Sequential extractions on mine tailings samples after and before bioassays: implications on the speciation of metals during microbial re-colonization

Mine tailings may be remediated using metal tolerant microorganisms as they may solve the limiting conditions for healthy development of plants (i.e., low organic mater content and poor physical conditions). The aim of this study was to investigate the consequences of microbial colonization on the chemical speciation of trace metals. Surface samples from the Valenciana mine tailings (Guanajuato, Mexico) were used for long-term bioassays (BA), which consisted in the promotion of microorganisms, development on tailings material under stable laboratory conditions (humidity, temperature, and light exposure). A five-step sequential extraction method (exchangeable, carbonate/specifically adsorbed, Fe–Mn oxides, organic matter (OM)/sulfide, and residual fractions) was performed before and after BA. Extraction solutions and leachates were analyzed by inductively coupled plasma-mass spectrometry. OM content, cationic exchange capacity, and pH values were also assessed before and after BA. The results indicate that trace elements are generally present in nonresidual fractions, mainly in the Fe–Mn oxides fraction. The concentration of total Zn, As, Se, Pb, and exchangeable Cu and Pb is above the recommendable limits for soils. Despite the high bioavailability of the former elements, biofilms successfully colonized the tailing samples during the BA. Cyanobacteria and green algae, heterotrophic fungi, aerobic bacteria, and anaerobic bacteria composed the developed biofilms. Chemical controls of trace elements could be attributed to absorption onto inorganic complexes (carbonates, metal oxides), while biofilm occurrence seems to enhance complexation and immobilization of Cr, Ni, Cu, Zn, As, and Pb. The biofilm developed does not increase the bioavailable forms and the leaching of the trace elements, but significantly improves the OM contents (natural fertilization). The results suggest that biofilms are useful during the first steps of the mine tailings remediation.     

青岛城区土壤重金属环境地球化学研究

为研究青岛城区土壤的环境地球化学特征,对青岛市南区、市北区、四方区、李沧区、崂山区5区进行了广泛的土壤地质调查。在每1km2一个样品的取样密度下取得表层土样(0～10cm深度)319个,经前期处理后,利用多种仪器如X射线荧光光谱(XRF)、等离子体发射光谱(ICP-OES)和等离子体质谱(ICP-MS)等分析测得所有样品的72种元素的含量,本文探讨了重金属元素Cd、Cr、Cu、Ni、Pb和Zn及类金属元素As的含量分布。结果表明,人类活动导致表层土壤中元素Cd、Cu、Pb和Zn含量的增加,而元素As、Cr和Ni主要是地质起源,但也会受到人类活动的影响。其中Zn的含量值变化较大,Zn元素含量值增高的地区是工业、交通密集处等人类活动频繁的地区。     

Selenium and heavy metals content in some Mediterranean soils

The study of metal contents in industrial, agricultural or/and polluted soils compared with natural or unpolluted soils is currently necessary to obtain reference values and to assess soil contamination. Nonetheless, very few works published appear in international journals on elements like Se, Li and Sr in Spanish soils. This study determines the total levels of Se, Li, Sr, As, Cd, Co, Cr, Cu, Ni, Pb, V, Zn, Fe, Mn and Ba in 14 natural (unpolluted) soils (Gypsisols, Leptosols, Arenosols and Acrisols), 14 agricultural soils (Anthrosols, Fluvisols and Luvisols), and 4 industrial–urban affected-surface soil horizons (Anthrosols and Fluvisols) of Eastern Spain. The geochemical baseline concentrations (GBC) and reference values (RV) have been established, and the relationships among elements and also between soil properties and elemental concentrations have been analysed. The RV obtained in this study were (mg kg⁻¹): Se 2.68, Li 115, Sr 298, Cd 0.97, Co 35, Cr 217, Cu 46, Ni 50, Pb 137, V 120, Zn 246, Fe 124,472, Mn 2691, and Ba 743. The RV for Se and Li were used as a preliminary approach to assess soil contamination in Spanish soils. The results confirm human impact on Sr, As, Cd, Cr, Cu, Ni, Pb and Zn soil concentrations, but evidence no deviation from natural Se, Li, Co, V, Fe, Mn and Ba concentrations. The results obtained from the statistical analysis reveal significant correlations between some elements and clay and soil organic matter (SOM) contents, indicating that metal concentrations are controlled by soil composition. One particularly interesting finding is the high correlation coefficients obtained between SOM and Se, Cd, Cr, V, Fe, and Mn, and between clay and Cd, Zn, V, Fe and Mn. Once again, these facts confirm the role of SOM and clay minerals in soil functions and that soil is an ecosystem element responsible for maintaining environmental quality.     

