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1.
The speciation of cadmium, lead, copper, zinc, manganese and iron into exchangeable, carbonate, reducible and organic bound fractions was studied in sediments from coastal and freshwater environments in Ghana. This was relevant as the species in which metals are stored within specific sediment components is important in determining their impact on the environment. For both coastal and inland sediments, a higher percentage of cadmium was associated with the more available exchangeable and carbonate fractions, while iron, zinc and manganese were mainly associated with the reducible and organic fractions. Lead and copper were found to have the greatest ability to form different species in the samples examined and were more evenly associated with all the fractions. The metals generally showed more ability to form different species in inland freshwaters than in coastal relatively saline waters. However, differences between inland and coastal waters were based more on whether the environments were oxidising or reducing than on whether they were fresh or saline. The metals may be divided into three groups of high mobility consisting of lead and copper; moderate mobility made up of cadmium, manganese and zinc; and low mobility, represented by iron.  相似文献   

2.
Soils from cocoa plantations treated with Boudreaux mixture in two southwestern states of Nigeria were collected at different depths, 0–15 cm and 15–30 cm, and subjected to five-stage sequential extraction to obtain the speciation forms of copper: exchangeable, carbonate, manganese and iron oxides, organic and residual fractions. The Cu content in the extracts from the sequential extraction was read with an Atomic Absorption Spectrophotometer (AAS). The total Cu content of the soil and the physicochemical parameters of the soils were also determined. The results from the study showed that the soils had high organic matter and copper is mostly bounded to the more mobile exogenic phase much more than the stable lithogenic phase, indicating higher mobility. Within the exogenic species, carbonate fraction was the highest followed by the organic bound and the exchangeable fraction in decreasing order. Cu was not detected in the Fe/Mn bound fraction. The implication is that the fate of the administered Cu-based pesticide is more in the relatively stable carbonate bound species than the other, more mobile phase. The results showed variation in the distribution of the copper species from one depth to another. The most transported metal from the surface to the lower layer is the exchangeable fraction. The carbonate bound species is less mobile and is not readily transported into the bottom soil layer. The organic bound Cu has nearly equal distribution between the top and bottom soils and there was little or no transport of the residual metal specie from the top to the bottom. The existence of copper in the soil largely in the anthropogenic (exogenous) phase is not the most desirable for the ecosystem. This may increase the availability of Cu in the cocoa plant and bean and may lead to potential exposure risk.  相似文献   

3.
A sequential extraction scheme was combined with sorption isotherm analysis in order to investigate sorption of sewage sludge-derived Cu and Zn to the A-horizon of a humic-gley soil as a whole, and to the operationally defined exchangeable (1?M MgCl2), carbonate (1?M NaOAc), Fe/Mn oxide (0.04?M NH2OH.HCl), and organic (0.02?M HNO3+30% H2O2) soil fractions. Sorption parameters were compared for a sample of sludge leachate (with 97.4% of Cu and 63.2% of Zn present as dissolved metal-organic matter complexes, as calculated by geochemical modeling involving MINTEQA2 and verified using an ion exchange resin method) with that of a reference solution exhibiting the same chemical characteristics as the leachate, except for the presence of dissolved organic material. Dissolved metal-organic matter complexes were found to significantly (P<0.05) depress sorption to the bulk soil and each fraction. The greatest depression of Cu and Zn sorption was observed for the exchangeable, carbonate, and Fe/Mn oxide fractions, while the organic fraction of the soil was the least affected. This reflects a greater affinity for the exchangeable, carbonate, and Fe/Mn oxide fractions by the free divalent metal (Cu2+, Zn2+), with sorption by these fractions attributed to cation exchange, chemisorption, and co-precipitation processes. The sorption characteristics of the organic fraction indicated that Cu and Zn sorption by soil organic matter mostly involved dissolved metal-organic matter complexes. This may be attributed to hydrophobic interactions between nonpolar regions of the dissolved metal-organic matter complexes and solid-phase soil organic matter.  相似文献   

