Construction of MOFs-based nanocomposite membranes for emerging organic contaminants abatement in water

● Application of the MOF-composite membranes in adsorption was discussed. ● Recent application of MOFs-membranes for separation was summarized. ● Separation and degradation for emerging organic contaminants were described. Presence of emerging organic contaminants (EOCs) in water is one of the major threats to water safety. In recent decades, an increasing number of studies have investigated new approaches for their effective removal. Among them, metal-organic frameworks (MOFs) have attracted increasing attention since their first development thanks to their tunable metal nodes and versatile, functional linkers. However, whether or not MOFs have a promising future for practical application in emerging contaminants-containing wastewater is debatable. This review summarizes recent studies about the removal of EOCs using MOFs-related material. The synthesis strategies of both MOF particles and composites, including thin-film nanocomposite and mixed matrix membranes, are critically reviewed, as well as various characterization technologies. The application of the MOF-based composite membranes in adsorption, separation (nanofiltration and ultrafiltration), and catalytic degradation are discussed. Overall, literature survey shows that MOFs-based composite could play a crucial role in eliminating EOCs in the future. In particular, modified membranes that realize separation and degradation might be the most promising materials for such application.     

北京市地下水中高危害污染物筛选

地下水污染物对用水安全和人民健康造成了巨大的威胁.为开展地下水中高危害污染物筛选,改进了传统的危害评价方法,构建了涵盖毒理学优先指数法（Tox Pi）,吸收、分布、代谢、排泄（ADME）性质评估法和二模网络分析法的污染物危害评估-筛选-表征综合体系,针对北京市地下水中非靶检测到的234种疏水性有机污染物（HOCs）开展危害评估和毒害污染物筛选.利用Tox Pi方法筛选出危害潜力排名前20的污染物,在此基础上耦合其ADME性质进一步识别出17种高优先级HOCs,并通过二模网络分析,系统表征了这17种高优先级HOCs作用的基因分子靶点,通过关联性和加权平均度分析最终得到10种高危害的HOCs,并揭示其毒作用类型多集中于内分泌干扰效应、致癌效应以及遗传毒性.研究结果可为我国区域地下水污染物的防治提供技术支撑.     

Sorption of aromatic organophosphate flame retardants on thermally and hydrothermally produced biochars

• TPhP showed faster and higher sorption on biochars than TPPO. • Pyrochars had higher sorption capacity for TPPO than hydrochar. • Hydrophobic interactions dominated TPhP sorption by biochars. • The π-π EDA and electrostatic interactions are involved in sorption. Aromatic organophosphate flame retardant (OPFR) pollutants and biochars are commonly present and continually released into soils due to their increasingly wide applications. In this study, for the first time, the sorption of OPFRs on biochars was investigated. Although triphenyl phosphate (TPhP) and triphenylphosphine oxide (TPPO) have similar molecular structures and sizes, TPhP exhibited much faster and higher sorption than TPPO due to its stronger hydrophobicity, suggesting the dominant role of hydrophobic interactions in TPhP sorption. The π-π electron donor–acceptor (EDA) interactions also contributed to the sorption process, as suggested by the negative correlation between the sorption capacity of the aromatic OPFRs and the aromatic index (H/C atomic ratios) of biochar. Density functional theory calculations further showed that one benzene ring of aromatic OPFRs has no electrons, which may interact with biochar via π-π EDA interactions. The electrostatic attraction between the protonated P = O in OPFRs and the negatively charged biochar was found to occur at pH below 7. This work provides insights into the sorption behaviors and mechanisms of aromatic OPFRs by biochars.     

基于荧光素酶发光检测体系的几种工业污染物综合毒性评价

利用化工污染物能抑制荧光素酶催化发光反应这一特性,对水质中6种化工化合物分别进行毒性测试,建立一种快速检测水质中化工污染物毒性的生物学方法。实验结果表明,对苯二酚、4-氨基酚、苯胺、氯仿、盐酸邻联甲苯胺和硫柳汞的EC50值分别为:5.563、10.225、20.236、38.432、8.827和0.6 mg/L,6种污染物毒性大小依次为:硫柳汞>对苯二酚>盐酸邻联甲苯胺>4-氨基酚>苯胺>氯仿,相关系数>0.95。该方法为进一步研究基于荧光素酶反应体系检测水质中化工污染物综合毒性的生物传感器方法奠定基础。     

城市大气污染物对PEMFC性能的影响

论述了城市空气污染物(即阴极气体杂质)对质子交换膜燃料电池(PEMFC)性能的影响。提出了燃料电池汽车(FCV)进入商业化应用时即将面临的一个急待研究的课题。文中综述了CO、CO2、硫化物、碳氢化合物(HC)、氮氧化物(NOx)、NH3、卤素离子(X-)、酸沉降物以及大气颗粒物等对PEMFC性能的影响,同时对解决阴极气体杂质影响的途径进行了分析。     

黄河水体石油类污染物生物降解模拟实验研究

采用模拟实验的方法研究了自然条件下石油类污染物的生物降解规律.结果表明,向泥沙含量为0g/L或0.5g/L的黄河水样中加入大约10mg/L的石油类污染物,经过一星期左右的驯化期后,石油降解菌菌落水平逐步升高;当石油类污染物的初始浓度为11.64mg/L,温度为20℃时,泥沙含量为0.5g/L的黄河水样中大约85%的石油类污染物在63d内能得到微生物降解;水体中泥沙的含量和石油类污染物的初始浓度均显著影响石油类污染物的生物降解速率,且在不同时段的影响不一;水体中泥沙的存在亦影响到石油类污染物的生物降解动力学.     