Background levels and baseline values of available heavy metals in Mediterranean greenhouse soils (Spain)

This study determines extractable levels of Cd, Cu, Pb, Zn, Ni and Co in western Almería (Spain) greenhouse surface soil horizons using EDTA solution, which is identified as the fraction available for organisms and plants. It also establishes background levels, geochemical baseline concentration and reference values (RV), and investigates the possible relationships between soil properties and elemental concentrations. The results show that the soil concentration of these extractable heavy metals was high as those reported by other authors for Spanish agricultural soils. The available RV concentrations obtained (mg kg⁻¹) were: Cd 0.17, Cu 1.6, Pb 13.8, Zn 5.0 Ni 1.7 and Co 2.9. Using the upper baseline criterion, 95% of greenhouse soils present a relatively higher content of extractable heavy metals given their Cd and Cu concentration. Significant correlations between total and EDTA-extractable metal levels were found for Zn, Pb, Cu, Cd and Ni. Soil properties also related to heavy metals content, suggesting that Cd, Cu, Pb and Zn are of similar origin and relate to anthropic activities, and implies the same interactions and/or relationships among these metals.     

Prediction of the long-term performance of abandoned lead zinc mine tailings in a Welsh catchment

In this study we investigated the sulphidic mine tailings from Frongoch and Grogwynion, two abandoned lead zinc mines in mid-Wales, UK. Despite falling within the same ore field the mine waste characterisation has identified differences in the tailings from the two sites. Bulk concentrations range from 10 to 52 g kg^− 1 for Pb, 1.1 to 2.9 g kg^− 1 for Zn in Grogwynion and from 1.0 to 130 g kg^− 1 for Pb, 11 to 110 g kg^− 1 for Zn in Frongoch. An experimental (European standard leaching tests TS 14429 and TS 14405) and geochemical modelling approach was used to study the leaching composition as a function of pH and liquid/solid ratio. There was little correlation between the tailings bulk metal concentrations and the leachate composition, but variations in Pb and Zn concentrations were found to be consistent with control of dissolved Pb and Zn by secondary minerals and the mechanisms of dissolution/precipitation/sorption involving them. Specifically, the Grogwynion mine tailings with near-neutral pH have predominantly lead and zinc carbonates controlling Pb and Zn solubility in the leachates, whereas the Pb and Zn concentrations in Frongoch leachates are best modelled with a surface complexation model for metal sorption to oxyhydroxides. The different speciation results in a greater sensitivity of Grogwynion tailings to acidification with a potential release of Pb in solution up to 10 times higher than in Frongoch, despite similar bulk Pb concentrations. At acid pH, Zn is similarly dissolved to a greater extent in Grogwynion than in Frongoch tailings. There was no evidence of sulphide oxidation during the batch and column leaching tests and the suitability of using these European leaching standards for the characterisation of sulphidic mine waste materials for waste management purposes has been considered.     

Distribution and sequential extraction of some heavy metals in urban soils of Guiyang City,China

Sixty-two soil samples collected from different functional zones of Guiyang were analyzed for total concentrations and sequential extraction of Cr, Cu, Pb, Zn and Cd by ICP spectrometry. The average total concentrations ofCr, Cu, Pb, Zn and Cd in the soils of Guiyang were 92.9, 51.6, 44.1,139.3 and 0.28 mg/kg, respectively. The soils have been polluted by Cr, Cu, Pb, Zn and Cd to some extent in comparison with the background values of Guiyang. Significant differences were recognized in the concentrations of Cr, Cu, Pb, Zn and Cd in different functional zones. As for the sequential extraction, Cr, Cu and Zn were present mainly in the residual fraction, and Pb was present mainly in the oxidizable fraction. The reducible fraction of Cd accounts for 47.5%, and the residual fraction is lowest. The mobility and bioavailability of heavy metals follow the order of Cd〉Pb〉Cu〉Cr〉Zn.     

