光催化降解对抗生素藻类毒性效应影响研究进展

抗生素滥用带来环境中残留抗生素及其抗性基因的问题,近年来已成为全球关注的热点问题.光催化氧化技术是当前研究领域广泛采用的有效降解水环境中残留抗生素的热门方法;但光催化氧化无法使水环境中抗生素完全矿化,存在生态风险,探明光催化降解抗生素对其藻类毒理效应影响及内在机制,对研发高效、安全的光催化技术具有重要意义.本文在总结水...     

基于液相色谱法分析水环境中大环内酯类抗生素污染的研究进展

大环内酯抗生素广泛使用,在水环境中的残留越来越引起世界关注.本文综述了国内外基于液相色谱技术分析水环境中大环内酯的方法,比较不同预处理法以及分析方法的灵敏度和检出限.固相萃取法可以同时富集和净化,消耗试剂少,方便,野外操作可行,是理想的预处理技术.液相色谱串联质谱技术选择性好、特异性高、灵敏度高,可以检测浓度低于ng.L-1的目标物,是一种可靠理想的分析方法.最后对大环内酯分析研究进行了展望.     

虚拟模板分子印迹微球的制备及其对水中微囊藻毒素的吸附性能

本文以L-精氨酸为模板、丙烯酰胺(AM)为单体,N,N'-亚甲基双丙烯酰胺(MBA)为交联剂以及偶氮二异丁腈(AIBN)为引发剂,采用沉淀聚合法制备了微囊藻毒素分子印迹聚合物.采用量子化学密度泛函理论(DFT)模拟计算以确定模板分子(L-精氨酸)与功能单体(AM)的印迹比例,通过扫描电镜和红外吸收光谱对分子印迹聚合物微球进行表征,并利用平衡吸附实验考察了印迹微球对微囊藻毒素的吸附性能.结果表明,本虚拟模板法制备的印迹微球对MC-LR的吸附符合Langmuir模型,线性拟合得出MIPs的线性回归方程为Ce/Q=3.026×10-4+0.125(r=0.991),由此推导出对MC-LR的最大表观吸附量为80.3μg·g~(-1).实验还表明,印迹聚合物对MC-LR和MC-RR的吸附比非印迹聚合物具有更好的选择性,MIPs对MC-LR的初始吸附速率为58.8μg·g~(-1)·min~(-1),大于非印迹聚合物的初始吸附速率19.6μg·g~(-1)·min~(-1),具有选择性富集水体中MC-LR和MC-RR等微囊藻毒素的应用前景.     

中空硅球表面分子印迹温敏聚合物吸附溶液中的四环素

本文开展了中空温敏分子印迹聚合物(HTMIPs)吸附溶液中四环素(TC)的实验研究,采用牺牲酵母模板法制备的中空硅球作为基质材料,以TC为模板分子,N-异丙基丙烯酰胺为温敏单体,通过沉淀聚合法合成了中空温敏型TC分子的印迹聚合物,利用FT-IR和SEM等方法对HTMIPs的理化性能进行表征,通过静态吸附实验考察HTMIPs对TC的吸附性能.结果表明,HTMIPs对模板分子TC在pH值为5.0时,35℃条件下吸附容量最大,约为72.05μmol·g~(-1),表明该印迹吸附剂对TC具有良好的亲和性和选择吸附性.HTMIPs的等温吸附结果与Freundlich模型拟合更好,动力学吸附结果更符合准二级动力学吸附模型,表明HTMIPs对于TC分子的吸附主要是在非均匀表面共价键作用下的结果.同时,HTMIPs表现出良好的可重复利用性,5次重复吸附-解吸附后吸附量损失约6.64%.因此,所制备的中空温敏印迹聚合物在吸附分离环境水体中的抗生素方面有良好的实际应用前景.     

疏水缔合型有机高分子聚合物对水体中多环芳烃的富集性能

以芘分子为分子荧光探针测定了疏水缔合有机高分子聚合物HAP对多环芳烃类化合物的富集性能.实验证明,疏水缔合聚合物对芘具有良好的胶束增溶和富集作用,且随着聚合物浓度增大、疏水嵌段结构分布均匀适度,富集能力逐渐增强.絮凝实验证明,疏水缔合聚合物对多环芳烃的富集性能可作为有效的辅助手段,实现对水体中微量有机污染物的去除.     

