土壤中重金属形态分析及其环境学意义

介绍了土壤重金属的形态及各种分析方法,重点说明了土壤中重金属形态分布及影响因素;讨论了影响土壤环境中重金属形态转化的因素,重金属形态与重金属在土壤中的迁移性、可给性、活性的关系,重金属污染土壤修复与重金属形态分布的关系.形态分析在一定程度上反映自然与人为作用对土壤中重金属来源的贡献,并反映重金属的生物毒性.重金属可以因形态中某一个或几个方面不同而表现出不同的毒性和环境行为.     

污染土壤重金属形态分析及其影响因素研究进展

土壤重金属形态分析是污染土壤修复的关键｡基于现阶段土壤重金属污染的研究成果,在指出土壤中重金属形态研究的必要性基础上,对土壤重金属存在的形态和分析方法进行了论述,接着着重对土壤重金属形态分布的主要影响因素进行了深入分析,最后指出本领域研究中存在的问题并提出研究展望｡为深入了解土壤重金属的赋存形态､形态分布的影响因素以及提出切实可行的重金属污染土壤修复方式提供理论指导参考｡     

食品中重金属的存在形态及其与毒性的关系

简要介绍了近年来有关食品中重金属形态及其毒性关系的研究进展,归纳了食品中重金属的化学形态特征、不同类型食品中重金属的存在形态、食品中重金属形态与生物有效性和毒性的关系,以及该领域中急需研究解决的问题．     

异化铁还原诱导次生铁矿对土壤重金属形态转化的影响

土壤重金属具有残留时间长、毒性大、难迁移等特点,其形态转化又是影响重金属毒性和迁移的关键因子。同时,不同形态土壤重金属通过迁移进入到作物、水、大气循环中,对人类的健康构成极大威胁。厌氧条件下,土壤中丰富的铁含量和微生物异化铁还原过程为自然环境中不同晶型次生铁矿的形成提供了有利条件。微生物诱导生成的次生铁矿物有独特的形态和特征,如纳米颗粒、高表面积和高反应活性,这些矿物特征对土壤重金属形态转化起到重要作用。本文重点介绍在异化铁还原微生物驱动下次生铁矿形成过程对土壤重金属形态转化的影响效应及机制。次生铁矿物形成过程直接影响土壤中微量金属污染物的迁移转化及归宿,因此在重金属污染场地修复等方面具有很重要的应用前景。     

污染土壤重金属的生物有效性和移动性评价：四种方法比较

重金属在土壤中的积累可增加土壤对生态环境的危害,而这种危害与土壤中重金属的活性有关.本文以植物体重金属浓度和地表径流重金属浓度为依据,比较研究了总量法、化学形态分级法、有效成分提取法和淋洗法4种方法评价污染土壤中重金属的生物有效性和移动性的可行性.结果表明,不同方法的评价结果有较大的差异.由于不同土壤的重金属组成有很大的差异,总量法难以反映土壤重金属的生物有效性和移动性;化学形态分级法中的交换态重金属可较好地反映土壤重金属的生物有效性和移动性,有机质结合态和碳酸盐结合态的某些重金属与其生物有效性和移动性也有一定的联系,而氧化物结合态、残余态重金属与重金属的生物有效性和移动性无关;用淋洗方法溶出的重金属量可很好地反映地表径流中重金属的浓度,也可较好地反映重金属的生物有效性;5种化学提取剂提取有效态重金属的结果表明,稀盐(0.01 mol·L^-1 CaCl₂)和1 mol·L^_-1 NH₄OAc提取的土壤重金属量与植物中重金属的积累和地表径流中重金属浓度均显著相关,可较好地表征土壤中重金属的生物有效性和移动性,其中稀盐(0.01 mol·L^-1 CaCl₂)提取的重金属最适于评价重金属的可移动性.     

