土壤环境生态对重金属元素迁移影响分析

作物中重金属元素主要来自土壤，其含量与作物种类和土壤环境有关。土壤中重金属元素含量、土壤pH值、Eh值、土壤化学组成、土壤质地等环境因素都影响作物中重金属元素含量。土壤pH值和Eh值影响重金属元素的活动性。重金属元素的水溶态容易被作物吸收，而难溶态和被土壤胶体固定的重金属元素，不能被作物吸收。同种作物重金属元素含量的差异主要取决于土壤环境。     

西北旱田黄土中铅的赋存形态与转化规律研究

采用Tessier连续提取法分析不同条件下旱田黄土中Pb的形态分布与转化规律,通过正交试验确定影响Pb形态转化的主要因素,借助Mul1er地积累指数法初步评价污染状况。结果发现:所用黄土样品中Pb总量为68.85mg·kg-1,低于国家标准《土壤环境质量标准》二级标准。不同形态Pb含量分布为残渣态Fe-Mn氧化态有机结合态碳酸盐结合态可交换态,其中残渣态Pb占Pb总量的64.04%。土壤pH值、含水率、秸秆加入量、老化时间等环境因素能改变Pb的形态分布,但残渣态Pb含量始终最高。pH值是影响土壤Pb赋存形态的最主要因素,Pb的地积累指数Igeo为0.3314,说明采样区土壤人为污染比较严重。     

三峡库区重庆段几种土壤元素全量与其有效态含量的相关关系分析

利用重庆市沿江经济带地球化学调查所得土壤分析数据,研究了三峡库区重庆段土壤中元素的丰缺状况及其全量与有效态含量的相关关系。在进行相关关系分析时,主要考虑了不同土壤类型和土壤的pH值两个因素。结果表明,研究区B、Cu、Mn、Zn、K、Fe元素全量现状水平充足;N、P、Mo元素全量现状水平缺乏;有效态B、Mo、P、Zn含量缺乏;有效态Cu含量丰富;有效态Mn、N、Fe和速效K含量充足。元素有效态含量易受土壤类型和土壤的pH值影响,在很大程度上受土壤类型影响较大。在研究区的四类土壤类型中N、Mn元素全量与其有效态含量相关关系较好;P元素在石灰土和水稻土中其全量和有效态含量相关关系显著。     

城市土壤不同颗粒中重金属的分布及其对人体吸入重金属的影响

采集了9个不同质地的城市土壤,按颗粒大小分为6个粒级,分别测定了4种重金属(Cu、Cd、Co和Pb)的全量和有效态含量。结果表明,细颗粒中重金属有明显的富集,其中<0.002 mm粒组的重金属含量约为土壤的1.57~13.95倍。有效态重金属占其总量的比例一般是0.250~0.125 mm和0.125~0.050 mm粒组高于其它粒组。质地对重金属在不同颗粒中的分配有很大的影响;虽然重金属含量一般是质地较黏的土壤高于质地不黏的土壤,但砂质土壤中细颗粒组分中的重金属的含量却一般要高于黏质土壤的相应粒组。因此,在相同的重金属含量条件下,砂质土壤对人体的潜在影响要远高于黏质土壤。     

基于长期定位监测的稻田土壤理化变化和镉污染风险评价

土壤镉(Cd)污染及由此造成的水稻籽粒Cd超标是近年来我国农业环境和农产品安全领域面临的一项重要问题,对人体健康造成严重威胁。为明确Cd在稻田土壤理化变化和镉污染风险评价及相互关系,通过51个定位监测点连续5年对水稻籽粒和其对应的根系土壤进行协同监测。结果表明,监测区域内土壤酸化比较严重,土壤养分含量较高,年度之间差异不明显。土壤总Cd变化范围为0.067~1.260 mg·kg-1;土壤有效Cd含量变化范围为0.018~0.992 mg·kg-1;水稻籽粒Cd含量变化范围为0.003~1.170 mg·kg-1,籽粒Cd富集系数变化范围为0.013~2.396。5年内总体上土壤Cd与水稻籽粒Cd污染、潜在生态风险指数(Ei)及健康风险评价(HQ)较低并呈下降趋势,但土壤Cd生物活性较高。随机森林模型(Random forest mode)分析显示土壤性质显著影响土壤总Cd和有效态Cd,土壤交换能力是影响水稻籽粒对Cd吸收的主要因子。当pH≤6.5时,随着土壤pH值升高,土壤总Cd含量、土壤有效Cd含量及水稻籽粒Cd含量均升高,但当pH值≥6.5时,随着土壤pH值升高,土壤总Cd含量、土壤有效Cd含量及水稻籽粒Cd含量却均下降。研究结果可为受污染耕地分类管控和水稻安全生产提供科学依据。     