类特异性分子印迹聚合物微球的制备及其吸附性能研究

采用分子印迹技术,以氯磺隆(CS)为模板分子,甲基丙烯酸乙二胺乙酯(DEMEA)为功能单体,三羟甲基丙烷三甲基丙烯酸酯(TRIM)为交联剂,偶氮二异丁腈(AIBN)为引发剂,通过沉淀聚合法合成了类特异性印迹聚合物微球(MIPM),并利用HPIJC、SEM等手段对微球的吸附性能进行了表征.结果表明,聚合物微球对印迹分子及...     

诺氟沙星分子印迹共混膜的制备及应用

本文以诺氟沙星为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用本体聚合法制备分子印迹聚合物,与聚砜铸膜液混合,制备出可以在低压力下对诺氟沙星有特异性截留作用的分子印迹共混膜.采用红外光谱对共混膜的结构进行表征,利用扫描电子显微镜对共混膜微观形貌进行表征.研究了聚合物的质量分数对共混膜水通量和截留率的...     

分子印迹固相萃取技术及其在环境中多环芳烃测定中的应用进展

多环芳烃（Polycyclic aromatic hydrocarbons, PAHs）具有致癌性、致突变性和致畸性等毒性作用,被列为需优先控制的有机污染物.由于持久性和生物蓄积性,环境中存在的PAHs会对人体健康产生不利的影响.本文简要阐述了利用分子印迹聚合物作为吸附剂的固相萃取技术的原理及工作模式,着重介绍了其在环境中多环芳烃检测中的应用进展,并分析了当前存在的问题与应用前景.     

氯霉素分子印迹聚合物的合成及其在固相萃取中的应用

研究了氯霉素(CAP)分子印迹聚合物(MIP)的合成及其在固相萃取(SPE)中的应用,并对保留机理进行了探讨,结果显示,MIP应用到固相萃取过程中对CAP有较好的保留性能.     

双模板分子印迹微球的制备及其在海水溶液中的分子识别行为研究

以萘和蒽为双模板分子,以甲基丙烯酸为功能单体、二甲基丙烯酸乙二醇酯为交联剂、聚乙烯醇（PVA）为分散剂,通过悬浮聚合制备了双模板分子印迹微球.采用紫外光谱法分析了双模板分子印迹效应产生的机制,用静态吸附实验考察了印迹微球对海水中2—3环多环芳烃的吸附选择性,并以分子印迹-分散固相微萃取法分析了海水中2—3环的多环芳烃.结果表明,双模板-功能单体分子间的多位点协同作用,优化了分子印迹材料的印迹孔穴,提高了双模板分子印迹微球的分子识别能力;所制备的双模板分子印迹材料使用3次后其选择识别性能未显著降低,显示出其富集与分离海水样品中2—3环多环芳烃的良好前景.     

Occurrence and fate of antibiotics in advanced wastewater treatment facilities and receiving rivers in Beijing,China

The occurrence and removal of 13 antibiotics were investigated in five wastewater treatment plants （WWTPs） with advanced wastewater treatment processes in Beijing, China. Most of the target antibiotics were detected in the secondary and tertiary effluents, with the concentrations of 4.8-1106.0 and 0.3-505.0ng·L^-1. Fluoroquinolone antibiotics showed relatively high concentrations in all samples （782-1814ng·L^-1）. Different tertiary treatment processes showed discrepant antibiotics removal performances. Ozonation process was found more effective in removing target antibiotics compared to the coagulation-flocculation-sedimentation process and sand filtration process. Investigation of the target antibiotics in three typical urban rivers in Beijing was carried out to understand antibiotics occurrence in surface water environment. Eight antibiotics were detected in the studied rivers, with highest concentration of antibiotics in the fiver which was mainly replenished by reclaimed water. This study showed the necessity of employing more effective advanced treatment facilities to further reduce the discharge amount of antibiotics.     

