饮用水中抗生素残留检测方法的研究进展

抗生素作为一种杀灭或抑制细菌生长的药物,在食品、临床、兽药、农业等方面得到了广泛的应用。然而,抗生素的大量应用导致其残留物进入地表水,进而污染自来水厂水源,而标准的水处理不能将其完全清除,从而对人体产生较大的危害,引起过敏、发热、耐药性甚至再生障碍性贫血等症状。因此,针对饮用水中抗生素残留检测的研究引起了人们广泛的关注。本文对近年来可应用于饮用水中抗生素残留的分析方法(高效液相色谱、太赫兹时域光谱技术、免疫分析法、表面增强拉曼光谱法)的研究进展进行了综述,并对今后抗生素残留检测的发展方向作了展望。     

抗生素荧光光谱法检测研究

利用荧光光谱法对水中四环素类抗生素(盐酸金霉素)、喹诺酮类抗生素(盐酸左氧氟沙星)的残留进行了检测。探讨抗生素光谱特征峰强度与浓度之间的关系,建立了含量检测模型函数,并利用回收率和相对误差对模型函数进行分析评价。结果表明:在0～27.5μg/mL范围内的盐酸金霉素和在0～1.5μg/mL范围内的盐酸左氧氟沙星模型相关系数都超过0.99,相对误差均小于2%,回收率均在96%～102%内。证明基于荧光光谱所构建的检测模型能够实现水中抗生素的检测,并具有很好的有效性和稳定性。     

浙江地区抗生素残留的环境分布特征及来源分析

近年来在天然水体、土壤、动植物及其排泄物中都检测到了抗生素的存在,抗生素在环境中的残留已经引起广泛关注。本文调研和梳理了2011~2019年间针对浙江地区各种环境介质中抗生素残留状况的相关研究工作,对浙江地区废水、地表水、地下水、土壤和养殖畜禽粪便等环境介质中抗生素残留的主要种类、污染水平和分布特征进行了分析总结,并对抗生素残留的可能来源进行了分析。结果显示,浙江地区环境中抗生素残留的主要种类为四环素类、磺胺类、氟喹诺酮和氯霉素类。杭州、金华、嘉兴等地的畜禽养殖废水中检测出较高浓度抗生素,最高至994 μg·L^-1;畜禽粪便中达到了66.62 mg·kg^-1,为浙江地区环境中抗生素污染的主要来源之一。制药废水中的抗生素浓度更是达到了5.7 mg·L^-1,这些废水虽然经过污水处理厂处理,但在部分处理过的废水中仍能检出抗生素,浓度最高达88 μg·L^-1,并被直接排入天然水体。水产养殖区域中残留的抗生素也会不经处理直接进入地表水中,导致地表水污染,浙江地表水中抗生素浓度最高为508.7 ng·L^-1,但是大部分流域小于100 ng·L^-1。迄今为止,尚未在千岛湖、丽水石塘水库、衢州江山碗窑水库和东西苕溪等饮用水水源地中检测到抗生素,但舟山地区饮用水源中抗生素浓度达到了55 ng·L^-1。虽然地表水中抗生素残留水平相对较低,由于这些水体用于水产养殖、畜禽饮水及农田灌溉,使得环境中的抗生素流入畜禽及农作物中,最终可能导致食品污染。因此,未来工作中需要对浙江各地区进行抗生素环境残留的全面、持续调查,结合浙江地区地域特征及经济发展特色,加强环境中抗生素迁移转化规律的研究,并及时开展抗生素环境污染对生态系统和人体健康效应的研究。     

GC／MS法测定杀菌剂残留标准将实施

不久前,赛默飞世尔科技在德克萨斯州奥斯汀发布了一篇用DSQII单四极杆质谱进行饮用水中农药残留和阻染剂分析的应用文献,该项新应用记录标题为“以美国EPA527方法为标准,使用单四极杆GC／MS进行饮用水中农药残留和阻燃剂的分析”,     

离子色谱法快速测定饮用水中溴酸盐时干扰物质的消除

溴酸盐(BrO3-)是臭氧对饮用水消毒时产生的一种消毒副产物,其致癌性已被人们广泛关注[1]。国际上对饮用水中的溴酸盐进行了大规模的研究,并且制定了饮用水中溴酸盐的最大容许浓度[2]。目前,我国在饮用水、矿泉水国家标准中均将溴酸盐列为常规检测项目,且限值均在μg·L-1级别[3],这对溴酸盐的检测技术提出了更高的要求。离子色谱法是检测水中阴离子的一种有效手     

液相色谱-串联三重四极杆质谱对牛奶中10种磺胺类药物残留的同时测定

磺胺类药物是畜牧和牛乳生产中应用最广泛的治疗动物细菌感染的药物.牛奶中残留此类药物能引起肾损害,特别是乙酰化磺胺在尿中溶解度低,析出结晶质对肾脏损害更大.因此,及时寻求简便、快速、准确、灵敏度高的牛奶中磺胺类药物残留的检测方法才能满足日趋严格的残留限量要求,保障人们饮用牛奶的卫生和安全.     

