Lithogenic thallium behavior in soils with different land use     

Aleš Vaněk  Vladislav Chrastný  Martin Mihaljevič  Petr Drahota  Tomáš Grygar  Michael Komárek 《Journal of Geochemical Exploration》2009

In order to evaluate the effect of different land use on lithogenic Tl geochemistry, two forest and grassland soils developed on an identical Tl-rich substrate were examined. For this purpose a complex soil-plant investigation supplemented by mineralogical methods was performed. The modified BCR sequential extraction combined with X-ray diffraction analysis (XRD) and voltammetry of microparticles (VMP) were performed for a detailed insight on lithogenic Tl speciation and availability in both contrasting soils. It was revealed that soil forming processes like bioturbation and probably dust deposition may influence the increased input of lithogenic Tl into the forest floor. Thallium was predominantly bound within the residual fraction (up to 95%) corresponding to primary silicates (mainly orthoclase and muscovite) and probably secondary illite, which were detected by XRD in all studied horizons. Thus, stable silicates can be thought as the phases controlling the solubility of lithogenic Tl in both the forest and grassland soils. The highest portion (~ 5%) of “labile” Tl was found in the organic horizons of the forest soil indicating a distinct role of forest soil organic matter (SOM) on Tl mobilization and availability. Thallium adsorption was dominated by an identified non-crystalline Mn(III,IV) oxide detected by VMP proving thus its strong affinity for Mn oxides in mineral soils. On the contrary, Tl adsorption by more abundant Fe(III) oxides (goethite and ferrihydrite) was evaluated to be negligible. Organically bound Tl in the forest floor was found to be associated with primary SOM corresponding to the raw and partially decomposed litter of Norway spruce (Picea abies L.). Moreover, a relatively high Tl uptake was recorded by this species. In contrast, lithogenic Tl uptake by common grasses like red clover (Trifolium pratense L.) or timothy grass (Phleum pratense L.) seems to be very low.  相似文献   

Simplification of a Sequential Extraction Scheme To Determine the Mobilisable Heavy Metal Pool in Soils     

Tim Koeckritz  Jorg Thming  Christine Gleyzes  Knut E. degrd 《洁净——土壤、空气、水》2001,29(4):197-205

This investigation had the purpose of evaluating the reliability of a sequential extraction procedure according to Zeien and Brümmer (1989) which is performed routinely to analyse the distribution of heavy metals to different soil phases. Reliability was tested by two hypotheses. According to the first hypothesis an error propagation increased during a morefold extraction of heavy metals from a single soil sample to such an extend that it does not allow a statistical comparison of different analyses. This assumption was confirmed in an interlaboratory study of five participants applying the sequential extraction scheme on two different soils. The heavy metal amounts extracted by the different partners were of the same magnitude, but from the results no statistical correspondence at the 95% confidence level could be observed. The second hypothesis stated that also weak extraction agents were able to release metals from the more immobile soil fractions, especially if the amount of easily soluble metals was comparatively small. To answer this question the sequential extraction was modified by carrying out selected weak extraction steps several times. As expected the intensified extraction conditions caused a decrease of the element content within the more resistant phases. However, the additional release in the first four extraction steps of Pb, Mn, Fe, and Zn was only in the range of 5 to 10%. Furthermore, it was observed that a single EDTA extraction (step four within the sequential extraction scheme) was capable to extract the same amount of metals as the first four extraction steps of the original scheme at a variation of about 15%. From these results it was concluded that the EDTA step alone already represents a reliable pool of mobilisable metals. Thus it can be maintained that such a simple single EDTA extraction can be used to assess the environmental risk from heavy metal contaminated soils or to predict the potential heavy metal release of soil remediation processes.  相似文献   

Copper complexation by fulvic acid affects copper toxicity to the larvae of the polychaete Hydroides elegans   总被引：1，自引：0，他引：1  

Qiu JW  Tang X  Zheng C  Li Y  Huang Y 《Marine environmental research》2007,64(5):563-573

Copper toxicity is influenced by a variety of environmental factors including dissolved organic matter (DOM). We examined the complexation of copper by fulvic acid (FA), one of the major components of DOM, by measuring the decline in labile copper by anodic stripping voltammetrically (ASV). The data were described using a one-site ligand binding model, with a ligand concentration of 0.19micromol site mg(-1) C, and a logK' of 6.2. The model was used to predict labile copper concentration in a bioassay designed to quantify the extent to which Cu-FA complexation affected copper toxicity to the larvae of marine polychaete Hydroides elegans. The toxicity data, when expressed as labile copper concentration causing abnormal development, were independent of FA concentration and could be modeled as a logistic function, with a 48-h EC(50) of 58.9microgl(-1). However, when the data were expressed as a function of total copper concentration, the toxicity was dependent on FA concentration, with a 48-h EC(50) ranging from 55.6microgl(-1) in the no-FA control to 137.4microgl(-1) in the 20mgl(-1) FA treatment. Thus, FA was protective against copper toxicity to the larvae, and such an effect was caused by the reduction in labile copper due to Cu-FA complexation. Our results demonstrate the potential of ASV as a useful tool for predicting metal toxicity to the larvae in coastal environment where DOM plays an important role in complexing metal ions.  相似文献   

