有机酸对土壤中镉形态及其生物有效性影响的研究进展

根系分泌的低相对分子质量有机酸与土壤中镉之间相互作用影响着土壤中镉的吸附、解吸，使镉在土壤-水-植物系统中的迁移、转化规律发生重大改变，从而影响到镉在土壤中的形态及其生物有效性。对近二十年来有关有机酸与重金属镉交互作用的研究进展、有机酸对土壤中镉的有效性、毒性的影响以及作用机制进行了综述，并对现在研究存在的问题以及今后的研究趋势做了初步展望。     

成都经济生态区大气降尘中镉赋存形态的研究

采用Tessier连续提取法对成都经济生态区不同区域的24个大气降尘样中镉的赋存形态进行了研究。研究结果表明,大气降尘中的镉主要以残留态形态存在;各形态镉在总镉中所占百分比含量由大到小排列顺序依次是:残留态,碳酸盐结合态,交换态,铁锰结合态,有机结合态;交换态镉、碳酸盐结合态镉这两种具有较高生物有效性的形态镉在总镉中所占的平均百分比含量分别是6.420%和8.917%;铁锰氧化物结合态、有机结合态、残留态镉这三种形态镉生物有效性很低,分别在总镉中所占的平均百分比含量分别是3.419%、2.365%和78.907%。通过分析可得出,汽油和煤的燃烧以及工厂排放镉能加大城市大气降尘的镉污染。     

生态地球化学评价样品中镉的测定方法及其形态分析研究进展

对近10年国内外生态地球化学评价样品中镉的测定方法以及形态分析方面的研究进展作了综述。内容涉及样品的前处理方法,镉的各种测定方法和形态分析以及土壤样品中各种形态镉的提取方法。对上述有关问题的发展前景提出了展望。     

川芎栽培土壤中重金属镉的动态监测

目的：连续多年监测彭州敖平镇川芎药材栽培土壤中重金属镉的含量,分析其对川芎药材中镉含量的影响。方法根据前期研究结果选取敖平镇部分川芎种植地固定采集样品。按照国家标准方法,采取0～20 cm连续根系土柱和川芎药材。采用火焰法对抽样土壤及川芎药材中镉的含量进行检测分析。结果采样区域内土壤中镉含量均符合国家二级土壤环境质量标准;部分土壤中镉的含量呈明显增长趋势。结论川芎种植土壤中镉含量与环境有较高关联,水泥厂粉尘等污染源是土壤中镉含量增加的重要来源。     

镉对植物根系的毒害作用

镉是一种毒性很强的重金属,可严重影响植物的生长。当镉对植物产生毒害作用时,首先表现在根系的形态和生理功能改变上。综述了镉胁迫下植物根系的形态学变化及生理生化改变,以及镉在植物体内的代谢过程,初步探讨了根际土壤对植物吸收镉的影响,并简单介绍了目前测定根系指标的常用方法。     

典型低阶煤热解过程中镉元素的释放规律

将新疆淖毛湖煤(NMH)和内蒙高硫煤(GL)逐级化学提取,考察镉(Cd)在原煤中的赋存形态分布;分别在400-800℃、卧式/立式管式炉对原煤热解,考察赋存形态、热解终温、升温速率和停留时间对Cd释放规律的影响;利用FactSage软件模拟在理想条件下Cd的迁移和转化。结果表明,NMH和GL中Cd的赋存形态分布分别为有机质结合态(46%与37%)、碳酸盐结合态(32%与24%)、二硫化物结合态(12%与1%)、铝硅酸盐结合态(10%与38%)。Cd的赋存形态分布严重影响其挥发行为,有机质结合态易在低温区挥发,而碳酸盐、铝硅酸盐和硫化物结合态需在中高温区挥发;降低热解速率与延长停留时间有助于Cd的释放。FactSage模拟表明,NMH和GL中Cd的气态产物主要有Cd、CdO、Cd(OH)x和CdS,Cd在两种煤中挥发行为的差异主要是由热解温度、赋存形态分布以及煤阶决定,模拟与实验结果吻合较好。     

