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1.
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.  相似文献   

2.
The mobility and solid-state speciation of zinc in a pseudogley soil (pH = 8.2-8.3) before and after contamination by land-disposition of a dredged sediment ([Zn] = 6600 mg kg−1) affected by smelter operations were studied in a 50 m2 pilot-scale test site and the laboratory using state-of-the-art synchrotron-based techniques. Sediment disposition on land caused the migration of micrometer-sized, smelter-related, sphalerite (ZnS) and franklinite (ZnFe2O4) grains and dissolved Zn from the sediment downwards to a soil depth of 20 cm over a period of 18 months. Gravitational movement of fine-grained metal contaminants probably occurred continuously, while peaks of Zn leaching were observed in the summer when the oxidative dissolution of ZnS was favored by non-flooding conditions. The Zn concentration in the <50 μm soil fraction increased from ∼61 ppm to ∼94 ppm in the first 12 months at 0-10 cm depth, and to ∼269 ppm in the first 15 months following the sediment deposition. Higher Zn concentrations and enrichments were observed in the fine (<2 μm) and very fine (<0.2 μm) fractions after 15 months (480 mg kg−1 and 1000 mg kg−1, respectively), compared to 200 mg kg−1 in the <2 μm fraction of the initial soil. In total, 1.2% of the Zn initially present in the sediment was released to the environment after 15 months, representing an integrated quantity of ∼4 kg Zn over an area of 50 m2. Microfocused X-ray fluorescence (XRF), diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy techniques were used to image chemical associations of Zn with Fe and Mn, and to identify mineral and Zn species in selected points-of-interest in the uncontaminated and contaminated soil. Bulk average powder EXAFS spectroscopy was used to quantify the proportion of each Zn species in the soil. In the uncontaminated soil, Zn is largely speciated as Zn-containing phyllosilicate, and to a minor extent as zincochromite (ZnCr2O4), IVZn-sorbed turbostratic birnessite (δ-MnO2), and Zn-substituted goethite. In the upper 0-10 cm of the contaminated soil, ∼60 ± 10% of total Zn is present as ZnS inherited from the overlying sediment. Poorly-crystalline Zn-sorbed Fe (oxyhydr)oxides and zinciferous phyllosilicate amount to ∼20-30 ± 10% each and, therefore, make up most of the remaining Zn. Smaller amounts of franklinite (ZnFe2O4), Zn-birnessite and Zn-goethite were also detected. Further solubilization of the Zn inventory in the sediment, and also remobilization of Zn from the poorly-crystalline neoformed Fe (oxyhydr)oxide precipitates, are expected over time. This study shows that land deposition of contaminated dredged sediments is a source of Zn for the covered soil and, consequently, presents environmental hazards. Remediation technologies should be devised to either sequester Zn into sparingly soluble crystalline phases, or remove Zn by collecting leachates beneath the sediment.  相似文献   

3.
The natural speciation of Mn (0.19 g/kg), Ni (46 mg/kg), and Zn (42 mg/kg) in the argillic horizon (120 cm depth, pH = 5.6) of an Ultisol from a paddy soil in northern Taiwan was investigated by advanced X-ray synchrotron techniques. Microchemical associations were imaged by synchrotron-based X-ray microfluorescence, host minerals were identified by standard and micrometer-resolved X-ray diffraction, and the local coordination environment of Mn, Ni, and Zn was probed using extended X-ray absorption fine structure (EXAFS) spectroscopy on a powdered sample and a soil thin section, and polarized EXAFS spectroscopy on a highly textured self-supporting clay film from the <2 μm fraction of the soil. Manganese was concentrated in Fe-Mn soft mottles (44.4 g/kg) as turbostratic hexagonal birnessite and lithiophorite having Mn3+/Mn4+ atomic ratios of ∼20% and 50%, respectively. Quantitative analysis of high-order scattering paths of the EXAFS spectrum for natural and synthetic lithiophorite revealed that Mn3+ and Mn4+ are ordered in the layer. A structural model is proposed, in which Mn4+ and Mn3+ are ordered similarly to Al and Li in the layer, with Mn3+ cations being surrounded by six Mn4+, and Mn4+ cations by three Mn3+ and three Mn4+. Similar cation ordering in the manganese and aluminum layers likely provides a more homogeneous local balance of the excess and deficit of charges in each layer and increases the stability of lithiophorite. Ni (r = 0.70 Å) substitutes for Mn (r(Mn4+) = 0.54 Å, r(Mn3+) = 0.65 Å) in the manganese layer in the natural lithiophorite. In contrast, Zn (r = 0.74 Å) fills vacant sites in the gibbsitic layer of natural lithiophorite, in a similar manner as lithium (r = 0.74 Å) in synthetic lithiophorite. The partitioning of Ni and Zn between the two layers is a result of the general preference of Ni, whose size is intermediate between those of Mn3+ and Li+, for slightly smaller sites. In contrast with nickel, which is detected only where there is lithiophorite, the Zn-lithiophorite association found in Fe-Mn mottles is not representative of the bulk soil. The combined use of X-ray diffraction, and powder and polarized EXAFS spectroscopy revealed that Zn is predominantly bound to hydroxy-Al interlayers sandwiched between 2:1 vermiculite layers in the fine soil matrix. The incorporation of Zn in the gibbsitic layer of both lithiophorite and vermiculite helps increase the stability of these minerals by providing positive charge to balance the negative charge from the 2:1 phyllosilicate layer and the layer of lithiophorite. This binding environment for zinc is probably the main mechanism by which zinc is sequestered in acidic to near-neutral aluminum-rich clayey soils.  相似文献   

