湖北典型地区茶叶-土壤重金属相关性研究

本文旨在分析湖北典型地区茶叶以及土壤中各种元素的含量,采用原子荧光法(AFS)和电感耦合等离子体质谱法(ICP-MS)等方法对135对茶叶及土壤样品进行测定,并探讨各种元素之间的相互关系和影响。研究结果表明,土壤中元素的分布对茶叶中元素含量分布有一定意义,典型区土壤养分有效磷和碱解氮较丰富,有机质和速效钾较缺乏。典型区茶叶作物表层土壤 Cd、Pb、Cu、Cr、As 均存在不同程度的超标。土壤 Cd 和 Hg 的污染指数高,潜在生态风险强。典型区茶叶可食部分重金属含量均值依次为 Cu>Pb>Cd>Hg>As>Cr,重金属元素在茶叶中含量均为中等变异性。 茶叶对 Cu、Pb 的富集系数明显高于 Hg、As、Cd、Cr,不同茶叶对同一元素的富集能力存在差异。土壤重金属含量与土壤 pH 值、CEC、有效磷、总氮等理化指标关系密切。茶叶重金属含量与土壤重金属含量水平相关性较弱,但与茶叶对重金属的富集能力均呈显著正相关关系。     

定南县废弃稀土矿区土壤中重金属元素Pb、Cr和Cu的测定

为了解废弃稀土矿土壤及周边土壤的重金属污染及对环境的影响,采用HNO3-HClO4湿法消解土壤样品,用原子吸收分光光度计及标准曲线法对消解样品中的重金属元素Pb、Cr、Cu含量进行了测定。根据国家土壤环境标准评价这3种重金属元素在该土壤中是否超标及超标程度。结果表明,赣州市定南县废弃稀土矿区及周边土壤中铅含量严重超标;矿区及周边土壤Cr含量未见超标;周边土壤铜含量接近超标。可见该废弃稀土矿区重金属元素污染以Pb为主,建议在土壤植物修复过程中着重考虑对Pb元素的清除。     

土壤重金属迁移转化实验应用于环境化学实验教学的探索——以室内土柱淋滤模拟实验为例

设计了一套土壤淋滤模拟实验装置,并将其引入一个典型的环境化学实验中。在淋滤装置的上端加入一定浓度的重金属溶液,重金属在土柱中进行不同层位的迁移,从淋滤柱下端滤出,实现其在土壤中的迁移与转化。然后应用X射线衍射（XRD）光谱仪和电感耦合等离子体发射光谱仪（ICP-OES）分别测定土柱中不同深度处土壤矿物组成和重金属元素含量,并结合重金属元素含量测试结果分析探讨重金属元素的纵向迁移转化规律。该实验可引导学生进一步理解环境化学中关于土壤的基本理论知识,了解重金属在土壤中的迁移转化机制及相关测试仪器的基本操作方法与原理,提高学生的综合实验操作技能,激发学生科学研究的潜在能力,培养学生的科研创新能力。     

不同混合酸消解样品对电感耦合等离子体原子发射光谱法测定土壤中重金属含量的影响

为探究不同混合酸对电感耦合等离子体原子发射光谱法测定土壤中重金属元素(铜、锌、铅、镍和铬)的影响,对土壤进行多晶衍射分析,采用硝酸-高氯酸、盐酸-硝酸、盐酸-硝酸-氢氟酸-高氯酸、盐酸-硝酸-氢氟酸混合酸对4种不同类型土壤(黑钙土、褐土、棕壤、红壤)进行了分析。结果表明:该4种混合酸对标准样品的测定都具有较高的准确性与精确性;不同的混合酸的对不同类型土壤中重金属元素的测定具有一定的影响,其中对铬的影响最大;完全消解体系(盐酸-硝酸-氢氟酸-高氯酸、盐酸-硝酸-氢氟酸混合酸)的测定结果不同程度地高于不完全消解体系(硝酸-高氯酸、盐酸-硝酸混合酸)的结果。所以对于土壤重金属元素的测定,混合酸需要针对土壤类型,重金属元素种类等因素进行选择。     

利用BCR改进法和Tessier修正法提取不同类型土壤中Cu、Zn、Fe、Mn的对比研究

连续提取法作为一种重要的化学分析方法,是土壤中重金属元素形态分析的主要环节,但同一种提取法对于不同的土壤类型及同类土壤中不同重金属形态的提取效果差异很大.该文采用改进的连续提取法对山东省常见的褐土、棕壤和潮土3种土壤分别进行实验并对重金属进行测定.分析结果显示土壤中4种重金属含量大小依次为:Fe＞Mn＞Zn＞Cu,重金属元素形态以残渣态为主,水溶态含量较低;不同土壤类型中重金属含量大小依次为:褐土＞潮土＞棕壤.同时对BCR改进法和Tessier修正法进行了对比和探讨.     

