纳米银在多孔介质中的迁移过程与机制研究进展

纳米银(AgNPs)作为消费品中最常用的人工纳米材料,由于其优异的抗菌性能,在织物、医疗设备和食品及饮料包装中广泛使用.AgNPs可通过大气沉降、地表水径流、污水灌溉和生物污泥的土地施用等多种途径进入土壤等多孔介质,甚至进入地下水.AgNPs进入环境后可在动物和植物体内累积并产生毒性效应,对生态环境构成危害.因此,全面了解AgNPs在土壤等多孔介质中的迁移过程对正确评估其环境归趋和生态效应具有重要的理论和现实意义.本文针对近年来已发表的不同表面稳定剂、环境有机质、土壤矿物及微生物等对AgNPs性质及在多孔介质中迁移过程中产生的影响进行了全面的总结,并就目前研究中存在的问题和后续研究的发展方向进行了展望.     

近红外长余辉纳米颗粒经小鼠眼部暴露后体内分布和代谢情况

为了研究纳米颗粒通过眼部暴露后进入体内的路径及在体内的分布和代谢情况,实验采用近红外长余辉纳米探针作为示踪剂,对小鼠进行眼部暴露,随后利用活体成像技术观察其进入小鼠体内的过程及分布情况,于暴露第4天收集代谢产物,第7天取重要脏器和血液,并检测纳米探针的存在情况.结果显示纳米探针可由眼经口腔进入胃肠道中,并且纳米颗粒暴露4天后在小鼠的粪便中检测到强荧光信号,而尿液中的荧光信号较弱,暴露7 d后在小鼠的眼睑结膜、胃及眼球中检测到强荧光信号,而其余器官的荧光信号较弱.这表明通过眼部暴露后,纳米颗粒主要分布在眼和消化系统中,最后大部分经消化系统代谢.     

顺式和反式氯丹在家鸡体内的分布和转运

通过工业氯丹口服暴露实验,研究了顺式氯丹(CC)和反式氯丹(TC)在家鸡体内的吸收、代谢、排泄和在各个器官组织内富集的动态过程.分别测定了未暴露个体和一次性暴露后60、120、160、200、300、500、1000和2000min时脑、肝、肠、肌肉、皮、脂肪等组织和器官样品以及胃部和肠道残余物、排泄物中的氯丹含量.研究发现,暴露2000min后,95%以上的氯丹通过代谢途径被消除,只有少量氯丹通过排泄方式被消除;体内氯丹的消除满足一级反应动力学.研究还发现,在代谢过程中,反式氯丹快于顺式氯丹.另外,在吸收和代谢的过程中,有明显的手性特征,(+)-CC和(-)-TC更易被消除,但各个器官组织存在明显差异.     

海洋沉积物中的镉及不同形态镉的生物有效性

镉是一种生物非必需的毒副作用很强的重金属元素.进入海洋环境中的镉,最终有相当部分进入沉积物中,并对底栖生物造成危害.通过测定不同镉质量浓度暴露条件下海水、沉积物和生物体内的镉的形态和含量,研究了海洋沉积物中不同形态镉的生物有效性.结果表明,菲律宾蛤仔对Cd的蓄积随着时间增加,呈现先快速增加的趋势,在24 h内其蓄积速率最大,96 h后生物体内镉的质量分数出现缓慢下降趋势.在蓄积时间一定的条件下,在任何Cd含量沉积物下,菲律宾蛤仔都可以蓄积Cd,而且随着沉积物中镉质量分数升高,生物体内蓄积的镉的质量分数也呈现上升趋势.活性镉(可交换态)是沉积物中镉存在的主要形式(45.48x.96%),硅酸盐结合态和黄铁矿结合态的金属只占较小的比例,活性镉是影响沉积物中重金属镉生物可利用性的最有效形态.     