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。     

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。     

缺氧沉积物中重金属形态连续萃取方法的稳定性研究

考察了海水养殖区域缺氧沉积物中重金属形态连续萃取法萃取过程中溶液pH值、温度变化和胶体形成对形态分离结果的影响。结果表明,连续萃取法Step1萃取酸溶态时,萃取液pH值的轻微升高使Pb和Zn的萃取结果明显降低;Step2萃取还原态时,萃取液pH值明显升高对重金属的萃取结果影响很小;Step3萃取有机质结合态时,萃取液pH值的降低对重金属萃取结果影响较小(除Pb外)。由于连续萃取法中各步萃取反应的热力学过程不同,Step1和Step2萃取后溶液温度轻微升高而在Step3中溶液温度稍微降低,溶液温度变化(<2.5℃)对重金属形态的影响很小。在Step1、Step2和Step4萃取过程中胶体的形成和存在,对萃取液Cd、Zn和Cu有明显的吸附影响;而在Step3萃取中萃取剂的分散作用有效控制了溶液中胶体的形成。因此采用连续萃取方法评价沉积物中的重金属形态时,控制萃取液pH值和胶体形成有利于提高萃取结果的稳定性和准确性。     

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。     

环境标准中pH值限值的合理性探讨

鉴于在不同的温度下水(或溶液)的pH值会有所不同,对环境标准中不规定pH值限值的温度条件是否合理进行了论证。通过分析各环境标准的特点、各环境标准中pH值参数的控制目的,结合各环境标准指定的监测方法的技术内容,得出以下结论:《海水水质标准》、《地表水环境质量标准》、《污水综合排放标准》和《土壤环境质量标准》中pH值限值不规定温度条件是合理、可操作的;《危险废物鉴别标准腐蚀性鉴别》pH值限值应该规定温度条件;对于《地下水质量标准》,有待于进一步实验验证温度对pH值的影响程度。     

The Analysis of Inorganic and Organic Pollutants in Soil with Special Regard to Their Bioavailability

Abstract

The most important inorganic pollutants in soil are the heavy metals. Problems related to the determination of the total and soluble content are discussed. Soluble contents are of interest in connection with studies about bioavailability. Because some of the heavy metals are essential for plant growth, most of the work about bioavailability has been done in the field of plant nutrition. Much less is known about the situation in polluted soils.

It was shown that neutral salt solutions which do not really change the pH of soil during the extraction procedure are best suited to define thresholds of excess. This is in contrast to much stronger extractants like EDTA or DTPA often proposed for the analysis of soils which are deficient in trace elements.

With three sets of experiments the correlation between the contents of cadmium, copper, nickel and zinc extracted by 0.1 M NaNO₃ (as an example of a neutral salt solution) and the plant response (phyto- or zootoxicity) are shown:

—pot experiments using soils which were contaminated by metal salt solutions

—pot experiments using soils from contaminated areas

—field studies in polluted areas. In these studies the aspect of heavy metal leaching was also considered.

The results were converted to indicative values in the Swiss Ordinance of Pollutants in the Soil. These indicative values derived from plant reactions were checked by the carbon mineralisation as an example of a soil microbiological process.

As it was found that organic pollutants are not easily taken up by plant roots the problem of bioavailability is much less important. However, the biodegradation and formation of metabolites has to be considered.     

