面向人体暴露评价的植物中抗生素分析进展

抗生素通过动物粪便或生物固体的施用、再生水灌溉进入农业土壤后可以被蔬菜和粮食作物吸收,从而造成人体的被动暴露。为了评估抗生素对人体暴露的健康风险,需要基于植物样品,发展灵敏、稳定且针对性强的分析方法。本文综述了植物样品中抗生素残留分析的研究进展,重点介绍了样品提取、净化等前处理方法及其仪器分析方法,并对植物样品中抗生素分析的研究方向进行了展望。     

室内空气和灰尘中全(多)氟烷基化合物的研究进展

全(多)氟烷基化合物(per(poly)fluoroalkyl substances,PFASs)在环境各个介质及人体样品中广泛被检出,近年,在室内空气和灰尘中也普遍发现PFASs.研究表明,室内空气中PFASs的含量普遍高于室外空气,室内空气和灰尘中的PFASs可能是室外空气的污染来源及人体暴露源,因此室内环境中PFASs成为环境领域的又一个研究热点.但目前为止,我国还没有开展室内空气中PFASs的相关研究,室内灰尘中PFASs的研究也相对较少.本文就室内空气和灰尘中PFASs的采样与分析方法、污染现状、来源分析及人体暴露等4个方面进行了综合阐述,以期为我国室内环境中PFASs的研究提供参考.     

猪粪中21种常见抗生素的同步提取检测方法研究及应用

为实现猪粪中抗生素的有效削减及控制,迫切需要开发快速、同步兽用抗生素的检测分析方法,明确猪粪中多种类抗生素赋存特征.本研究建立并优化了猪粪中21种常见抗生素的同步分析方法.该方法采用甲醇和Na2EDTA-McIlvaine缓冲溶液（1∶1,V/V）提取,提取液经固相萃取净化后高效液相色谱串联质谱检测.猪粪样品中5种四环素类、2种β-内酰胺类、6种大环内酯类、4种磺胺类和4种喹诺酮类抗生素的内标定量回收率29.53%—116.36%,检出限0.90—26μg·kg^-1 DS,定量限2.91—85.20μg·kg^-1DS,相关系数R2均大于0.997.采用该方法对单个猪场不同畜舍样品加标回收率的单因素方差分析发现,除了四环素-D6（TC-D6）有显著性影响之外,其它内标回收率在不同样品中无显著性影响.分别采集不同地区2个猪场的猪粪样品进行验证分析,发现猪粪样品中单个抗生素含量范围在ND—99.37 mg·kg^-1DS.结果表明,该方法可用于猪粪中多种类抗生素的同步检测.     

长江流域氧氟沙星和金霉素的人体健康水质基准研究

抗生素因其潜在的生态和健康风险而引起全球关注。目前,中国长江流域抗生素的人体健康水质基准研究尚处于空白阶段,不利于国家进一步开展抗生素新污染物的管控和风险评估工作。为促进长江流域抗生素污染物的人体健康水质基准研究和人体健康风险评估工作的开展,分别在长江流域宜宾段(上游)、重庆段(上游)、宜昌段(上游)、武汉段(中游)和上海段(下游)采集并分析了表层水样和不同营养级鱼样中氧氟沙星(OFL)和金霉素(CTC)的含量(采样点涉及长江干流、支流、沿江水库以及沿江城镇密集区)。通过分析长江流域OFL和CTC在第2、3、4营养级鱼类的最终营养级生物累积系数(A_fi),结合抗生素毒理参数和人群暴露参数,在饮水和消费水产品两种暴露途径下,推导出了长江流域OFL和CTC的人体健康水质基准(AWQC)。结果表明,长江流域水体中OFL和CTC的质量浓度分别为ND-1.55×10^-4、ND-4.17×10^-4 mg·L^-1,鱼体中OFL和CTC的质量分数分别为ND-4.94×10^-2、ND-0.108...     

