Sequential extraction and speciation of Ba,Cu, Ni,Pb and Zn in soil contaminated with automotive industry waste

Abstract

Sequential extraction or fractionation of heavy metals in the solid phase and their speciation in soil solution are important tools for assessing changes resulting from land use and/or pollution. The distribution of the various forms of Ba, Cu, Ni, Pb and Zn was evaluated in soil samples taken from a polluted area, and the speciation of cations and anions in a soil solution contaminated with automotive industry waste. We evaluated the sequential extraction and speciation of Ba, Cu, Ni, Pb and Zn in a Leptosol associated with a Cambisol and contaminated with automotive industry waste. Soil samples were collected at 0-0.2 m (a mix of soil and waste); 0.2-0.4 m (waste only), and 0.4-0.6 m (soil only) both in the polluted area and in two contiguous unpolluted areas: a sugarcane plantation and a forest fragment. Total concentrations of metals in the polluted area were above limits for intervention established by European Community regulations. Cu was mostly distributed in the residual and in the oxide-bonded fractions, except for the waste-only sample, in which the carbonate-bonded fraction was significant. Zn was concentrated in the residual and carbonate-bonded fractions, while Ba, Ni and Pb predominated in the residual fraction of the contaminated samples. Metals in the soil solution were predominantly in the hydroxyl forms, except for Ba, which was mostly in the ionic form (Ba²⁺).     

2020污染土壤的生物修复专刊序言

生物修复技术,作为可持续发展的重要方向,因其环境友好、高效且无二次污染并能从根本上解决土壤污染问题而受到关注,已经在土壤污染治理中得到了广泛的应用。为了梳理和凝练生物修复技术的发展状况,本专刊收录了该研究领域的16篇论文,分别从植物修复、微生物修复、联合修复、重金属吸收积累的相关分子机制、资源化再利用等方面,详细阐述生物修复技术的发展动态,展望未来的发展趋势,为促进生物修复技术的发展提供参考。     

Distribution of extractable heavy metals in different soil fractions

Abstract

Due to the difficulties of precisely characterizing environmentally contaminated soil, the effects of heavy metals on plants are studied using uncontaminated soil spiked with known quantities of heavy metals. One problem in using spiked soils is how accurately the distribution of metals mimics stabilized natural soils. We studied the distribution of cadmium, chromium, copper, lead, nickel, and zinc in soil fractions after application in soluble form. The soil samples included a control (an uncontaminated Typic Argiudoll) and two samples spiked with either a moderate or high heavy metal concentration). After application of the salts the soils were subjected to wet/dry cycles over the course of three months. The soils were fractionated using a sequential chemical extraction procedure employing: (1) CaCl₂,(2) NaOH, (3) Na₂EDTA and (4) HNO₃, HCl, and HF. Soil physical separation was carried out by ultrasonic dispersion. The heavy metal levels were determined using ICP-AES. Each heavy metal displayed a unique behavior when added to soil in the form of soluble salts. Cadmium and zinc remained in the soluble fraction, indicating that no equilibrium was attained, while nickel primarily appeared in the insoluble fraction. Chromium, copper and lead were distributed among various soil chemical fractions. The highest levels of all metals appeared in the clay fraction except lead which was mainly present in the silt fraction.     

Leaching of Cd,Zn, Pb,and Cu in Packed and Undisturbed Columns of Soils Affected by the Spill from a Pyrite Mine in the South of Spain

A study has been made of the leaching of Cd, Zn, Pb, and Cu in three representative soils within the zone affected by the spill from a pyrite mine in Aznalcollar (Sevilla, Spain) employing packed soil columns. According to the breakthrough and cumulative leaching curves, the relative mobilities of the different toxic elements in the columns are as follows: Cd> Zn> Cu> Pb. The effect of leaching on the distribution of metals as a function of depth using intact soil cores was also studied. The results showed that the soils themselves have a good capacity for immobilizing the soluble fraction of the elements from the spilled mud. This capacity varied as follows: clayey soil with a high carbonate content > clayey soil with a moderate carbonate content > sandy-clay loam soil with a low carbonate content. However, sandy soils with a low carbonate content could pose a risk to groundwater if initial contamination was high. These results could be considered during the evaluation of remedial technologies for the immobilization of soil metals.     

