Zinc speciation in mining and smelter contaminated overbank sediments by EXAFS spectroscopy

Overbank sediments contaminated with metalliferous minerals are a source of toxic metals that pose risks to living organisms. The overbank sediments from the Geul river in Belgium contain 4000-69,000 mg/kg Zn as a result of mining and smelting activities, principally during the 19th century. Three main Zn species were identified by powder Zn K-edge EXAFS spectroscopy: smithsonite (ZnCO₃), tetrahedrally coordinated sorbed Zn (sorbed ^IVZn) and Zn-containing trioctahedral phyllosilicate. Smithsonite is a primary mineral, which accounts for approximately 20-60% of the Zn in sediments affected by mining and smelting of oxidized Zn ores (mostly carbonates and silicates). This species is almost absent in sediments affected by mining and smelting of both sulphidic (ZnS, PbS) and oxidized ores, presumably because of acidic dissolution associated with the oxidation of sulphides, as suggested by the lower pH of this second type of sediment (pH(CaCl₂) <7.0 vs. pH(CaCl₂) >7.0 for the first type). Thus, sulphide minerals in sediment deposits can act as a secondary source of dissolved metals by a chemical process analogous to acid mine drainage. The sorbed ^IVZn component ranges up to approximately 30%, with the highest proportion occurring at pH(CaCl₂) <7.0 as a result of the readsorption of dissolved Zn²⁺ on sediments constituents. Kerolite-like Zn-rich phyllosilicate is the major secondary species in all samples, and in some the only detected species, thus providing the first evidence for pervasive sequestration of Zn into this newly formed precipitate at the field scale.     

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system.The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn₂SiO₄), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn₂SiO₄, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.     

Aqueous and solid phase arsenic speciation in the sediments of a contaminated wetland and riverbed

Mobility of As in the environment is controlled by its association with solid phases through adsorption and co-precipitation. To elucidate the mobilization potential of As deposited in wetland and riverbed sediments of the Wells G & H wetland in Woburn, MA as the result of decades of industrial activity, As retention mechanisms were inferred from aqueous and solid phase geochemical measurements of sediment cores. Testing included a sequential extraction method designed for and standard-tested with As phases and pE/pH equilibrium modeling. The uppermost sediments in the Wells G & H wetland contain elevated concentrations of both dissolved and solid phase As (up to 2,000 μg/L and 15,000 μg/g, respectively) and a maximum concentration between 30 and 40 cm depth. Measurements obtained in this study suggested that As in the wetland sediments was predominantly adsorbed, likely onto amorphous Fe (hydr)oxide phases and mixed valence Fe phases. In the riverbed sediments, however, a relatively greater proportion of the solid As was associated with more reduced and crystalline phases, and adsorbed As was more likely associated with Al oxide or secondary reduced Fe phases. pH–pe modeling of the Fe–As–S system was consistent with observations. The association of As with more oxidized phases in the wetland compared with the riverbed sediments may result from a combination of plant activities, including evapotranspiration-driven water table depression and/or root oxygenation.     

Geological and anthropogenic factors influencing mercury speciation in mine wastes: an EXAFS spectroscopy study

The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600 °C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345 °C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500–2000 μm and <45 μm size fractions (e.g., from 97–810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8–18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases. The speciation of Hg in mine wastes is similar to that in distributed sediments located downstream from the same waste piles, indicating that the transport of Hg from mine waste piles does not significantly impact Hg speciation. Hg L_III-EXAFS analysis of samples from Au mining regions, where elemental Hg(0) was introduced to aid in the Au recovery process, identified the presence of Hg-sulfides and schuetteite (Hg₃O₂SO₄), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments.     