全氟烷基化合物在人体肝脏中的富集特征及其与肝损伤的关系

全氟烷基化合物(polyfluoroalkyl substances,PFASs,F(CF_2)_n-R)是广泛用于生产生活中的有机污染物,研究发现PFASs的暴露会对人体造成危害.为分析人体肝脏中PFASs的富集特征,本研究采用高效液相色谱串联质谱(HPLC-MS/MS)的方法,对天津市31例肝癌患者肝脏中10种PFASs(全氟己烷磺酸PFHxS、全氟辛烷磺酸PFOS、全氟十二酸PFDoDA、全氟己酸PFHxA、全氟庚酸PFHpA、全氟十一酸PFUnDA、全氟壬酸PFNA、全氟癸酸PFDA、全氟辛酸PFOA、全氟戊酸PFPeA)进行检测分析.结果表明,PFOS、PFOA、PFNA、PFUnDA和PFHxS具有较高的检出率(80%);∑PFASs浓度范围为8.97—181.87 ng·g~(-1),其中PFOS的平均浓度最高(40.87 ng·g~(-1)),占∑PFASs的77%;∑PFASs的平均浓度在男性肝脏样品中(64.04 ng·g~(-1))与女性样品中(36.82 ng·g~(-1))存在显著性差异,PFHxS、PFOS和PFDA的浓度在性别上也均呈显著差异,PFOA的浓度与年龄呈显著负相关性.此外,PFOA和PFHpA的浓度分别与肝细胞损伤标志物ALT和GGT之间存在显著正相关性.本研究是国内首次对人体肝脏中PFASs的暴露分析,PFOS是肝脏的主要暴露物;PFASs对男性的暴露风险高于女性,且青年人群PFASs的暴露风险相对较高;另外,浓度水平进行分析,PFASs的暴露与人体肝脏损伤存在统计学关联.     

沈阳细河流域土壤和作物中汞的潜在生态危害及健康风险评价

为研究沈阳市细河流域土壤汞(Hg)的污染和健康风险状况,对该区土壤和农作物中Hg的含量和分布进行了调查和分析。采用Hakanson潜在生态风险危害指数法评价土壤Hg的污染状况,并利用健康风险评价模型对Hg通过不同暴露途径所引起的健康风险作出评价。研究结果表明,细河流域土壤Hg的潜在生态危害相对较大,其中43.21%样品处于中等危害程度,26.62%属于强及以上风险级别。健康风险评价模型计算表明,人体经食物摄取是土壤Hg暴露的主要途径,Hg日平均暴露剂量依次为食物摄取呼吸暴露皮肤暴露;成人和儿童的非致癌危害指数分别为0.315和0.713,均低于风险阈值1,表明Hg不会对人体造成健康危害。     

氯化石蜡的人体暴露研究进展

短链氯化石蜡具有持久性有机污染物的特性，是列入《关于持久性有机污染物的斯德哥尔摩公约》全球管控的有机物，氯化石蜡在人体内蓄积，造成健康风险.为研究氯化石蜡的人体暴露情况，对近20年来的相关论文进行综述.氯化石蜡的人体暴露途径可以大致分为外部暴露途径和内部暴露途径.外部暴露主要来自食物（饮食摄入）、空气（呼吸吸入）和室内灰尘（灰尘摄入和皮肤吸入）.对于内部暴露，目前在人体血液（血浆或血清）、母乳、胎盘、头发和指甲中均已检测到氯化石蜡.与普通成年人群相比，儿童以及婴幼儿外部暴露氯化石蜡的风险较高.中国由于较大的生产和使用量，人群暴露量相对较高.目前需加强氯化石蜡分析方法的可比性，以及氯化石蜡在人体的蓄积代谢研究等.同时，血液（血清或血浆）和母乳以外的其他生物指标中链和长链氯化石蜡人体暴露风险评估的研究也应得到重视.     

高分辨双晶X射线荧光光谱测定某些环境样品中硫的化学状态

本文用高分辨双晶X射线荧光光谱仪分析了煤、植物叶、土壤等环境样品中硫的化学状态。同时参照有关方法,设计了较为适用的非线性最小二乘法谱线分离程序。部分样品测定结果与其它方法做了对照比较,其结果基本相近。证明本法是一种样品预处理简便、测定快速而又可靠的化学状态分析方法。     

甲基硅氧烷的分析方法研究进展

甲基硅氧烷的产量及消耗量巨大.作为全球环境中的新型污染物,部分甲基硅氧烷已在工业生产中被限制使用.甲基硅氧烷的同系物丰富,存在于多种样品基质中,且含量差异较大.为了更好地表征甲基硅氧烷的污染程度,以评估其对环境和人体健康的可能风险,需要建立准确、灵敏、高效的分析方法.本文系统地综述了国内外有关甲基硅氧烷的样品前处理技术及仪器分析方法,比较了不同方法的优缺点,提出了分析过程中要特别关注的问题,并就未来的研究方向进行了展望.     