重金属超富集植物及植物修复技术研究进展

植物修复技术（Phytoremediation)是近年来发展起来的一种主要用于清除土壤重金属污染的绿色生态技术,重金属超富集植物（hyperaccumulator)及植物修复技术是当前学术界研究的热点领域,目前虽已有Cd、Co、Cr、Cu、Mn、Ni、Pb、Zn等超富集植物发现的报道,但尚无一例报道来自于中国,中国具有广袤的国土面积、丰富的植物类型和多种（处）古老的矿山开采与冶炼场所,在中国开展超富集植物的寻找,研究与开发工作,将会有重要突破,并具有重要的理论与实践意义,本文拟就国内外在这一领域的研究进展作一简要综述。     

重金属污染土壤植物修复基本原理及强化措施探讨

阐述了植物修复的基本概念及主要作用方式 ,并从土壤中重金属存在形态 ,植物对重金属吸收、排泄和积累以及植物生物学特性与植物修复的关系等方面讨论了重金属污染土壤植物修复的基本原理及局限性和限制性因素 ,从超富集植物性能强化和技术强化两方面探讨了植物修复的强化措施 ,并指出与现代化农业技术相结合是植物修复重金属污染土壤大规模商业应用的一条捷径     

Distribution of heavy metals in soils and vegetables and health risk assessment in the vicinity of three contaminated sites in Guangdong Province,China

Due to rapid industrialization and urbanization, human activities like industrial and agricultural production, transportation, aggravate heavy metal pollution in soil and continue to endanger vegetables and human health. In this study, three contaminated areas affected by heavy metal pollution in Guangdong Province were investigated in terms of Cu, Zn, Pb, and Cd concentrations in soil and vegetables. Further analyses of the contamination status and potential risks to the health of residents consuming these vegetables were conducted. Results showed the following average heavy metal concentrations in vegetables and soil: Shaoguan > Guangzhou > Dongguan, indicating that mining has caused massive soil-heavy metal pollution. The heavy metal concentrations and Bioconcentration factors (BCFs) showed the following trend: leaf-vegetables > fruit-vegetables > root-vegetables, and those of vegetable type were as follows: Cd > Zn > Cu > Pb. The Nemero pollution index (PI) of all research region soils and hazard index (HI) exceeded 1. Hence, more attention should be paid to the potential for adverse health effects caused by the consumption of vegetables produced in these sites . Thus, effective measures are encouraged, with a focus on children due to their vulnerability to these heavy metals.     

Effects of biochar amendments on speciation and bioavailability of heavy metals in coal-mine-contaminated soil

An incubation experiment was executed on applying biochar as a soil remediation amendment to discuss an effect of the various addition rates on the speciation and bioavailability of heavy metals in mining-contaminated soil. The result showed that the content of Cd in soil was 9.51 times higher than the Huainan soil background values. The contents of Cu, Zn and As were 2.97, 1.60 and 1.42 times the background values, respectively, and the total contents of all heavy metals were higher than the standard values of soil environment quality GB15618-1995 set by the China Ministry of Environmental Protection. Speciation analysis indicated that Cu and Cd were mainly associated with the reducible fraction, while Zn and As were dominated by the residual fraction. After biochar was added to contaminated soil, the residual fractions of heavy metals increased, while the acid-soluble fractions reduced. According to the results of CaCl₂ extraction experiment, CaCl₂-extractable concentrations of Cu, Zn, As, and Cd were observed with a biochar dosage rate of 10%, which were 57.26%, 51.37%, 6.94% and 42.04% lower than those of control soil samples, respectively, but there were no obvious changes of CaCl₂-extractable As.     