基于形态学分析铅锌矿不同功能区土壤重金属元素的分布特征及污染评价

为掌握尤溪铅锌矿区土壤重金属元素分布特征和污染现状,通过采集尤溪铅锌矿不同功能区0~20cm表层土壤样品,测定土壤中Pb、Zn、Cd、Cu、Cr 5种重金属元素的总量及其化学形态,分析不同功能区土壤重金属污染及分布特征,同时采用次生相与原生相比值法(RSP)进行污染评价。结果表明,尤溪铅锌矿不同功能区土壤中Pb、Zn、Cd含量均超过国家土壤环境质量三级标准,废弃冶炼区土壤Cd、Cu、Pb、Zn含量均最高,分别为标准值的14.78、1.13、3.73、1.34倍,采矿区Cr含量最高,但未超过标准限值。重金属形态结果表明,相比其他元素,Cd弱酸提取态所占比例最高,Cu可交换态比例最高,Pb、Zn、Cr以残渣态为主。RSP法评价表明,不同重金属的污染程度表现为:Cu(1.15)Cd(0.80)Pb(0.59)Zn(0.57)Cr(0.54);不同功能区土壤重金属污染表现为:尾矿库区冶炼区废弃冶炼区采矿区。SPEF法评价表明,尤溪铅锌矿区受人为污染明显,采矿区和尾矿库区Zn污染最为严重,冶炼区和废弃冶炼区Pb污染最为严重,功能区污染顺序为:尾矿库区冶炼区废弃冶炼区采矿区。     

Mineralogy and trace element relative solubility patterns of shallow marine sediments affected by submarine tailings disposal and artisanal gold mining,Buyat-Ratototok district,North Sulawesi,Indonesia

Shallow marine sediments of the Buyat-Ratototok district of North Sulawesi, Indonesia, are affected by submarine disposal of industrial gold mine tailings and small-scale gold mining using mercury amalgamation. Industrial mine tailings contained 590–660 ppm arsenic, 490–580 ppm antimony, and 0.8–5.8 ppm mercury. Electron microprobe survey found both colloidal iron–arsenic-phases without sulphur and arsenian pyrite in tailings and sites to which tailings had dispersed, but only arsenopyrite in sediments affected by artisanal mining. Antimony in tailings was present as antimony oxides, colloidal iron–antimony phases, colloidal iron–antimony phases, and stibnite in sediments affected by both types of mining. A sequential extraction found that 2% of arsenic held in tailings and tailings-contaminated sediments was exchangeable, 20–30% was labile, including weakly adsorbed, carbonate- and arsenate bound, 20–30% was metastable, probably incorporated into iron or manganese oxyhydroxides, or strongly adsorbed to silicate minerals, and 40–48% was relatively insoluble, probably incorporated into sulphides or silicates. Arsenic in sediments affected by artisanal gold mining was 75–95% relatively insoluble. Antimony in all sediments was >90% relatively insoluble. Relative solubility patterns of most other metals did not differ between industrial tailings-affected, artisanal-mining affected areas, and fluvial sediments. Results suggest that submarine tailings disposal is not suitable for refractory Carlin-like gold deposits because ore processing converts arsenic to forms unstable in anoxic marine sediments. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

石家庄污灌区表层土壤中重金属环境地球化学研究

对石家庄市污灌区上、中、下游3条剖面中的农田表层土壤重金属元素Pb、Hg、cr、Cd、As、Cu、Zn的含量、污染状况、形态等进行了调查与研究.结果发现.研究区表层土壤中的重金属(除As外)在污灌区上、中、下游均有不同程度的富集,其中Hg、Cd含量较高,下游表层土壤中重金属平均含量均高于上、中游.运用Muller的地积累指数法进行了污染评价,结果表明,以河北省土壤背景值计算,As未对研究区表层土壤造成污染,研究区上、中、下游表层土壤受到了Hg、Cd的污染,主要为轻度一中等的污染程度.研究区表层土壤中Pb、Hg、Cr、As、Cu、Zn的形态主要为残渣态,Cd的形态主要为离子交换态和碳酸盐态,Cd具有一定的生物有效性和潜在生态危害性.     