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

The maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies such as phytoremediation. In the present work, the mineralogical transformations of Zn-containing phases induced by two graminaceous plants (Agrostis tenuis and Festuca rubra) in a contaminated sediment ([Zn] = 4700 mg kg⁻¹, [P₂O₅] = 7000 mg kg⁻¹, pH = 7.8), untreated or amended with hydroxylapatite (AP) or Thomas basic slag (TS), were investigated after two yr of pot experiment by scanning electron microscopy coupled with energy-dispersive spectrometry (SEM-EDS), synchrotron-based X-ray microfluorescence (μ-SXRF), and powder and laterally resolved extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. The number and nature of Zn species were evaluated by principal component (PCA) and least-squares fitting (LSF) analysis of the entire set of μ-EXAFS spectra, which included up to 32 individual spectra from regions of interest varying in chemical composition. Seven Zn species were identified at the micrometer scale: sphalerite, gahnite, franklinite, Zn-containing ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted kerolite-like trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra.In the untreated and unvegetated sediment, Zn was distributed as ∼50% (mole ratio of total Zn) sphalerite, ∼40% Zn-ferrihydrite, and ∼10 to 20% (Zn-Al)-hydrotalcite plus Zn-phyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20% and were replaced by Zn-phosphate (∼30∼40%). In the presence of plants, ZnS was almost completely dissolved, and the released Zn bound to phosphate (∼40-60%) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite (∼20-40%). Neither the plant species nor the coaddition of mineral amendment affected the Zn speciation in the vegetated sediment. The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)-hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result from heterogeneous precipitation on mineral surface.     

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.     

Analysis of arsenic speciation in mine contaminated lacustrine sediment using selective sequential extraction,HR-ICPMS and TEM

In order to determine how As speciation in lacustrine sediment changes as a function of local conditions, sediment cores were taken from three lakes with differing hydrologic regimes and subjected to extensive chemical and TEM analysis. The lakes (Killarney, Thompson and Swan Lakes) are located within the Coeur d’ Alene River system (northern Idaho, USA), which has been contaminated with trace metals and As, from over 100 a of sulfide mining. Previous analyses of these lakebed sediments have shown an extensive amount of contaminant metals and As associated with sub-μm grains, making them extremely difficult to analyze using standard methods (scanning electron microscopy, X-ray diffraction). Transmission electron microscopy offers great advantages in spatial resolution and can be invaluable in determining As speciation when combined with other techniques. Data indicate that because of differences in local redox conditions, As speciation and stability is dramatically different in these lakes. Killarney and Thompson Lakes experience seasonal water-level fluctuations due to drawdown on a downstream dam, causing changes in O₂ content in sediment exposed during drawdown. Swan Lake has relatively constant water levels as its only inlet is dammed. Consequently, Killarney and Thompson Lakes show an increase in labile As-bearing phases with depth, while Swan Lake data indicate stable As hosts throughout the sediment profile. Based on these observations it can be stated that As in lakebed sediments is much less mobile, and therefore less bioavailable, when water is kept at a constant level.     

FeSO4稳定铬污染土的铬赋存形态及浸出特性研究

采用硫酸亚铁（FeSO4）对Cr(VI)污染土进行稳定化处理。研究了Fe(II)/Cr(VI)摩尔比和养护龄期对污染土稳定过程中的铬赋存形态及浸出特性的影响规律。结果表明：随着Fe(II)/Cr(VI)摩尔比和养护龄期的增加,Cr(VI)和总Cr的浸出浓度降低,稳定土中Cr(VI)的含量降低,当摩尔比为3时,Cr(VI)和总Cr的浸出浓度均低于我国《危险废弃物鉴别标准 浸出毒性鉴别》（GB/T50853―2007）的限值;当摩尔比为10时,稳定土中Cr(VI)的含量低于我国《土壤环境质量标准》（GB15618―2008）中工业和商业用地的限值（30 mg/kg）;当摩尔比为20时,低于居住用地限值（5 mg/kg）。形态提取试验结果表明：FeSO4改变稳定土中铬的赋存形态,可促使铬从弱酸态向可还原态和可氧化态转化,而对残渣态的铬影响不大。Cr(VI)的浸出浓度与稳定土中的Cr(VI)含量均存在指数函数关系,且浸出试验不能全面、客观地评价铬污染土稳定效果。     