深圳铁岗水库水体中抗生素污染特征分析及生态风险评价

近年来水体中不断被检出的抗生素逐渐成为研究者关注的焦点。许多国家的河流、湖泊、地下水中均检出了抗生素残留。目前国内外关于抗生素污染特征的研究主要集中在河流、河口湾和污水处理厂等水环境中,对于抗生素在饮用水源地水体中的污染状况研究极少。利用高效液相色谱-串联质谱技术（HPLC-MS/MS）检测分析了5类典型抗生素在深圳铁岗饮用水源地型水库中的污染特征。结果表明,9种目标抗生素中,有8种在铁岗水库水体中被检出,浓度范围为1.1～203 ng·L^-1,其中,林肯霉素检出浓度最高,红霉素次之,阿莫西林未检出;入库支流抗生素污染程度普遍高于铁岗水库,其中大官陂河中抗生素质量浓度最高（277.0 ng·L^-1）,九围河次之（196.4 ng·L^-1）;枯水期抗生素浓度高于丰水期。采用风险商值法初步评价的结果表明,枯水期时料坑水中红霉素、大官陂河中磺胺甲噁唑和林肯霉素,以及丰水期时九围河中林肯霉素的生态风险商（RQ）均大于1,对生态环境具有高风险;风险简单叠加模型计算结果显示,枯水期时料坑水、塘头河、大官陂河以及丰水期时九围河中抗生素的联合毒性风险商（RQsum）均大于1,对生态环境可能会产生较高的风险。     

Occurrence and fate of typical antibiotics in wastewater treatment plants in Harbin,North-east China

• The concentration distributions and removals of 12 antibiotics were investigated. • Macrolides and fluoroquinolones presented relatively higher concentrations. • The removal of antibiotics did not differ among the different treatment processes. As a new pollutant, antibiotics in the environment and their removal in wastewater treatment plants (WWTPs) have gained considerable attention. However, few studies investigated antibiotics in the north-eastern areas of China. By employing high-performance liquid chromatography-tandem mass spectrometry, the concentration distribution and removal of 12 antibiotics belonging to four types (cephalosporins, sulfonamides, fluoroquinolones, and macrolides) were investigated in influents and effluents as well as the removal efficiencies of four typical treatment processes in 18 wastewater treatment plants of Harbin City, north-eastern China. Macrolides and fluoroquinolones presented relatively higher detection concentrations and rates both in the water and in the sludge phases. Sulfonamides and cephalosporins displayed higher detection concentrations in the water phase. The representative antibiotics in influents and effluents included ROX, NOR, OFL, SMX, AZI, and CLA, with detection rates above 95%. The detection rates of the other six antibiotics exceeded 30%. In the sludge, the other five antibiotics, except SMX, presented relatively higher detection concentrations and rates, with detection rates greater than 95%. For cephalosporin, the detection rates of CTX and CFM in the sludge were 0. The removal efficiencies for the 12 antibiotics differed greatly, with average values ranging from 30% to 80% and the highest values for cephalosporin. The removal of antibiotics did not differ significantly among the four different treatment processes.     

山阴地区高砷饮用水处理技术

通过对山西省山阴县高砷地下水分布和污染程度的实地调查,对高砷水环境中砷的形态及富集转化规律进行了研究,并在此基础上形成一套以曝气氧化和加药(加入FeCl2和FeCl3的混合物作为混凝剂)过滤工艺为基础的联合水处理方法.结果表明,在山阴县砷污染严重的地段,地下水的氧化还原电位Eh为-50～142 mV,pH值为8.28～8.73,这种Eh下降、pH升高的地下环境给高砷地下水的形成创造了条件.当地下水中ρ(硫化氢)<140μg·L-1时,用功率为5 W的松宝SB-648双头氧气泵连续曝气1.5 h即可达到基本去除的效果.以25 m深处地下水为例,其ρ(As)为275 μg·L-1,待硫化氢去除后在水中加入摩尔比n(FeCl2):n(FeCl3)=1:1的混合物,连续曝气5 h,水体中60%以上的As(Ⅲ)可转变为As(V).经投加药品和曝气氧化处理后的地下水若能及时通过简易过滤装置,过滤后的水体中ρ(As)仅为5～8 μg·L-1,达到GB 5749-2006<活饮用水卫生标准>,且过滤后的水体中ρ(Fe)为0.03 mg·L-1,远小于GB/T 14848-93<地下水水质标准>规定的Ⅰ类标准.该水处理方法可快速有效地将As(Ⅲ)转化为As(V),并使As(V)与混凝剂发生吸附共沉淀反应,从而达到高效除砷的效果.过滤过程则可以防止氢氧化物胶体与砷酸盐形成的絮体二次进入环境,同时进一步降低水体中铁离子含量.该方法适用于我国广大高砷水地区家庭分散式供水的处理.     