浅谈重金属元素在土壤中的迁移及黏土矿物对其修复作用

重金属元素在土壤中的存在形式有多种,且迁移能力各不相同,而影响重金属元素形态的因素是土壤p H、土壤植物根际环境,重金属元素迁移的过程还受到土壤类型、含水量以及土壤中有机和无机配体的影响。黏土矿物具有良好的吸附作用,它主要是通过离子交换、配合反应和共沉淀反应来修复土壤中的重金属污染。     

湛江湾红树林湿地土壤重金属含量分析及污染评价

采用电感耦合等离子体发射光谱仪(ICP-AES)和电感耦合等离子体质谱仪(ICP-MS)对湛江湾红树林湿地土壤中8种重金属(As、Cu、Cd、Cr、Hg、Ni、Pb、Zn)含量进行测定,采用单因子污染指数法、内梅罗综合污染指数法和地累积指数法进行污染评价,并结合相关性分析和因子分析方法探讨重金属来源。结果表明:除Ni外,其余7种重金属元素含量平均值均未超过国家土壤环境质量标准(GB15618-2018);但Ni、Zn、Cu、Hg、As和Cd元素均超过广东砖红壤环境背景值,其中As、Ni、Hg和Zn元素超标情况严重。8种重金属元素内梅罗综合污染指数评价结果为0.373~22.576,平均值为3.378,整体处于重度污染;单因子污染指数依次为Ni>Hg>Zn>Cd>As>Cu>Pb>Cr。单个重金属元素地累积指数评价结果与内梅罗综合污染评价相一致,均显示红树林土壤中Hg、Zn和Ni元素污染严重,是影响研究区土壤环境质量的重要因素。从站位看,位于湾内北部的北涯村、观海长廊以及西部的世乔村站位污染较严重,高污染站位约占总站位数的33%,主要为Cd、Hg和Zn。统计分析结果显示,除Ni外,湛江湾红树林土壤中7种重金属元素之间显著相关;结合实地调查结果推测重金属污染主要来自工业污染、船舶排污、养殖排污、生活排污及农业面源污染等人为活动的输入,其次为自然因子的输入。     

湛江湾红树林湿地土壤重金属含量分析及污染评价

采用电感耦合等离子体发射光谱仪(ICP-AES)和电感耦合等离子体质谱仪(ICP-MS)对湛江湾红树林湿地土壤中8种重金属(As、Cu、Cd、Cr、Hg、Ni、Pb、Zn)含量进行测定,采用单因子污染指数法、内梅罗综合污染指数法和地累积指数法进行污染评价,并结合相关性分析和因子分析方法探讨重金属来源。结果表明:除Ni外,其余7种重金属元素含量平均值均未超过国家土壤环境质量标准(GB15618-2018);但Ni、Zn、Cu、Hg、As和Cd元素均超过广东砖红壤环境背景值,其中As、Ni、Hg和Zn元素超标情况严重。8种重金属元素内梅罗综合污染指数评价结果为0.373～22.576,平均值为3.378,整体处于重度污染;单因子污染指数依次为NiHgZnCdAsCuPbCr。单个重金属元素地累积指数评价结果与内梅罗综合污染评价相一致,均显示红树林土壤中Hg、Zn和Ni元素污染严重,是影响研究区土壤环境质量的重要因素。从站位看,位于湾内北部的北涯村、观海长廊以及西部的世乔村站位污染较严重,高污染站位约占总站位数的33%,主要为Cd、Hg和Zn。统计分析结果显示,除Ni外,湛江湾红树林土壤中7种重金属元素之间显著相关;结合实地调查结果推测重金属污染主要来自工业污染、船舶排污、养殖排污、生活排污及农业面源污染等人为活动的输入,其次为自然因子的输入。     

微波消解技术在农业样品分析中的应用

利用光纤压力自控密闭微波消解系统对土壤和植株样品中重金属元素测定的影响进行了研究，确立了样品消解试剂、微波消解每件及样品预处理方法。结果表明，该方法与常压湿法消解相比，具有样品消解时间短、消解试剂用量少、样品污染小等特点，是准确可靠的土壤及植株样品中重金属元素检测样品消解处理方法。     