4.
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(Mg1.65Zn1.35)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.  相似文献   

5.
Recent studies demonstrated that Zn-phyllosilicate- and Zn-layered double hydroxide-type (Zn-LDH) precipitates may form in contaminated soils. However, the influence of soil properties and Zn content on the quantity and type of precipitate forming has not been studied in detail so far. In this work, we determined the speciation of Zn in six carbonate-rich surface soils (pH 6.2-7.5) contaminated by aqueous Zn in the runoff from galvanized power line towers (1322-30,090 mg/kg Zn). Based on 12 bulk and 23 micro-focused extended X-ray absorption fine structure (EXAFS) spectra, the number, type and proportion of Zn species were derived using principal component analysis, target testing, and linear combination fitting. Nearly pure Zn-rich phyllosilicate and Zn-LDH were identified at different locations within a single soil horizon, suggesting that the local availabilities of Al and Si controlled the type of precipitate forming. Hydrozincite was identified on the surfaces of limestone particles that were not in direct contact with the soil clay matrix. With increasing Zn loading of the soils, the percentage of precipitated Zn increased from ∼20% to ∼80%, while the precipitate type shifted from Zn-phyllosilicate and/or Zn-LDH at the lowest studied soil Zn contents over predominantly Zn-LDH at intermediate loadings to hydrozincite in extremely contaminated soils. These trends were in agreement with the solubility of Zn in equilibrium with these phases. Sequential extractions showed that large fractions of soil Zn (∼30-80%) as well as of synthetic Zn-kerolite, Zn-LDH, and hydrozincite spiked into uncontaminated soil were readily extracted by 1 M NH4NO3 followed by 1 M NH4-acetate at pH 6.0. Even though the formation of Zn-precipitates allows for the retention of Zn in excess to the adsorption capacity of calcareous soils, the long-term immobilization potential of these precipitates is limited.  相似文献   

6.
We determined the speciation of Zn in 49 field soils differing widely in pH (4.1–7.7) and total Zn content (251–30,090 mg/kg) by using extended X-ray absorption fine structure (EXAFS) spectroscopy. All soils had been contaminated since several decades by inputs of aqueous Zn with runoff-water from galvanized power line towers. Pedogenic Zn species identified by EXAFS spectroscopy included Zn in hydroxy-interlayered minerals (Zn-HIM), Zn-rich phyllosilicates, Zn-layered double hydroxide (Zn-LDH), hydrozincite, and octahedrally and tetrahedrally coordinated sorbed or complexed Zn. Zn-HIM was only observed in (mostly acidic) soils containing less than 2000 mg/kg of Zn, reflecting the high affinity but limited sorption capacity of HIM. Zn-bearing precipitates, such as Zn-LDH and Zn-rich trioctahedral phyllosilicates, became more dominant with increasing pH and increasing total Zn content relative to available adsorption sites. Zn-LDH was the most abundant Zn-precipitate and was detected in soils with pH > 5.2. Zn-rich phyllosilicates were detected even at lower soil pH, but were generally less abundant than Zn-LDH. Hydrozincite was only identified in two calcareous soils with extremely high Zn contents. In addition to Zn-LDH, large amounts of Zn in highly contaminated soils were mainly accumulated as sorbed/complexed Zn in tetrahedral coordination. Soils grouped according to their Zn speciation inferred from EXAFS spectroscopy mainly differed with respect to soil pH and total Zn content. Clear differences were observed with respect to Zn fractionation by sequential extraction: From Zn-HIM containing soils, most of the total Zn was recovered in the exchangeable and the most recalcitrant fractions. In contrast, from soils containing the highest percentage of Zn-precipitates, Zn was mainly extracted in intermediate extraction steps. The results of this study demonstrate that soil pH and Zn contamination level relative to available adsorption sites are the most important factors controlling the formation of pedogenic Zn-species in aerobic soils and, consequently, Zn fractionation by sequential extraction.  相似文献   