南方典型水源地及水产养殖区抗生素的复合污染特征及生态风险

抗生素作为生长促进剂和疾病预防控制药物在水产养殖领域得到广泛应用,目前在许多环境水体中检测到不同类型的抗生素。环境中抗生素的残留问题也是目前环境研究的热点问题之一。本研究选择南方某市8个水源地和5个典型水产养殖区作为研究对象,采用固相萃取、高效液相色谱串联三重四级杆质谱联用仪方法,调查了32种常用抗生素在水体中的含量水平和空间分布特征,揭示了抗生素的来源,并对其生态风险进行了评价。水源地共检出12种抗生素,浓度范围为0.12～44.6 ng·L~(-1),以磺胺甲噁唑含量最高;水产养殖区检出14种抗生素,浓度范围为0.95～716 ng·L~(-1),以氯四环素检出浓度最高。整体上水产养殖区抗生素的浓度高于水源地。抗生素浓度与环境因子的冗余分析表明,水产养殖和生活污水排放是水体中抗生素的主要来源。对检出的13种抗生素进行生态风险评价,单一抗生素而言,环丙沙星、氧氟沙星、磺胺嘧啶、氯四环素和脱水红霉素的风险商值大于0.01而小于0.1,表现为低风险。总抗生素风险商值加和在大部分水源地大于0.01而小于0.1,表现为低风险;总抗生素风险商值加和在2个水产养殖区大于0.1,表现为中等风险,水产养殖区抗生素的长期生态风险应该引起关注。     

Tetracycline antibiotics in the environment: a review

Tetracycline antibiotics are one of the primarily antibiotics groups used for veterinary purposes, for human therapy and for agricultural purposes. Amongst the different antibiotics used, more attention is paid to tetracycline’s as it exhibits serious environmental problems including ecological risks and human health damages. Due to their extensive usage, most of the actual evidence suggests that tetracycline antibiotics are omnipresent compounds found in different ecological compartments. After medication, more than 70 % of tetracycline antibiotics are excreted and released in active form into the environment via urine and feces from humans and animals. Their highly hydrophilic character and low volatility have resulted in significant persistence in the aquatic environment. Very few studies describe the fate and toxicity of tetracycline antibiotics in the environment. Here, we review several important issues with regard to: (1) the toxicity of these compounds on aquatic and terrestrial organisms; (2) their estrogenic effects; (3) their behavior in different ecological systems and; (4) the by-products generated during water treatment. These antibiotics residues promote the development of antibiotic resistant microorganisms, which can induce adverse effect to human health by increasing the risk of certain infections. Based on recent research results, the occurrence of tetracycline antibiotics in the environment inhibits the growth of some terrestrial and aquatic species. Besides, the residual concentrations of such drugs could affect steroidogenic pathway and consequently may cause endocrine disruption of aquatic species. Most of the wastewater treatment plants are not capable of removing effectively the tetracycline antibiotics. Therefore, there is a need to develop alternative processes to remove them from waters. Advanced oxidation processes have been proposed as alternative methods to ensure higher degradation and mineralization of tetracycline antibiotics are present in waters.     

