北京东南郊土壤剖面氟喹诺酮类抗生素分布特征

采用Geoprobe在北京东南郊地区实施了土壤剖面钻探,针对8种不同类型土地利用状况的土壤剖面进行土壤采集工作,11个采样点共采集86个土壤样品,分析了土壤样品的理化参数,并且采用高效液相色谱法对土壤样品中5种氟喹诺酮类抗生素(FQs)进行了定量分析.结果表明,北京地区土壤样品中5种氟喹诺酮类抗生素总含量的平均值为46.1μg·kg-1,组成以氧氟沙星(OFL)为主,其次为诺氟沙星(NOR),而恩诺沙星(ENR)、环丙沙星(CIP)和洛美沙星(LOM)的含量很低;不同土壤剖面中氟喹诺酮类抗生素的含量和组成差异明显.5种氟喹诺酮类抗生素总含量的平均值随土壤深度的增加呈现降低的趋势.OFL、NOR、LOM和ENR的平均含量随着深度增加而降低;CIP的平均含量随深度增加先降低后升高.对42个位于浅层(0~3 m)的土壤样品进行模糊聚类分析,结果表明,蔬菜大棚、树林、再生水灌区、地下水灌区(清灌区)、养殖场、排污河沉积物的浅层土壤样品中的喹诺酮类抗生素具有相似的组成特征,即抗生素污染水平较低、种类较少;而制药企业及垃圾填埋场的组成特征与前者明显不同,即抗生素污染水平中等、种类较多.     

Evaluation of the Fertilization Capability of Paracentrotus Lividus Sea Urchin Storaged Gametes by the Exposure to Different Aqueous Matrices

Several experiments were performed to evaluate the fertilization capability of Paracentrotus lividus sea urchin gametes, which are usually used in fertilization tests, but which, until now, were employed only for few hours after spawning.The aim of this work is to evaluate the possibility of performing the bioassay for longer periods, employing ‘conserved' gametes. As far as the method, the sperm was stored ‘dry' at 4 ^∘C; eggs were conserved in an antibiotic solution at 4 ^∘C, and they were exposed both to copper solutions as reference toxicant and to aqueous matrices.The use of conserved gametes in the fertilization bioassay lead to EC50 values which were acceptable for about 3 days. Moreover, these experiments permitted to identify the limiting factor: the male gamete.     

基于分散固相萃取-超高效液相色谱串联质谱法测定沉积物中大环内酯类抗生素

采用分散固相萃取与超高效液相色谱串联质谱技术,建立了快速测定沉积物中9种大环内酯类抗生素(螺旋霉素、阿奇霉素、替米考星、竹桃霉素、红霉素、泰乐菌素、吉他霉素、罗红霉素和交沙霉素)的检测方法.沉积物经磷酸盐缓冲液和乙腈混合液浸提,再经过石墨化炭黑和C18硅胶分散固相萃取材料净化.采用超高效液相色谱串联质谱仪(UPLC-M...     

水产养殖水、沉积物中抗生素检测方法优化及残留特征研究

抗生素作为疾病预防和促进生长的药物被广泛用于水产养殖业中,不可避免地造成了周围环境抗生素的残留,从而带来各种潜在风险。为了对水产养殖水和沉积物中的抗生素残留特征进行研究,建立了环境样品中抗生素的富集方法。对沉积物中抗生素的提取溶剂、HLB小柱活化溶剂和洗脱溶剂进行了筛选,利用高效液相色谱串联质谱仪对15种抗生素进行检测分析,并检测了上海市某水产养殖区7个养殖塘2018年9、12月抗生素的残留水平。结果表明,选用乙腈/磷酸盐缓冲溶液(V∶V=1∶1)作为提取溶剂,依此用甲基叔丁基醚、甲醇和超纯水作为活化溶剂,甲醇作为洗脱溶剂时目标抗生素的回收率最高;在养殖塘水体中共检测出10种抗生素,检出浓度中间值依次为:磺胺类>甲氧苄啶>阿莫西林>氟喹诺酮类>喹乙醇>四环素类和呋喃唑酮。养殖塘沉积物中共检测出13种抗生素,检出浓度中间值依次为:氟喹诺酮类>四环素类>磺胺类>甲氧苄啶>喹乙醇>阿莫西林和呋喃唑酮;不同品种的养殖塘中抗生素的检出种类均不相同,其中青鱼塘和白水鱼塘10种、虾塘9种、扣蟹塘仅5种。对比抗生素检出浓度发现:氟喹诺酮类抗生素在鱼类养殖塘中检出浓度最高,磺胺甲恶唑仅在蟹塘检出,喹乙醇在虾塘检出浓度达3 612.85 ng·L~(-1)。9月与12月抗生素的残留水平也存在差异,抗生素在9月的平均含量比12月高。     