Effects of in situ remediation on the speciation and bioavailability of zinc in a smelter contaminated soil

We report results from an extensive study on the speciation of zinc (Zn) and its relation to the mobility and bioavailablity of this element in a smelter contaminated soil and an in situ remediated area of this soil 12 yr after the application of cyclonic ash and compost. Emphasis was placed on the role of neoformed precipitates in controlling Zn speciation, mobility and bioavailability under different environmental conditions. Twelve years after remediation, the pH of the treated and non-treated soil differed by only 0.5 pH unit. Using state-of-the-art electron and X-ray microscopies in combination with micro-focused extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, no major differences in Zn speciation were found between samples of the treated and non-treated soil. In both soils, 30% to 50% of Zn was present in smelter related minerals (willemite, hemimorphite or gahnite), while 50% to 70% of Zn was incorporated into newly formed Zn precipitates. Contrary to the non-treated soil, the treated soil did not contain gahnite or sphalerite; it is possible that these minerals were dissolved under the higher pH conditions at the time of treatment. Desorption experiments, using a stirred flow technique with a 0.1 mol/L CaCl₂ (pH 6.5) and a HNO₃ (pH 4.0) solution were employed to determine the exchangeable Zn fraction and the Zn fraction which will be mobilized under more extreme weathering conditions, respectively. No significant differences were found in desorption behavior between the treated vs. non-treated soil. Bioavailability tests, using the R. metallidurans AE1433 biosensor showed that ∼8% of total Zn was bioavailable in both the treated and non-treated soils. It was concluded that the incorporation of Zn into newly formed precipitates in both the treated and non treated soils leads to a significant natural attenuation of the exchangeable/bioavailable Zn fraction at near neutral pH conditions. At lower pHs, conditions not favorable to the formation of Zn precipitates, the pool of Zn associated with the secondary Zn precipitates is potentially more bioavailable.     

Effects of soil type and fertilizer on As speciation in rice paddy contaminated with As-containing pesticide

Inorganic arsenic (As) pesticides have been widely used for decades in many countries. However, insufficient data are available on the chemical speciation of inorganic arsenicals in tropical paddy soils. Inorganic As-containing pesticides were used in tropical countries, a few decades ago, however, their fate have not been studied. Hence, the objective of this study was to determine fractionation of inorganic arsenicals and to assess As lability with/without fertilizer application using a static incubation experiment. Eight soils from wet and dry regions of Sri Lanka were amended with 1,000 mg/kg arsenate for this purpose. The FT-IR and XRF results suggested that soils in the wet region were rich in Fe/Al-oxides. Paddy soils in the dry zone showed high As lability. These low-humic gley soils have low Fe/Al oxyhydroxide and alkaline pH. In contrast, the wet zone had soils with higher As retention capacity, high amounts of Fe/Al oxyhydroxide, and acidic pH. Arsenic lability increased considerably 30 days after fertilizer application. Overall, As lability was mainly influenced by soil mineralogical and chemical properties, i.e., Fe/Al oxyhydroxide, pH, organic matter, and fertilizer application.     

模拟厌氧水稻土中氮、砷变化及迁移研究

矿渣和酸性矿山废水的排放会使矿区周围的农田受到污染。为研究厌氧条件下矿区农田中氮和砷之间的联系,本文通过摇瓶实验探究了含砷水铁矿在厌氧含氮农田中释放的砷形态的变化,通过柱实验探究了水稻生长对氮、砷形态和浓度的影响。研究结果发现,在厌氧条件下,外源氮的加入促进了砷污染水稻土中As(Ⅴ)的还原,使生成的As(Ⅲ)浓度最高达396μg/L;在柱实验模拟的厌氧农田不同层位中,水稻的生长过程促进了氮和砷的还原以及砷向下层位的迁移,使装置中的As(Ⅲ)浓度最高达517μg/L;摇瓶实验和柱实验在相近的厌氧条件下,NO^-₃的存在能够直接参与As(Ⅴ)还原。研究结果为农田砷污染的治理提供了一定的参考价值。     