Comparing Contaminant Removal Costs for Aquifer Recharge with Wastewater with Water Supply Benefits

The use of waters of impaired quality has been suggested as a means to expand available water resources supply for water‐limited communities. An ongoing concern is the safety of supplies that use wastewater because of the potential for introduction of emerging contaminants such as pharmaceuticals into drinking water supplies. Prior research into contaminants of emerging concerns (CECs) have included a variety of methods, but the only consistent removal is with reverse osmosis (RO) membranes, ultraviolet light (UV), and advanced oxidation processes (AOP). However, few of these prior studies have measurable quantities of these contaminants in the influent wastewater, so determining actual removal percentages is difficult. This project was designed to evaluate the removal of CECs to verify that a 3‐log removal of common constituents was realized. Spike testing was used to compare to prior research and to evaluate whether the project costs were competitive with other forms of reuse or other water supplies. The combination of RO/UV/AOP was effective at obtaining a 3‐log removal of CECs, but the RO and UV/AOP processes alone were not capable of removing all substances. However, despite the extensive treatment, the proposed process was both competitive cost‐wise and met the water quality goals.     

病死猪热解炭化物的特性及其对水中Cu2+的去除

研究了病死猪热解炭化物对水中Cu~(2+)的去除效果,并借助扫描电子显微镜、X射线光谱仪及傅里叶红外光谱仪等分析手段对病死猪热解得到的炭化物理化学性质进行了表征,分析了其微观结构及官能团.结果发现,病死猪热解炭化物内部具有大量孔状结构,表面出现了PO3-4等结构.最后,利用热解得到的炭化物对水中的Cu~(2+)进行处理研究,考察了初始p H值、反应温度、吸附时间等对水中Cu~(2+)去除效果的影响.结果表明,病死猪热解炭化物对水中Cu~(2+)的吸附效果较好,最佳初始p H值为5.0,温度的升高有利于热解炭化物对Cu~(2+)的去除.通过对实验数据进行动力学及吸附等温线分析,发现实验中使用的病死猪热解炭化物对Cu~(2+)的吸附动力学数据符合准二级吸附动力学方程,Langmuir模型能较好地描述Cu~(2+)在猪热解炭化物上的吸附行为.     

Determination of polycyclic aromatic hydrocarbons in dry tea

Twenty-eight different tea samples sold in the United States were evaluated using high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) for their contamination with polycyclic aromatic hydrocarbons (PAHs). Many PAHs exhibit carcinogenic, mutagenic, and teratogenic properties and have been related to several kinds of cancer in man and experimental animals. The presence of PAHs in environmental samples such as water, sediments, and particulate air has been extensively studied, but food samples have received little attention. Eighteen PAHs congeners were analyzed, with percentage recovery higher than 85%. Contamination expressed as the sum of the 18 analyzed PAHs was between 101 and 1337 μg/kg on dry mass and the average contents in all of the 28 examined samples was 300 μg/kg on dry mass. Seven of the congeners were found in all samples with wide ranges of concentrations as follows: fluorene (7–48 μg/kg), anthracene (1–31 μg/kg), pyrene (1–970 μg/kg), benzo(a)anthracene (1–18 μg/kg) chrysene (17–365 μg/kg), benzo(a)pyrene (1–29 μg/kg), and indeno(1,2,3-cd)pyrene (4–119 μg/kg). The two most toxic congeners benzo(a)pyrene and dibenzo(a,h)anthracene were found at high concentrations only in Earl Grey Twinnings, Earl Grey Harney& Sons Fine Teas, and Chai Ultra Spice Black Tea Twinnings. Six PAH congeners are considered as suspected carcinogens (U.S.EPA), formed the basis of the estimation of the toxic equivalent (TEQ), Chai Ultra-Spice Black Tea Twinnings had the highest TEQ (110.9) followed by two grey tea samples, Earl Grey Harney & Sons Fine Tea (57.7) and Earl Grey Twinnings (54.5). Decaffeinated grey teas had the lowest TEQs, decaffeinated Earl Grey Bigelow (9.4) and Green Tea Honey Lemon Decaffeinated Lipton (9.6).     

Kinetics of the sensitized photodegradation of nonylphenol

Nonylphenol (nonyl‐P) belongs to the classification of persistent organic pollutants. In this work we demonstrate that the contaminant suffers photooxygenation when exposed to visible light Eosin‐photosensitized irradiation. The mechanism was identified as a singlet molecular oxygen‐mediated photooxidation. Rate constants for the process, determined by time‐resolved phosphorescence detection of singlet molecular oxygen, are in the range 10⁵‐10⁷ M^‐1 s^‐1, depending on the characteristics of the reaction medium. The photooxidative process is more efficient when performed in highly polar alkaline medium.

The aggregation of nonyl‐P molecules in pure water decreases the rates of sensitized photooxidation of nonyl‐P and also those of polychlorophenolic contaminants, employed as photooxidizable model compounds, when photolyzed in the presence of nonylphenol. These results are discussed in terms of a micellar effect.