Occurrence and ecological hazard assessment of selected veterinary medicines in livestock wastewater treatment plants

The occurrence of some veterinary medicines in the livestock wastewater plants (WWTPs) was investigated. This investigation represented the occurrence of veterinary medicines to treat in the livestock WWTPs or be discharged into the water system in Korea since the sampling sites were widely distributed across the nation and samples were collected from the 11 livestock WWTPs. Nine antibiotics, two analgesics, and two disinfectants occurred in the livestock wastewater plants (WWTPs). From 11 livestock WWTP influents, chlortetracycline, oxytetracycline, acetylsalicylic acid, and disinfectants frequently occurred with the high concentrations. Meanwhile, sulfamethoxazole, erythromycin-H₂O, and trimethoprim did not occur during sampling periods. The values for log Kow of each chemical showed a high correlation with the number of hydrogen bonding acceptors and were important parameters to estimate and understand the biodegradability and toxicity of a compound in the environment. The biodegradability of each compound was proportional to the hydrophilicity of each compound and the toxicity was proportional to the number of hydrogen bonding acceptors of each compound. The expected introductory concentration (EIC), predicted exposure concentration (PEC), and hazard quotient showed that the livestock WWTP effluents were hazardous to ecosystems.     

人工湿地中抗生素抗性大肠杆菌和抗性基因的去除与分布

抗生素的滥用导致抗生素抗性菌和抗性基因随生活污水和养殖废水的排放在环境中肆意散播,其去除及环境行为越来越受到关注。采用K-B纸片法测定了9套不同工艺构型模拟人工湿地中大肠杆菌对7种抗生素的抗性率,并应用多重PCR检测磺胺类sul1、2、3与四环素tetA、B、C、D抗性基因,探究人工湿地对抗性菌的去除效率及抗性菌、抗性基因的分布规律。结果显示,人工湿地能有效去除污水中70%左右的抗性大肠杆菌,有效降低了细菌抗性的传播风险;共计分离出535株大肠肝菌中有378株对一种以上抗生素有抗性性,以四环素、磺胺类和氨苄西林抗性率最高,达到25%以上,其他4种抗性率较低,不足20%;2种抗性基因的检出率都在70%以上;对不同采样点大肠杆菌的抗性性及抗性基因的比较发现,各部分大肠杆菌的抗性水平、多重抗性指数(MRI)以及抗性基因(sul、tet)检出率和组合数表现出:基质≥出水>进水,推测抗性菌被湿地基质截留,在基质生物膜上发生抗性基因的重组,并释放抗性菌,提高了出水中抗性水平和抗性基因检出率。     

Determination of chloramphenicol, enrofloxacin and 29 pesticides residues in bovine milk by liquid chromatography-tandem mass spectrometry

A sensitive method for determination of chloramphenicol, enrofloxacin and 29 pesticides residues in bovine milk by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed. Residues of the targets were extracted from milk with acetonitrile, cleaned up by C₁₈-SPE cartridge, and then determined by HPLC-MS/MS. The MS detection was operated in positive or negative ionization mode, depending on the compounds. For confirmation of each target compound, two precursor ion > product ion transitions were selected by multi-reaction monitoring mode (MRM). The method showed good linearity for all the tested compounds over the studied concentration range with correlation coefficient higher than 0.9910. Recoveries for the studied compounds at three spiked levels (0.05, 0.10, 0.19 mg kg⁻¹) in bovine milk were in the range of 71-107% with RSDs not larger than 13.7%, except that recoveries of trifluralin ranged between 62% and 70% at the spiked levels. Limits of quantitation for the analytes were estimated to range between 0.03 × 10⁻³ and 14.5 × 10⁻³ mg kg⁻¹. The proposed method was applied for the determination of the analytes residues in real samples. The found levels of the analytes in milk samples were lower than maximum residues levels (MRL).     