Mercury speciation in sediments at a municipal sewage sludge marine disposal site   总被引：3，自引：0，他引：3  

Shoham-Frider E  Shelef G  Kress N 《Marine environmental research》2007,64(5):601-615

Mercury speciation was performed in excess activated sewage sludge (ASS) and in marine sediments collected at the AAS disposal site off the Mediterranean coast of Israel in order to characterize the spatial and vertical distribution of different mercury species and assess their environmental impact. Total Hg (HgT) concentrations ranged between 0.19 and 1003ng/g at the polluted stations and 5.7 and 72.8ng/g at the background station, while the average concentration in ASS was 1181+/-273ng/g. Only at the polluted stations did HgT concentrations decrease exponentially with sediment depth, reaching background values at 16-20cm, the vertical distribution resulting from mixing of natural sediment with ASS solids and bioturbation by large populations of polycheates. Average Methyl Hg (MeHg) concentration in ASS was 39.7+/-7.1ng/g, ca. 3% of the HgT concentration, while the background concentrations ranged between 0.1 and 0.61ng/g. MeHg concentrations in surficial polluted sediments were 0.7-5.9ng/g (ca. 0.5% of the HgT) and decreased vertically, similar to HgT. A positive correlation between MeHg and Hg only at the polluted stations, higher MeHg concentrations at the surface of the sediment and not below the redoxline, and no seasonality in the concentrations suggest that the MeHg originated from the ASS and not from in situ methylation. By doing selective extractions, we found that ca. 80% of the total Hg in ASS and polluted sediments was strongly bound to amorphous organo-sulfur and to inorganic sulfide species that are not bioavailable. The fractions with potential bioaccessible Hg had maximal concentrations in the range in which biotic effects should be expected. Therefore, although no bioaccumulation was found in the biota in the area, the concentration in the polluted sediments are not negligible and should be carefully monitored.  相似文献   

Geochemical behavior and speciation modeling of rare earth elements in acid drainages at Sarcheshmeh porphyry copper deposit,Kerman Province,Iran     

Reza Sharifi  Farid MooreBehnam Keshavarzi 《Chemie der Erde / Geochemistry》2013

Acid mine drainage is a major source of water pollution in the Sarcheshmeh porphyry copper mine area. The concentrations of heavy metals and rare earth elements (REEs) in the host rocks, natural waters and acid mine drainage (AMD) associated with mining and tailing impoundments are determined. Contrary to the solid samples, AMDs and impacted stream waters are enriched in middle rare earth elements (MREEs) and heavy rare earth elements (HREEs) relative to light rare earth elements (LREEs). This behavior suggests that REE probably fractionate during sulfide oxidation and acid generation and subsequent transport, so that MREE and HREE are preferentially enriched. Speciation modeling predict that the dominant dissolved REE inorganic species are Ln³⁺, Ln(SO₄)₂⁻, LnSO₄⁺, LnHCO₃²⁺, Ln(CO₃)₂⁻ and LnCO₃⁺. Compared to natural waters, Sarcheshmeh AMD is enriched in REEs and SO₄²⁻. High concentrations of SO₄²⁻ lead to the formation of stable LnSO₄⁺, thereby resulting in higher concentrations of REEs in AMD samples. The model indicates that LnSO₄⁺ is the dissolved form of REE in acid waters, while carbonate and dicarbonate complexes are the most abundant dissolved REE species in alkaline waters. The speciation calculations indicate that other factors besides complexation of the REE's, such as release of MREE from dissolution and/or desorption processes in soluble salts and poorly crystalline iron oxyhydroxy sulfates as well as dissolution of host rock MREE-bearing minerals control the dissolved REE concentrations and, hence, the MREE-enriched patterns of acid mine waters.  相似文献   

Total,methyl and organic mercury in sediments of the Southern Baltic Sea     

《Marine pollution bulletin》2014,88(1-2):388-395

Distribution of sedimentary mercury in the Southern Baltic was investigated. Sediment samples were collected from the Southern Baltic in the period from 2009 to 2011, and concentrations of sedimentary total mercury (average 102 ng/g, range 5.8–225 ng/g) and methyl mercury (average 261 pg/g, range 61–940 pg/g) were measured in the manner that the influence of both patchiness and seasonal changes were assessed. Moreover, sedimentary mercury extracted with organic solvent- the so-called organic mercury was also analyzed (average 425 pg/g, range 100–1440 pg/g). There is a statistically significant dependence between organic mercury and both methyl mercury and total mercury concentrations in the sediments. Methyl mercury contribution to total mercury varied from 0.12% to 1.05%, while organic mercury contributed to 2% of total concentration on average. The area studied, although mercury concentrations exceed threefold the geochemical background, can be regarded as moderately contaminated with mercury, and methylmercury.  相似文献   

The variability of δ34S and sulfur speciation in sediments of the Sulejów dam reservoir (Central Poland)     