好氧高温猪粪堆肥中重金属砷、铜、锌的形态变化及钝化剂的影响

采用连续提取法研究了猪粪好氧堆肥处理中重金属浓度和形态的变化以及添加不同比例的重金属钝化剂对其浓度和形态的影响.结果表明：经过堆肥处理后,猪粪中重金属As、Cu和Zn的总浓度均有所增加.从重金属结合形态的变化来看,可交换态As和Zn含量降低,残渣态As和Zn含量升高,表明As和Zn存在着向有效性相对较低的形态转化的趋势;重金属Cu则表现出不同的变化趋势,即可交换态与残渣态Cu含量下降,而碳酸盐结合态、铁锰结合态及有机结合态Cu含量有所增加,在今后的堆肥利用中应注意其可能带来的环境风险;3种重金属钝化剂及不同添加比例的处理中,5.0%的海泡石和2.5%的膨润土分别对重金属As、Zn表现出较好的钝化效果,堆肥后残渣态As和Zn的增幅分别达到79.8%和158.6%,均高于不加钝化剂处理.与对照相比,堆肥后7.5%的海泡石对残渣态Cu的降低幅度最小,为39.3%.猪粪堆肥中添加适量的重金属钝化剂,可以在一定程度上降低重金属的有效性以及猪粪堆肥利用中重金属污染的风险.     

芜湖钢铁厂周边土壤及油菜籽中镉、铜、锌、铅含量和形态分布研究

研究了污染土壤、油菜籽中Cd、Cu、Zn、Pb含量、形态分布特征和重金属富集状况及可能存在的生物毒性.结果表明,土壤中Cd、Zn、Pb以铁锰氧化物结合态、Cu以残留态占5种形态最高比例,分别为31.1%、39.3%、53.79%、46.24%;Cd、Pb交换态比例较高,为23.47%、16.32%,Cu、Zn的交换态比例较小,为3.14%、0.54%;土壤中不同重金属与各重金属形态相关关系有差别,5种重金属形态转化为有效态重金属难易程度不同;油菜籽和油菜籽壳中不同重金属累积趋势有差异,Cu易在油菜籽壳中累积,Cd、Zn、Pb易在油菜籽中累积;油菜籽中不同重金属累积率不同,Cd累积率最高,为0.56.油菜籽中重金属累积率与土壤中重金属总量呈显著负相关关系(P＜0.05),土壤中重金属的形态、转化差异是此种负相关关系的主要原因;油菜籽中Cd、Cu、Pb以氯化钠态为主,分别为32.50%、22.94%、34.69%,Zn以EDTA态为主,为45.97%.油菜籽中重金属形态可能影响其毒性,但其毒性的人类膳食风险还需进一步研究证实.油菜籽中重金属形态与油菜中重金属总量相关性不好.     

磷酸盐修复重金属污染土壤的研究进展

从研究方法、反应机理以及风险评价等方面综述了磷酸盐修复重金属污染土壤的研究进展,分析和讨论了其中存在的问题和不足,提出了今后加强研究的重点。目前磷酸盐修复重金属污染土壤时,使用的主要研究方法有化学形态提取法、化学平衡形态模型法和光谱及显微镜技术,各个方法都有其优缺点,应该结合使用并探索新方法。磷酸盐稳定重金属的作用机理主要有3个:磷酸盐诱导重金属吸附、磷酸盐和重金属生成沉淀或矿物和磷酸盐表面吸附重金属,但磷酸盐与重金属反应的机理十分复杂,人们尚不完全清楚,因此难以有效区分和评价诱导吸附机理和沉淀机理或其它固定机理,相应地对磷酸盐修复重金属的长期稳定性难以预测。磷酸盐修复重金属污染土壤时由于其较高的施用量可能会造成磷的积聚从而引发一些环境风险,如磷淋失造成水体富营养化,营养失衡造成作物必需的中量和微量元素缺乏以及土壤酸化等。所以应该谨慎选择磷肥种类和用量,最好是水溶性磷肥和难溶性磷肥配合、磷肥与石灰物质等配合施用。今后应着重研究磷酸盐与重金属相互作用的机理区分和评价;关注磷酸盐修复重金属污染土壤时存在的潜在风险,特别是加强植物长期不断吸收磷或其它环境条件变化致使土壤磷素持续减少过程中稳定的重金属溶解性和移动性的研究,磷酸盐修复重金属污染土壤的长期田间实践等。     