不同暴露途径下有机污染物对大鼠急性毒性的相关性研究

不同暴露途径下有机物在生物体内的吸收分布不同,导致毒性效应亦不同,研究化学品在不同暴露途径下对生物体的毒性,对化学品的安全性评价有实际意义。本文通过研究静脉注射、腹腔注射、肌肉注射与经口灌胃4种暴露途径下527个有机物对大鼠的急性毒性数据相关性,比较了不同暴露途径下大鼠对有机污染物的敏感度顺序,结果为:静脉注射>腹腔注射>肌肉注射>经口灌胃途径,静脉注射途径下log1/LD50与其他几种注射途径下的log1/LD50有较显著的相关性,但是与灌胃途径下毒性值之间的相关性较差,相关系数r的范围为0.82~0.97。通过逐项分析研究不同暴露途径下化合物对大鼠的急性毒性与生物利用度、吸收速率、消除速率以及代谢过程的关系,结果表明,导致这种差异的原因主要是有机污染物在大鼠体内的吸附动力学过程不同所致。     

3,3',4,4',5?五氯联苯(PCB126)在食用罗非鱼不同组织 中的蓄积、净化、迁移规律的动力学研究

为明确二■英及其类似物通过饲料在食用鱼体内的蓄积、净化、迁移规律,了解模型在预测可食部和饲料中污染水平及计算动力学参数方面的准确性,本研究测定了饲料暴露的二■英样多氯联苯(3,3′,4,4′,5-五氯联苯,PCB126)在养殖食用罗非鱼的肝脏、肌肉、肾脏、血液中的含量,利用非线性模型拟合了各组织的污染水平和清除速率常数等PCB126的蓄积、净化动力学参数.结果表明,该模型对肌肉中PCB126的污染水平有很好的预测效果(R~2=0.95),对各组织中污染物半衰期的预测也与实际接近.本研究用逸度表征污染物在各组织中的迁移趋势,结果表明肝脏可快速蓄积、清除PCB126,并在高浓度污染物刺激下生长以提高蓄积能力;肌肉中污染物的迁移不受暴露时长的影响,清除期污染物由其它组织迁移入肌肉,引起肌肉中污染物含量峰值的延后.     

金矿区中国林蛙体内DNA甲基化水平

采集金矿附近山区河流水质、沉积物和当地两栖类动物中国林蛙样品,应用高效液相色谱仪测定污染区和对照区林蛙体内各组织器官的胞嘧啶(c)和5-甲基胞嘧啶(5-mc)含量,探讨因金矿开采引起的汞污染以及对林蛙体内组织器官DNA甲基化水平的变化,研究汞胁迫下,两栖类动物体内分子水平的影响。结果表明:金矿开采区河流水质和沉积物已受到甲基汞污染,污染区林蛙体内甲基汞含量远高于对照区;林蛙体内各组织器官中DNA甲基化水平发生不同的变化:污染区林蛙肝脏和皮肤中DNA甲基化水平高于对照区,肌肉和脑干DNA甲基化水平低于对照区;雄性林蛙肝脏和脑干DNA甲基化水平高于雌性,肌肉和皮肤DNA甲基化水平却低于雌性。以上结果说明汞胁迫下,中国林蛙体内组织器官DNA甲基化水平可以发生一定的变化,环境中重金属汞离子进入林蛙体内含量的不同,可以促进或抑制其体内甲基化水平的变化,引起基因毒性作用。     

海洋无脊椎动物重金属富集研究进展

污染物通过多途径进入海洋,以多种方式在海水和海洋沉积物中积累,成为海洋生物尤其是底栖生物体内污染物的主要来源.海洋无脊椎动物作为海洋食物链中的低营养级生物,多数种类均为底栖生活,具有较强的污染物富集能力.通过食物链的生物放大作用,其体内富集的污染物会传递到高营养级生物和人类体内,最终对海洋生物和人类产生危害,甚至引发公害事件.重金属(heavy metal)作为主要的污染物之一,具有毒性大、持续性长、耐还原性和耐降解性的特点,长久以来得到广泛的关注和研究.本文以海洋无脊椎动物为代表,从机体暴露途径、机体组织分布情况及过程、污染物在组织间的转移规律和变化因素4个方面入手,全面归纳和总结了重金属污染物在海洋生物体内富集的相关研究进展,并对目前的研究热点、存在的问题进行分析总结,对今后的研究方向进行展望,以期为国内外学者进一步开展海洋无脊椎动物重金属富集相关的研究提供有效参考.     