基于滤纸基底表面增强拉曼光谱法的水中毒死蜱农药的循环快速检测研究

该文基于常用滤纸材料,制备了复合银纳米粒子(AgNPs)和ZnO纳米粒子的拉曼检测复合基底材料,建立了复合基底用于毒死蜱农药残留的表面增强拉曼检测方法,并成功实现了对环境水样中毒死蜱的循环稳定检测。所制备的滤纸复合基底材料表面拉曼活性检测位点分布均匀,检测稳定性好,对毒死蜱农药的检出限达48.53μg/L,线性范围50～500μg/L。在紫外光照条件下考察了基底的循环检测稳定性,结果表明,毒死蜱农药在ZnO纳米粒子光催化剂及紫外光照下可实现循环降解,同时检测基底仍能保持高的拉曼检测活性。将该基底材料用于实际地表水中毒死蜱农药的检测,回收率为111%～139%,相对标准偏差不大于12%。所建立的基于复合滤纸表面增强拉曼基底的水中毒死蜱农药残留检测方法,其检出限满足地下水质量标准对农业用水中毒死蜱的限值要求以及食品中农药残留限制标准对水果蔬菜中毒死蜱最大残留限值要求。该方法具有操作简单、耗时短及检测成本低等特点,在农残快速检测方面有巨大的应用潜力。     

在线富集-超高效液相色谱-线性离子阱串联质谱法测定饮用水中38种抗生素残留EI北大核心CSCD

建立了在线富集-超高效液相色谱-线性离子阱串联质谱法同时测定饮用水中38种抗生素残留的方法。样品经离心过滤后,先经XBrigde C_(18)Direct Connect HP(30 mm×2.1 mm, 10μm)在线富集,使用Waters sunfire C_(18)(4.6 mm×250 mm, 5μm)色谱柱,以甲醇和0.1%甲酸溶液为流动相进行梯度洗脱。采用电喷雾离子源,以多反应监测触发增强子离子扫描方式进行质谱检测,在线增强子离子扫描(EPI)谱库定性分析,外标法定量。结果表明,饮用水中38种抗生素残留在0.0412~18.5μg/L范围内线性关系良好,线性相关系数均大于0.9898,回收率均在80.6%~123.8%之间,相对标准偏差均大于11%,检出限为0.012~0.14μg/L,定量限为0.041~0.46μg/L。     

基于自组装技术制备硫酸链霉素修饰电极及其对DNA的检测

抗生素(antibiotics)又称抗菌素,是由一些微生物合成的、能抑制或杀灭某些病原体的化学物质.由于抗生素对革兰氏阳性菌及革兰氏阴性菌等引起的多种感染有良好的杀灭和抑制作用,被广泛地应用于临床、兽药、农业等方面,但是抗生素在动物性食品中的残留对人体的危害也越来越引起人们的关注,因此对于抗生素检测的研究开发得到迅速发展.硫酸链霉素为氨基酸糖苷类抗生素,临床上主要用于治疗结核病及敏感革兰氏阴性杆菌感染.     

动物源性食品大环内酯类抗生素残留检测样品前处理技术研究综述

大环内酯类抗生素在全球饲料添加剂中仅次于四环素类抗生素,使用广泛,可通过食物链进入人体,对人体健康造成影响.因此,开发相应的残留检测技术有重要的社会意义.而样品前处理技术的发展与革新对抗生素残留检测技术发展具有巨大的推动作用.本文综述了近年来动物源性食品大环内酯类抗生素残留检测样品前处理技术研究进展,并对样品前处理技术在动物源性食品大环内酯类抗生素残留检测中的应用前景进行了展望,以期为相关研究者提供技术参考.     

Sulphonamide Residues in Italian Surface and Drinking Waters: A Small Scale Reconnaissance

The occurrence of antibiotics in the aquatic environment is an important emerging issue due to potential adverse effect of these compounds on ecosystem and human health. For a correct environmental risk assessment there is a need for appropriate analytical methods for monitoring antibiotic residues in a variety of water matrices. This paper describes a method for the determination of eleven sulphonamide compounds in surface and drinking waters using solid-phase extraction and liquid chromatography-tandem mass spectrometry. Recoveries of the analytes in both surface and drinking water matrices at different fortification levels, always exceed 87%; the limits of quantification in surface water samples are between 0.005 and 0.021 μg L⁻¹ depending on the compound, and the interday method precision is less than 12%. Matrix effects were evaluated in drinking and surface water samples. The method has been applied to a small scale reconnaissance of river, lake, mineral and municipal water samples; results indicate the occurrence of sulphonamides in some surface and mineral waters analyzed.     