水生双翅目昆虫监测水体重金属污染的研究

水生双翅目昆虫是监测水体重金属污染的理想对象。文章归纳用于监测重金属污染的水生双翅目昆虫的种类,重点介绍水生双翅目昆虫在重金属污染下外部形态、内部结构、生化及分子水平的变化,以及相关生物标志物的研究,为水生双翅目昆虫用于水体重金属污染的生物监测提供科学依据。     

模拟酸雨对污泥堆肥中重金属形态转化及其环境行为的影响

通过模拟酸雨淋溶土柱的方法,研究了酸雨（pH=5．0和2．9）作用下污泥堆肥中Zn、Cu和Ni的溶出和迁移性。分析了酸雨对重金属形态分布规律的影响。结果表明,在相同酸雨强度下,淋出液中重金属含量与其在土柱中迁移距离大小次序为Zn〉Cu〉Ni;重金属在相同深度的土层中含量大小次序为Zn〉Ni〉Cu。淋溶液pH的降低和污泥堆肥施加比例的提高均会增加重金属在淋出液和土柱中的含量,但不影响重金属在土柱中的迁移距离。土壤酸化会促使土壤中重金属形态向活性形态转化,而且迁移距离增加。     

Liquid chromatography of active principles in Sophora flavescens root

Herbal medicines were one of the major resources for healthcare in earlier stages, and some traditional herbal medicines have been in use for more than 2000 years. Currently, they are attracting more and more attention of the modern pharmaceutical industry, as scientists has become aware that herbs have almost infinite resources for medicine development. This review provides an overview of the analytical approaches applied in the researches concentrated on various aspects of the matrine-type alkaloids in Sophora flavescens root. Emphasis will be laid on the analytical processes of high-performance liquid chromatography (HPLC), capillary electrophoresis (CE), as well as gas chromatography (GC) methods. The sample extraction, separation and detection have been summarized. In addition, the applications of chromatographic determinations are introduced for the main matrine-type alkaloids in S. flavescens root, such as matrine, sophoridine, sophocarpine, lehmannine, sophoramine, oxymartine, oxysophocarpine, cytosine and aloperine. The advantages and limitations of HPLC, CE and GC methods in the analytical applications of the alkaloids are also discussed.     

A simulation-based evaluation of methods for inferring linear barriers to gene flow

Different analytical techniques used on the same data set may lead to different conclusions about the existence and strength of genetic structure. Therefore, reliable interpretation of the results from different methods depends on the efficacy and reliability of different statistical methods. In this paper, we evaluated the performance of multiple analytical methods to detect the presence of a linear barrier dividing populations. We were specifically interested in determining if simulation conditions, such as dispersal ability and genetic equilibrium, affect the power of different analytical methods for detecting barriers. We evaluated two boundary detection methods (Monmonier's algorithm and WOMBLING), two spatial Bayesian clustering methods (TESS and GENELAND), an aspatial clustering approach (STRUCTURE), and two recently developed, non-Bayesian clustering methods [PSMIX and discriminant analysis of principal components (DAPC)]. We found that clustering methods had higher success rates than boundary detection methods and also detected the barrier more quickly. All methods detected the barrier more quickly when dispersal was long distance in comparison to short-distance dispersal scenarios. Bayesian clustering methods performed best overall, both in terms of highest success rates and lowest time to barrier detection, with GENELAND showing the highest power. None of the methods suggested a continuous linear barrier when the data were generated under an isolation-by-distance (IBD) model. However, the clustering methods had higher potential for leading to incorrect barrier inferences under IBD unless strict criteria for successful barrier detection were implemented. Based on our findings and those of previous simulation studies, we discuss the utility of different methods for detecting linear barriers to gene flow.     