湿地植物香蒲体内氮、磷含量的季节变化及适宜收割期

通过实地调查,研究了南四湖湿地生态自然保护区香蒲对氮、磷元素的吸收与蓄积规律.结果表明:氮磷元素在香蒲体内的蓄积含量具有季节性规律,随生长发育时期的延长,香蒲组织内氮、磷均具有随季节而向上输送蓄积或向下进行"营养回流"的特点.结合香蒲资源化利用的途径,香蒲的收割方式应按照其分布特点,分区域交替收割,既要保证香蒲的正常繁殖,还要保证香蒲能够从湿地环境带出一定量的氮磷,收割期宜在10月下旬或11月份.从香蒲吸收氮磷元素的年际间对比,发现2008年度地上部较2007年度有明显的累积,香蒲具有年际间的累积特点,但在生长后期一部分营养可能转运至土壤环境,使得累积现象不明显.氮磷营养元素在植物体内的高度分布规律在湿地生态管理中具有重要的指导意义,调研结果显示,生长初期与生长后期香蒲体内营养元素的高度分布具有近似相反的规律性.     

铅暴露对人体健康风险评价的模型综述

铅是一种在暴露环境下,可以通过手口途径或者皮肤接触而进入人体,从而对人体许多组织器官都产生毒性作用的重金属,其对儿童的危害尤为突出.我国对暴露在铅环境下人体健康的风险评价研究起步较晚,基于血铅指标的铅污染土壤风险评估方法导则仍在探讨建立中.而国外已经存在一些较为成熟的用于成人及儿童的铅暴露吸收和生物动力学模型,其中被广泛接受和使用的是成人血铅模型(ALM)以及儿童在铅中的综合暴露吸收生物动力学模型(IEUBK).前者描述了关于非居住区土壤中铅暴露物对成人风险的评估,且重点针对污染土壤的铅暴露物所导致的孕妇体内胎儿的血铅浓度进行评估;后者则重点预测6—84个月的儿童在铅的综合暴露下的健康风险.本文旨在通过对这些模型进行对比总结,从而提出可用于我国铅污染风险评估的理论依据及指导方法.     

Translocation and biotoxicity of metal (oxide) nanoparticles in the wetland-plant system

• Aquatic plants are more likely to absorb TiO₂ NPs that are beneficial to them. • Ag NPs inhibited the growth of aquatic plants under both 5- and 60-day exposure. • CeO₂ NPs had positive/negative impact on plant in 5/60-day exposure, respectively. • TiO₂ NPs presence could enhance the photosynthesis and increase the plant biomass. • The ENPs changed plant activity, which resulted in changes of wetland performance. Engineered nanoparticles (ENPs) threaten the environment through wastewater discharging. Generally, constructed wetlands (CWs) are efficient methods for ENPs removal. However, the biotoxicity of ENPs on plants in CWs is unclear. Here, we investigated the distribution and bio-impacts of different ENPs (Ag NPs, TiO₂ NPs, and CeO₂ NPs) in plants under 5- and 60-day exposure to 1 and 50 mg/L concentrations. Results showed that ENPs appeared in the vascular bundle and mesophyll cell space, which induced the variation in antioxidase activities (e.g., superoxide dismutase [SOD], peroxidase [POD], and catalase [CAT] activities) as well as overproduction of malondialdehyde (MDA). Additionally, Ag NPs inhibited photosynthesis rate and root activity during two exposure phases. CeO₂ NPs had positive and negative impacts on plants in 5- and 60-day exposure, respectively. Inversely, TiO₂ NPs enhanced photosynthesis and root activity under 60-day exposure. Finally, the contents of the C, N, and P elements in plants fluctuated in response to ENPs stress. All results have a positive correlation with the wetland performance under ENPs exposure except for TiO₂ NPs treatment. Overall, our study systematically reveals aquatic plants' responses to ENPs and provides a reference for building ecological treatment systems to purify wastewater containing ENPs.     