Effect of soil aging on arsenic fractionation and bioaccessibility in inorganic arsenical pesticide contaminated soils

Ingestion of As – contaminated soil by children is a growing concern in former agricultural lands converted to residential or recreational land use areas. The mobility and bioavailability of As is controlled by its reactions with soil particles. The degree and strength of As retention by soil constituents may vary greatly with time. The present authors hypothesize that aging results in reduced mobility of As thereby decreasing As release and its bioavailability. The present study is aimed at evaluating the effect of aging on soil As fractionation and bioaccessibility in a temperature and humidity-controlled greenhouse setting. The design allowed the evaluation of dynamic interactions between soils, pesticides, water, and plants. Therefore, 4 soil types (Immokalee, Millhopper, Pahokee Muck, and Orelia) were selected based on their potential differences in As reactivity. The soils were amended with the pesticide Na arsenate at two rates. Rice was used as the test crop. Soil samples collected after different time periods (0, 6 months, 1 a and 3 a) were extracted for soil-As forms via a sequential extraction technique. Bioaccessible As was extracted via an in vitro gastrointestinal method. At time 0, most of the extractable As in soil was in the soluble form, resulting in high bioaccessibility. As expected, soluble and exchangeable fractions decreased with time for up to 6 months, but remained constant thereafter. After 3 a of soil–pesticide equilibration, As bioaccessibility was still high in all the soils except for the Pahokee Muck. No significant difference in As bioaccessibility was observed between the soils. Arsenic was present predominantly as As(V) with 5–10% of the total dissolved As being present as As(III). Data obtained suggest that although aging had an impact on the geochemical forms, gastric pH was the sole important factor effecting As bioaccessibility.     

Durations of soil formation and soil development indices in a Holocene Mediterranean floodplain

Holocene and late Pleistocene alluvial sequences of the mid-Medjerda floodplain (Northern Tunisia) reveal three types of soils with gradual transitions: Fluvisols (Calcaric), Cambisols (Calcaric) and Calcic Luvisols (Chromic). Stratigraphic cross-correlations, palaeomagnetic secular variation, and ¹⁴C and IRSL dating enable detailed information about ages and durations of soil formation in the floodplain.Weakly developed Fluvisols (Calcaric) commonly reveal late Holocene ages with soil formation durations lasting between 100 and 300 years. Hence, Holocene soil formation is detectable in the exposures from durations of around 100 years onwards. Cambisols show predominantly mid-Holocene ages. The durations of soil formation are between 800 and 5000 years. Calcic Luvisols (Chromic) feature late Pleistocene ages, with durations of soil formation between 10,000 and 40,000 years.Profile Development Indices were computed from simple field parameters like soil structure, soil colour, horizon thickness and leaching features. The derived development indices show good correlation (R² = 0.804) with the calculated durations of soil formation. Field parameters are well suited for a quantitative development index of Holocene soil formation, even if very weak developed soils are predominant. The study shows that maturity stages of Holocene alluvial soils in a homogeneous Mediterranean environment are predominantly driven by soil formation duration.     

Surfactant-enhanced remediation of contaminated soil: a review

Extracting aqueous solutions with or without additives are employed to solubilize contaminants in soil. Since water solubility is the controlling removing mechanism, additives are used to enhance efficiencies. These additives can reduce the time to treat a site compared to the use of water alone. Additives must be of low toxicity and biodegradable. The research in this area has focussed mainly on halogenated volatile organic compounds (VOCs) and is still quite limited for metal removal. Additives include surfactants, organic and inorganic acids, sodium hydroxide, which can dissolve organic soil matter, water-soluble solvents such as methanol, displacement of cations with nontoxic ones, complexing agents such as EDTA, acids in combination with complexing agents or oxidizing/reducing agents. Cationic, anionic and nonionic surfactants are particularly used for soil washing or flushing. They contain both hydrophobic and hydrophilic portions, making them ideal for solubilization of hydrophobic compounds. Numerous studies have indicated that surfactants enhance recoveries of non-aqueous phase liquids (NAPLs). There have also been indications that pretreatment of soil with surfactant washing to solubilize hydrophobic compounds such as PAHs enhances biodegradation of these contaminants. A few in situ field studies have been performed with surfactants. Large-scale treatment has been done mostly for organic removal. Soil pH, soil type, cation exchange capacity (CEC), particle size, permeabilities and contaminants all affect removal efficiencies. High clay and organic matter contents are particularly detrimental. Understanding the chemistry of the binding of the contaminant and the hydrogeology of the site are very important. Once the water is pumped from the soil, it must be extracted and then treated to remove the hydrocarbons and metals. Several technologies exist such as sodium hydroxide or sodium sulfide precipitation, ion exchange, activated carbon adsorption, ultrafiltration, reverse osmosis, electrodialysis and biological processes. Recycling of the surfactants is desired to decrease treatment costs.