Determination of Hg,As, Pb,and Cd in Orchard Soils by Sequential Injection Vapor Generation Atomic Fluorescence Spectrometry

An analytical procedure was developed for determination of Hg, As, Pb, and Cd in soil samples using sequential injection vapor generation atomic fluorescence spectrometry (SI-VG-AFS) with sample preparation by microwave digestion system. The effects of analytical conditions on the fluorescence intensity were investigated and optimized. Under the optimized condition, the detection limits of the method were 5, 68, 40, and 3 ng L^?1 for Hg, As, Pb, and Cd, respectively. The accuracy of method was verified by the determination of the certified reference soil, and the recoveries for Hg, As, Pb, and Cd were in the range of 98.7–106.1%. The proposed method has been successfully applied to determine the heavy metals in navel orange orchard soils in Ganzhou, and the environmental quality of the orchard soils was assessed based on the content of the heavy metals. According to the second criterion of environmental quality standard for soils, Pb content in all soil samples collected from the orchards of 18 districts were within safe limits, but a few orchards were slightly contaminated with Hg, As, and Cd. Comparison of heavy metal mean concentrations with the safe limits of environmental quality standard for soils, the quality of Ganzhou navel orange orchard soils were in line with the request of the green food production base.     

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。     

长株潭地区土壤环境地球化学研究

通过长株潭地区环境地球化学调查工作的实施,对长株潭地区土壤环境地球化学研究的工作方法进行了初步研究。结果显示,工业区重金属中Cu、Zn、Pb、As、Cd的污染较严重,尤其是Cd,这说明工业生产所产生的废水、废气、废渣是引起土壤中重金属污染的主要原因;各功能区重金属含量由高到低顺序为:工业区,居民区,商业办公区,休闲区,居民区和休闲区中重金属超标可能是由生活废水、生活垃圾和汽车尾气引起的。     

Dynamics of Heavy Metals in Soils of a Reed Bed System

Abstract

Heavy metal balances of a reed bed system (soil pH > 7, carbonate content about 30%) continuously flooded with sewage during 5 years indicate that only Pb, Zn, Cd and Cu were partly stored in the soil. Strong reductive conditions, high sewage percolation and metal complexation with soluble organic compounds caused a considerable leaching of Fe, Mn, Ni and Cr from the soil and formation of amorphous iron oxides. The results indicate that continously flooded reed bed systems with high percolation rates are not suitable for the elimination of heavy metals. Conversely, it should be possible to purify metal contaminated soils through percolation of sewage with low metal content.     

Characterization of Heavy Metals in Soil Near Coal Mines and a Power Plant in Huainan,China

The environmental and health hazards posed by heavy metals are significant due to their toxicity and bioavailability. Thirty-two soil samples were collected from residential areas around three coal mines and a power plant to assess the environmental and health implications caused by mining activities. The concentrations of heavy metals in soil were determined by inductively coupled plasma mass spectrometry. To evaluate the risk levels, the geo-accumulation index and health risk assessment were determined. The concentrations of metals in power plant soil were generally higher than those in coal mine soil, suggesting a higher release during coal combustion. The results demonstrate that the soils in the vicinity of Xinzhuangzi Mine and Luohe Power Plant are moderately contaminated by arsenic and cadmium. The analysis of the health risk of the metals indicated that the non-carcinogenic and carcinogenic adverse effects to residents due to heavy metal exposure are negligible. However, more attention should be paid around the power plant for the unacceptable level of carcinogenic risk. Based on the results of the environmental and health risk assessment, priority control components in Huaian have been identified. The study provides a comprehensive assessment of soil heavy metal implications derived from mining activity in this region in China and is helpful for pollution control and environmental management.     

Desorption of Heavy Metals from Typical Soil Components (Clay,Peat) with Glycine

Abstract

Natural organic chelating agents take part in the mobilization and translocation of heavy metals in unpolluted and polluted soils. They also have to be considered as possible extracting agents for the decontamination of heavy metal polluted soils. For an assessment of the desorption capability of glycinc, heavy metals (Cd, Cu, Ni, Pb, Zn) were adsorbed onto typical soil components (bentonite and peat). The metal loaded sorbents were resuspended in aqueous solutions of glycine at pH 7.0 and 4.5 and the quantities of the desorbed metals were analysed in the liquid phase. Furthermore, the dependency of the desorption rate on the duration of experiments and the metal content were investigated. The remobilization of heavy metals from bentonite by glycine at pH 7.0 decreases following the order Cu > Ni > Zn > Cd > Pb and ranges from 95% to 9.5%. The desorption rate was significantly lower at pH 4.5 and in suspensions of peat.     