7.
The objective of this study was to determine the local coordination of Zn in hydroxy-interlayered smectite (HIS) as a function of Zn loading and synthesis conditions and to assess the importance of hydroxy-interlayered minerals (HIM) for Zn retention in contaminated soils. Published and newly collected extended X-ray absorption fine structure (EXAFS) spectra of HIS reacted with Zn at molar Zn/hydroxy-Al ratios from 0.013 to 0.087 (corresponding to final Zn contents of 1615-8600 mg/kg Zn) were evaluated by shell fitting. In Zn-HIS, Zn was octahedrally coordinated to oxygen at 2.06-2.08 Å and surrounded by Al atoms at 3.03-3.06 Å in the second-shell. With increasing molar Zn/hydroxy-Al ratio, the coordination number of second-shell Al decreased from 6.6 to 2.1. These results were interpreted as a progressive shift from Zn incorporation in the vacancies of gibbsitic Al-polymers to Zn adsorption to incomplete Al-polymers and finally uptake by cation exchange in the polymer-free interlayer space of HIS with increasing Zn loadings. In a second part, we determined the speciation of Zn in eight contaminated soils (251-1039 mg/kg Zn) with acidic to neutral pH (pH 4.1-6.9) using EXAFS spectroscopy. All soils contained hydroxy-Al interlayered vermiculite (HIV). The analysis of EXAFS spectra by linear combination fitting (LCF) showed that a substantial fraction of total Zn (29-84%) was contained in HIM with high Zn loading. The remaining Zn was adsorbed to organic and inorganic soil components and incorporated into phyllosilicates. In sequential extractions of Zn-HIS spiked into quartz powder and the Zn contaminated soils, Zn was mainly released in the two most resistant fractions, in qualitative agreement with the findings from LCF. Our results suggest that formation of Zn-HIM may strongly retain Zn in pristine and moderately contaminated acidic to neutral soils. Due to their limited sorption capacity, however, HIM do not allow for the accumulation of high levels of Zn in response to continued Zn input into soils.  相似文献   

8.
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.  相似文献   

9.
The detection of phyllosilicates and sulfates on Mars has revealed a complex aqueous history which suggests distinct geochemical environments separated temporally and spatially. Recent observations by MRO CRISM in Mawrth Vallis have shown that phyllosilicate deposits exhibit a specific stratigraphy, which remains incompletely understood. Moreover, MER Spirit has evidenced association between phyllosilicates, amorphous silica and sulfates. We investigated the hypothesis that these parageneses resulted from the acidic weathering of older phyllosilicate deposits. We exposed nontronite (Fe-rich smectite), montmorillonite (Al-rich smectite) and kaolinite to H2SO4 solutions at pH 0, 2 and 4, and at a temperature of 60 °C. After the acid treatment, a combination of mineralogical techniques was used to assess the degree of alteration of the three phyllosilicate minerals. XRF, XRD and ESEM measurements show that nontronite was the most unstable when acid leached, followed by montmorillonite and then kaolinite. Progressive acidic leaching of nontronite leads to alteration of the phyllosilicate to amorphous silica, along with Fe-sulfate and anatase, and the formation of an acidic Al,Fe-rich solution. Alteration of montmorillonite resulted in the formation of Fe-, Al-, Ca- and Mg-sulfates, and a Al-rich leaching solution. Comparatively, leaching of kaolinite resulted in the formation of Al-sulfates and a Al-rich solution as well, with only slight alteration of the primary mineralogical features. The effects of acid leaching of the phyllosilicates were also observed in NIR reflectance spectra, allowing a comparison with CRISM spectra from Mawrth Vallis. Based on our results, we propose a new model where acid leaching of mixed phyllosilicate deposits leads to kaolinite overlaying montmorillonite, which in turn caps Fe,Mg-smectites. Leaching of cations and subsequent evaporation leads to sulfate deposits, as supported by geochemical modeling, while amorphous silica remains as a residue. Depending on the intensity (pH) and length of exposure of acidic leaching, our model can explain the stratigraphic distribution of phyllosilicates, and the association of sulfates, silica and smectites.  相似文献   

