合成麝香的研究新进展与当前挑战:从人体护理、环境污染到人体健康

合成麝香(Synthetic Musks,SMs)因具有类似天然麝香的芬芳气味,被广泛添加于各种日化产品中。由于这类化合物的大量使用以及我国现有污水处理系统的局限性,目前在各种环境介质、人体内频繁检出SMs,从某种意义上来说该类化合物已经对生态环境和人类健康造成了一定潜在危害,因此是一类重要的新兴有机污染物。本文详细综述了SMs的环境污染水平、迁移转化机制、环境归趋、环境危害以及健康效应等方面的最新研究进展;发现虽然这类污染物在环境转化过程中存在毒性增强等潜在的危害,但其在环境与生物体内的迁移转化机制尚未明确,且相关代谢转化产物的毒性效应研究并不多见,尤其在SMs暴露模式与人体损伤机制之间的相互关系研究方面还存在空白。此外,新型SMs如大环麝香与脂环麝香的健康效应的研究也有待进一步加强。     

季铵盐类化合物环境问题研究进展

季铵盐类化合物(quaternary ammonium compounds, QACs)是一类广泛使用的阳离子表面活性剂,在环境介质(水、沉积物、污泥等)中普遍存在,尤其在污泥/沉积物中其浓度可达数百甚至上千mg/kg水平。QACs具有高表面活性和中/高毒性,低浓度下即对鱼类、藻类、细菌和无脊椎动物等产生毒害作用,并显著影响与其共存污染物的迁移性和生物有效性,其环境问题已经引起发达国家广泛关注,但在我国研究尚未成熟。因此,本文综述了QACs在环境介质中的来源、分析方法、污染现状、环境行为及毒性效应,并讨论了目前研究存在的问题,以期为我国开展QACs环境问题的研究提供参考。     

人工合成麝香的分析方法及环境污染现状

人工合成麝香作为天然麝香的替代物被大量用于日化产品中,按其化学结构可分为硝基麝香、多环麝香和大环麝香3种。人工合成麝香的大量生产及广泛使用使之通过各种途径进入环境,而该物质亲脂性和持久性的特点,导致其在生物体内积累并产生毒理效应,故引起了广泛关注,成为一类新型污染物。该文综述了目前人工合成麝香的分类、环境污染现状及不同基体样品的分析检测方法,为今后合成麝香的风险评价研究提供参考。     

纳米富勒烯(nC60)的生态毒性效应

随着纳米技术的飞速发展,纳米材料的应用日趋广泛.同时,纳米材料的大规模生产和应用对人体健康与生态环境可能产生的安全风险也引起了人们的普遍关注.富勒烯是应用最广泛的纳米材料之一,在水中能形成稳定的水溶性纳米颗粒,进而增大其在环境中的迁移性与生物暴露几率.然而目前对纳米富勒烯(nC60)的环境和毒性效应还知之甚少.本文综合评述了水溶性nC60纳米颗粒的制备、稳定机制、在环境中的迁移特性及其与环境中污染物的相互作用,并着重阐述了nC60可能产生的生物毒性效应.分析表明,nC60的生物毒性效应主要与nC60的表面化学特性和颗粒大小有关,同时环境介质也影响nC60的毒性.最后讨论了nC60生态环境效应研究中应加强的若干方面.     

我国环境化学研究新进展

因环境问题复杂性而产生的学科交叉特性既是环境化学的特色,又是学科生长点。2010年以来,新型污染物和纳米材料的污染问题以及化学污染导致的健康影响日益引起关注,环境化学的研究范围亦随着实际问题的出现而延展,新型污染物种类持续上升。继2010年首次在氟化工厂环境中发现并报道了新型持久性有机污染物全氟碘烷的存在,2011年又基于效应分析成功甄别了一种具有神经毒性的新型溴代污染物,标志着我国在污染物研究方面已从全面跟踪国外研究到部分引领方向转化。继青藏高原环境介质污染物归趋行为研究之后的极地环境科学考察进一步将视野着眼于全球尺度环境问题的解决。得益于上海光源等一批大科学装置的建成,污染物环境界面行为探索已达到分子水平。在纳米材料广泛应用所引发的纳米污染层面,其形成、转化和环境归趋行为的研究亦取得突破。污染生态化学研究方面,借助于先进的表面等离子体共振和理论模拟等先进手段,在污染物与生物大分子相互作用探索和联合毒性机制研究上取得了显著进步,环境与健康开始受到广泛关注。这些成果极大丰富了学科内涵,为学科今后的发展奠定了坚实基础。共引用参考文献45篇。     