4.
The ligands iodide (I?) and thiocyanate (SCN?), alone or in admixture, in combination with a non-ionic surfactant, Triton X-100, were evaluated as washing agents for heavy metal desorption from a contaminated soil. After seven successive washings, selective sequential extraction (SSE) was performed to determine the heavy metal content that remained associated with each geo-chemical fraction of the soil. The surfactant with 0.336 mol L?1 of ligand I? removed 75% Cd and 23% Cu, whereas the mobilization of Zn and Pb were not significant after 7 washings. At a concentration of 0.286 mol L?1, the ligand SCN? in the presence of surfactant removed 36% Cd, 44% Cu and 77% Zn. Among the washing agents, the combination of I? and SCN? produced the highest desorption efficiencies 95% Cd, 48% Cu, and 3.1% Pb, but not for Zn. The SCN? ligand extracted the most Zn (77%). The SSE procedure indicated that the I? removed metals from the exchangeable, carbonate and oxide fractions whereas SCN? removed metals only from the exchangeable fraction. Both ligands, in the presence of surfactant, removed Cu from all fractions except the exchangeable sites, whereas only SCN? plus surfactant removed Zn from all fractions. The ligand mixture plus surfactant mobilized only limited quantities of Pb from the oxide and residual fractions.  相似文献   

5.
Accumulative phases for heavy metals in limnic sediments   总被引:3,自引:1,他引:2  
Förstner  Ulrich 《Hydrobiologia》1982,91(1):269-284
Data from mechanical concentrates of recent sediments indicate that clay minerals, clay-rich aggregates and heavy minerals are the major carriers of heavy metals in detrital sediment fractions. Hydrous Fe/Mn oxides and carbonates and sulfides, in their specific environments, are the predominant accumulative phases for heavy metals in autochthonous fractions. Sequential chemical extraction techniques permit the estimation of characteristic heavy metal bonding forms: exchangeable metal cations, easily reducible, moderately reducible, organic and residual metal fractions, whereby both diagenetic processes and the potential availability of toxic compounds can be studied. The data from lakes affected by acid precipitation indicate that zinc, cobalt and nickel are mainly released from the easily reducible sediment fractions and cadmium from organic phases. In contrast at pH 4.4, neither lead nor copper seem to be remobilized to any significant extent. Immobilization by carbonate precipitation seems to provide an effective mechanism for the reduction of dissolved inputs 9f metals such as zinc and cadmium in pH-buffered, hard water systems.  相似文献   

6.
为了研究露地栽培向设施大棚栽培转变对土壤重金属含量的影响,对武汉市郊区露地和设施塑料大棚两种栽培条件下菜田土壤重金属Cd、Cr和Pb各形态含量及分布特征进行了研究。结果显示,露地和大棚栽培条件下土壤重金属元素Cr和Pb各种形态含量之间没有明显差异,但Cd各种形态含量间有显著差异;从露地到大棚,土壤中Cd酸可提取态含量从露地的0.62 mg/kg上升到大棚的1.19 mg/kg,其次是Cd残渣态、有机结合态、氧化态和碳酸盐结合态;Cd总含量从露地的0.79 mg/kg升高到大棚的1.58 mg/kg,显著超过土壤环境质量标准中的Cd含量标准值(0.3 mg/kg),达到严重污染水平。Cd碳酸盐结合态和氧化态占总量的比例有所降低,而酸可提取态占总量的比例有所升高。说明从露地到设施大棚栽培,促使了土壤中部分Cd碳酸盐结合态和氧化结合态向酸可提取态转变,提高了土壤中Cd的生物有效性。因此,在设施大棚栽培快速发展的情况下,要加强重金属Cd对土壤污染的治理,减少重金属Cd对蔬菜的毒害。  相似文献   

7.
Abstract

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

8.
Chelating agents such as EDTA and DTPA are often used to remove metals from soil. However, their toxicity, bio-recalcitrance, and problems with recovery of heavy metal and chelating agents severely limit their applications. A biodegradable chelating agent, LED3A, and two surfactants, SDS and Triton X 100, were evaluated as potential alternatives for remediation of metal-contaminated soil.