抗生素在地下水系统中的环境行为及生态效应研究进展

抗生素在环境中的残留已引起广泛关注。随着对地下水污染的报道日益增多,抗生素对地下水系统的潜在影响不容忽视。本文系统地阐述了地下水中抗生素的来源、污染水平及迁移转化规律,总结了抗生素对地下水微生物群落的影响以及抗生素诱导产生的抗性基因的潜在污染趋势。因地下水赋存隐蔽,一旦污染难以及时察觉,抗生素进入地下水系统后易长期残留。目前,针对抗生素及抗性基因在地下水系统中的环境行为及生态效应研究还十分有限,本文据此指出了当前形势下开展相关研究的必要性,并对今后的研究方向进行了展望。     

抗生素抗性基因在环境中的来源、传播扩散及生态风险

近年来,由于抗生素的滥用首先诱导动物体内产生抗生素抗性基因(antib iotic resistance genes,ARGs),从而加速了抗性基因在环境中细菌间的传播扩散.目前,抗生素抗性基因作为一类新型环境污染物,在不同环境介质中的传播、扩散可能比抗生素本身的环境危害更大.本文针对抗生素抗性基因在地表水、地下水、医疗废水、城市污水处理厂、养殖场、土壤、沉积物以及大气环境中的来源、分布、传播情况以及国内外最新研究动态进行综述.分析了抗生素抗性基因在环境中的潜在传播途径及其可能影响因素,并指出光照,厌氧,高温处理可以有效遏制抗生素抗性基因在环境中的传播和扩散.揭示了抗生素抗性基因可能造成的生态风险,针对我国对该类污染物的研究现状,提出了今后的研究重点.     

甲基异噻唑啉酮对斑马鱼胚胎的急性毒性和机制研究

甲基异噻唑啉酮(methylisothiazolinone,MIT)作为防腐剂,广泛用于个人护理品、日用品和涂料中。MIT随着污水进入地表水循环,普遍存在于水体中,但目前关于MIT对水生生物毒性的研究还比较少。本文以模式生物斑马鱼的胚胎作为受试对象,评价MIT对斑马鱼胚胎的毒性。将受精后3 h的健康斑马鱼胚胎暴露于梯度浓度的MIT下,观察其对胚胎生长发育的影响,用吖啶橙(AO)染色检测细胞凋亡情况。结果发现,48 h暴露浓度大于1.0 mg·L-1的胚胎孵化被显著抑制,72 h浓度大于1.52 mg·L-1的幼鱼心率显著降低,统计96 h幼鱼死亡和畸形数,并重复验证和计算得到96 h半致死浓度(96 h 50%lethal concentration,96 h-LC50)为6.15 mg·L-1,96 h半致畸浓度(96 h 50%teratogenesis concentration,96 h-TC50)为3.89 mg·L-1,测量96 h胚胎体长,分析最小生长抑制浓度(minimum concentration to inhibit growth,MCIG)为2.31 mg·L-1,AO染色显示72 h胚胎的凋亡细胞主要集中在脑部和尾部。不同时期下镜检观察到,胚胎出现的畸形主要包括尾部发育不良,脊柱弯曲,卵黄囊水肿和心包水肿。此外,高浓度处理组24 h胚胎自主抽动次数增加,72 h和96 h活动能力减弱,触碰反应迟钝。因此,推断MIT对斑马鱼胚胎的发育有较大影响,同时有一定的神经毒性。根据《危险化学品鱼类急性毒性分级试验方法》,判定MIT对斑马鱼胚胎为高毒,该毒性实验结果可为MIT在工业生产和环境中的风险管理提供依据。     

Photocatalytic degradation of ciprofloxacin in aqueous media: a short review

The frequent detection of antibiotics such as ciprofloxacin in surface and drinking waters around the world has attracted concern from various researchers. Such presence is an indication that the decontamination of water polluted by antibiotics is beyond the conventional treatment methods. However, among the different treatment methods that have been developed in the area of water purification, heterogeneous photocatalysis using semiconductor as a mediator has been rated as an efficient and a green wastewater treatment method. This is because, the process is effective in degrading and mineralizing organic pollutants, using UV or visible light. The present review paper covers a brief survey over a range of publications in the last decade, involving photocatalytic materials that have been employed in the purification of water contaminated by ciprofloxacin.