粉末压片-X射线荧光光谱法测定富硅土壤和沉积物样品中的5种重金属元素

X射线荧光光谱法测定土壤和沉积物中的重金属具有简便、快速、准确等优点,但现有的环境行业标准方法不适用于SiO2含量大于80%的土壤和沉积物。为提高X射线荧光光谱法测定土壤和沉积物中的重金属在环境监测领域中的适用性,建立基于粉末压片-X射线荧光光谱法测定富硅土壤和沉积物中重金属的分析方法。通过选取富硅的土壤和沉积物标准物质提高校准曲线的测量范围以及优化各元素的测量条件,探讨基体效应和谱线重叠干扰、研究压片制样的最佳压力等途径,测定富硅土壤和沉积物中的Pb、Cr、Cu、Ni、Zn。结果表明在已优化的测定条件下,通过延长校准曲线的测量上限,保证待测元素含量在校准曲线范围内,同时采用经验系数法和康普顿散射内标法校正基体效应,可进一步提高方法的准确度和精密度。方法比对结果显示该方法的测定结果与原子吸收光谱法的测定结果无显著性差异。选用2种不同的富硅标准物质进一步验证方法的精密度和准确度,Pb、Cr、Cu、Ni、Zn的测定结果与标准物质认定值的对数误差为0.002~0.08,相对标准偏差为1.0%~4.6%。该方法的精密度和正确度满足土壤和水系沉积物环境监测分析的技术要求,具有良好的应用前景。     

Soil-modified carbon paste electrode: a useful tool in environmental assessment of heavy metal ion binding interactions

Carbon paste electrodes (CPEs) modified with different soils in their native form were prepared to create a soil-like solid phase suitable for application in studies of heavy metal ion uptake and binding interactions. The preparation of CPEs modified with five different soils was examined and their heavy metal ion uptake behavior investigated using a model Cu(II) aqueous solution. Metal ions were accumulated under open circuit conditions and were determined after a medium exchange using differential pulse anodic stripping voltammetry, applying pre-electrolysis at –0.7 V. The soil-modified CPE accumulation behavior, including the linearity of the current response versus Cu(II) concentration, the influence of the pH on the solution, and the uptake kinetics, was thoroughly investigated. The correlation between the soil-modified CPE uptake capability and the standard soil parameters, such as ion exchange capacity, soil pH, organic matter and clay content, were evaluated for all five examined soils. The influence of selected endogenous cations (K(I), Ca(II), Fe(III)) on the transfer of Cu(II) ions from a solution to the simulated soil solid phase was examined and is discussed. Preliminary examinations of the soil-modified CPE uptake behavior with some exogenous heavy metal ions of strong environmental interest (Pb(II), Hg(II), Cd(II) and Ag(I)) are also presented. This work demonstrates some attractive possibilities for the application of a soil-modified CPE in studying soil-heavy metal ion binding interactions, with a further potential use as a new environmental sensor appropriate for fast on-site testing of polluted soils.     

Soil-modified carbon paste electrode: a useful tool in environmental assessment of heavy metal ion binding interactions

Carbon paste electrodes (CPEs) modified with different soils in their native form were prepared to create a soil-like solid phase suitable for application in studies of heavy metal ion uptake and binding interactions. The preparation of CPEs modified with five different soils was examined and their heavy metal ion uptake behavior investigated using a model Cu(II) aqueous solution. Metal ions were accumulated under open circuit conditions and were determined after a medium exchange using differential pulse anodic stripping voltammetry, applying preelectrolysis at -0.7 V. The soil-modified CPE accumulation behavior, including the linearity of the current response versus Cu(II) concentration, the influence of the pH on the solution, and the uptake kinetics, was thoroughly investigated. The correlation between the soil-modified CPE uptake capability and the standard soil parameters, such as ion exchange capacity, soil pH, organic matter and clay content, were evaluated for all five examined soils. The influence of selected endogenous cations (K(I), Ca(II), Fe(III)) on the transfer of Cu(II) ions from a solution to the simulated soil solid phase was examined and is discussed. Preliminary examinations of the soil-modified CPE uptake behavior with some exogenous heavy metal ions of strong environmental interest (Pb(II), Hg(II), Cd(II) and Ag(I)) are also presented. This work demonstrates some attractive possibilities for the application of a soil-modified CPE in studying soil-heavy metal ion binding interactions, with a further potential use as a new environmental sensor appropriate for fist on-site testing of polluted soils.