Heavy metals uptake by vegetables growing in sewage irrigated soil: relationship with heavy metal fractionation in soil

Abstract

Concentrations of the heavy metals Cd, Ni, Cr, Zn, Mn, Co and Cu in soils and vegetable samples (i.e. green chili and gourd) taken from six vegetable fields in the vicinity of Lahore, Pakistan were measured. These soils have been irrigated for a long time with untreated sewage effluents. A control site was selected that has history of fresh canal water irrigation. The sequential extraction procedure developed by Tessier was adopted to demarcate five metal fractions: exchangeable, acid soluble, reducible, oxidizable and residual. The extractants and digests were analysed by atomic absorption spectrometry. The fractionation procedure showed that all the metals were dominant (>50%) in the residual phase in control as well as in waste waster irrigated soils. The concentrations of all the metals in edible parts of the vegetables collected from wastewater irrigated soils, were above critical levels. The total metal concentrations in wastewater irrigated soils followed the order Mn> Co> Zn> Cr> Ni> Cu> Cd, while in control soils the ord er was Mn> Zn> Ni> Co> Cr> Cu> Cd. In order to understand the uptake of metals from soil to vegetables, correlation analyses were performed between metal concentrations in different fractions of soil and their concentrations in vegetables. Correlation analysis was performed at 95% and 99% confidence level. The meaningful significant negative correlation was observed between Cd_F5–Cd_chili,Cr_Total–Cr_gourd,Mn_F5–Mn_Chili,Gourd, Co_F5, _Total–Co_chili, Cu_Total–Cu_Chili which indicate the non availability of total content and residual fraction to studied vegetables. The positive correlation was observed between Cd_Fl-Cd_ChiU, Cd_Fl–Cd_gourd, Ni_{Fi, F3}–Ni_Gourd, Cr_{Fi, F3}, _F4–Cr_ChiU, Cr_F2–Cr_Gourd, Zn_{Fi, F2}–Zn_Gourd, Mn_F3–Mn_Chili, Mn_Fi–Mn_Gourd, Co_F2–Co_Chili, Cu_Fi–Cu_Chili. The positive correlation, especially for the first (exchangeable) second (acid soluble) and for the third (reducible) extraction steps, was obtained which indicate the bioavailability of these metal fractions to plant.     

Lead fractionation and bioaccessibility in contaminated soils with variable chemical properties

Abstract

The hazard imposed by trace elements within soils is dependent on soil properties and the relative distribution of metal species. Hence, a greenhouse column study was conducted to investigate the geochemical speciation and bioaccessibility of lead (Pb) as a function of soil properties. Four different soil types (Immokalee, Belle Glade, Tobosa and Millhopper series) varying in physico-chemical properties were selected and amended with Pb as Pb(NO₃) at 400, 800, and 1,200 mg kg^?1. A sequential extraction was employed to define the reactive metal pool, which was correlated with Pb bio-accessibility as determined by the physiologically based extraction test. Results show that Pb was mainly distributed in soluble+exchangeable phase in Immokallee (82%) and Millhopper (45%) series, and carbonate and Fe+Mn oxide fractions in Belle Glade (14–74%) and Tobosa (31–64%) series at time zero. With soil aging, Pb underwent chemical transformations in the soils and the majority of added Pb was associated with Fe+Mn oxide fraction (64–81%). Also, Pb bioaccessibility varied widely as a function of soil type and soil aging. Gastric phase (IVG-S) extracted 34–81% and 29–75% and the absorbed intestinal phase (IVG-AI) extracted 12–79% and 12–45% of amended Pb in all the soils at time zero and 6 months, respectively. Among soil types, Tobosa and Belle Glade showed reduced bioaccessibility relative to Immokalee and Millhopper. Statistical analysis revealed that the IVG-S Pb decreases as soil organic matter and cation exchange capacity (CEC) increases and total P decreases. While the Mehlich extractable P and Ca+Mg, total Fe+Al and organic matter predicted the Pb in an intestinal system.     