短链氯化石蜡的分析方法、污染现状与毒性效应

作为一种新型有机污染物,短链氯化石蜡(SCCPs)在2006年被列入斯德哥尔摩公约持久性有机污染物(POPs)候选名单。2017年5月第8次《关于持久性有机污染物的斯德哥尔摩公约》缔约方大会上,SCCPs最终被列入了《公约》附件A受控POPs清单。我国是氯化石蜡(CPs)生产使用大国,其在环境介质中的含量处于较高水平。本文对SCCPs的分析方法、污染现状、环境中来源与释放及其毒性效应进行了综述,并针对目前存在的问题及研究需求进行了总结。     

微塑料介导重金属在陆生植物中迁移及生物效应的影响

随着地膜在现代化农业中的广泛应用,微塑料在土壤中的残留问题日益严重。环境中释放的微塑料可能会与先前存在的重金属相互作用,导致生物效应(生物积累/毒性),并对人类健康和农产品安全构成威胁。目前,大多数研究集中于单一影响因素在土壤系统中的暴露和转化分析,有关微塑料和共存金属对环境联合影响的相当有限。本文综述了微塑料与重金属来源、相互作用机理与影响因素的研究现状,阐述了陆生植物对二者联合污染的生理响应。此外,未来的研究还应重点探讨微塑料与重金属共同在植物上暴露的具体分子机制、通过食物链对人类健康的影响、与其他混合污染物联合作用及微塑料老化过程对重金属迁移动态变化过程的影响。     

全氟辛酸和全氟辛烷磺酸人体暴露途径解析及其污染控制技术*

全氟辛酸（PFOA）和全氟辛烷磺酸（PFOS）是人工合成全氟化合物的典型代表。近年来,大量的环境调查数据表明它们普遍存在于多种环境介质、生物体甚至人体中,呈现出全球分布的态势,具有环境持久性和生物富集性,对人体健康存在潜在的危害,已成为一类新的环境持久性有机污染物而引起人们广泛的关注。本文介绍了PFOA和PFOS的环境来源和传输途径,解析了人体暴露的三种主要途径以及在食物、饮用水和空气/灰尘中的污染现状,并就围绕着它们所开展的污染控制技术方面的研究进行了评述。在此基础上,通过分析目前研究中所存在的问题,对今后的发展方向和研究重点进行了展望。     

基于质谱成像和组学分析的环境毒理研究

生物体多器官的空间异质性导致环境污染物在生物体内的毒性分子机制错综复杂。基于传统化学和生物分析的环境毒理学研究,通常将研究对象看作“均一”整体,无法从空间上准确定位污染物及其代谢。以质谱成像和组学分析为基础的技术,同时对污染物、污染物代谢活化途径及其诱导的生物分子进行定性、定量和空间分析,从而确定污染物迁移、生物学效应及其毒性作用的靶器官,是目前最有前景的分析方法之一。本文综述了质谱成像和组学研究策略和特征,介绍了本课题组在相关领域取得的研究进展。同时简单展望了单细胞质谱成像、微流控芯片-质谱成像联合策略等先进技术在环境毒理研究中的潜在应用。     

发现新型化学污染物的技术途径

具有持久性有机污染物环境行为特性(持久性、生物累积性、毒性和长距离迁移能力)的新型化学污染物日益受到政府和研究学者的广泛关注.分析方法学的研究是发现新型化学污染物的关键,其主要难点在于无指定的目标化合物为研究对象,有机污染物环境赋存浓度往往处于痕量水平,且基质干扰效应严重.因此需综合运用前沿技术手段,拓展识别分析的新方法体系.本文从样品前处理方法的应用、引导发现策略的设计、多重结构信息的获取和整合三方面介绍了部分关键技术途径和研究进展,并初步探讨了当前的知识空缺和发展趋势.     