中草药及其生长土壤中6种重金属元素含量相关性初探

采用电感耦合等离子体原子发射光谱法测定了中草药中重金属元素(铁、锰、铜、锌、镉、铅)的含量,并对中草药的生长环境土壤中重金属元素的化学形态及其分布进行了研究。文中提出了中草药样品用硝酸-过氧化氢-水(5+2+1)混合溶液消解,并叙述了土壤样品中元素的各种形态(水溶态、可溶态、碳酸盐结合态、铁锰氧化物态、有机质结合态)的提取方法和试液。结果表明:所测中草药中重金属元素含量明显低于土壤中元素的含量;土壤中铁、锌、铜主要以有机质结合态存在,锰以铁锰氧化物态为主。几种药材中均含有较高量的铁、锰、锌,土壤中也含有较高量的有效态铁、锰、锌,说明中草药与土壤中重金属之间存在有生物迁移作用。     

The Effect of Supramolecular Humic Acids on the Diffusivity of Metal Ions in Agarose Hydrogel

Humic acids are known as natural substances of a supramolecular nature. Their self-assembly ability can affect the migration of heavy metals and other pollutants in nature. The formation of metal-humic complexes can decrease their mobility and bioavailability. This study focuses on metal ions diffusion and immobilization in humic hydrogels. Humic acids were purchased from International Humic Substances Society (isolated from different matrices—peat, soil, leonardite, water) and extracted from lignite mined in Czech Republic. Copper(II) ions were chosen as a model example of reactive metals for the diffusion experiments. The model of instantaneous planar source was used for experimental data obtained from monitoring the time development of copper(II) ions distribution in hydrogel. The effective diffusion coefficients of copper(II) ions showed the significant dependence on reaction ability of humic hydrogels. Lower amounts of the acidic functional groups caused an increase in the effective diffusion coefficient. In general, diffusion experiments seem to act as a valuable method for reactivity mapping studies on humic substances.     

Silver binding by humic acid as determined by equilibrium ion-exchange and dialysis

One of the major challenges in environmental analytical chemistry is to develop methods for determining metal speciation in natural waters that contain low metal concentrations and dissolved organic matter (DOM). Because of its complex heterogeneous nature, metal binding to DOM cannot be predicted accurately using equilibrium models. Two independent speciation methods, the equilibrium ion-exchange technique (IET) and equilibrium dialysis (EqD), were used to determine silver binding by standard Suwannee River humic acid. Both approaches gave very similar results, although for a given silver loading, the concentration of free silver obtained by IET was somewhat higher than that determined by EqD. Our results suggest that any high-affinity binding sites present within the humic acid are likely saturated at [Ag(T)] > 10(-9) M. This comparison of free metal ion concentrations with two independent methods provides useful speciation information in the absence of reliable complexation constants for the reaction of silver with humic acid.     

Theoretical Researches on the Charge Transport Properties of Humic Acid Coordinating with Fe~(3+)\Cu~(2+)\Al~(3+) Metal Ions

Humic acid is a key component of extracellular electron acceptor. Experimental study elucidates that humic acid molecular ligand with different metal elements has different abilities to accept electrons. By using density functional theory, this article selected the leonardite humic acid(LHA) organic macromolecule as ligand to study interactions between the ligand and different metals. At the same time, the calculation of binding energy, the analysis of characteristics for the complex structure and the distribution of frontier molecular orbital were also completed. On the basis of Marcus theory, the reorganization energy, matrix element and charge transport rate constant were calculated. The results show that the order of the charge transfer rates is Fe~(3+)Cu~(2+)Al~(3+) for different metal complexes, and are in good agreement with the experimental ones.     

腐殖质与铀和超铀元素相互作用的研究进展

腐殖质是一类广泛存在于自然界中的高分子有机化合物,能与放射性核素相互作用,从而影响其在自然环境中的化学形态、迁移沉降、氧化还原行为等。本文介绍了目前国内外关于腐殖质与铀和超铀元素相互作用的研究现状和进展,并对存在的问题及今后的发展方向进行了初步讨论。     

Humic acid adsorption on fly ash and its derived unburned carbon

Fly ash is solid waste from combustion process, containing oxide minerals and unburned carbon. In this investigation, fly ash has been separated into metal oxide mineral section and unburned carbon. The fly ash with different contents of unburned carbon was employed for humic acid adsorption to investigate the influence of unburned carbon on adsorption. It is found that metal oxides and unburned carbon in fly ash exhibit significant difference in humic acid adsorption. The unburned carbon plays the major role in adsorption. Higher content of unburned carbon in fly ash results in higher surface area and thus higher humic acid adsorption. Fly ash and unburned carbon exhibit adsorption capacity of humic acid of 11 and 72 mg/g, respectively, at 30 degrees C, pH 7. Humic acid adsorption is also affected by ion strength, pH, and temperature. The thermodynamic calculations indicate that the adsorption is endothermic nature with DeltaH(0) and DeltaS(0) as 5.79 kJ/mol and 16.0 J/K mol, respectively.     