固相萃取-高效液相色谱法分析蔬菜中6种磺胺类抗生素

建立了固相萃取-高效液相色谱同时测定蔬菜中6种磺胺类抗生素的分析方法.以每克蔬菜(干样)加5ml乙腈(添加2g无水硫酸钠、0.1g乙酸钠、O.1gNa2EDTA)超声提取25min,采用正己烷液-液萃取去脂,C18柱净化富集.以磷酸(0.01mol·1-1,pH2.5):乙腈=80:20(V:V)溶液作为流动相,检测波长为270nm.蔬菜样品中6种磺胺类抗生素的回收率为50.8%-98.9%,定量限为21.9-72.8μg·k-1.利用该方法对不同蔬菜样品进行了分析,6种磺胺类抗生素均不同程度被检出,总含量在0.38-2.24 mg.kg-1(鲜重)之间.     

抗生素与三唑类杀菌剂混合物对羊角月牙藻的长期毒性相互作用研究

地表水中抗生素与农药的混合暴露及其潜在生态与健康风险受到广泛关注。然而,目前关于抗生素与农药混合毒性研究大多仅考虑急性毒性,缺乏其长期毒性相互作用的研究。以较为广泛使用的2种抗生素土霉素(OXY)、环丙沙星(CIP)和1种三唑类杀菌剂农药戊唑醇(TCZ)及其二元混合物为研究对象,以生态系统中初级生产者绿藻(羊角月牙藻)为受试生物,研究目标混合物在暴露时间为96、120、144和168 h的长期毒性相互作用。结果表明,单一物质及其混合物随暴露时间延长而毒性增大;同一暴露时间点的单一污染物毒性大小顺序为OXYTCZCIP;混合物毒性相互作用与浓度、混合物组分和暴露时间三者密切相关;混合体系的拮抗作用均出现在高浓度区域,而中、低浓度区域呈协同作用或加和作用; OXY-CIP与CIPTCZ混合体系的协同作用随着暴露时间延长而协同作用逐渐增大。研究结果对水环境中抗生素与农药复合污染生态风险评估具有重要的现实意义。     

畜禽环境中抗生素的去除及其风险评估

抗生素作为饲料添加剂广泛应用于畜禽养殖业,造成养殖环境抗生素大量蓄积,尤其是在畜禽粪便中,长期的积累不仅污染养殖场内土壤环境,残留的抗生素还会随畜禽粪便进入周边水体及农田环境,威胁农作物及人体健康。目前,国内相关研究主要集中在抗生素的降解工艺及降解规律方面,而对其去除效率的影响因素及风险评价研究相对较少。笔者综述了国内外抗生素的降解转化及去除方式等的研究进展,并概述了抗生素在畜禽环境中的生态风险评估的研究现状,为抗生素的高效去除、风险预估及畜禽粪便资源化安全利用提供理论基础和技术支撑。     

几种抗生素对蛋白核小球藻的时间毒性微板分析法

抗生素在不同的暴露时间可能具有不同的毒性变化规律。本文以蛋白核小球藻(C.pyrenoidosa)为受试生物,96孔微板为暴露实验载体,5种抗生素硫酸安普霉素、氯霉素、双氢链霉素、硫酸新霉素和硫酸链霉素为研究对象,通过在C.pyrenoidosa生长周期内选取6个暴露时间节点(即0、12、24、48、72和96 h),建立了抗生素在不同暴露时间对C.pyrenoidosa生长抑制毒性的微板测试方法(简称T-MTA),并应用T-MTA方法系统测定了5种抗生素对C.pyrenoidosa在不同暴露时间的生长抑制毒性。结果表明,抗生素对C.pyrenoidosa生长抑制毒性具有明显的时间依赖特征,即在开始的时候基本无毒性,而后毒性迅速增加,然后毒性增加速度减慢;不同抗生素的毒性随着暴露时间的延长增加速率不同;同一暴露时间内,5种抗生素对C.pyrenoidosa的毒性大小不同;且毒性顺序随着暴露时间延长而发生变化。     