Mobility of heavy metals as a function of pH of samples from an overbank sediment profile contaminated by mining activities

Parts of the flood plains north of the Harz Mountains are contaminated with heavy metals, such as Pb, Cu, Zn and Cd derived from mining, which has been carried out in the Harz Mts. since the Middle Ages. It is important to know the mobility of the heavy metals in these overbank sediments in order to estimate the danger to the environment arising from this source. This paper deals with the effect of pH on heavy-metal mobility, using a constant-pH method. The investigations were carried out on an overbank sediment profile near Salzgitter Bad, north of the Harz Mts. The mobility of the heavy metals in the overbank sediment profile is described as a function of pH and depth. Besides the mobile heavy-metal fraction at a certain pH, the buffering capacity of the sediment at this pH must be taken into consideration. The different layers of the overbank sediment profile show distinct differences in buffering capacity and a natural pH harrier could be identified in the upper part of the profile. Therefore, to avoid increasing heavy-metal mobility the natural layering of the overbank sediment profile should not be disturbed. Two different kinds of desorption experiments at constant pH are also discussed, as well as the conversion of the heavy-metal species in the ore minerals into the species in the sediment.     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Prediction of phytoavailability of trace metals to plants: Comparison between chemical extractions and soil-grown radish

One of the major routes of human exposure to toxic metals is the consumption of vegetables grown on contaminated soils. Radishes were grown in three different soils (kitchen garden, agricultural and industrial soils), presenting various contamination levels. A sequential extraction procedure was compared with EDTA and HCl simple extractions methods in order to predict the metals phytoavailabilty to radish. The analysis of the results shows that the simple HCl and sequential chemical extractions bring complementary results, since HCl is correlated in the phytoavailability of Cd, Mn and Zn, whereas the sequential extraction is correlated in the phytoavailability of Cr, Fe, Mn, Ni. EDTA simple extraction brings here less interesting results than the two other tested extractions.     

重金属污染土壤萃取方法选择及参数优化

土壤重金属污染是国际土壤与环境研究的热点和难点问题之一。重金属在土壤中存在的形态和各种形态的比例是决定其迁移性和生态影响的关键因素。常用的形态分析方法包括Tessier五步萃取法、BCR三步萃取法和水萃取法等。在比较三种萃取方法的基础上,在法国北部冶炼厂周围土壤和焦作矿区土壤污染研究中采用水乙酸两步萃取法,采用蒸馏水和0 11 mol/L的乙酸,液固比20,25 ℃条件下恒温振荡16 h。     

Contamination,chemical speciation and vertical distribution of heavy metals in soils of an old and large industrial zone in Northeast China

Heavy metal pollution of soils has become a major concern in China as a consequence of rapid urbanization and industrialization in recent years. However, the evaluation on soil heavy metal pollution in Shenyang, the largest heavy industrial base city in China, has not yet been conducted. In this study, accumulation, chemical speciation, and vertical distribution Cu, Zn, Pb and Cd in soils were studied and pollution condition was assessed in Tiexi Industrial District of Shenyang, the largest and oldest industrial zone in Northeastern China. The results showed that in topsoil, the average concentration of total Cu, Zn, Pb, and Cd was 209.06, 599.92, 470.19 and 8.59 mg kg⁻¹, respectively, much higher than the national threshold limit. The values of pollution index and integrated pollution index showed that the pollution level was Cd > Cu > Zn > Pb, and Cd, Cu and Zn belong to heavy pollution level. The residual, Fe and Mn oxide-bound, and organic-bound species accounted for about 90%, while carbonate-bound and exchangeable species accounted for about 10%. This study indicates that the soils in the industrial zone were widely and extremely polluted by multi-heavy metals as a result of long-term industrial activities.     

土壤和沉积物中元素的化学形态及其顺序提取法

介绍了形态分析的概念和化学形态分析方法,探讨了广泛应用于土壤、沉积物重金属形态分析中的Tessier和BCR顺序提取方案及其异同,综述了顺序提取方法在地球化学、环境科学、农业科学等方面的应用及中国相关标准物质的研制现状。     

