17 β-estradiol mineralization in human waste products and soil in the presence and the absence of antimicrobials

Natural steroidal estrogens, such as 17 β-estradiol (E2), as well as antimicrobials such as doxycycline and norfloxacin, are excreted by humans and hence detected in sewage sludge and biosolid. The disposal of human waste products on agricultural land results in estrogens and antibiotics being detected as mixtures in soils. The objective of this study was to examine microbial respiration and E2 mineralization in sewage sludge, biosolid, and soil in the presence and the absence of doxycycline and norfloxacin. The antimicrobials were applied to the media either alone or in combination at total rates of 4 and 40 mg kg^?1, with the 4 mg kg^?1 rate being an environmentally relevant concentration. The calculated time that half of the applied E2 was mineralized ranged from 294 to 418 days in sewage sludge, from 721 to 869 days in soil, and from 2,258 to 14,146 days in biosolid. E2 mineralization followed first-order and the presence of antimicrobials had no significant effect on mineralization half-lives, except for some antimicrobial applications to the human waste products. At 189 day, total E2 mineralization was significantly greater in sewage sludge (38 ±0.7%) > soil (23 ±0.7%) > biosolid (3 ±0.7%), while total respiration was significantly greater in biosolid (1,258 mg CO₂) > sewage sludge (253 mg CO₂) ≥ soil (131 mg CO₂). Strong sorption of E2 to the organic fraction in biosolid may have resulted in reduced E2 mineralization despite the high microbial activity in this media. Total E2 mineralization at 189 day was not significantly influenced by the presence of doxycycline and/or norfloxacin in the media. Antimicrobial additions also did not significantly influence total respiration in media, except that total CO₂ respiration at 189 day was significantly greater for biosolid with 40 mg kg^?1 doxycycline added, relative to biosolid without antimicrobials. We conclude that it is unlikely for doxycycline and norfloxacin, or their mixtures, to have a significant effect on E2 mineralization in human waste products and soil. However, the potential for E2 to be persistent in biosolids, with and without the presence of antimicrobials, is posing a challenge for biosolid disposal to agricultural lands.     

群体感应抑制剂与磺胺甲恶唑、盐酸强力霉素对大肠杆菌的联合毒性及其机制初探

群体感应抑制剂(QSIs)具有不产生抗药性的特点，从而被作为抗生素的可能替代品，具有广阔的应用前景，因此其存在着与传统抗生素环境联合暴露的可能，但是目前尚缺乏相关联合效应的研究。本文以大肠杆菌(Escherichia coli)为受试生物，测定了7种QSIs(DL-焦谷氨酸、N-乙烯基吡咯烷酮、呋喃酮乙酸酯、2-甲基四氢呋喃-3-酮、3,4-二溴-2(5H)-呋喃酮、(R)-3-吡咯烷醇、D-脯氨醇)分别与磺胺甲恶唑(SMX)和盐酸强力霉素(DH)的二元联合毒性，并初步探讨了它们的联合作用机制。结果表明，前5种QSIs作用于AI-2类信号分子介导的群体感应系统，与AI-2类信号分子竞争结合LsrB蛋白，此通路与SMX、DH的作用通路互不影响，因此联合效应为相加；后2种QSIs作用于AI-1类信号分子介导的群体感应系统，与AI-1类信号分子竞争结合SdiA蛋白，而SMX、DH的作用可能刺激SdiA蛋白的表达，从而需要消耗更多的QSIs与SdiA结合，因而联合效应为拮抗。本实验研究可为传统抗生素与QSIs联合暴露的生态风险评价提供一定理论基础。     

强力霉素在凹凸棒土上的吸附行为

通过等温吸附平衡法研究了强力霉素在凹凸棒土上的吸附行为,考察了pH、反应时间、离子强度和离子类型等因素对吸附的影响,探讨了吸附机理.结果表明,pH=8.5时,饱和吸附容量最大,为293.35μmol.g-1;强力霉素在凹凸棒土上的吸附可用Langmuir型等温方程和准二级动力学方程很好地拟合;离子强度对强力霉素的吸附影响不是很明显;0.05 mol.L-1NaOH能显著地将强力霉素从凹凸棒土上解吸下来.红外表征结果说明凹凸棒土对强力霉素的吸附可能是化学吸附,酸性条件下,强力霉素主要通过阳离子交换、静电作用、氢键作用等吸附在凹凸棒土上,部分H+可能通过强力霉素质子化吸附到凹凸棒土上.弱碱性条件下主要通过水桥接,与凹凸棒土层间阳离子配位以及结合于凹凸棒土边缘吸附位点达到吸附.     