10.
The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe3(PO4)2 · 8H2O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe–O and Fe–P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99–2.05 Å; 2P atoms at 3.17–3.25 Å). One analysed grain displays evidence of a significant Fe3+ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 Å; 2P atoms at 3.17 Å). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption.  相似文献   

11.
This paper presents the results of a comprehensive investigation of the interaction of layered silicates with Ca(OH)2 in hydrothermal conditions. The study is intended to evaluate the stability of the clay buffer in radioactive waste repositories, at the intermediate stages of concrete leaching, when the pH is controlled by the dissolution of portlandite. The influence of layer nature, octahedral occupation, presence of tetrahedral Al and degree of crystallinity will be assessed by analysing the behaviour of a set of well-selected phyllosilicates and using the combined capabilities of 29Si and 27Al MAS-NMR spectroscopy, powder X-ray diffraction and SEM/EDX. The results show that the main factor affecting the stability of the clay is the octahedral occupation, so that trioctahedral phyllosilicates are much more stable than dioctahedral ones. The nature and expandability of the layer does not seem to much influence the stability of the clay, so that a 2:1 expandable phyllosilicate shows the same stability as a chemically analogous 1:1 non-expandable phyllosilicate. However other factors like the poor crystallinity of the starting material or the presence of Al in the tetrahedral sheet of trioctahedral phyllosilicates weaken the clay structure in alkaline conditions and favour the transformation towards other phases.  相似文献   

12.
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.  相似文献   

13.
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.  相似文献   

14.
In order to better understand the long-term speciation and fractionation of Zn in soils, we investigated three soils naturally enriched in Zn (237–864 mg/kg Zn) from the weathering of Zn-rich limestones (40–207 mg/kg Zn) using extended X-ray absorption fine structure (EXAFS) spectroscopy and sequential extractions. The analysis of bulk EXAFS spectra by linear combination fitting (LCF) indicated that Zn in the oolitic limestones was mainly present as Zn-containing calcite (at site Dornach), Zn-containing goethite (Gurnigel) and Zn-containing goethite and sphalerite (Liestal). Correspondingly, extraction of the powdered rocks with 1 M NH4-acetate at pH 6.0 mobilized only minor fractions of Zn from the Gurnigel and Liestal limestones (<30%), but most Zn from the Dornach rock (81%). In the Dornach soil, part of the Zn released from the dissolving limestone was subsequently incorporated into pedogenic hydroxy-interlayered vermiculite (Zn-HIV, 30%) and Zn-containing kaolinite (30%) and adsorbed or complexed by soil organic and inorganic components (40%). The Gurnigel and Liestal soils contained substantial amounts of Zn-containing goethite (50%) stemming from the parent rock, smaller amounts (20%) of Zn-containing kaolinite (and possibly Zn-HIV), as well as adsorbed or complexed Zn-species (30%). In the soil from Liestal, sphalerite was only found in trace amounts, indicating its dissolution during soil formation. In sequential extractions, large percentages of Zn (55–85%) were extracted in recalcitrant extraction steps, confirming that Zn-HIV, Zn-containing kaolinite and Zn-containing goethite are highly resistant to weathering. These Zn-bearing phases thus represent long-term hosts for Zn in soils over thousands of years. The capability of these phases to immobilize Zn in heavily contaminated soils may however be limited by their uptake capacity (especially HIV and kaolinite) or their abundance in soil.  相似文献   