Influence of [S, S]-EDDS on phytoextraction of copper and zinc by Elsholtzia splendens from metal-contaminated soil

Two pot experiments were conducted to investigate the time course effects of the (S, S)-N, N'-ethylenediamine disuccinic acid (EDDS) addition to contaminated soil on the uptake of Cu and Zn by the Cu accumulator Elsholtzia splendens and on plant Cu and Zn concentrations at different growth stages. EDDS increased the amounts of Cu and Zn soluble in the soil, taken up by plants, concentrated in the xylem sap, and translocated from roots to stems and leaves. The increase in soil-soluble metals, especially Cu, resulted in a corresponding increase in metal concentrations in the xylem sap and leaves. The addition of EDDS to the soil increased plant Cu and Zn concentrations, especially in the leaves, and changed the proportions of Cu and Zn taken up by different plant parts. The proportions of Cu and Zn taken up by the roots were higher than by the leaves of control plants, but EDDS-treated plants showed the opposite trend. EDDS exerted greater effects at the end of the vegetative growth stage than at the start of the flowering or reproductive stages.     

Chemical fractionation of heavy metals in soils around oil installations,Assam

Abstract

The chemical fractionation of lead, cobalt, chromium, nickel, zinc, cadmium and copper in soils around Lakwa oil field, Assam, India was studied using a sequential extraction method. It is evident from the study that the residual fraction is the most important phase for the seven heavy metals under study. Among non-residual fractions metals are mostly associated with the Fe–Mn oxides fraction. The association of heavy metals with organic matter was observed in the following order: copper> cadmium> zinc> lead. The concentration of Pb in the carbonate fraction for both the seasons is higher compared with other metals, which may pose environmental problems due to its highly toxic nature. The comparatively low concentration of metals in the exchangeable fraction indicates low bioavailability. Correlations between physicochemical parameters and metal fractions of soil do not show consistent behaviour. The local mean values of metals when compared with the accepted values of normal abundance and geochemical background, indicates two to four fold increases in this area. However, the values are within the range of normal abundance. As well as from natural soil geochemical behaviour, anthropogenic influence might have a close bearing on the association of metals with the soil system in the studied area.     

绿洲土Cd、Pb、Zn、Ni复合污染下重金属的形态特征和生物有效性

通过模拟基于干旱区绿洲土壤Cd-Pb-Zn-Ni复合污染下的油菜盆栽试验,采用Tessier五步连续浸提法探究了重金属复合污染对油菜生长的影响及其各形态的转化归趋和生物有效性.结果显示,随着Cd-Pb-Zn-Ni复合胁迫水平的升高,油菜的干重先增加后减小,根系的生长由促进作用转变为抑制作用;对照土壤中4种重金属元素均以残渣态为主要赋存形态,可交换态的含量均很小;随着外源重金属的添加,油菜种植土壤中4种重金属元素的各形态含量随之增加,Cd、Pb、Zn的可交换态和Ni的碳酸盐结合态对外界胁迫响应强度最大,Cd、Pb、Zn、Ni的活性增加,且Cd、Pb的主要赋存形态迅速转变为碳酸盐结合态和铁锰氧化态,Zn的主要赋存形态由残渣态和碳酸盐结合态过渡到碳酸盐结合态和铁锰氧化态,Ni的主要赋存形态为碳酸盐结合态;Cd、Zn在茎叶中的含量大于根系,Pb、Ni反之,油菜能将Cd、Zn更多的运输至茎叶,Pb、Ni则主要积累在根系;油菜茎叶吸收Cd和油菜各部位吸收Zn的主要贡献形态为可交换态,根吸收Cd的主要贡献形态由可交换态转变为有机结合态,根吸收Pb和油菜各部位吸收Ni的主要贡献形态为碳酸盐结合态.     