This paper will provide an overview of the laboratory research, field demonstration and full-scale application of surfactants for the remediation of contaminated soil. The majority of pilot scale in situ flushing tests, particularly in the United States, have involved the use of surfactants and co-solvents. There are only a few full-scale projects however. Recent laboratory scale efforts by the authors concerning the use of biosurfactants, biologically produced surfactants, to enhance the removal of copper, cadmium and zinc from contaminated soils and sediments are discussed. Three types of biosurfactants were evaluated for their effectiveness. They included a lipopeptide called surfactin from Bacillus subtilis, a rhamnolipid from Pseudomonas aeruginosa and a sophorolipid from Torulopsis bombicola. The results indicated the feasibility of removing the metals with the anionic biosurfactants even though the exchangeable fractions were not significant.     

Simultaneous stabilization of arsenic, lead, and copper in contaminated soil using mixed waste resources

In the present study, stabilization treatment using waste resource stabilizers was performed for soil contaminated with As and heavy metals (Pb and Cu). Calcined oyster shell (COS) and coal mine drainage sludge (CMDS) were used as a mixed stabilizing agent for a wet-curing duration of 28 days. After the stabilization treatment, the treatment process efficiency was evaluated by the results of various batch- and column-leaching tests. Neutral and weak acid extraction methods, such as water-soluble extraction and SPLP, did not exhibit satisfactory results for heavy metal stabilization, even if they showed very low leachability. On the other hand, TCLP and 0.1 M HCl extraction showed that the stabilizers significantly reduced the amount of heavy metals leached from the soil, which strongly supports the thesis that the stabilization treatment is efficient in the acidic leaching conditions that were explored. Specifically, in the 0.1 M HCl extraction, the reduction efficiencies of As, Pb, and Cu leachings were more than 90 %, compared with control experiments. This study demonstrates that the application of waste resources for the stabilization of As and heavy metals is feasible. However, some limitations observed in the experiments should be considered in future studies, such as the mobilization of alkali-soluble elements, and in particular, exchangeable fractions of Cu. In addition, the treatment efficiency can be evaluated by different leaching methods, which suggests that multidirectional approaches are required for the proper evaluation of stabilization treatment.     

基坑土体卸荷平面应变试验离散元数值分析

对基坑开挖影响范围内土体的应力路径进行平面应变试验离散元数值模拟,以研究结构性与卸荷形式对坑周土体宏微观力学特性的影响。首先,将一个描述土颗粒间胶结效应的简单三维胶结接触模型植入三维离散元软件PFC3D;其次,对初始K0固结状态的重塑土、结构性土试样分别进行常规三轴以及平面应变条件下4种不同卸荷应力路径的离散元模拟;最后,对经历不同卸荷形式的坑底土体单元进行再加荷模拟。模拟结果表明,在卸荷过程中,被动区土体峰值强度以及破坏时竖向应变随卸荷比增大而增大,且其强度小于主动区土体强度;在卸荷、再加荷过程中,被动区土体峰值强度随卸荷比增大而增大,但均小于不卸荷而直接加荷条件下的峰值强度;由于结构性的存在,土体由应变硬化向应变软化过渡,且强度增长;结构性与卸荷形式显著影响土体体积改变。在微观尺度,增大卸荷比或结构性均会增大垂直大主应力方向的平面上的法向接触力,进而提高其强度。     

