Fe(III)–EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe²⁺ under UV irradiation of the iron complex and the photochemical formation of HO^? from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H₂O₂ concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe²⁺ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H₂O₂ concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.     

铜、镉联合胁迫对羊角月牙藻的自由基氧化损伤影响研究

分析了铜和镉联合胁迫对羊角月牙藻(Selenastrum capricornutum)的影响,运用国内应用较少的新型技术——叶绿素荧光技术检测了胁迫下微藻的最大光能转化效率(Fv/Fm)受到的影响,并尝试通过膜脂过氧化损伤产物丙二醛(MDA)和其他指标在胁迫下的变化,对铜、镉联合胁迫机制进行初步探究。结果表明:(1)羊角月牙藻在铜、镉联合胁迫下生长受到抑制,表现出明显的浓度-效应关系。铜、镉的联合胁迫的相加指数为-1.63,表现为典型的拮抗作用。(2)通过叶绿素荧光技术的应用,探明Fv/Fm随毒性浓度的变化表现为浓度-效应关系,毒性浓度越大,羊角月牙藻的Fv/Fm越低,但在低毒性浓度刺激时随胁迫时间延长有回升迹象。(3)随毒性浓度的增加,羊角月牙藻的MDA增加,表现为显著的浓度-效应关系;可溶性蛋白质大体呈先升后降的趋势。(4)铜、镉联合胁迫下,MDA与羊角月牙藻生物量、Fv/Fm呈显著负相关。脂质过氧化是导致生物量下降和Fv/Fm受抑制的原因之一。(5)在微藻体内铜、镉发生拮抗作用的机制也可能与重金属的脂质过氧化作用由于拮抗受到抑制有关。     

钱塘江引水降氮示范工程的构建和运行研究

针对杭州西湖钱塘江引水低碳高氮的特点,提出以改性水草塘—复合垂直流人工湿地(IVCW)相耦合的生物—生态工艺进行引水处理,对该引水降氮示范工程的构建和运行效果进行了跟踪研究。结果表明,整个稳定运行期间(2012年7月19日至11月19日),耦合工艺对COD、TN、硝酸盐氮、TP的平均去除率分别为52.27%、52.49%、53.69%、52.79%,系统出水满足《地表水环境质量标准》(GB 3838—2002)Ⅳ标准;改性水草塘和IVCW单元作为耦合工艺的两个重要组成部分,在脱氮、除磷方面优势互补,从而共同保证出水水质的稳定;在改性水草塘单元,温度与COD的去除效果呈负相关关系,进水C/N与TN去除效果呈正相关关系;而在IVCW单元,温度与COD、TN的去除效果均呈线性正相关关系,进水C/N与两者的去除效果也呈正相关关系,且对COD的影响要大于对TN的影响。     

农业源水污染物削减技术探讨

农业面源污染是水体中COD、氮、磷等指标的主要来源。它包括农药化肥施用、畜禽养殖和农村生活污水排放。对农业源水污染物进行削减是实现污染物总量控制的重要手段。通过详细总结国内外现有农业源水污染物削减技术方法,分析对比其优缺点和实用性,筛选出适用于不同农业污染来源的污水处理技术。结果表明,畜禽养殖废水的适宜处理技术有厌氧/缺氧/好氧(A/A/O)、序批式活性污泥法(SBR)、膜生物反应器(MBR)、升流式厌氧污泥床(UASB)、厌氧沼气池;农地施肥污水的适宜处理技术有SBR、MBR、UASB;农村生活污水的适宜处理技术有厌氧沼气池、生物滴滤池、人工湿地、稳定塘。     

中国工业水污染及其成因的de Bruyn模型分析

选取废水、挥发酚、氰化物、COD、石油类和氨氮为中国工业水污染指标,利用分解分析方法将2004—2010年间的污染变化分解为规模效应、结构效应、污染治理效应、清洁技术效应和广义技术效应。结果显示,这5类效应的平均作用强度分别为2.08%、3.04%、15.61%、17.37%和32.88%,其中规模效应和广义技术效应是影响工业水污染的主导效应。各类效应对不同污染物的作用方向并不完全一致,规模效应促进污染物排放量的增加;结构效应以加重污染为主,污染治理效应和清洁技术效应以减轻污染为主;广义技术效应的平均作用强度和负向作用概率均最大,是现阶段中国工业水污染控制最为有效的手段。     

Comparison of lignin peroxidase and horseradish peroxidase for catalyzing the removal of nonylphenol from water