Effect of Namomaterials on Heavy Metal Transport in Alkaline Soil

A high level of heavy metals in soil would negatively impact human health if these metals are consumed by humans through the food chain. The effect of nanomaterials, including SiO₂-Al₂O₃-Fe₂O₃, on heavy metals in alkaline soil was studied through simulating leaching in the soil column. Nanomaterials that weighed 4%, 6%, and 10% of the soil mass were added to a soil column in which garlic was planted. Leaching tests were conducted. Heavy metals in the soil leachate of different soil depths and different parts of the plant planted in the soil column were determined using a high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS). The results indicated that the migration of heavy metals through alkaline soil was inhibited. In the test with nanomaterials of 4% soil mass, 63% Cu, 79% Cd, 68% Pb, 89% Zn, and 76% Ni were decreased compared to the control. When the addition of nanomaterials was up to 6% of soil mass, 82% Cu, 92% Cd, 76% Pb, 91% Zn, and 88% Ni were reduced, respectively. No additional apparent results were observed with more nanomaterials added to the soil column. The nanomaterials effectively prevented heavy metal migration, especially inhibiting heavy metal migration downward. Nanomaterials will be promising in subsequent studies.     

Distribution and chemical fractionation of some heavy metals in bottom sediments of Lake Nasser

Distribution and phase association of Cd, Cr, Cu, Fe, Mn, Ni,Pb, Zn and organic matter in Nile sediments taken from LakeNasser (Aswan, Egypt) were investigated. The sediment sampleswere subjected to selective chemical extraction proceduresdesigned to fractionate the particulate heavy metals into sixfractions: (A) ammonium acetate-extractable metals; (B) sodiumacetate-extractable metals; (C) acid oxalate-extractablemetals; (D) hydroxylamine HCl-extractable metals; (E) aquaregia-extractable metals and (F) total metals (HF/HCl/HNO₃destruction). Exchangeable metals which can be extracted byammonium acetate solution are generally considered readilybioavailable as they are weakly bound and may equilibrateeasily with the aqueous phases. In the present study very smallconcentrations of all heavy metals considered were found inthis phase. Between this phase and the metal phases which arenot bioavailable (those exist in highly resistant phases) thereexist several geochemical phases (fractions B, C & D) that maypotentially release their associated metals under changingenvironmental conditions, such as pH and redox potential in thewater sediment interface. This revised version was published online in July 2006 with corrections to the Cover Date.     

盐角草在Cd、Pb、Li污染盐土修复中的应用潜力

滩涂和内陆盐碱地是重要的后备土地资源。近年来镉(Cd)、铅(Pb)等土壤重金属和锂(Li)污染对盐碱地开发利用和生产安全造成严重威胁。利用盐生植物修复污染盐土是最经济有效的方法。本研究以盐生植物盐角草SalicorniaeuropaeaL.为材料,采用盆栽方式,通过比较分析盐角草在不同浓度Cd(0-50mmol/L)、Pb(0-50 mmol/L)和Li(0-400 mmol/L)处理下的生长和生理生化指标及离子含量的变化,研究盐角草对3种金属污染物胁迫的耐性及积累特性,以期探讨盐角草在Cd、Pb、Li污染盐土修复中的应用潜力。结果显示,随着Cd、Pb处理浓度升高,盐角草的株高、鲜重和干重均显著下降。低浓度Li(≤20 mmol/L)处理促进盐角草的生长,而高浓度Li(≥20mmol/L)处理则抑制植物生长。盐角草对Cd、Pb、Li的耐受性顺序为Li>Pb>Cd。Cd、Pb、Li胁迫可能降低了盐角草对Na和K的吸收与转运而影响植株的生长。另一方面,盐角草抗氧化酶系统对Cd、Pb、Li胁迫表现出不同的响应机理,多种抗氧化物酶协同作用,抵制Cd、Pb、Li胁迫造成的氧化毒害。盐角草根和地上部分Cd、Pb、Li含量随着处理浓度的升高而增加,其中Cd和Pb的分布特征为根>地上部分,Li的分布特征为地上部分>根。研究结果表明盐角草对Cd、Pb、Li的胁迫均具有较强的耐受性与自我调节能力,且具有富锂特性,具备修复Cd、Pb、Li污染盐土的潜力。本研究为深入研究盐角草耐受Cd、Pb、Li胁迫的机制奠定了基础,揭示了利用盐角草修复高盐碱土壤中Cd、Pb、Li污染的应用潜力。     

污染土壤生态修复的理论内涵、方法及应用

讨论了污染土壤生态修复的理论内涵、修复方法的优化组合及其应用案例.将污染土壤生态修复的目标拓展为:目标污染物降低到可接受程度、土壤生态毒理性降低到可接受程度、部分恢复或全部恢复土壤的生态服务功能.归纳出污染土壤生态修复的5个特点、5个原则.初步提出污染土壤生态修复方法优化组合的原则.污染土壤生态修复方法优化组合表现出以...     