Arsenic in soil and vegetation of a contaminated area

Plant and soil samples were collected from one uncontaminated and four contaminated sites (in the Dashkasan mining area western Iran). Total and water-soluble arsenic in the soil ranged from 7 to 795 and from 0.007 to 2.32 mg/kg, respectively. The highest arsenic concentration in soil was found at the ore dressing area (up to 1,180 mg/kg) and lowest at an uncontaminated area (up to 11 mg/kg). A total of 49 plant species belonging to 15 families were collected from four sampling sites. A significant positive correlation was detected between the concentrations of arsenic in plant dry matter and those in soils. The highest arsenic concentrations were found in Hyoscyamus kurdicus Bornm. (up to 205 mg/kg) and Helichrysum oligocephalum DC. (up to 162 mg/kg). These two accumulator species could have potential for soil clean-up by phytoextraction. The data have been compared with those for the Zarshuran mining area (north-western Iran) obtained in a former study.     

Rare earth element behavior and Pb,Sr, Nd isotope systematics in a heavy metal contaminated soil

The aim of this study is to characterize the processes and phases which control migration and retention of rare earth elements (REE) in a heavy metal contaminated soil. In addition to concentration data, we used Pb, Sr and Nd isotopic compositions in order to distinguish between natural and anthropogenic trace metals and to characterize the phases leached away during the sequential extraction procedure.The samples were sequentially extracted in 3 steps with 1 N acetic acid (HAc), 1 N HCl and 1 N HNO₃. The Pb isotope data showed that anthropogenic Pb had mainly been retained in the uppermost 10 cm by the organic matter of the topsoil. The⁸⁷Sr/⁸⁶Sr ratios of the HAc extracts are almost constant and indicate that soil carbonate is derived from regionally outcropping carbonate-rich sediments. Most HCl and HNO₃ extracts have more radiogenic Sr isotopic compositions, but it is unclear whether this reflects a growing influence of anthropogenic or silicate-derived Sr.The depth distribution of the REE is mainly controlled by two different parameters: soil pH for the HAc extractable REE and FeMn oxides for the REE in the HCl and HNO₃ extracts. A part of the HNO₃ extractable REE was also bound to the organic matter of the topsoil. The REE concentrations in the HAc extractable phase increase with depth and increasing soil pH, which indicates that they are derived from the surface and hence are of anthropogenic origin. This is confirmed by¹⁴³Nd/¹⁴⁴Nd isotope ratios which show a mixing between a natural end-member at the top and an anthropogenic end-member at the base of the profile. We assume that the anthropogenic REE were transported in dissolved form as carbonate complexes and then precipitated during downward migration as soil pH increased.     

Biochar effects on metal bioaccumulation and arsenic speciation in alfalfa (<Emphasis Type="Italic">Medicago sativa L</Emphasis>.) grown in contaminated soil

Mining and geogenic activities can lead to elevated concentrations of potentially toxic elements in soil. Biochar amendment to soil is a cost-effective technology and environmentally friendly approach to control soil pollution, improve phytoremediation and mitigate health risks due to agricultural products. Greenhouse pot experiments were conducted to investigate the effects of rice husk biochar on alfalfa biomass, metal bioaccumulation and arsenic speciation. Results indicated that rice husk biochar amendments to contaminated soil increased plants biomass by improving soil fertility and available nutrients. Biochar also increased soil cation change capacity, dissolved organic carbon, while decreased available concentrations of potentially toxic elements (except for arsenic). The accumulation of nickel, lead, cadmium and zinc (except for chromium and arsenic) significantly (P ≤ 0.05) decreased as compared with unamended control plants. In addition, increases were observed for inorganic arsenite and arsenate. Current findings demonstrate that rice husk biochar can be used as a beneficial amendment for contaminated soil. However, further field experiments are needed to validate its long-term effectiveness where environmental factors are diverse and complex.