缓冲期碳酸盐型尾矿重金属释放机制——柱淋滤实验研究

碳酸盐型尾矿在缓冲期/中性矿山废水(NMD)释放期的重金属污染问题易被忽视。本文以广西大厂锡石-硫化物尾矿作为研究对象,采用柱淋滤实验方法,探讨碳酸盐型尾矿在缓冲期重金属的释放机制,为此类型尾矿重金属污染的防治提供依据。实验结果表明,大厂尾矿在缓冲期(约7年,pH值为6. 6～8. 0)存在Sb、Zn、Cd、As(Pb)释放污染问题。在尾矿堆放初期(0. 5年,pH值由7. 6降至7. 2),Zn、Sb、Cd快速、大量释出;中期(0. 5～2. 5年,pH值由7. 2波动升高至8. 0),Sb较平稳释出;后期(2. 5～7年,pH值变化范围为8. 0～6. 6,呈降低趋势),受气温及pH值影响,As、Sb(Pb)呈波动或间歇振荡释出,即在夏季高温、pH值较高时,释出元素浓度较高,反之,在冬季低温、pH值较低时,释出元素浓度较低。重金属的释放与尾矿中硫化物的氧化程度高低及氧化先后顺序有关。这些矿物的氧化顺序大致为:闪锌矿(Zn、Cd)、辉锑锡铅矿(Sb)→脆硫锑铅矿(Sb)→毒砂(As)、方铅矿(Pb)。因此,对于(广西大厂)碳酸盐型尾矿在缓冲期的重金属污染应分阶段、季节(夏季),采取有针对性的防治措施;在缓冲期(7年)后应注意尾矿酸性矿山废水(AMD)+重金属(如As、Sb)复合污染的防治。     

Changes in mobility and speciation of heavy metals in clay-amended incinerator fly ash

The generation of municipal solid waste incinerator fly ash (MSWIF) has been increasing significantly over the recent past, and its disposal is problematic and costly due to high concentration of leachable heavy metals present in the material. This study explored a potential stabilization of MSWIF by blending with a natural sorbent material with low permeability, clay, and assessed the potential release of heavy metals from the stabilized mixtures under various simulated subsurface environments. The leachability of heavy metals such as Pb, Cd, Cr, Zn and Cu in the MSWIF-clay mixtures cured for 1 to 360 days was investigated by performing leaching tests and sequential chemical extractions (SCE). Leaching tests were performed at acidic, neutral and alkaline pH values. The leaching test results suggested that the natural clay could turn the MSWIF into non-hazardous material. All the MSWIF-clay mixtures demonstrated leaching behavior different from that of the original MSWIF. SCE results revealed that the acidic and reducing conditions were the most unfavorable to the immobilization of the heavy metals in the stabilized MSWIF-clay matrix. Conversely, the oxidizing and alkaline conditions were not critical to the stabilized MSWIF-clay mixtures. Apparently, clay in the mixtures could function as an adsorptive micro-barrier to retain the heavy metals within the MSWIF-clay matrices.     

Correlations between heavy metals and organic carbon extracted by dry oxidation procedure in urban roadside soils

The organic fraction in soils has a significant influence on heavy metal transport. In this study, the organic carbon content was measured by dry oxidation procedure from 21 Xuzhou urban roadside soils to assess the relationships between the concentrations of heavy metals (Pb, Cu, Zn, and Cr) and the amount of organic carbon. The anthropogenic heavy metals (e.g. Pb, Cu, Zn) were strongly correlated with organic carbon (denoted by C_org−c) extracted by dry oxidation while natural heavy metal (e.g. Cr) showed no correlation to the C_org−c. The anthropogenic heavy metals were also strongly correlated with the amount of the total carbon. These results show that the anthropogenic heavy metals are mainly enriched in the organic matter in the Xuzhou urban roadside soils.     

Speciation and mobility of heavy metals in mud in coastal reclamation areas in Shenzhen,China