纳米银和银离子对斑马鱼胚胎早期生长发育的影响及作用机制

为探究纳米银对水生生物的毒性作用,选取斑马鱼胚胎为受试生物,考察了纳米银对斑马鱼胚胎早期生长发育的影响,同时比较了纳米银与银离子对斑马鱼胚胎的毒性作用和机理。实验将受精后4小时(4 hpf)的斑马鱼胚胎分别暴露于不同浓度的纳米银和银离子溶液中至96 hpf,观察并记录了胚胎的死亡、孵化和畸形等指标。应用吖啶橙(AO)染色实验研究了胚胎暴露之后的细胞凋亡情况,并且应用荧光定量PCR技术分析了相关基因的表达水平。研究结果表明,随着暴露浓度的增加,纳米银和银离子均能导致斑马鱼胚胎的死亡率增加和孵化率降低,并且引起孵化延迟。纳米银和银离子的96 h半数致死浓度(96 h-LC50)分别为11.75 mg·L-1和0.054 mg·L-1。银离子毒性远大于纳米银毒性。暴露的斑马鱼胚胎均表现出体长变短和卵黄囊肿大的畸形。AO染色结果表明,纳米银和银离子处理组胚胎的躯干和卵黄囊部位存在细胞凋亡信号。基因表达分析结果显示,1.93 mg·L-1纳米银显著提高了斑马鱼胚胎caspase9的表达(P0.05),而0.006 mg·L-1的银离子就能显著上调COX-2a(P0.01)和COX-17(P0.05)基因的表达,同时0.036 mg·L-1银离子增加了斑马鱼体内p53基因的表达(P0.05)。以上研究结果说明,纳米银可能通过caspase通路诱导细胞凋亡进而影响斑马鱼胚胎的生长发育;而银离子不但影响氧化系统基因通路,还能通过p53诱导凋亡进而阻滞斑马鱼胚胎的生长发育。     

全氟辛烷磺酸盐(PFOS)对半滑舌鳎(Cynoglossus semilaevis)免疫相关基因表达的影响

为了解全氟辛烷磺酸盐(perfluorooctane sulfonate, PFOS)暴露对半滑舌鳎(Cynoglossus semilaevis)免疫功能的影响,在实验室条件下,运用RT-PCR方法分析了PFOS暴露对半滑舌鳎热休克蛋白hsp70、hsp90、C型凝集素(c-type lectin)和细胞色素c氧化酶(cytochrome c oxidase, cox)等4种免疫相关基因表达水平的影响。实验测定了上述4种基因在半滑舌鳎肝、鳃、肠及肌肉4种不同组织中随时间(0、24 h、48 h、96 h和7 d)的表达变化情况。结果表明,在4种组织中,hsp70基因的表达与对照相比为上调,其中,肝组织hsp70基因的表达量显著高于其他各组织,且表达高峰值的出现也早于其他各组织;hsp90基因在肝和鳃组织中表达量随时间不同而波动,在肠组织中表达上调,在肌肉中表达显著下调;c-type lectin基因表达量与对照组相比表达显著下调或无明显差异;cox基因在肝组织和肠组织中表达下调,在鳃和肌肉中表达上调。上述研究结果表明,PFOS能引起免疫相关基因的表达变化,对半滑舌鳎具有潜在的免疫毒性。肝组织中各免疫基因对PFOS胁迫的响应高于其他组织。本研究可为阐明全氟辛烷磺酸盐对半滑舌鳎的免疫毒性提供基础数据。     

水体中金属(氧化物)纳米颗粒的环境行为与污染控制研究进展

金属(氧化物)纳米材料在生产和使用过程中,可以通过各种途径进入到水环境中,对水生生物、生态环境和人体健康产生威胁.理解纳米颗粒在水体中的环境行为,对于评估纳米材料的归趋及其对环境和人体的健康风险至关重要.本文概述了金属(氧化物)纳米颗粒的性质、来源和毒性危害,汇总了表征纳米颗粒浓度、粒径及形貌的分析方法与技术,分析了它们在水环境中的环境行为以及影响其稳定性的主要环境因素,并总结了水体中金属(氧化物)纳米颗粒的去除方法和效果的最新研究进展.随着金属(氧化物)纳米材料的广泛应用,未来有必要加强对自然水体中纳米颗粒环境行为的研究,并系统开展纳米颗粒健康风险评估工作,为预测纳米材料进入水环境后的归趋和风险提供科学依据.     