固相萃取–气相色谱法测定饮用水中5种有机磷农药

建立了固相萃取–气相色谱法测定饮用水中敌敌畏、乐果、甲基对硫磷、马拉硫磷及对硫磷的方法。采用Cleanert PEP–SPE固相萃取柱,以二氯甲烷、乙酸乙酯、甲醇及纯水活化固相萃取柱,以5 m L/min流量富集水样,然后用二氯甲烷及乙酸乙酯洗脱浓缩后进行气相色谱分析。5种有机磷农药线性相关系数均大于0.995,方法测定下限为0.16~0.80μg/L,加标回收率为59.8%~109.0%,测定结果的相对标准偏差小于16%(n=6)。该方法灵敏度高,准确度好,适用于饮用水中5种有机磷农药的检测。     

Natural organic matter removal by coagulation during drinking water treatment: A review

Natural organic matter (NOM) is found in all surface, ground and soil waters. An increase in the amount of NOM has been observed over the past 10-20 years in raw water supplies in several areas, which has a significant effect on drinking water treatment. The presence of NOM causes many problems in drinking water and drinking water treatment processes, including (i) negative effect on water quality by causing colour, taste and odor problems, (ii) increased coagulant and disinfectant doses (which in turn results in increased sludge volumes and production of harmful disinfection by-products), (iii) promoted biological growth in distribution system, and (iv) increased levels of complexed heavy metals and adsorbed organic pollutants. NOM can be removed from drinking water by several treatment options, of which the most common and economically feasible processes are considered to be coagulation and flocculation followed by sedimentation/flotation and sand filtration. Most of the NOM can be removed by coagulation, although, the hydrophobic fraction and high molar mass compounds of NOM are removed more efficiently than hydrophilic fraction and the low molar mass compounds. Thus, enhanced and/or optimized coagulation, as well as new process alternatives for the better removal of NOM by coagulation process has been suggested. In the present work, an overview of the recent research dealing with coagulation and flocculation in the removal of NOM from drinking water is presented.     

Drugs That Changed Society: History and Current Status of the Early Antibiotics: Salvarsan,Sulfonamides, and β-Lactams

The appearance of antibiotic drugs revolutionized the possibilities for treatment of diseases with high mortality such as pneumonia, sepsis, plaque, diphtheria, tetanus, typhoid fever, and tuberculosis. Today fewer than 1% of mortalities in high income countries are caused by diseases caused by bacteria. However, it should be recalled that the antibiotics were introduced in parallel with sanitation including sewerage, piped drinking water, high standard of living and improved understanding of the connection between food and health. Development of salvarsan, sulfonamides, and β-lactams into efficient drugs is described. The effects on life expectancy and life quality of these new drugs are indicated.     

Molecularly Imprinted Polyresorcinol Based Capacitive Sensor for Sulphanilamide Detection

A molecularly imprinted polymer (MIP) based capacitive sensor for antibiotic detection in drinking water and milk has been developed on a gold coated silicon electrode (Au Electrode). The electrode was fabricated by electropolymerizing monomer resorcinol (RN) on Au surface in presence of sulphanilamide (SN) as a template molecule, to get insulated RN polymer antibiotic composite. The insulation of the polymer film was improved by incubation of electrode in 1‐Dodecanethiol solution. Subsequently MIP sensor was obtained by extraction of SN in ethanol and acetic acid solution. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) measurements were performed for characterization of the developed MIP electrode at different steps of fabrication. The surface morphology of MIP electrode was characterized using atomic force microscopy (AFM), X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive x‐ray spectroscopy (EDS). Performance of MIP sensor was evaluated by measuring change in capacitance against varying concentration of SN using EIS. A linear response in the range 1 to 200 μg L^?1 SN was recorded for MIP sensor with a detection limit of 0.1 μg L^?1. The developed MIP sensor exhibited good selectivity towards SN in water and milk with recoveries in the range 92 % to 105 %. The obtained results suggest the usability of MIP based sensor for SN estimation in water and milk samples.     