手性药物分析方法研究进展

综述了近10 年来手性药物分离检测方法的发展,包括高效液相色谱法、气相色谱法、毛细管电泳法,以及超临界流体色谱法等,旨在为该领域的进一步发展提供参考。     

Bias Assessment of General Chemistry Analytes using Commutable Samples

Harmonisation of reference intervals for routine general chemistry analytes has been a goal for many years. Analytical bias may prevent this harmonisation. To determine if analytical bias is present when comparing methods, the use of commutable samples, or samples that have the same properties as the clinical samples routinely analysed, should be used as reference samples to eliminate the possibility of matrix effect. The use of commutable samples has improved the identification of unacceptable analytical performance in the Netherlands and Spain. The International Federation of Clinical Chemistry and Laboratory Medicine (IFCC) has undertaken a pilot study using commutable samples in an attempt to determine not only country specific reference intervals but to make them comparable between countries. Australia and New Zealand, through the Australasian Association of Clinical Biochemists (AACB), have also undertaken an assessment of analytical bias using commutable samples and determined that of the 27 general chemistry analytes studied, 19 showed sufficiently small between method biases as to not prevent harmonisation of reference intervals. Application of evidence based approaches including the determination of analytical bias using commutable material is necessary when seeking to harmonise reference intervals.     

Separation and detection methods for covalent drug-protein adducts

Covalent binding of reactive metabolites of drugs to proteins has been a predominant hypothesis for the mechanism of toxicity caused by numerous drugs. The development of efficient and sensitive analytical methods for the separation, identification, quantification of drug-protein adducts have important clinical and toxicological implications. In the last few decades, continuous progress in analytical methodology has been achieved with substantial increase in the number of new, more specific and more sensitive methods for drug-protein adducts. The methods used for drug-protein adduct studies include those for separation and for subsequent detection and identification. Various chromatographic (e.g., affinity chromatography, ion-exchange chromatography, and high-performance liquid chromatography) and electrophoretic techniques [e.g., sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), two-dimensional SDS-PAGE, and capillary electrophoresis], used alone or in combination, offer an opportunity to purify proteins adducted by reactive drug metabolites. Conventionally, mass spectrometric (MS), nuclear magnetic resonance, and immunological and radioisotope methods are used to detect and identify protein targets for reactive drug metabolites. However, these methods are labor-intensive, and have provided very limited sequence information on the target proteins adducted, and thus the identities of the protein targets are usually unknown. Moreover, the antibody-based methods are limited by the availability, quality, and specificity of antibodies to protein adducts, which greatly hindered the identification of specific protein targets of drugs and their clinical applications. Recently, the use of powerful MS technologies (e.g., matrix-assisted laser desorption/ionization time-of-flight) together with analytical proteomics have enabled one to separate, identify unknown protein adducts, and establish the sequence context of specific adducts by offering the opportunity to search for adducts in proteomes containing a large number of proteins with protein adducts and unmodified proteins. The present review highlights the separation and detection technologies for drug-protein adducts, with an emphasis on methodology, advantages and limitations to these techniques. Furthermore, a brief discussion of the application of these techniques to individual drugs and their target proteins will be outlined.     

Review of the methods used in the determination of phytoestrogens

Interest in analytical methods for plant estrogens (phytoestrogens) has risen sharply in the past 10 years. In this review, we examine the existing analytical methods based on separations by gas-liquid chromatography, high-performance liquid chromatography and capillary electrophoresis in addition to methods of detection by ultraviolet absorption, fluorescence, electrochemical oxidation/reduction and mass spectrometry. These methods are compared with other methods of phytoestrogen analysis utilizing immunoassay approaches. The advantages and disadvantages of each of these methods are highlighted and potential areas for further development identified.     

Analytical approaches to determine cytochrome P450 inhibitory potential of new chemical entities in drug discovery