LED3A alone only removed 40% of cadmium the addition of surfactant significantly enhanced its cadmium removal capacity up to 80% for a wide range of pH (5 to 11). The enhancement increased with both surfactant concentrations and LED3A concentrations. Because LED3A had a much higher removal capacity for copper, the synergistic effect of surfactant-LED3A mixture was less obvious. Sequential extraction analysis indicated that the LED3A not only removed copper from carbonate and Fe-Mn oxide fraction, but also from organic fractions. A three-dimension electrolysis reactor could effectively recover both metals and LED3A-SDS within thirty minutes. The combined soil washing by LED3A-surfactants and electrolysis provides a potential approach for remediation of copper- and cadmium-contaminated soils.  相似文献   


9.
Past studies have shown that dissolved organic carbon (DOC) washing can effectively remove heavy metals from contaminated soil. In this study, we used alkaline DOC solutions for remediation of arsenic (As)-contaminated soil (with an initial As concentration in the topsoil of 390 mg kg?1). The removal of As and the change in soil nutrients during DOC washing were studied for 60 min at pH 10 with a 60:1 liquid/soil ratio (v/m). Approximately 88% of As was removed by washing the soil twice using a 3000 mg L?1 DOC solution at 25°C. Following this treatment, the pH of the soil had increased from 5.6 to 9.2; organic carbon content had increased from 3.5% to 4.1%; cation exchange capacity, ammonium-N, and available phosphorus had increased to 2.3, 1.4, and 6.6 times their original levels, respectively; and exchangeable K, Na, Ca, and Mg had increased to 91, 6.1, 4.2, and 2.2 times their original levels, respectively. A sequential extraction investigation revealed that residual As and easily exchangeable As in the fraction were initially 10.2% and 9.2%, respectively, but that the former became the maximum remainder (64%) after the ultimate DOC washing.  相似文献   

10.
Abstract

Concentrations of surface soil Zn and Cd from agricultural areas of the Henan Province were measured. About 234 soil samples were collected. Total metal analyses, sequential chemical fractionation which were divided into seven fractions according to the method of the Geological Survey Technical Standard (DD2005-03) set by the China Geological Survey were carried out on the samples. Total Cd and Zn concentrations of the topsoil were 0.1909 (0.1–0.549) and 63.07 (33.3–344.3) mg kg?1 respectively. Compared with the values permitted in China’s control standards for soil (GB 15618–1995) and background value in Henan Province, the soil samples showed high levels of Cd. The soil organic carbon has a significantly positive correlation with Cd and Zn concentration in the soil. Significant positive correlation between pH and Cd, Zn concentration was observed. On average, the order of Cd in each fraction was exchangeable, (27.3%)>weakly bound to organic matter; (22.7%)>strongly bound to organic matter; (16.4%)>residual; (15.1%)>carbonate; (12.1%)>Fe/Mn oxide bound; (4.5%)>water soluble; (2.0%), Zn was residual; (66.3%)>Fe/Mn oxide bound; (10.9%)> weakly bound to organic matter; (9.4%)> exchangeable; (6.0%)> strongly bound to organic matter; (3.9%)> carbonate (2.9%)> water soluble (0.6%). The accuracy of the sequential extraction was judged by the relative error (RE). RE for Cd ranged from 0 to 45% with a mean of 16.3%. RE for Zn ranged from 0.1 to 11.4% with a mean of 3.4%. On average, bioavailability index (BI) for Cd and Zn was 39.1% and 9.0% respectively. The mobility of the elements in the order Cd> Zn corresponds with the plant-availability of individual elements. Comparisons between activities of Cd2+ and Zn2+ calculated by Sauve semi-mechanistic equations and that of the water soluble fractions were demonstrated. The activities of Cd2+ and Zn2+ calculated by the semi-empirical equation are lower than its water soluble fraction.  相似文献   