Diffuse Reflectance Infrared Fourier Transform Spectra of Biofilm-Containing Sediments: Influence of Sample Lyophilization and Drying Temperature

Monitoring of biofilms in sediments formed inside drinking water distribution systems is important due to their destructive activity and their degradation of water quality. The goal of this study was to examine the influence of drying mode and temperature upon sediments containing biofilms using diffuse reflectance infrared Fourier transform spectroscopy. Sediments were collected from sections of potable water pipes and dried at 22, 40, 105 degrees Celsius, or lyophilized. The presence of biofilm residues was demonstrated. Lyophilization of biofilms and drying at temperatures higher than 22 degrees Celsius affected the infrared spectra. The least invasive method involved air-drying of the biofilms at 22 degrees Celsius.     

Ultralow Cost Electrochemical Sensor Made of Potato Starch and Carbon Black Nanoballs to Detect Tetracycline in Waters and Milk

Detection of traces from pharmaceutical drugs such as antibiotics in drinking water and foodstuff is essential for guaranteeing human health in some environments, and this has to be done with low cost technologies to be widely deployed in public services and industry. In this paper, we describe an ultralow cost (<US$ 0.005 per unit of sensing layer) electrochemical sensor to detect the antibiotic tetracycline, which is made of a homogeneous thin film of potato starch (PS) and carbon black (CB) deposited on glassy carbon electrodes (GCE). Detection of tetracycline was also performed in real samples consisting of tap water, river water, milk and in solutions prepared with commercial tablets of this medicine in the range between 5.0 and 120 μmol L⁻¹, with a detection and quantification limit of 1.15 and 4.47 μmol L⁻¹, respectively. The high sensitivity was attributed to the enhanced conductivity and larger surface area induced by incorporating the carbon black into potato starch. The CB‐PS/GCE electrodes were reproducible and stable, thus serving as a generic platform for detection of other antibiotics and hormones whose redox potentials are similar to those of tetracycline.     

Detection of benzylpenicillin sodium and ampicillin residue based on flower-like silver nanostructures using surface-enhanced Raman spectroscopy

Research on Chemical Intermediates - The capability to evaluate antibiotic residues in a sensitive, rapid, and reliable manner, is of great importance. Surface-enhanced Raman spectroscopy (SERS) is...     

Analytical methodologies for the determination of nitroimidazole residues in biological and environmental liquid samples: A review

Nitroimidazoles (NDZs) are antiprotozoal drugs that are typically used in veterinary and human medicine. NDZs and their metabolites are believed to possess genotoxic, carcinogenic and mutagenic properties, and this is (one reason) why their use has been banned within the European Union. Hence, the determination of trace residues of these substances in edible animal tissues has been of growing concern over the past few years. Even, though there has been a need to develop sensitive and reliable analytical methods to study the residues of these compounds in different matrices, available methodologies in environmental samples are rather limited. These and other pharmaceutical compounds have become one of the most important new classes of environmental pollutants that have been detected in wastewater-treatment-plant (WWTP) effluents, receiving waters, drinking water and groundwater. A compilation of the most representative analytical methodologies for the determination of NDZ residues during the last decade is presented in this paper. Its scope is the two main areas which require their determination, namely biological and environmental matrices. A detailed explanation of both areas, including sample treatment and detection systems, and future trends is presented, focusing on the difficulties of confirming analytes at low concentration levels.     

Fluoroquinolones and sulfonamides: features of their determination in water. A review

Sulfonamides and fluoroquinolones are two group of antibiotics widely used in the treatment of bacterial infections. Monitoring these residues in live animals and animal products is commonly legislated; however, the environmental occurrence and fate is still sporadically assessed. The development of adequate analytical methods is a key issue to provide accurate data on concentrations of antimicrobial compounds and their residues in different organic matters. This review presents an overview of proposed methods published between 2008 and 2013 for analysis of fluoroquinolones and sulfonamides with special emphasis on sample preparation and detection systems employed. The coupling of high-performance liquid chromatography and mass spectrometry has been the most widely used method to determination of sulfonamides and fluoroquinolones, concomitantly to other antibiotics residues, due to high sensitivity and selectivity. The main drawbacks of this technique are the high cost and the equipment complexity. The coupling high-performance liquid chromatography and fluorescence detection has also been used to fluoroquinolones determination. Their fluorescent properties allowed the development of several methods with limits of detection in ng L^?1 range. Sample preparation is an important tool to reach lower detection limits and the online solid-phase extraction has a broader use. The hydrophilic–lipophilic balance polymeric are the mostly applied sorbents for sulfonamides and fluoroquinolones preconcentration. These sorbents have allowed reaching better recoveries and sensitivity improvement. Physico-chemical properties of these antibiotic groups in addition to trends on papers occurrence and frequency of analysis in different types of water (surface water, groundwater, drinking water and wastewater) are discussed.