成都市土壤-植物系统中镉的分布特征

对成都市蔬菜及根系土中镉含量数据进行了综合分析。结果发现,成都市土壤镉存在明显的区域分布规律;镉在莴笋体内主要分布在叶片部位;土壤和植物中镉的总量无显著相关关系,可为给城市的环境规划及治理提供科学依据。     

涡旋提取-石墨炉原子吸收光谱法测定土壤中有效态镉

土壤作为农业生产的重要载体,是保障农产品质量安全的关键源头。近年来,随着经济的快速发展,土壤中重金属污染问题日益凸显,已成为世界性的重大环境问题之一。目前针对土壤中重金属的调查分析大多处于总量水平,这并不能全面地评价重金属的生态风险,因为土壤-重金属-生物体之间存在复杂的动态相互作用,土壤中只有部分重金属能被生物体吸收,这部分能被生物体吸收利用的元素以特定的形态存在,这种特定的形态被称之为有效态。土壤中重金属能否被植物吸收主要取决于该元素的有效态[1],因此土壤中重金属有效态含量的测定,对评价和控制其生物毒害作用具有更实际的意义。镉是生物蓄积性强、具有"三致"作用的剧毒元素,会通过食物链富集到人体,从而对人体健康造成危害[2]。目前我国暂未制定土壤中有效态镉的限量标准,关于土壤中有效态镉含量测定方法的研究也较少[3-5],国家标准方法 GB/T 23739-2009(S)《土壤质量有效态铅和镉的测定原子吸收法》前处理采用振荡器低效提取,提取时间长,试剂用量大,提取液根据含量高低选用火焰原子吸收光谱仪或者石墨炉原子吸收光谱仪,操作较繁琐,无法满足批量样品快速分析的要求。文献[3-4]采用超声提取-电感耦合等离子体质谱法,前处理操作简单,但仪器成本较高,方法应用的推广有一定的局限性,且由于土壤样品基体复杂,容易堵塞雾化器导致仪器故障。     

恒温平台石墨炉原子吸收光谱法测定土壤中镉

正常土壤中镉的含量为0.03～0.3mg·kg~(-1),一般不会超过1mg·kg~(-1)。镉和锌的化学性质相似,都会随水中CaCO_3的沉积而沉淀。所以在石灰岩和石灰岩发育的土壤中富含锌,也可能含有较多的镉。当土壤受到电镀、染料、电池等工厂的废弃物污染后,含镉量会异常地增高。如果土壤的pH值较高,并含有多量的碳酸钙则镉不易迁移;而在酸性土壤中镉的迁移性较强,危害也更大。土壤环境质量标准规定,一般农田、蔬菜地、果园、牧场等土壤,当pH值小于7.5时,含镉量不能超过0.30mg·kg~(-1)。 测定土壤中镉的一般过程是:先将样品消解,然后用萃取一火焰原子吸收法测定,操作较繁琐。Slavin W等提出的恒温平台石墨炉(STPF)技术是一项近乎无干扰的先进技术,它包括快速电子测量技术、使用装有L'vov平台的热解涂层石墨管、最大功率原子化、峰面积测量、准确的背景扣除、原子化阶段停气、使用基体改进剂等。本文将它应用于土壤中镉的测定,重现性和准确度均较理想。     

大米中镉检测能力验证

镉是剧毒物质,常通过土壤或水被农作物(特别是水稻等)吸收。世界各国对大米中镉含量均有严格限制,我国粮食卫生标准GB 2715—2005中镉的限量为0,2 mg·kg~(-1)。近年来,国家大米监督抽查结果显示,我国南方部分省份的大米镉含量超标,据调查环境污染是造成大米中镉超标的主要原因。本工作通过对2008年国家认监委能力验证计划《大米     

Speciation of Metals in Soils

Abstract

Our studies have centred around the speciation of cadmium and manganese in three soils, one of which has been amended with sewage sludge. We report here some of our preliminary results, obtained by a coupled high performance liquid chromatography (HPLC)—graphite furnace atomic absorption spectroscopy (GFAAS) technique.

The results indicate that cadmium may exist in different forms in soil, but only one form in soil-pore waters. Manganese is present in different soil-pore waters in different forms. The presence of sewage sludge in the soil can also affect the quantity and form of metals in water extracts.     