11.
Bioavailability and mobility of heavy metals (HMs) in soils are determined by their partitioning between solution and solid-phase and their further redistribution among solid-phase components. A study was undertaken to determine the effects of organic matter (OM) and salinity on cadmium (Cd) and lead (Pb) distribution among soil fractions. Three agricultural soils were treated with 20 mg Cd/kg as Cd (NO3)2·4H2O, 150 mg Pb/kg as Pb (NO3)2, 20 g/kg alfalfa powder, and 50 mmol/kg of NaCl, and then incubated at 60% water holding capacity (60% WHC) and constant temperature (25°C) for 12 weeks. Various fractions of Cd and Pb were extracted from the soils after 2 and 12 w of incubation using a sequential extraction technique. Results showed that in the early stage of incubation (2 w), added Pb were found mainly in the specifically sorbed (SS) and amorphous Fe oxides (AFeO) fractions and added Cd found in SS and Mn oxides (MnO) fractions. Addition of 2% OM decreased the exchangeable (EXC) Pb fraction almost in all soils, whereas it had a different effect on the EXC Cd fraction depending on soil pH. Addition of NaCl increased the EXC Cd fraction in two soils, but it did not alter Pb fractions. At the end of the incubation period, Pb decreased in the EXC and MnO fractions except in the neutral soil and Cd decreased mainly in the SS fraction.  相似文献   

12.
Distribution of extractable heavy metals in different soil fractions   总被引:1,自引:0,他引:1  
Abstract

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

13.
Citric acid industrial wastewater (CAIW) and phosphonates are potentially useful for enhancing remediation of metal-contaminated soil. This study aimed to investigate the effects of these enhancement agents on temporal change of Cd distribution in a clayey soil, which probably correlates with the metal lability and bioavailability in the environment. Sequential extractions were performed on the soil samples from batch desorption experiments between 5 and 4320 min. The CAIW primarily enhanced Cd extraction from weakly bound fractions (i.e., exchangeable and carbonate fractions), which was relatively fast and took place in the first 60 min. On the other hand, (nitrilotrimethylene)-triphosphonic acid (NTMP) and ethylene diaminetetra-methylenephosphonic acid (EDTMP) provided a more significant Cd extraction from exchangeable, carbonate, and oxide fractions, with the change of Cd distribution occurring over the first 300 min. The differences in the extent and temporal change of metal extraction reflected the weaker complexation strength of CAIW compared to that of NTMP and EDTMP. Moreover, an increase of pH from 4 to 10 shifted the remaining Cd from exchangeable fraction to carbonate and oxide fractions. These distribution changes indicated that both CAIW and phosphonates were efficient at removing weakly bound Cd fractions in a short period of time, but alkaline conditions could hinder their effectiveness.  相似文献   

14.
Leaching column experiments were conducted to determine the degree of mobility and the distribution of zinc (Zn), cadmium (Cd), and lead (Pb) because of an application of spiked sewage sludge in calcareous soils. A total of 20 leaching columns were set up for four calcareous soils. Each column was leached with one of these inflows: sewage sludge (only for two soils), spiked sewage sludge, or artificial well water (control). The columns were irrigated with spiked sewage sludge containing 8.5 mg Zn l?1, 8.5 mg Cd l?1, and 170 mg Pb l?1 and then allowed to equilibrate for 30 days. At the end of leaching experiments, soil samples from each column were divided into 18 layers, each being 1 cm down to 6 cm and 2 cm below that, and analyzed for total and extractable Zn, Cd and Pb. The fractionation of the heavy metals in the top three layers of the surface soil samples was investigated by the sequential extraction method. Spiked sewage sludge had little effect on metal mobility. In all soils, the surface soil layers (0-1 cm) of the columns receiving spiked sewage sludge had significantly higher concentrations of total Zn, Cd and Pb than control soils. Concentration of the heavy metals declined significantly with depth. The mobility of Zn was usually greater than Cd and Pb. The proportion of exchangeable heavy metals in soils receiving spiked sewage sludge was significantly higher than that found in the control columns. Sequential extraction results showed that in native soils the major proportion of Zn and Pb was associated with residual (RES) and organic matter (OM) fractions and major proportion of Cd was associated with carbonate (CARB) fraction, whereas after leaching with spiked sewage sludge, the major proportion of Zn and Pb was associated with Fe-oxcide (FEO), RES, and CARB fractions and major proportion of Cd was associated with CARB, RES and exchangeable (EXCH) fractions. Based on relative percent, Cd in the EXCH fraction was higher than Zn and Pb in soils leached with spiked sewage sludge.  相似文献   