The use of a cassette incubation of probe substrates with human liver microsomes (HLM) - also known as the 'cocktail' approach - is becoming a widely accepted approach to determine the interaction of new chemical entities (NCEs) with cytochrome P450 enzymes (CYP450) in early drug discovery. This article describes two LC-MS/MS-based analytical methods used at the high-throughput (HT) stage and late discovery (LD) stage for analysis of 'cocktail' incubates to analyze the probe metabolites 1'-hydroxymidazolam (CYP3A4), 4'-hydroxydiclofenac (CYP2C9), dextrorphan (CYP2D6), 1'-hydroxytacrine (CYP1A2) and 4'-hydroxymephenytoin (CYP2C19). The analytical methods are advantageous over currently reported methods due to their sensitivity, shorter analyses times (<2 min/sample for the HT method and 4 min/sample for the LD method) and their ability to monitor a unique set of clinically relevant probe metabolites from a biological incubate containing low microsomal protein (0.1mg/mL). The analytical methods employ the same mobile phase, acetonitrile and 0.1% formic acid, under similar LC-MS/MS conditions. In the HT method, the chromatographic method consists of a short robust step-gradient where the probe metabolites are simultaneously and quickly eluted to enhance throughput. The probe metabolites are chromatographically resolved in the LD stage by utilizing a true linear gradient to obtain optimal peak separation. The IC50 data generated by both analytical methods using single incubations versus cocktail incubations for various test compounds are in good agreement (correlation coefficient (r2)>or=0.98). The scientist conducting the analysis is provided with a choice of method selection depending on the stage of the test compound and on whether throughput or minimizing interference from other co-eluting metabolites is the most important criterion.     

Product and contaminant measurement in bioprocess development by SELDI‐MS

Bioprocesses for therapeutic protein production typically require significant resources to be invested in their development. Underlying these efforts are analytical methods, which must be fit for the purpose of monitoring product and contaminants in the process. It is highly desirable, especially in early‐phase development when material and established analytical methods are limiting, to be able to determine what happens to the product and impurities at each process step with small sample volumes in a rapid and readily performed manner. This study evaluates the utility of surface‐enhanced laser desorption ionization mass spectroscopy (SELDI‐MS), known for its rapid analysis and minimal sample volumes, as an analytical process development tool. In‐process samples from an E. coli process for apolipoprotein A‐IM (ApoA‐IM) manufacture were used along with traditional analytical methods such as HPLC to check the SELDI‐MS results. ApoA‐IM is a naturally occurring variant of ApoA‐I that appears to confer protection against cardiovascular disease to those that carry the mutated gene. The results show that, unlike many other analytical methods, SELDI‐MS can handle early process samples that contain complex mixtures of biological molecules with limited sample pretreatment and thereby provide meaningful process‐relevant information. At present, this technique seems most suited to early‐phase development particularly when methods for traditional analytical approaches are still being established. © 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2010     

Determination of iminosugars in mulberry leaves and silkworms using hydrophilic interaction chromatography-tandem mass spectrometry

Mulberry 1-deoxynojirimycin (DNJ, a potent α-glycosidase inhibitor) has been investigated thoroughly for its analytical methods and therapeutic potential against diabetes, whereas little attention has been given to other iminosugars such as 2-O-α-d-galactopyranosyl-DNJ (GAL-DNJ) and fagomine. For instance, concentration and composition of these iminosugars in mulberry leaves as well as sericulture products have not been fully characterized due to lack of suitable analytical methods. Here we developed a simultaneous determination method for DNJ, GAL-DNJ, and fagomine using hydrophilic interaction chromatography (HILIC) with tandem mass spectrometry (MS/MS). When mulberry leaf extracts were subjected to HILIC-MS/MS with multiple reaction monitoring (MRM), individual iminosugars could be separated and detected. The developed method is sufficiently sensitive for determining iminosugars in mulberry leaves as well as silkworms, providing new information (e.g., different amounts of iminosugars in mulberry leaf varieties; high DNJ and low GAL-DNJ in the silkworm body, especially in the blood) that is useful for producing iminosugar-rich products for nutraceutical purposes.     

Studies on some trace and minor elements in blood

Blood is one of the widely used specimens for biological trace element research because of its biological significance and ease of sampling. We have conducted a study of the blood of the Kalpakkam township population for trace and minor elements. For this purpose, analytical methods have been developed and standardized in our laboratory for the elemental analysis of blood plasma and red cells. Inductively coupled plasma-mass spectrometry (ICP-MS), a relatively new technique, has been applied for the analysis of trace elements. Details regarding spectral interference and matrix interference encountered in the analysis of blood and the methods of correcting them have been discussed. Flame atomic absorption spectrometry (AAS)/atomic emission spectrometry (AES) has been applied for the determination of minor elements. Precision and accuracy of these methods have also been discussed.