Sequential extraction procedure for speciation of inorganic cadmium in emissions and working areas

A sequential extraction procedure for separating and concentrating soluble Cd(II) salts, CdO, Cd(0), CdS, CdSe and cadmium-aluminosilicates, has been developed for the cadmium speciation in samples such as particulate matter in emissions and working areas. The proposed procedure has been tested first on synthetic samples prepared in a laboratory with the different cadmium salts, then also in the presence of atmospherical particulate matter sampled in a laboratory of the Department of Analytical Chemistry, previously checked for the absence of cadmium. Finally the speciation was tested on particulate matter collected near the emission of a power plant fed by coal, after emission's treatment by electrostatic precipitator: matrix spiking and recovery analyses have been evaluated and the repeatability of the cadmium speciation was assessed by performing multiple analyses of the spiked samples. Quantitative determinations have been made by FAAS and GFAAS through the standard additions method.     

Extraction of soil organic phosphorus

Organic phosphorus is an important component of soil biogeochemical cycles, but must be extracted from soil prior to analysis. Here we critically review the extraction of soil organic phosphorus, including procedures for quantification, speciation, and assessment of biological availability. Quantitative extraction conventionally requires strong acids and bases, which inevitably alter chemical structure. However, a single-step procedure involving sodium hydroxide and EDTA (ethylenediaminetetraacetate) is suitable for most soils and facilitates subsequent speciation by nuclear magnetic resonance spectroscopy. Analysis of extracts by molybdate colorimetry is a potential source of error in all procedures, because organic phosphorus is overestimated in the presence of inorganic polyphosphates or complexes between inorganic phosphate and humic substances. Sequential extraction schemes fractionate organic phosphorus based on chemical solubility, but the link to potential bioavailability is misleading. Research should be directed urgently towards establishing extractable pools of soil organic phosphorus with ecological relevance.     

Chemical speciation and contamination assessment of Zn and Cd by sequential extraction in surface sediment of Klang River, Malaysia

The concentration and chemical speciation of Cd and Zn as well as total organic carbon (TOC) were studied in surface sediments from 21 stations along Klang River. Sequential extraction technique (SET) was applied to assess the four (exchangeable, acid-reducible, oxidisable-organic and residual) fractions in surface sediment. And also, to obtain an overall classification of cadmium and zinc pollution in this area. This investigation was the first study on the basis of the chemical speciation of Cd and Zn in surface sediments of the Klang River. The total concentrations of metals were ranged (0.60–2.26 µg g^{− 1}) for Cd and (33.26–268.24 µg g^{− 1}) for Zn. The chemical speciation of Cd and Zn in most sampling stations were in the order of residual > acid-reducible > oxidisable-organic > exchangeable, and it showed that the Zn in Klang River surface sediments existed in the nonresistant fractions, whilst Cd existed in the resistant fraction. The degree of surface sediments contamination was determined for individual contamination factors (ICF) and global contamination factor (GCF). The result of ICF and GCF values showed that those stations located vicinity of municipal area had high potential risk to fauna and flora of the Klang River. The relationship between the concentration of cadmium and zinc at the oxidation-organic fraction with TOC in surface sediment was identified. The results showed that TOC had a positive function to complex with Cd and Zn in the surface sediment of Klang River.     

Complexation of cadmium and copper by fluvial humic matter and effects on their toxicity

The effects of humic acids and fulvic acids isolated from the River Arno (Italy) on the bioavailability and toxicity of cadmium and copper were assessed in relation to changes in their speciation. Measurements of the complexing capacity of solutions containing these organic ligands were carried out by a titration procedure followed by DPASV and toxicity tests were carried out using lysosomes isolated from rat liver. The complexing capacity of the physiological medium containing about 13 mg/L of humic acids, expressed as ligand concentrations, was 0.30 and 0.072 micromol/L for cadmium and copper respectively; the corresponding conditional stability constants were 4.2 x 10(11) and 1.3 x 10(8) (mol/L)-1. The complexing capacities of the solution containing the same amount of fulvic acids were 0.33 and 0.164 micromol/L for cadmium and copper respectively, the conditional stability constants were 3.2 x 10(11) and 2.4 x 10(7) (mol/L)-1. The humic acids reduced the toxicity of cadmium by about 5 times: the EC50 changed from 4.4 to 20.4 micromol/L. The dose effect curve of copper presented a bi-sigmoid trend and two EC50 values can be determined: The EC50(1) in the presence of humic acids changed from 2.0 to 3.1 micromol/L, while the EC50(2) increased from 22.3 to 45.3 micromol/L. The fulvic acids reduced the cadmium toxicity by about the same amount as humic acids, from 4.4 to 18.6 micromol/L, but they had no effect on copper toxicity. Analysing the chemical speciation of cadmium and copper in the presence of humic components and under toxicity test conditions we can say that the appreciable decrease of EC50 is not related to changes in their speciation; we can hypothesize that this is due to different processes, as well as to blocking of the lysosomal membrane. On the basis of the shape of the dose-effect curves obtained for cadmium and copper respectively, we can say that the toxic effects of the two metals are different and we can hypothesize that copper could exercise its toxic activity by inhibiting the ATP-driven proton pump and the function of the Cl- selective channel.     