15.
Abstract

Selected heavy metals Fe, Cd, Ni and Cr were studied in contaminated soil samples collected from south-eastern Nigeria. Geochemical differentiation into different chemical fractions, using Ma and Rao six-step sequential chemical extraction procedure, was carried out to assess the potential mobility and bioavailability of the heavy metals in the soil profiles. The residual fraction was the most important phase for the four heavy metals with the following average percentage values 74.43 for Fe, 37.69 for Cd, 70.11 for Ni and 62.47 for Cr. The carbonate fraction contained an appreciable proportion of Fe, Cd and Ni with the average percentage values of 16.29, 14.86 and 10.47 respectively, while organic fraction was of next importance for Cr with an average percentage value of 27.14. The Fe-Mn oxide fraction also contained 15.86% of Cd. Relatively low amounts of the metals were associated with water soluble and exchangeable fractions. The mobility factors for the metals in all the sites ranged from 8.55 to 40.04 for Fe, 8.66 to 56.58 for Cd, 12.74 to 30.19 for Ni and 0.82 to 7.22 for Cr. The generally low values of mobility factors coupled with significantly high levels of association of the metals with the residual fraction, indicate that the metals do not pose any environmental risk nor hazard.  相似文献   

16.
Abstract

Metal fractionation is a powerful tool for studying the mobility, bioavailability and toxicity of metals in sediments and soils. A seven-step sequential extraction technique was used to determine the potential mobility of selected heavy metals (Fe, Mn, Zn, Cu, Pb, Cd and Ni) in the sediments of Lake Naivasha. Results indicate that residual fraction was the most important phase for the elements Fe, Mn, Cu and Zn. However, Pb and Cd are highly enriched in the non-residual phases. Nickel on the other hand was distributed evenly between the non-residual and the residual fractions.

The total concentrations of the heavy metals suggested a decreasing order of iron ?> manganese ? zinc > nickel > copper ? lead > cadmium. However, the detailed sequential extraction data indicated an order of release or mobility of cadmium > lead ? nickel ? zinc > manganese > copper > iron. The high percentage of Cd and Pb in the mobile fractions suggests high bioavailability of these two elements in the study area and maybe a pointer to anthropogenic input of the two elements in the study area.  相似文献   

17.
Endogeneous levels of zinc and copper were found to be 1.2±0.1×10−2 and 0.3±0.1×10−2 μg/A260 unit, respectively, in polysomal fractions from control animals; cadmium, however, was undetectable. In experimental animals (injected with cadmium) zinc, copper, and cadmium were found in polysomal fractions isolated by two different methods. One hour after a cadmium injection there was a rise in both the zinc and copper content of the polysomal fractions, which then declined steadily to below control levels by 16 h. Neither zinc nor cadmium were dialyzable from these fractions by a TRIS buffer; however, addition of 0.01M EDTA to the buffer resulted in removal of 75% of the zinc and all of the detectable cadmium. The addition of cadmium (CdCl2) to control supernatants (adjusted to the cadmium concentration present in supernatants 6 h after in vivo exposure) resulted in metal binding to polysomal fractions in levels comparable to those observed after in vivo exposures to the metal. When cadmium was added in the form of cadmium thionein, a smaller fraction of the metal was isolated with the polysomal fraction. Cadmium bound to polysomal fractions in vivo (24 h after exposure) was sensitive to release by protease digestion, but insensitive to release by ribonuclease digestion.  相似文献   