Concentrations of aqueous-phase nonylphenol (NP), a well-known endocrine-disrupting chemical, are shown to be reduced effectively via reaction with lignin peroxidase (LiP) or horseradish peroxidase (HRP) and hydrogen peroxide. We systematically assessed their reaction efficiencies at varying conditions, and the results have confirmed that the catalytic performance of LiP toward NP was more efficient than that of HRP under experimental conditions. Mass spectrum analysis demonstrated that polymerization through radical–radical coupling mechanism was the pathway leading to NP transformation. Our molecular modeling with the assistance of ab initio suggested the coupling of NP likely proceeded via covalent bonding between two NP radicals at their unsubstituted carbons in phenolic rings. Data from acute immobilization tests with Daphnia confirm that NP toxicity is effectively eliminated by LiP/HRP-catalyzed NP removal. The findings in this study provide useful information for understanding LiP/HRP-mediated NP reactions, and comparison of enzymatic performance can present their advantages for up-scale applications in water/wastewater treatment.     

Enhanced degradation of ortho-nitrochlorobenzene by the combined system of zero-valent iron reduction and persulfate oxidation in soils

ortho-Nitrochlorobenzene (o-NCB) in soil poses significant health risks to human because of its persistence and high toxicity. The removal of o-NCB by both zero-valent iron (ZVI) and chemical oxidation (persulfate) was investigated by batch experiments. The o-NCB removal rate increases significantly from 15.1 to 97.3 % with an increase of iron dosage from 0.1 to 1.0 mmol g^?1. The o-NCB removal rate increases with the decrease of the initial solution pH, and a removal efficiency of 90.3 % is obtained at an initial pH value of 6.8 in this combined system. It is found that temperature and soil moisture could also increase the o-NCB removal rate. The o-NCB degradation rate increases from 83.9 to 96.2 % and from 41.5 to 82.4 % with an increase of temperature (15 to 35 °C) and soil moisture (0.25 to 1.50 mL g^?1), respectively. Compared to the persulfate oxidation system and ZVI system, the persulfate–iron system shows high o-NCB removal capacity. o-NCB removal rates of 41.5 and 62.4 % are obtained in both the persulfate oxidation system and the ZVI system, while the removal rate of o-NCB is 90.3 % in the persulfate–iron system.     

Tree bark as a passive air sampler to indicate atmospheric polybrominated diphenyl ethers (PBDEs) in southeastern China

The different barks were sampled to discuss the influence of the tree species, trunk circumference, and bark thickness on the accumulation processes of polybrominated diphenyl ethers (PBDEs) from air into the bark. The results of different PBDE concentrations indicated that barks with a thickness of 0–3 mm collected from weeping willow, Camphor tree, and Masson pine, the trunk circumferences of which were 100 to 150 cm, were better PBDEs passive samplers. Furthermore, tree bark and the corresponding air samples were collected at Anji (AJ), Hangzhou (HZ), Shanghai (SH), and Wenling (WL) to investigate the relationship between the PBDE concentrations in bark and those in air. In addition, the significant correlation (r ²?=?0.906; P?<?0.05) indicated that atmospheric PBDEs were the principle source for the accumulation of PBDEs in the barks. In this study, the log K _BA (bark–air partition coefficient) of individual PBDE congeners at the four sites were in the range from 5.69 to 6.79. Finally, the total PBDE concentration in WL was 5 to 20 times higher than in the other three cities. The result indicated that crude household workshops contributed a heavy amount of PBDEs pollution to the environment, which had been verified by the spatial distribution of PBDEs levels in barks collected at Wenling (range, 26.53–1317.68 ng/g dw). The good correlation between the PBDE concentrations in the barks and the air samples and the variations of the PBDE concentrations in tree barks collected from different sites reflected that the bark could be used as a passive sampler to indicate the atmospheric PBDEs.     

CuO/γ-Al2O3类Fenton试剂降解丁基黄药

CuO/γ-Al2O3类Fenton试剂是降解丁基黄药的优良试剂。该试剂与传统的Fenton试剂相比,提高了反应的pH值,可在较高pH(4~5)条件下反应,而传统的Fenton试剂的适宜pH值一般在3以下。采用单因素实验和正交实验相结合的方法研究了pH、催化剂投加量、过氧化氢投加量以及反应时间对丁基黄药降解效果的影响,并对催化剂的使用寿命进行了探讨。研究结果表明,反应的最佳条件为:pH为4~5,催化剂投加量为6 g/L,过氧化氢用量为30 mg/L,反应30min。在此反应条件下,丁基黄药的降解率达98%以上;影响丁基黄药降解效果的因素大小顺序为:pH>反应时间>H2O2用量>催化剂投加量,其中pH对CuO/γ-Al2O3类Fenton试剂降解丁基黄药的影响最为显著。