3种氨基糖苷类抗生素对水生生物的时间依赖联合毒性作用比较

以3种氨基糖苷类(AG)抗生素:硫酸安普霉素(APR)、双氢链霉素(DIH)和硫酸链霉素(STS)为研究对象,以生态系统中2类重要的水生生物分解者如青海弧菌(Vibrio qinghaiensis sp.-Q67,Q67)和生产者蛋白核小球藻(Chlorella pyrenoidosa,CP)为受试生物,运用均匀设计射线法设计抗生素三元混合物体系,共5条具有不同浓度配比的射线,应用已建立的分别基于Q67和CP的时间毒性微板分析法系统测试抗生素及其三元混合物射线对Q67和CP在不同暴露时间的毒性。对于Q67和CP,暴露时间分别为0.25、2、4、8、12 h和12、24、48、72、96 h。应用浓度加和(CA)模型分析混合物在不同暴露时间的毒性相互作用。结果表明:APR、DIH和STS及其5条混合物射线对2种指示生物的毒性均具有明显的时间依赖性,且Q67对AG抗生素及其混合物射线的响应比CP的灵敏;以半数效应浓度的负对数p EC50值为毒性大小指标,3种抗生素对2种指示生物的毒性大小顺序随暴露时间的变化而变化,3种AG抗生素对Q67和CP分别在12 h和96 h的毒性大小顺序均为STSDIHAPR;5条具有不同浓度配比的混合物射线对Q67在不同暴露时间的毒性均呈加和作用,但对CP的毒性既有加和作用也有拮抗作用,且拮抗作用随暴露时间和组分浓度配比的变化而变化,表明AG抗生素毒性的联合毒性作用与暴露生物、暴露时间以及混合物组分的浓度配比等有关。     

2种经典模型对抗生素与重金属锌的蛋白核小球藻时间依赖联合毒性作用的评估比较

污染物在环境中普遍以混合物的形式存在,其累积毒性与毒性相互作用具有潜在的环境风险。因此,本研究以水环境中普遍存在的氨基糖苷类抗生素(硫酸链霉素、硫酸安普霉素和双氢链霉素)和重金属锌(Zn)为目标污染物,以蛋白核小球藻(Chlorella pyrenoidosa,C. pyrenoidosa)为指示生物,应用直接均分射线法设计3种抗生素与Zn的3个二元混合物体系,应用时间毒性微板分析法系统测定3种抗生素和重金属Zn及其二元混合物射线的时间-浓度-毒性数据,以浓度加和(concentration addition,CA)与独立作用(independent action,IA)为标准加和参考模型,分析混合物毒性相互作用及其随时间变化规律。结果表明,随着暴露时间延长,3种抗生素和重金属Zn对C. pyrenoidosa的毒性逐渐增强; 2种模型对3个二元混合物体系的毒性相互作用评估基本一致,即在低浓度区域始终呈现加和作用,而在高浓度区域随暴露时间延长由协同作用逐渐转变为加和作用;而对于同一混合物体系,CA和IA模型预测毒性之间的差距随着浓度增加而增加,且IA预测曲线始终位于CA预测曲线上方,显示了IA模型在评估具有相异组分混合物的毒性时较CA模型接近实际观测值。     

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.     

Edible wild plants growing in contaminated floodplains: implications for the issuance of tribal consumption advisories within the Grand Lake watershed of northeastern Oklahoma,USA