Overview of analysis of carcinogenic and/or mutagenic metals in biological and environmental samples. I. Arsenic, beryllium, cadmium, chromium and selenium

One of the most dangerous and pernicious forms of pollution arises from the potential mobilization of a spectrum of toxic trace metals and metalloids in our environment. Among the most important elements in this regard are arsenic, beryllium, cadmium, chromium and selenium whose adverse toxic effects are now well recognized including their carcinogenicity and/or mutagenicity. These agents (and their derivatives) can be widely dispersed throughout the environment as a result of fossil fuel combustion, industrial and agricultural processes and natural processes. The trend for the immediate future appears to be of greater exposure to these metals not only as a result of generally increased usage patterns but also because of prospective enhanced use of fossil fuels for space heating and electricity generation. In order to more readily evaluate trends of human exposure as well as the toxicity, bioavailability, bioaccumulation and transport of these elements, sensitive analytical procedures are required for the determination of their various oxidation states (as well as their organic derivatives) in complex matrices such as those found in both environmental and biological samples. Hence, the principal objective of this overview is to highlight the more recent trends and state-of-the-art methodologies for the determination of arsenic, beryllium, cadmium, chromium and selenium (in their various forms) in environmental compartments such as air, water, soil and in human tissues (primarily blood, urine, and milk). Techniques to be discussed primarily include atomic absorption spectrometry, neutron activation analysis, gas chromatography, differential pulse polarography and electrochemical analysis. The importance of quality control and differentiation according to speciation will also be stressed.     

Microplastics and associated emerging contaminants in the environment: Analysis,sorption mechanisms and effects of co-exposure

Microplastics (MPs) and other emerging pollutants exist together in the environment and their co-exposure represents a source of increasing concern as MPs have been reported to act as carriers of pollutants due to their high sorption capacity. The ingestion of contaminated MPs by organisms can enhance the desorption of pollutants, increasing their bioavailability and toxicity. This review examines the role of MPs as vectors of environmental emerging contaminants. First, the main tools used to identify and characterise MPs and the analytical methods used for the determination of associated emerging contaminants are discussed. Insightful explanations of the sorption interaction between several groups of emerging pollutants and MPs are provided. MP type (polarity, crystallinity, size) and aging process together with the environmental conditions and pollutant properties (hydrophobicity and dissociated forms) are key factors influencing the sorption process. The literature review showed that polyethylene and polystyrene were the most commonly studied polymers. Antibiotics, perfluoroalkyl compounds and triclosan showed high sorption capacities onto MPs. Finally, the effect of co-exposure to MPs-emerging pollutants and bioaccumulation in aquatic and terrestrial organisms is discussed. The combined exposure may impact the toxic effects in different ways, through synergistic or antagonic interactions. Examples of different scenarios are provided, but in general the research conducted on terrestrial systems is scarce. The results revealed a lack of standardization in laboratory studies and in the testing conditions that reflect actual environmental exposure.     

Degradation of petroleum hydrocarbons in seawater by ionizing radiation

Summary A major concern with leaking petroleum is the environmental contamination by the toxic and water-soluble components such as benzene, toluene and xylenes (BTX). These hydrocarbons have relatively high pollution potential because of their significant toxicity. All BTX compounds are depressants to the central nervous system. Consequently, BTX are priority pollutants and their occurrence has led to the development of several physical, chemical and biological methods for their removal. The use of nuclear technology for protection and conservation of the environment, by the destruction of toxic organic compounds present in the environmental, drinking water, soils and industrial sewage has been the object of study of several authors in Brazil and in the world. The objective of this paper is to present the preliminary results of the study of contamination of the seawater by the main pollutants of the output and transport of petroleum, such as benzene, toluene and xylene, and their removal by the exposure to the ionizing radiation.     

土壤中多环芳烃修复技术的研究进展

近年来我国的土壤污染问题日益严重,严重危害着人类的生活环境与身体健康,其中主要的有机污染物之一为多环芳烃(PAHs)。PAHs作为一种持久性有机污染物在全球范围内广泛存在,其主要污染来源于人为因素。由于PAHs复杂的杂环芳环结构、较强的疏水性和较高的热稳定性等,使其在土壤中不易自然降解因而具有较高的持久性。本文综述PAHs的主要污染来源、暴露途径及其对人体的危害,并从物理、化学和生物三个方面简要介绍土壤中PAHs的修复方法,并分析每种方法的优势以及面临的挑战。新兴的修复技术结合三种修复技术的优点,具有更好的修复效果和应用前景,但仍存在着一些亟待解决的问题。期望本文能为土壤中PAHs的修复提供借鉴,并为今后的研究方向提供新的思路。     