Toxicity and transfer of metal oxide nanoparticles from microalgae to sea urchin larvae

Nanoparticles (NPs) contained in commercial products are released and enter into the aquatic ecosystem, posing serious possible risks to the environment and affecting the food chain. Therefore, investigating the potential toxicity of NPs on aquatic organisms has become an important issue. This study assessed the toxicity and trophic transfer of metal oxide NPs from marine microalgae (Cricosphaera elongata) to the larvae of the sea urchin Paracentrotus lividus. Larvae (24 h old) were fed on 2000 cell mL^?1 48 h of microalgae contaminated with 5 mg L^?1 of several metal oxide NPs (SiO₂, SnO₂, CeO₂, Fe₃O₄) for 15 days. Larval viability and development were monitored from the 4-arm stage to the 8-arm pluteus stage. A significant decrease in survival was observed in larvae fed with microalgae exposed to SiO₂ and CeO₂ NPs. Abnormal development, characterised by skeletal degeneration and altered rudiment growth, was observed in all larvae fed with contaminated NP algae. Our findings revealed that SiO₂ and CeO₂ NPs exerted a toxic effect in the trophic interaction analysed, by reducing sea urchin larval viability, and all metal oxide NPs induced toxicological effects. In conclusion, metal oxide NPs may enter the food chain and become bioavailable for marine organisms, affecting their development.     

Antioxidant enzyme activities of <Emphasis Type="Italic">Microcystis aeruginosa</Emphasis> in response to nonylphenols and degradation of nonylphenols by <Emphasis Type="Italic">M. aeruginosa</Emphasis>

The aim of this study was to examine the effects of chemical nonylphenols (NPs) on the antioxidant system of Microcystis aeruginosa strains. The degradation and sorption of NPs by M. aeruginosa were also evaluated. High concentrations of NPs (1 and 2 mg/l) were found to cause increases in superoxidase dismutase (SOD) and glutathione-S-transferase (GST) activities and in glutathione (GSH) levels. These results suggest that toxic stress manifested by elevated SOD and GST levels and GSH contents may be responsible for the toxicity of NPs to M. aeruginosa and that the algal cells could improve their antioxidant and detoxification ability through the enhancement of enzymatic and nonenzymatic prevention substances. The observed elevations in GSH levels and GST activities were relatively higher than those in SOD activities, indicating that GSH and GST contributed more in eliminating toxic effects than SOD. Low concentrations of NPs (0.05–0.2 mg/l) enhanced cell growth and decreased GST activity in algal cells of M. aeruginosa, suggesting that NPs may have acted as a protecting factor, such as an antioxidant. The larger portion of the NPs (>60%) disappeared after 12 days of incubation, indicating the strong ability of M. aeruginosa to degrade the moderate persistent NP compounds. The sorption ratio of M. aeruginosa after a 12-day exposure to low nominal concentrations of NPs (0.02–0.5 mg/l) was relatively high (>30%). The fact that M. aeruginosa effectively resisted the toxic effects of NPs and strongly degraded these pollutants indicate that M. aeruginosa cells have a strong ability to adapt to variations in environmental conditions and that low and moderate concentrations of organic compounds may favor its survival. Further studies are needed to provide detailed information on the fate of persistent organic pollutants and the survival of algae and to determine the possible role of organic pollutants in the occurrence of water blooms in eutrophic lakes.     