Coastal reclamation has been carried out along the coastal areas near Shenzhen, China in a large scale since 1980s by dumping fill materials over the marine mud at the sea bottom. Usually the area to be reclaimed is drained first and some of the mud is air-dried for a few weeks before it is buried by fill. After reclamation, the terrestrial groundwater, which is relatively acidic and with high dissolved oxygen, gradually displaces the seawater, which is alkaline with high salinity. The changes in the burial conditions of mud and the properties of the pore water in the mud may induce the release of some heavy metals into the mud. Field survey confirms that the pH and salinity of the groundwater in the reclamation site are much lower than the seawater. Chemical analyses of mud and groundwater samples collected from the reclamation sites reclaimed in different years indicate that most of the heavy metals in the mud decrease gradually with time, but the heavy metals in the groundwater are increased. The release of heavy metals into pore water due to reactivation of heavy metals in the mud is of environmental concern. To understand why some of the heavy metals can be released from the mud more easily than others, a sequential extraction method was used to study the operationally determined chemical forms of five heavy metals (Cu, Ni, Pb, Zn, and Cd) in the mud samples. Heavy metals can be presented in five chemical forms: exchangeable, carbonate, Fe–Mn oxide, organic, and residual. Ni and Pb were mainly associated with the Fe–Mn oxide fraction and carbonate fraction; Zn was mainly associated with organic fraction and Fe–Mn oxide fraction, while Cu and Cd were associated with organic fraction and carbonate fraction, respectively. If the residual fraction can be considered as an inert phase of the metal that cannot be mobilized, it is the other four forms of heavy metal that cause the noticeable changes in the concentration of heavy metals in the mud. On the basis of the speciation of heavy metals, the mobility of metals have the following order: Pb (36.63%) > Cu (31.11%) > Zn (20.49%) > Ni (18.37%) > Cd (13.46%). The measured metal mobility fits reasonably well with the degree of concentration reduction of the metals with time of burial observed in the reclamation site.     

Speciation and solubility of heavy metals in contaminated soil using X-ray microfluorescence, EXAFS spectroscopy, chemical extraction, and thermodynamic modeling

Synchrotron-based X-ray radiation microfluorescence (μ-SXRF) and micro-focused and powder extended X-ray absorption fine structure (EXAFS) spectroscopy measurements, combined with desorption experiments and thermodynamic calculations, were used to evaluate the solubility of metal contaminants (Zn, Cu, Pb) and determine the nature and fractional amount of Zn species in a near-neutral pH (6.5-7.0) truck-farming soil contaminated by sewage irrigation for one hundred years. Zn is the most abundant metal contaminant in the soil (1103 mg/kg), followed by Pb (535 mg/kg) and Cu (290 mg/kg). The extractability of Zn, Pb, and Cu with citrate, S,S-ethylenediaminedisuccinic acid (EDDS), and ethylenediaminetetraacetic acid (EDTA) was measured as a function of time (24 h, 72 h, 144 h), and also as a function of the number of applications of the chelant (5 applications each with 24 h of contact time). Fifty-three percent of the Zn was extracted after 144 h with citrate, 51% with EDDS and 46% with EDTA, compared to 69, 87, and 61% for Cu, and 24, 40, and 34% for Pb. Renewing the extracting solution removed more of the metals. Seventy-nine, 65, and 57% of the Zn was removed after five cycles with citrate, EDDS and EDTA, respectively, compared to 88, 100, and 72% for Cu, and 91, 65, and 47% for Pb. Application to the untreated soil of μ-SXRF, laterally resolved μ-EXAFS combined with principal component analysis, and bulk averaging powder EXAFS with linear least-squares combination fit of the data, identified five Zn species: Zn-sorbed ferrihydrite, Zn phosphate, Zn-containing trioctahedral phyllosilicate (modeled by the Zn kerolite, Si₄(Mg_1.65Zn_1.35)O₁₀(OH)₂ · nH₂O), willemite (Zn₂SiO₄), and gahnite (ZnAl₂O₄), in proportions of ∼30, 28, 24, 11, and less than 10%, respectively (precision: 10% of total Zn). In contrast to Cu and Pb, the same fractional amount of Zn was extracted after 24 h contact time with the three chelants (40-43% of the initial content), suggesting that one of the three predominant Zn species was highly soluble under the extraction conditions. Comparison of EXAFS data before and after chemical treatment revealed that the Zn phosphate component was entirely and selectively dissolved in the first 24 h of contact time. Preferential dissolution of the Zn phosphate component is supported by thermodynamic calculations. Despite the long-term contamination of this soil, about 79% of Zn, 91% of Pb, and 100% of Cu can be solubilized in the laboratory on a time scale of a few days by chemical complexants. According to metal speciation results and thermodynamic calculations, the lower extraction level measured for Zn is due to the Zn phyllosilicate component, which is less soluble than Zn phosphate and Zn ferrihydrite.