Stability and Mobility of Metal-Humic Complexes Isolated from Different Soils

The contamination of potable water aquifers by heavy metals is one of the most severe environmental threats. For the transport of heavy metals from various types of contaminated sites into the ground water and also into surface water aquifers, humic substances (HS) are recognized to be of main importance. Dissolved in natural waters humic substances are readily complexed with a variety of metal ions. Therefore, humic substances are of cardinal importance for the migration and, consequently, the pollution of ground waters with heavy metals. Our paper presents the results of a comprehensive comparison of several isolated humic acids of soils of different origin (different geochemical milieu) and their metal complexes. Two polluted sites in Germany, which differ in their geochemical milieu (pH-value) were selected. The aim of our experiments was to describe the properties of terrestrial humic substances depending on their origin and genesis as well as the effects of the transport of humic substance-bound metals into the water-unsaturated soil zone. After determination of heavy metals in the soils by photon activation analysis the activated soil was used as an inherent tracer in batch experiments with the isolated humic acid. After adsorption of the loaded humic acid on an XAD-8 resin column, the partition of metals mobilized by humic acids could be quantified. There are correlations of the formation of metal-humic complexes with the soil pedogenes, with the pH-value as well as with the humic acid concentration.     

Adsorption of europium(III) and americium(III) on kaolinite and montmorillonite in the presence of humic acid

Distribution of trace amount of Eu(III), or Am(III), in the aqueous/solid system containing humic acid and kaolinite, or montmorillonite, was studied by batch experiments. Humic acid was also adsorbed on the clay minerals and its adsorption isotherm can be regarded as a Langmuir type. It is shown that Eu(III), or Am(III), exists as humate complex either in the aqueous or on solid phase in the system including kaolinite, or montmorillonite. These results suggest that the organic-inorganic complex like clay minerals coated with humic substances is important as metal reservoir in the environment.     

Solvation Excess of Urea over Water in Humic Acid in Three-Component Solutions Saturated with the Biopolymer

Humic acids were extracted from brown coals of the Kara-Keche deposit (Kyrgyzstan) and characterized. The solubility of humic acid in aqueous urea solutions was studied. The solvation excess of urea over water on humic acid in solution was calculated. The possibility of simultaneous binding of urea molecules on three independent centers of humic acids was shown. An estimation of humic acid molecular dimensions in aqueous urea solutions is given.     

腐殖酸自水溶液中吸附亚甲基蓝的热力学与机理研究

腐殖酸是自然界植物残体经腐解后的产物 ,为一种复杂的天然大分子有机质 ,分子内主要含有羰基、羧基、醇羟基、酚羟基等多种活性官能团 ,因此它具有弱酸性、亲水性、吸附性和络合性 ,能够与许多有机、无机物发生相互作用。腐殖酸能作为水处理过程中的吸附剂 ,研究它对水中各类污染物的吸附规律和机理是十分有意义的。赵振国等[1～ 3] 运用吸附过程的ΔＧ 、ΔＨ 、ΔＳ 等热力学函数的变化来探讨吸附机理 ,得出了一些有意义的结论。我们将这一方法应用到水溶液体系中 ,探讨在不同吸附条件下各吸附热力学函数的变化 ,以期对吸附过程有更进一…     

Adsorption of humic substances by macro weakly basic ion-exchange resin and their effects on removal of Cu2+ and Pb2+

<正>Adsorption ofhumic,tannic and gallic acids by a macro weakly basic ion-exchange resin JN-01 was studied.The adsorption capacity of this resin for gallic and tannic acids is much higher than that for humie acid,which can be explained on the basis of both their molecular size and ionization degree.Furthermore,humic acid is separated into different components with molecular weight in the range from 2000 Da to 100000 Da by ultra-filter,and their adsorption isotherms on resin JN-01 indicate that humic acid's molecular weight is an important factor which makes significant influence on adsorption.Finally,changes in the amount of Cu~(2+) and Pb~(2+) adsorbed on resin JN-01 as a function of the concentration of each of these three acids were studied.A large increase in the heavy metal ions uptake is observed in the presence of humic substance,such advantages are due to the interactions between the heavy metal ions and the unbound functional groups of the adsorbed organic acids.