污水处理厂生物气溶胶抗生素抗性污染特征

为探究污水处理厂生物气溶胶抗生素抗性基因（ARGs）污染特征,在济南市某污水处理厂采用宏基因组测序技术对厂界内及周边生物气溶胶样本及污水或污泥样本进行分析.结果表明,相比于上风向,厂界内和下风向生物气溶胶具有更多的ARGs亚型种类数和更高的总相对丰度.厂界内与上风向生物气溶胶ARGs组成存在显著的差异性,差异度为47.57%;而厂界内与下风向生物气溶胶ARGs组成的差异性不显著,且差异度下降至33.98%.上风向背景空气和污水或污泥均是厂界内生物气溶胶ARGs的重要来源,两者总的源的贡献大于63.92%.共检测到43种ARGs亚型（8种ARGs主型）在至少一处污水处理单元极易负载于生物气溶胶颗粒逸出.本研究可为污水处理厂生物气溶胶抗生素抗性污染的风险评估和控制提供理论依据.     

北京市城市河流中抗生素的污染特征及多层次生态风险评估

为评估北京市河流中抗生素的污染特征和生态风险,利用固相萃取结合高效液相色谱串联质谱检测了4类共35种常见抗生素的浓度水平,并利用风险商法（RQ）和联合概率曲线法（JPCs）评估了抗生素的生态风险.结果表明,北京市10条河流地表水中共检测出33种抗生素,总浓度范围是N.D.~1573.57 ng·L^-1,磺胺甲噁唑的浓度最高（N.D.~160.04 ng·L^-1）,其次为磺胺嘧啶（0.09~147.90 ng·L^-1）和氧氟沙星（0.28~94.72 ng·L^-1）,其中检出率 > 50.0 %的抗生素有16种;RQ法显示有12种抗生素存在生态风险,四环素、克拉霉素和甲氧苄氨嘧啶的风险最高,其风险商分别为3.99、1.86和1.01,污水处理厂出口的风险高于其所在河流干流的风险.四环素、克拉霉素和甲氧苄氨嘧啶的预测无效应浓度超标率均为2.3 %,基于JPCs发现,克拉霉素的最大风险乘积为1.66 %,对0.3 %~7.0 %的物种具有低等风险,其余抗生素的风险可忽略.抗生素的检出率、浓度分布、最敏感物种和物种敏感性分布对生态风险评估具有重要影响,采用多层次生态风险评估法能有效避免保护不足和过保护现象,有助于在全区域范围内对抗生素进行分级和分区管理.     

超高效液相色谱串联质谱法同时测定叶菜中13种抗生素

建立了超高效液相色谱串联三重四极杆质谱(UPLC-MS/MS)同时检测叶菜类蔬菜中磺胺类、喹诺酮类、大环内酯类13种抗生素的分析方法.优化蔬菜基质中抗生素的提取液种类、净化方式、洗脱液种类,以及探讨环境变化和实验条件对实验结果的影响后,确定最优方案为称取500 mg的蔬菜样品,加入20 mL甲醇-Mcllvaine-Na_2EDTA溶液,超声和离心提取3次后,旋转蒸发至20 mL过HLB固相萃取柱.以6 m L甲醇洗脱,收集洗脱液,氮吹近干,用乙腈∶水(体积比2∶8)混合溶液复溶,离心、过滤后采用UPLC-MS/MS进行检测.流动相A相为1‰的甲酸水溶液,B相为乙腈,梯度洗脱.结果显示,小白菜在300ng·g~(-1)加标时,13种抗生素的加标回收率为38. 05%～96. 97%,150 ng·g~(-1)时,加标回收率为34. 52%～111. 10%,50 ng·g~(-1)时,加标回收率为41. 75%～107. 13%,相对偏差RSD值均小于8. 68%.检出限为0. 4～1 ng·g~(-1)、定量限为1. 5～3 ng·g~(-1),在不同种类的叶菜上也表现出较好的提取和回收效率,具有较好的分析应用效果.实际的样品检测发现,4种叶菜不同程度地检测出了抗生素的残留.总的含量范围(以干重计)为1. 59～32. 01 ng·g~(-1).小白菜所含抗生素含量最高,其次为白菜、生菜和芫荽.磺胺二甲基嘧啶为叶菜中含量最高的抗生素种类.各抗生素检测出的含量虽很低,但仍不能忽略长期食用带来的潜在健康风险.