Extraction,Recovery, and Biostability of EDTA for Remediation of Heavy Metal-Contaminated Soil

Chelation removal of heavy metals from contaminated soil is seen as a viable remediation technique. A useful chelating agent should be strong, reusable, and biostable during metal extraction and recovery operations. This work tested the extraction, recovery, and biostability of EDTA as a potential remediating agent. Parameters, including EDTA concentration, soil type, soil content, washing cycle, precipitant concentration and type, and pH, were varied and tested during metal extraction and recovery operations. Factors, including EDTA concentration, aqueous and 5% soil slurry, presence of Pb, acclimated and unacclimated activated sludges, along with abiotic control, were varied and studied in the biodegradation of EDTA. The results showed that EDTA was able to extract lead completely from the tested soils, amenable to recovery by addition of cationic and anionic precipitants in the alkaline pH range, relatively biostable even under conditions very favorable toward biodegradation. Thus, EDTA is a strong, recoverable, and relatively biostable chelating agent that has potential for soil remediation application.     

Stabilization Pb,Zn, and Cd-Contaminated Soil By Means of Natural Zeolite

This article aims to investigate the stabilization of Pb, Zn, and Cd contained in contaminated soil from a former mining site in Montevecchio, Sardinia, using clinoptilolite-rich tuff from Pentalofos, Evros. The study included (1) batch experiments and their environmental characterization and (2) column experiments. The first tests involved 1-month pot experiments with varying soil-zeolite mixtures, and their evaluation was carried out by standard USEPA leaching tests (TCLP, EPT test, SPLP). Moderate solubility reductions were recorded according to the TCLP (Pb: 38%, Zn: 33%, and Cd: 32%) due to the introduction of competing Na ions in the solution, while the EPT test showed more significant variations (Pb: 55%, Zn: 74%, and Cd: 46%). A major decrease is achieved in both cases by 10% w/w zeolite addition. The study was complemented by column experiments involving soil-zeolite mixtures eluted by CH3COOH solutions (0.003N and 0.05N). The solubility of Pb was reduced by 50 to 60% compared with the control column, thus indicating the considerable selectivity of clinoptilolite for Pb. In addition, Na and Ca measurements in the leachates confirmed that the immobilization of Pb was mainly attributed to ion exchange reactions.     

Site-specific risk assessment and integrated management decision-making: A case study of a typical heavy metal contaminated site,Middle China

A typical contaminated land was spatially investigated and assessed based on Chinese guidelines to establish remediation strategy for exploring the shortcomings of the current guidelines to suggest improvements. Results showed that Cr, As, Pb, and Cd should be regarded as the priority pollutants under sensitive land use, while Cr and As should be regarded as the priority pollutants under insensitive land use. Ingestion of soil for each studied metal appeared to be the main exposure pathway under both the land uses. The calculated screening values of the priority metals were conservative to certain extent—even some were lower than their background values. Therefore, an integrated risk management strategy was suggested and the hierarchic clean-up values were proposed considering the health risk, local background value, land remediation cases, current remediation technology, and financial cost. Consequently, it was suggested the clean-up values of Cr(VI), Cr, As, Pb, and Cd, under future sensitive land use, should be 7.5, 1000, 30, 250, and 1.4 mg/kg in the first class control layer, respectively. For future insensitive land use, the clean-up values of Cr(VI), Cr, As, Pb, and Cd should be 20.4, 8000, 60, 580, and 4.3 mg/kg in the first class control layer, respectively.