Ecotoxicological assessment of doxycycline in soil

Doxycycline has been used in continually increasing quantities for mass treatment of food animals because of its greater bioavailability relative to older tetracyclines. The study presented in this paper was undertaken to investigate the degradation rate of the tetracycline derivative in manure-amended soil. In the present experiment, following composting, the doxycycline-contaminated manure was applied to agricultural land, and a field study was performed to investigate the degradation rate of doxycycline in soil. By the end of the 20-week sampling period, about 20 %, 33 % and 18 % of the initial doxycycline concentrations could be measured in soil samples taken at three different soil depths. The calculated half-life of doxycycline in the soil was 66.5, 76.3 and 59.4 days at depths of 0 cm, 25 cm and 50 cm, respectively. The potential effect of doxycycline on soil microbial activity was demonstrated by the nitrogen transformation test performed in compliance with the Organisation for Economic Co-operation and Development (OECD) Guideline No. 216. On day 28, the following nitrate concentrations of the control soil sample were found in the soil samples treated with different amounts of doxycycline: 76.9 %, 53.0 %, 65.6 %, 59.7 % and 77.1 %.     

土壤中单一及复合抗生素的降解及微生物响应

基于LC-MS/MS、MicroRESP^TM等技术,对比了磺胺二甲嘧啶（SM2）和强力霉素（DOX）在单一和共存条件下,在青紫泥和小粉土中的短期降解及土壤微生物代谢特征.结果表明,单一条件下,小粉土中SM2和DOX的3d和7d降解率总体高于青紫泥,SM2和DOX共存条件下可对土壤中二者的短期降解产生一定抑制,这种抑制作用在小粉土中更为明显.抗生素对土壤微生物代谢的影响与其赋存时间及土壤类型有关.在供试浓度10~20mg/kg下,SM2和DOX在单一和复合条件下总体是促进土壤微生物代谢,但影响随赋存时间增加而减弱.青紫泥中,SM2和DOX共存下的土壤微生物代谢多样性高于二者单一存在,且青紫泥中DOX浓度与土壤代谢活性和微生物群落代谢多样性呈显著正相关,而小粉土中无类似的现象,但SM2与DOX复合污染对土壤微生物代谢的影响总体源于DOX的作用.     

铟掺杂PbO2电极制备及电催化降解强力霉素

采用电沉积技术制备了铟掺杂PbO₂电极 （In-PbO₂）. 利用扫描电子显微镜 （SEM）、X射线衍射 （XRD）、循环伏安 （CV）、极化曲线 （LSV）、强化寿命试验和荧光光谱分析了铟掺杂对电极物理、电化学性能的影响,并考察了铟掺杂PbO₂电极对强力霉素模拟废水的电催化降解能力.结果表明,与未掺杂PbO₂电极相比, In掺杂后PbO₂电极表面更加平整致密,裂纹数量减少,晶粒明显细化,比表面积增加,产生羟基自由基的能力增强.当掺杂量为2g/L,制备的电极电化学性能最高,析氧电位最高（1.73V）,电极强化寿命从84h提高到148h.电解150min后,强力霉素降解率、TOC去除率、矿化电流效率（MCE）分别为98.2%、30.4%和3.01%,优于未掺杂PbO₂电极（90.1%、26.4 %、2.63%）.     