15.
Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO4 amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg LIII- and S K-edge. In amended sediments, XRD, SEM and sulfur K-edge XANES indicated formation of gypsum in seawater experiments or ettringite-type (Ca6Al2(SO4)3(OH)12.26H2O) phases in fresh water experiments, depending on the final solution pH (seawater ∼8.5; freshwater ∼10.5). Analysis of Hg EXAFS spectra showed Cl and Hg ligands in the first- and second-coordination shells at distances characteristic of a polynuclear chloromercury(II) salt, perhaps as a nanoparticulate phase, in both seawater and fresh water experiments. In addition to the chloromercury species, a smaller fraction (∼20–25%) of Hg was bonded to O atoms in fresh water sample spectra, suggesting the presence of a minor sorbed Hg fraction. In the absence of amendment treatment, Hg sorption and resistance to extraction can be accounted for by relatively strong binding by reduced S species present in the marsh sediment detected by S XANES. Thermodynamic calculations predict stable aqueous Hg–Cl species at seawater final pH, but higher final pH in fresh water favors aqueous Hg-hydroxide species. The difference in Hg coordination between aqueous and solid phases suggests that the initial Hg–Cl coordination was stabilized in the cement hydration products and did not re-equilibrate with the bulk solution with aging. Collectively, results suggest physical encapsulation of Hg as a polynuclear chloromercury(II) salt as the primary immobilization mechanism.  相似文献   

16.
Zinc uptake in suspensions (?3.7 g L−1) of MX80 montmorillonite was investigated at pH 4.0 and 7.3, a total Zn concentration ([Zn]total) of 500 μM, and dissolved Si concentrations ([Si]aq) of ∼70 and ∼500 μM in 0.5 M NaCl, by kinetics experiments and polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Differential thermogravimetric analysis verified the cis-vacant character of the montmorillonite. No Zn uptake occurred at pH 4.0, confirming that cation exchange was hampered by the high ionic strength of the suspension. At pH 7.3 and low [Si]aq (∼70 μM), Zn uptake occurred rapidly during the first hour of reaction, and then leveled off to 50 μmol/g montmorillonite at 168 h. The uptake rate is consistent with Zn sorption on pH-dependent edge sites. At pH 7.3 and high [Si]aq (∼500 μM), the initial sorption rate was similar, but Zn sorption continued, reaching 130 μmol/g at 168 h, and was paralleled by Si uptake with a Si/Zn uptake ratio of 1.51(10), suggesting formation of a Zn (hydrous) silicate. P-EXAFS data indicated that the first oxygen coordination shell of sorbed Zn is split into two subshells at 1.97(2) and 2.08(3)-2.12(2) Å for all EXAFS samples. These two distances are assigned to a mixture of tetrahedral (IVZn) and octahedral (VIZn) Zn complexes. The proportion of IVZn was lower in the high [Si]aq samples and decreased with reaction time. Al low [Si]aq and 216 h of reaction, nearest cationic shells of 0.6(4) Al in the film plane and 0.5(4) Si out of the film plane were detected at 3.00(2) and 3.21(2) Å, respectively, and were interpreted as the formation of IVZn and VIZn mononuclear complexes at the edges of montmorillonite platelets, in structural continuity to the (Al, Mg) octahedral sheets. At high [Si]aq, in-plane Zn and Al and out-of-plane Si neighbors were detected at 4 h, indicating the formation of Zn phyllosilicate nuclei at the layer edges. At 313 h, Zn-Al pairs were no longer detected, and Zn atoms were surrounded on average by 3.4(5) in-plane Zn at 3.10(1) Å and 1.7(9) out-of-plane Si at 3.30(2) Å, supporting the precipitation of a Zn phyllosilicate. Thus, dioctahedral Al phyllosilicate may act as a nucleating surface for the heterogeneous formation of trioctahedral Zn phyllosilicate at [Si]aq relevant to natural systems.  相似文献   

17.
Contaminated soils and mine tailings pose major environmental and agricultural problems worldwide. These problems may be partially solved by an emerging new technology: phytoremediation. This technique uses plants to extract soil contaminants from the ground. Thlaspi caerulescens is known to accumulate in their tissues several heavy metals from soil and aerial deposition. This study was conducted to screen plants growing on a contaminated site to determine their potential for metal accumulation. Seeds of T. caerulescens metallicolous have been collected in the vicinity of F.T. Laurent le Minier in the Pb–Zn mining district of les Malines (North of Montpellier, Southern France), and seeds of T. caerulescens non-metallicolous were sampled on Larzac Plateau (North of Montpellier, Southern France). Soil substrates were collected from a mine site of Mibladen and Zaida (West, Morroco). Cultivated plant and surface soil samples were analyzed for zinc, lead, and cadmium concentrations by inductively coupled plasma mass spectrometry. A non-metallicolous (NM) ecotype of T. caerulescens and a metallicolous (M) ecotype are compared for Pb, Cd, and Zn accumulation in shoot and root in five metal-contaminated soils and one uncontaminated soil. The growth of individuals from uncontaminated soil was greater than that of individuals from metal-contaminated soils. The NM populations had markedly higher root/shoot ratio compared to M populations. The results indicate that both ecotypes of T. caerulescens are highly tolerant of zinc and Cd. Ecotype NM had constitutively higher Zn uptake capacity than the M ecotype. T. caerulescens species accumulate higher amount of Zn and Cd in their tissues in polluted soil and, in both of the two ecotypes, the root Pb concentrations were much greater than those of the shoot Pb contents. From both uncontaminated and metal-contaminated soils, we conclude that T. caerulescens are interesting material for phytoremediation of zinc and cadmium.  相似文献   