Soil bacteria sensitivity towards heavy metals – Experimental system optimisation using chemical speciation calculations

The ecotoxicological relevance of many laboratory studies on soil bacteria sensitivity towards heavy metals is limited because culture conditions are chosen which do not adequately represent field conditions. The influence of the composition of culture media on the speciation of copper in an oligotrophic model soil system has been investigated. The expected chemical speciation has been calculated to obtain information on the concentration of the bioavailable fraction and the totally dissolved copper. For control measurements of totally dissolved copper, vacuum filtration has been used. The results of the measurements are in a good agreement with the calculations. Therefore, the use of speciation calculations is postulated as a useful tool for the assessment of free metal concentrations at higher pH, where the concentrations of dissolved metals are too low to be measured by simple methods.     

Stability study on a Westöö-based methodology to determine organomercury compounds in polluted soil samples

This paper concerns with the evaluation of a speciation methodology for organomercury compounds in soil samples. The methodology used is based on the Westöö method, which includes an acid leaching of the soil followed by an organic solvent extraction and a re-extraction with a selective aqueous reagent (cysteine). The separation and quantification of organomercury compounds is achieved by capillary electrophoresis technique, using an ultraviolet-visible detection system (HPCE-UV). The main steps in the speciation process are discussed, from the point of view of possible degradation processes. Frozen, de-frozen and non-frozen soil samples have been analyzed, characterizing the influence of light and temperature. Equally, the effect of light and temperature, as well as the chemical form of cysteine, have been analyzed on aqueous extracts. Organomercury degradation has been observed in the aqueous phase and related results are discussed.     

Effect of <Emphasis Type="Italic">Deinococcus radiodurans</Emphasis> on speciation of radiocesium in soil

The chemical speciation of radiocesium which determines its environmental behavior could be affected by microbial processes in soil. However, the speciation of radiocesium in soil has not been well documented. The speciation of radiocesium in soil was investigated with the absence and presence of Deinococcus radiodurans and Pseudomonas sp., respectively. The content of radiocesium in residual phase was increased significantly (p<0.01) with the presence of bacteria in comparison to aseptic control, about 60% of adsorbed radiocesium existed in residual phase with the presence of bacteria. The proportions of radiocesium in different speciation were not significantly changed in the presence of D. radiodurans and Pseudomonas sp. with a longer incubation time. About 67.8% of the total absorbed radiocesium in D. radiodurans cells was extractable with ethanol.     

A review of the studies on environmental transport and speciation analysis of radionuclides in India

Department of Atomic Energy, India, has a systematic environmental monitoring program to ensure that the impact of radionuclides on human and environment is well within the limits, stipulated by the regulatory body. Concentrations of radionuclides are estimated in air, water, soil, sediment and biota in the environment around the power plant site on a regular basis. The environmental migration pattern and impact of radionuclides in the environment depends upon not only on the total concentration but the physico-chemical nature of radionuclide also. This paper presents a brief review of the studies of environmental transportation of radionuclides and influence of speciation with special reference to Indian conditions. A fairly good amount of results are available on the influence of speciation of radionuclides on the wet and dry deposition and preliminary results are available on the speciation analysis in dietary items, in soil and in ground water. Initial studies are concentrated on tritium, ¹³⁷Cs, Uranium, ⁹⁰Sr and their chemical analogues.