Genotoxic effects of Ag2S and CdS nanoparticles in blue mussel (Mytilus edulis) haemocytes

The use of functionalised metal sulphide nanoparticles (NPs) for nanoremediation and biomedical application is rapidly increasing, which could lead to significant inputs into the marine environment. The potential impact of some NPs on marine organisms is still poorly understood. In the present paper the genotoxic potential of Ag₂S and CdS NPs on Mytilus edulis haemocytes was assessed. MPEG-SH (thiol-terminated methyl polyethylene glycol), was used as capping agent to avoid NPs agglomeration. TEM analysis showed that the Ag₂S NPs size was 13±7 nm, whereas CdS quantum dots had an average diameter of 4±1 nm. DNA integrity was evaluated by Comet assay following exposure to increasing concentration series (0.01–10 mg/L). Both silver and cadmium NPs showed genotoxic effects at the highest dose. MPEG-SH was also found to exert a weak genotoxic activity, suggesting that at least part of the genotoxic potential of functionalised NPs on mussel cells might be attributable to the capping agent. These results confirm the genotoxic potential of Ag₂S NPs for mussel cells and demonstrated, for the first time, that CdS NPs is genotoxic in a marine organism.     

Environmental human silver exposure

Environmental exposure to silver (Ag) was assessed in occupationally non-exposed adult human population by analyzing Ag in the hair (H?·?Ag) and whole blood (WB?·?Ag). H?·?Ag was analyzed in 311 (123 men, M; 188 women, W); while WB?·?Ag was determined in 235 of these individuals (90 M, 145 W). Women had more H?·?Ag than men (M 0.05 vs. W 0.076), whereas WB?·?Ag concentrations in men and women were not significantly different. A natural distribution of the median derivatives was utilized to generate the dataset to fit the logistic sigmoid curve to assess the current human body burden of environmental Ag population exposure for M and W separately. The H?·?Ag (µg?g^?1) below 0.0105 for M and 0.0145 for W, reflects low level of environmental Ag exposure. The adaptive physiological saturation phase followed where H?·?Ag rose rapidly, first for M and then for W in parallel with biological assay. Both parallel saturation curves converged and plateaued at 0.215 for M and 0.965 for W (µg?g^?1). The current level of human environmental Ag exposure is low, but cases of high Ag exposure occurred sporadically. In conjunction with the medical histories overt clinical neural toxicity may be expected for H?·?Ag at 4?µg?g^?1and higher. There were no significant correlation between the H?·?Ag and WB?·?Ag.     

Toxicity of cadmium nanoparticles to Bacillus subtilis

The study deals with the toxicological impact of cadmium nanoparticles (Cd NPs) on Bacillus subtilis as a model Gram-positive bacterium. Cadmium oxide (CdO) NPs (～22 nm) and cadmium sulfide (CdS) NPs (～3 nm) were used in this study. Both the NPs were found to inhibit the cell viability of B. subtilis when added to the culture at mid-log phase, the viable cell number declined with increasing concentration of Cd NPs. At mid-log phase, 15 mg L^?1 CdO NPs inhibited growth by ～50%, whereas at 30 mg L^?1 growth completely ceased. Under the same conditions, CdS NPs inhibited growth by ～50% at a concentration of 8 mg L^?1, and at 20 mg L^?1 growth was completely retarded. The cells changed their morphological features to a filamentous form with increasing Cd NPs exposure time, leading to associated with clumping. NPs treated cells when stained with 4′, 6-diamino-2-phenylindole, showed filamentous multinucleated bead structure, suggesting irregularities in cell division. Increasing intracellular oxidative stress due to Cd NPs exposure might be one of the reasons for the cell morphological changes and toxicity in B. subtilis.     

鱼体中有机微污染物的定量及筛查研究进展

化学品通过多种途径进入环境水体,可对水生生物及人体健康造成潜在风险。鱼类作为水环境污染物监测的指示生物,分析鱼体内有机微污染物的分布特征是评估水环境安全的重要方法。现有污染物种类繁多,且在生物体内存在降解转化的过程,基于靶向定量分析的监测方法难以系统、准确地评估鱼体中有机污染物的暴露特征。由于具有高分辨率、高质量精度、高通量和回顾性分析等特点,高分辨质谱技术逐渐被用于鱼体中有机污染物的筛查研究,为鱼体中高风险及未知污染物的定性、定量分析提供可能。本文综述了鱼体中有机污染物的定量分析现状,筛查分析方法以及其在鱼体中有机微污染物筛查研究中的应用。