-基因碱基间相互作用及驱动机制.使用等温吸附-光纤固相萃取和定量-构效关系的方法,研究了模型化合物菲与4种基因碱基间的弱相互作用,并揭示了分子驱动机制.结果表明,p H=7.0条件下,腺嘌呤与菲间引力较弱;而鸟嘌呤、胞嘧啶和胸腺嘧啶对菲为分配吸附,引力较强.红外光谱和弱力等值面的分析表明,鸟嘌呤与腺嘌呤分子能够通过2组CN环(CN6环和5环)与菲的2个相互毗邻的苯核同时发生π-π引力作用;而胞嘧啶和胸腺嘧啶仅与菲弧角位置的碳原子通过电子"赠体-受体"发生静电引力作用.当环境体系变成酸性时,腺嘌呤对菲的吸附增强(分配,1/n=1),但胸腺嘧啶对菲的吸附变弱;碱性条件下,由于胞嘧啶和胸腺嘧啶存在羰基取代基,作为电子赠体的含氧嘧啶脱质子化,表面负电性增强,分子平面极化减弱,π电子更易于与菲弧角位的碳原子发生电子"赠体-受体"作用.能量计算的结果表明,对基因碱基作用位点的预测结果可信,属于自发的非共价成因的物理结合.该研究将为深入揭示芳香烃的基因污染提供理论基础,对于防治芳香烃污染、保障生态安全有重要意义.