18.
Desorption of Zinc (Zn) in the rhizosphere soil is the primary factor that affects bioavailability of Zn. To improve predictions of Zn availability in amended soil, it is important that time-dependent desorption behavior of Zn in the rhizosphere soil should be understood. The greenhouse experiment was performed to determine Zn desorption characteristics in the bulk and the bean rhizosphere soils amended with municipal sewage sludge (1 % w/w) using rhizobox. The kinetics of Zn desorption was determined by successive extraction with 10-mM citric acid in a period of 1–504 h at 25 ± 1 °C in the bulk and the rhizosphere soils. Moreover, Zn was extracted using three extractants (DTPA-TEA, AB-DTPA, and Mehlich 3) in the bulk and the rhizosphere soils. The results showed that Zn extracted and Zn desorption rate in the bean rhizosphere soils were significantly (P < 0.01) lower than in the bulk soils. The mean of Zn desorption in the bulk and the rhizosphere soils were 16.47 and 15.50 mg kg?1, respectively. Desorption kinetics of Zn conformed fairly well to first-order, parabolic diffusion, and power function equations. The results of kinetics study indicated that desorption rate coefficients decreased in the rhizosphere soils compared to the bulk soils. The correlation studies showed that the rate constants in the power function equation were significantly correlated (P < 0.05) with Zn extracted using DTPA-TEA, AB-DTPA and Mehlich 3 in the bean rhizosphere and the bulk soils. The results of this research showed that Zn desorption in citric acid in the bean rhizosphere of amended soils were lower than the bulk of amended soils.  相似文献   

19.
Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ66Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ66Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ66Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe2O4)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ66Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ66Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ66Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.  相似文献   

20.
Mineralogical and chemical analysis of Late Pennsylvanian and Early Permian paleosols from the eastern shelf of the Midland basin, north-central Texas, USA, are used to test hypothesized climate change in Late Paleozoic western equatorial Pangea, previously defined independently on the bases of sedimentologic and paleontologic proxies and climate models. The <0.2-μm size phyllosilicate fraction in the studied paleosols exhibits down-profile trends in mineralogy and chemical composition that are consistent with modern weathering profiles suggesting a dominantly pedogenic origin. A stratigraphic trend from kaolinite-dominated profiles in Upper Pennsylvanian paleosols to profiles dominated by smectite and hydroxy-interlayered 2:1 phyllosilicates in Lower Permian paleosols indicates a relatively rapid decrease in soil weathering and leaching in the latest Pennsylvanian followed by a more gradual decrease in leaching throughout the Early Permian. The chemical composition (cation ratios and exchange capacity) of these phyllosilicates further corroborates this shift toward less intensive leaching, presumably in response to climate change from humid to progressively more arid conditions.The phyllosilicates in the <0.2-μm size fraction and contemporaneous pedogenic calcites from the Permo-Pennsylvanian paleosols exhibit a long-term stratigraphic increase in their δ18O values of as much as ∼3.2‰ and ∼5.2‰, respectively. This long-term trend is consistent with a transition throughout the latest Pennsylvanian through Early Permian toward progressively more evaporatively enriched soil waters. Superimposed on the long-term trend is an apparent rapid enrichment (1.5 to 2‰) in phyllosilicate δ18O values immediately above the Pennsylvanian-Permian boundary. Observed oxygen isotope fractionation between the phyllosilicates and calcites within individual paleosols indicate isotopic disequilibrium between mineral pairs. This is attributed to a minor detrital component in the pedogenic clay-dominated phyllosilicate fraction coupled with the effects of seasonality of mineral formation. Inferred δ18O compositions of Late Paleozoic meteoric water (−2‰ to +4‰) are compatible with less intensive soil leaching under conditions of increasing aridity, possibly coupled with a shift in local precipitation from a continental source to a marine source.  相似文献   

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