离子液体双水相气浮溶剂浮选分离/富集水样中的盐酸多西环素研究

建立了以亲水性离子液体1-丁基-3-甲基咪唑四氟硼酸[Bmim]BF4和Na H2PO4形成的二元双水相作为气浮溶剂分离/富集水样中盐酸多西环素的新方法,并采用紫外分光光度法对盐酸多西环素进行测定。考察了离子液体的初始加入量、盐的种类及浓度、p H值、浮选时间及N2流速等因素对体系浮选分离盐酸多西环素的影响。结果表明,改变离子液体和无机盐的加入量,会使体系的富集倍数发生变化,从而使体系的浮选效率和浓集系数发生变化;随浮选时间增加,体系的浮选效率先增加后略微下降;过大或过小的N2流速都会使体系对盐酸多西环素的浮选效率降低;而p H值对体系浮选盐酸多西环素影响不大。当[Bmim]BF4溶液加入量为3 m L、Na H2PO4加入量为25 g(质量分数为33.3%)、气浮时间为40 min、气浮速率为50 m L/min时,体系的浮选效率最高,可达95.8%,浓集系数可达23.95,此时体系的p H值为4.38。与离子液体双水相萃取(ILATPE)相比,该方法的优点在于不仅有较高的浮选率、浓集系数,还有效减少了离子液体的用量,同时操作更简单、环境友好。     

具备微电解特性的改性泡沫铜去除强力霉素

通过改进的还原方法把纳米零价铁（nZVI）负载在多孔泡沫铜（CF）上,制备出具有微电解特性的泡沫铜材料（MCF）,并利用SEM,SEMMAPPING和EDX对其表面的形态特征及其元素分布进行了表征.考察了不同去除方式,不同MCF投加量和不同强力霉素（DC）初始浓度对降解效果的影响.结果表明：负载等量nZVI的MCF处理效果明显优于nZVI;当DC初始浓度为50mg/L,MCF的投加量为4.0g,反应20min时,DC去除率可达到99%;动力学分析表明,MCF降解DC符合准一级反应动力学,且随着MCF的投加量增加,反应速率常数k增大,投加量为5.0g时,k值最大为0.0609min^-1.     

群体感应抑制剂与磺胺甲恶唑、盐酸强力霉素对大肠杆菌的联合毒性及其机制初探

群体感应抑制剂(QSIs)具有不会产生抗药性的特点,从而被作为抗生素的可能替代品,具有广阔的应用前景,因此其存在着与传统抗生素环境联合暴露的可能,但是目前尚缺乏相关联合效应的研究。本文以大肠杆菌(Escherichia coli)为受试生物,测定了7种QSIs(DL-焦谷氨酸、N-乙烯基吡咯烷酮、呋喃酮乙酸酯、2-甲基四氢呋喃-3-酮、3,4-二溴-2(5H)-呋喃酮、(R)-3-吡咯烷醇、D-脯氨醇)分别与磺胺甲恶唑(SMX)和盐酸强力霉素(DH)的二元联合毒性,并初步探讨了它们的联合作用机制。根据结果分析,前5种QSIs作用于AI-2类信号分子介导的群体感应系统,与AI-2类信号分子竞争结合Lsr B蛋白,此通路与SMX、DH的作用通路互不影响,因此联合效应为相加;后2种QSIs作用于AI-1类信号分子介导的群体感应系统,与AI-1类信号分子竞争结合Sdi A蛋白,而SMX、DH的作用可能刺激Sdi A蛋白的表达,从而需要消耗更多的QSIs与Sdi A结合,因而联合效应为拮抗。本实验研究可为传统抗生素与QSIs联合暴露的生态风险评价提供一定理论基础。     

Production of monoclonal antibody against doxycycline for immunoassay of seven tetracyclines in bovine muscle and milk

The objective of this study was to produce a generic monoclonal antibody for multi-determination of the residues of tetracycline drugs in bovine muscle and milk. Two new immunogens of doxycycline were prepared that were used to produce the monoclonal antibodies. Results showed the obtained antibodies simultaneously recognized seven tetracycline drugs (doxycycline, tetracycline, chlortetracycline, oxytetracycline, minocycline, methacycline, demeclocycline). The obtained antibodies and three coating antigens were arranged into six combinations to optimize the reagents combination. After comparison of the performances of these combinations, a heterologous indirect competitive ELISA was then used to determine the seven tetracyclines in bovine muscle and milk. The crossreactivities to the seven analytes were in the range of 47%–102% and the limits of detection were in the range of 1.5–6.9 ng/mL depending on the compound. The recoveries of the seven drugs from fortified blank samples were in the range of 75.3%–106.8% with coefficients of variation lower than 10.9%. Therefore, this method could be used as a multi-analytes screen tool for routine monitoring of the residues of these tetracycline drugs in bovine muscle and milk.