18.
A comprehensive investigation of fractionation and environmental risk of nine heavy metals is carried out for 12 sediment samples collected from Kor River, Iran. For this purpose, the 5-stage sequential extraction method, along with individual contamination factor, global contamination factor, and Environmental Risk Index (ERI), is used. Total concentrations of Cr, Hg, Ni, and Zn were found to be beyond the threshold effect level. The results of fractionation patterns indicate that As, Cr, Ni, Pb, and Zn are mostly associated with Fe-Mn oxide fraction, organic fraction, and residual fraction, while Cd and Mo are predominantly associated with carbonate fraction. Cu and Hg are mostly associated with organic and exchangeable fractions. The results of ERI revealed High to Dangerous risks in 40% of Kor River stations. The applied approach in this study is beneficial to other environmental studies that require analysis of complex data.  相似文献   

19.
The mobility of selected heavy metals in contaminated soil at a previous industrial site in Brisbane, Australia, was assessed using a sequential extraction technique. Copper, Pb, Zn, Cr, Fe, and Mn were extracted from the soil solution/exchangeable, carbonate, Fe and Mn oxides, and organic matter fractions. The amounts of metals adsorbed by these fractions were used as an indicator of each metal's mobility in the soil. Copper and Pb were largely adsorbed by the organic and oxide fractions, while a significant amount of Zn was extracted from the carbonate fraction. The potential mobility and biological availability of the metals in these soils is Zn > Cr = Cu ≈ Pb. Soils were also analyzed using the toxicity characteristic leaching procedure (TCLP) to determine whether the contaminated soil could be disposed of by landfilling. The leachability of all metals from the soils was very low, with metal concentrations below the allowable limits. The TCLP also showed that Zn was the most mobile metal in these soils. An environmental and health risk assessment was undertaken, and it was concluded that the site did not represent a risk despite the “total”; concentrations of some metals being up to 40 times the investigation threshold value adopted in Australia.  相似文献   

20.
The Gulf of Cariaco is a marine ecosystem with high primary productivity, which gives it an ecological and socioeconomic importance. Nevertheless, anthropogenic activities around the Gulf produce wastes that are deposited directly or by runoff into the sediments, and consequently, increases concentrations of metals in this ecosystem. The objective of this study was to determine the distribution of cadmium, copper, lead, manganese, nickel and zinc in geochemical fractions of surface sediments, using modified BCR sequential extraction procedure. The concentrations were measured using flame atomic absorption spectroscopy. In addition, the contents of soluble and exchangeable metals associated to carbonate fractions, determined by BCR, were compared with those determined by the method of Campanella. Samples were collected in 12 stations during June 2007. The applied methodologies were evaluated with a certified reference material of marine sediments (HISS-1) and the results indicated that these methods provide adequate accuracy and precision for the extraction of metals. The total metal concentrations (microg g(-1)) were, Cd: < limit of detection (LD)-5.0; Pb: 1.79-60.41; Cu: no detected (ND)-42.18; Zn: 25.13-104.57; Mn: 66.31-80.29 and Ni: 3.29-24.58. Cd, Cu, Ni and Pb at several stations, exceeded the Canadian Sediment Quality Guidelines of the Lowest Effect Levels (LEL). Cadmium was identified as being the most mobile of the elements, having the highest concentrations in soluble and exchangeable cations and carbonates. However, Pb, Cu, Mn and Zn levels were found highly associated to organic matter and sulfide fractions. The methods did not show significant statistical differences for the extraction of soluble and exchangeable cations and the metals associated to carbonate fraction. There are several significant correlations between heavy metals, which suggest their common origin.  相似文献   

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