《Chemie der Erde / Geochemistry》2017,77(1):147-157

The study was carried out on the Sulejów dam reservoir (Central Poland). Water and sediment samples were collected between February and October 2006. Sulfur compounds in the sediment were chemically extracted and subjected to isotopic analysis.Large variability of SO₄²⁻ concentration in the water column (from 10.3 to 36.2 mg/dm³) and the isotopic composition of sulfur (δ³⁴S from 2.1 to 5.4‰) was observed. The main identified sources of SO₄²⁻ were watercourses, surface runoff, and phosphorus fertilizers.Both oxidized sulfur species (SO₄²⁻) and its reduced forms were found in sediments. Particular sulfur forms were characterized by large variations in both, concentrations and the isotopic composition of sulfur. SO₄²⁻ in the sediment and in the water column had different genesis. Bacterial oxidation of organic sulfur and its binding in SO₄²⁻ were observed in the sediment. Under reducing conditions, oxidized and organic sulfur is converted to H₂S which reacted with Fe or other metallic ions leading to metal sulfide precipitation. Monosulfides were shown to have a very low concentration, ranging up to 0.07 mg/g of sediment. The transformation of elemental sulfur from sulfides through their chemical oxidation occurred in the sediment.  相似文献   

Zum Einfluß des pH-Wertes und des Calciumgehaltes auf Metall-Fulvinsäure-Bindungen — Inversvoltammetrische und chemometrische Untersuchungen     

W. v. Tümpling  S. Geiß  J. Einax 《洁净——土壤、空气、水》1992,20(6):320-325

The Influence of pH and Calcium Concentration on Metal-Fulvic Acid Bonds – Stripping Voltammetric and Chemometric Investigations. Electrochemically available metal concentrations of Cd, Cu and Zn were analyzed in dependence of different concentrations of calcium, fulvic acids and pH by Differential Pulse Anodic Stripping Voltammetry (DPASV). A statistical experimental design was the base to minimize the number of experiments and to include the multifarious interactions between the independent variables (Ca concentration, concentration of fulvic acids and the pH value) and otherwise the electrochemically available metal concentrations of Cd, Cu and Zn. At first analysis of experimental data was carried out by multiple linear regression. The main influence on available metal concentrations is the pH value especially for Cu. The Ca ion influence has not competitive effect and is only significant for Cd and Cu. It has an effect on the metal-fulvic acid-bonds. Two factor interactions exist for pH/fulvic acids and for Ca/fulvic acids too. The partial least squares regression (PLS) model was used to include the interactions between the metals Cd, Cu and Zn. For proving these two models the three parameters pH, Ca and fulvic acid were varied within the calibration range of the models and predicted values were compared with the experimental values. The approach with the PLS model is better than the approach with the multiple linear regression (normally used mathematical method of analysis of a factorial plan) with a relative error of 9.7% for modelling of Cd, 6.0% for Zn and 58% for Cu in relation to multiple linear regression with errors of 12% for Cd, 8.6% for Zn and 65% for Cu. The PLS modelling is a suited tool for modelling chemical interactions also in simulated natural matrices.  相似文献   

Iron speciation in interaction with organic matter: Modelling and experimental approach   总被引：1，自引：0，他引：1  

T. Weber  T. Allard  M.F. Benedetti 《Journal of Geochemical Exploration》2006,88(1-3):166

The present study aims to model iron speciation when interacting with natural organic matter. Experimental data for iron speciation were achieved with insolubilized humic acid as an organic matter analogue for 1.8 × 10^− 3 M and 1.8 × 10^− 4 M iron concentrations and 2–5 pH range. Combining EPR spectroscopy and chemical analysis allowed us to fit NICA-Donnan model parameters for both organic complexation of iron and oxides precipitation.  相似文献   

Metal ion binding to colloids from database to field systems     

M.F. Benedetti   《Journal of Geochemical Exploration》2006,88(1-3):81

Nowadays, environmental problems related to soil pollution with heavy metals are numerous, therefore, it is important to understand metals behaviour in aquatic sediments and soils and to estimate their transfer. The fate of metals in the environment is closely related to their interactions with the major reactive compartments (organic matter, iron and manganese oxides, clays). The objective of this work is to develop an approach based on the combination of several models to study metal ion speciation in different environmental systems. Models used to describe the interactions of metals with the main reactive phases in the soil are CD-MUSIC (amorphous and crystallized iron oxides), NICA-Donnan (organic matter and manganese oxides) and cationic ion exchange model (clays). First, this work implies the definition of generic parameters to describe the interactions of the studied metals with iron and manganese oxides and part of this information is missing in the literature. Then, after a validation of the approach by comparison with analytical results, this multi-surface model is applied to test sites corresponding to one soil and two riverine environments.These new models give good predictions of the behaviour of major and trace metal ions even in heterogeneous systems characteristic of natural environment. The measured free metal concentrations in the solution are in agreement with those obtained from model calculations. In the case of the soil test site, the soil solution composition and speciation are predicted using the soil major constituents characteristics.  相似文献