Environmental exposure to metals of newborns, infants and young children

Anthropogenic emissions, such as those from combustion of fossil fuel, waste incineration and industrial use, contribute to higher levels of metal pollutants, including Cd, Pb and Sb, in the urban environment. These widespread and persistent environmental pollutants have the potential for developmental and reproductive toxicity. Health risks are particularly associated with exposure in utero and the early years of life, since the developing organism is at greater risk from permanent damage, and both absorption and retention can be considerably greater in infants than adults. In order to assess risk to humans, the information on environmental levels of pollutants (environmental monitoring) should be integrated with information on biomarkers of exposure, effect or susceptibility in biological fluids or tissues (biological monitoring). The analysis of tissue from the target organ obtained at autopsy provides a direct record of the accumulation of toxins and allows temporal and geographical trends to be studied. Few literature reports on tissue content of potentially toxic elements include data on newborns and young children since collections of autopsy samples in this age range are rare. Existing data are sometime questionable, because of inadequate sensitivity of the analytical techniques, insufficient control of contamination and lack of validation. Our recent work aimed to establish reliable reference values for the content of Cd, Pb and Sb in the liver of pediatric subjects.     

Metabolic activation of chemicals: in-silico simulation†

The role of metabolism in prioritising chemicals according to their potential adverse health effects is extremely important given the fact that innocuous parents can be transformed into toxic metabolites. Our recent efforts in simulating metabolic activation of chemicals are reviewed in this work. The application of metabolic simulators to predict biodegradation (microbial degradation pathways), bioaccumulation (fish liver metabolism), skin sensitisation (skin metabolism), mutagenicity (rat liver S-9 metabolism) are discussed. The ability of OASIS approach to predict metabolism (toxicokinetics) and toxicity (toxicodynamics) of chemicals resulting from their metabolic activation in a single modelling platform is an important advantage of the method. It allows prioritisation of chemicals due to predicted toxicity of their metabolites.

     

Metabolic activation of chemicals: in-silico simulation

The role of metabolism in prioritising chemicals according to their potential adverse health effects is extremely important given the fact that innocuous parents can be transformed into toxic metabolites. Our recent efforts in simulating metabolic activation of chemicals are reviewed in this work. The application of metabolic simulators to predict biodegradation (microbial degradation pathways), bioaccumulation (fish liver metabolism), skin sensitisation (skin metabolism), mutagenicity (rat liver S-9 metabolism) are discussed. The ability of OASIS approach to predict metabolism (toxicokinetics) and toxicity (toxicodynamics) of chemicals resulting from their metabolic activation in a single modelling platform is an important advantage of the method. It allows prioritisation of chemicals due to predicted toxicity of their metabolites.     

From Environmental Analytical Chemistry to Ecotoxicology—A Plea for More Concepts and Less Monitoring and Testing

The development of cultural and technical civilization has been marked with increasing interference in hydrogeochemical cycles and the production of a growing number of chemicals; this is accompanied by a growing concern on the potential adverse effects of chemicals on biological systems. Assessment of the potential toxicological and ecological effects of pollutants is of central importance. We are of the opinion that this cannot be accomplished by merely evaluating the harmfulness of a substance on the basis of toxicity tests with individual organisms and by monitoring analytically the environment for pollutants. We would like to encourage chemists to participate in the solution of ecotoxicological problems: chemodynamical concepts permit the estimation-on the basis of physical-chemical generalizations and with the help of compound-specific data-of the fate, the distribution, the potential for bioaccumulation in the food chain, and the approximate residence time of pollutants (and thus the attainable residual concentrations) in the environment and therefore to predict the relative risk of different pollutants.     

Quantitative prediction of biodegradability,metabolite distribution and toxicity of stable metabolites

An evaluation of the capability of organic chemicals to mineralize is an important factor to consider when assessing their fate in the environment. Microbial degradation can convert a toxic chemical into an innocuous one, and vice versa, or alter the toxicity of a chemical. Moreover, primary biodegradation can convert chemicals into stable products that can be difficult to mineralize. In this paper, we present some new results obtained on the basis of a recently developed probabilistic approach to modeling biodegradation based on microbial transformation pathways. The metabolic transformations and their hierarchy were calibrated by making use of the ready biodegradability data from the MITI-I test and expert knowledge for the most probable transformation pathways. A model was developed and integrated into an expert software system named CATABOL that is able to predict the probability of biodegradation of organic chemicals directly from their structure. CATABOL simulates the effects of microbial enzyme systems, generates the most plausible transformation pathways, and quantitatively predicts the persistence and toxicity of the biodegradation products. A subset of 300 organic chemicals were selected from Canada's Domestic Substances List and subjected to CATABOL to compare predicted properties of the parent chemicals with their respective first stable metabolite. The results show that most of the stable metabolites have a lower acute toxicity to fish and a lower bioaccumulation potential compared to the parent chemicals. In contrast, the metabolites appear to be generally more estrogenic than the parent chemicals.