Metal releases from the Tri-State Mining District (TSMD) that is located in southwestern Missouri, southeastern Kansas, and northeastern Oklahoma, have contaminated floodplain soils within the Neosho and Spring river watersheds of the Grand Lake watershed. Since the Oklahoma portion of the watershed lies within ten tribal jurisdictions, the potential accumulation of metals within plant species that are gathered and consumed by tribal members, as well as the resulting metal exposure risks to tribal human health, was a warranted concern for further investigation. Within this study, a total of 36 plant species that are commonly consumed by tribes were collected from floodplain areas that were previously demonstrated to have elevated soil metal concentrations relative to reference sites. A significant, positive correlation was shown for metal concentrations in plant tissues versus soil (n = 258; Cd: R = 0.72, p = 0.00; Pb: R = 0.52, p = 0.00; and Zn: R = 0.70, p = 0.00). Additionally, a significant difference in metal concentration distributions existed between reference and impacted plant samples (n = 210, p = 0.00 for all metals). These results proved that floodplain soils are a major contamination pathway for metal accumulation within plants, and the source of metal contamination is the result of mining releases from the TSMD. Metal accumulation within plants was found to vary according to specific metal and plant species. The lowest dietary exposure out of all plant organs sampled were associated with fruit, whereas the highest was associated with roots, stem/leaves, and low-lying leafy greens. Metals in plants were compared to weekly dietary intake limits established by the Joint FAO/WHO Expert Committee on Food Additives. Based on specific serving sizes established within this study for tribal children and adults, many plant species had sufficient concentrations to warrant tribal consumption restrictions within the floodplains of Elm Creek, Grand Lake, Lost Creek, Spring River, and Tar Creek. Importantly, these results highlighted the necessity for the issuance of plant consumption advisories for tribal communities in the watershed. A consumption restriction guide on the number of allowable servings of each species per week at specific streams was developed within this study for tribal children and adults. Results also demonstrated that soil metal concentrations do not need to be exceptionally elevated relative to reference sites in order for plants to accumulate sufficient metal concentrations to exceed dietary limits for one serving. Therefore, the exposure risk associated with the consumption of plants cannot be accurately predicted solely from metal concentrations within soils, but must be based on metal concentrations within specific plant tissues on a site-by-site basis. A weekly consumption scenario was created within this study in order to better understand the potential metal dietary exposures to child and adult tribal members who consume multiple servings of multiple plant species per day, as well as benthic invertebrates and fish from the watershed. These findings demonstrated that plants pose a greater consumption exposure risk for tribal members than benthic invertebrates or fish. Therefore, without the consideration of exposure risks associated with the consumption of plants within future human health risk assessments, tribal health risks will be severely underestimated.     

Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters

• Selective molecularly imprinted polymer (MIP) binding gel was prepared. • MIP-DGT showed excellent uptake performance for antibiotics. • In situ measurement of antibiotics in wastewaters via MIP-DGT was developed. • The MIP-DGT method was robust, reliable, and highly sensitive. Urban wastewater is one of main sources for the introduction of antibiotics into the environment. Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems. In this study, we report a novel diffusive gradient in thin films (DGT) method based on molecularly imprinted polymers (MIPs) for in situ measurement of two typical antibiotics, fluoroquinolones (FQs) and sulfonamides (SAs) in urban wastewater. MIPs show specific adsorption toward their templates and their structural analogs, resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment. The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH (4.0–9.0), ionic strength (1–750 mmol/L), and dissolved organic matter (DOM, 0–20 mg/L). MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials, where three SA (sulfamethoxazole, sulfapyridine, and trimethoprim) and one FQ (ofloxacin) antibiotics were detected, with concentrations ranging from 25.50 to 117.58 ng/L, which are consistent with the results measured by grab sampling. The total removal efficiency of the antibiotics was 80.1% by the treatment plant. This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.     

Assessing human exposure to aluminium,chromium and vanadium through outdoor dust ingestion in the Bassin Minier de Provence,France

The Western part of the “Bassin Minier de Provence”, a former coal mining area, is still occupied by old polluting industries such as a coal-fired power plant and an alumina factory. The identified pollution sources that raise more concern in the population are the emission of gases and dusts, as well as the storage of raw and transformed materials. In 2011, a preliminary survey was carried out in the area as the first step to an exposure and health risk-assessment study. This first survey intends to assess human exposure through ingestion and health risk associated with potentially harmful elements (PHEs) in ground-level dusts collected in recreational areas used by children. Dust samples were taken at 19 sites distributed across the study area, depending on the location of public parks, public gardens, playgrounds and schools. Pseudo-total concentrations of 53 elements were determined by ICP-MS. Bioaccessible concentrations were estimated using the unified bioaccessibility method. This study presents the results obtained for Al, V and Cr, which seem to be related with industry and show similar distribution patterns. PHEs presumably related to traffic or other urban pollution sources are not discussed in this study. The highest total concentrations occur in dusts near the alumina plant that have significant amounts of Al mineral phases (gibbsite and alumina). However, in these dusts only small fractions of the elements under study are in bioaccessible forms. The highest bioaccessible fractions occur in dusts collected near the coal-fired power plant. Further investigation is required to assess potential pathways of exposure and health risk in this area.