Distribution and mobility of scandium and yttrium in selected types of soils in Poland

Abstract

This study was conducted to investigate the chemical speciation of yttrium and scandium in selected types of soils and also determined the total content and profile distribution of those elements. The research was performed on soil samples from forest areas in Puszcza Borecka (Poland) known as a non-contaminated site. Soil samples were collected from natural brown, lessive and rusty soil profiles.

The sequential extraction procedure was applied to separate fractions of scandium and yttrium according to the Tessier method. The range of total content of scandium and yttrium was respectively: 0.63-6.48 mg kg^-1 and 2.25 to 27.93 mg kg^-1. Scandium and yttrium occurred predominantly in residual fraction (F5) in each genetic horizon. Also both elements occurred mainly in fraction bound to organic matter (F4). The mean percentage content of scandium measured in mobile fractions (∑F1-F2) reached about 3% (in Bbr, Bt horizons) to 14% (in Bv horizons) in relation to the total content of the element in the analysed soils. The percentage content of yttrium measured in mobile fractions reached about 4% (in A, Bv horizons) to 28% in Bt horizons in relation to the total content of the element in forest soils of Puszcza Borecka.     

Fate and Mobility of Copper in Soil of Cocoa Plantations in Two Southwestern States of Nigeria Treated with Copper-Based Fungicides

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.     

Impact of Pyrolysis Treatment on Heavy Metals in Sediment

This paper describes a laboratory study that examined the effect of pyrolysis treatment on the behavior of Hg, Cr, Zn, Pb, Cu and Cd in a stream sediment. The influences of pyrolysis on the evaporation, sequential extraction and leaching behavior of these metals were investigated. Cr, Zn, Pb and Cu were retained quantitively in the solid residue at temperatures up to 800°C while mercury and cadmium were completely or partially evaporated. The metal form distribution in the sludge samples was determined by the sequential extraction procedure. The procedure revealed that as a consequence of pyrolysis, the metals were more strongly fixed in the treated sediment, as could be seen by the decrease with temperature of the first two sequential-extracted fractions and increase of the residue fraction. The leaching results showed that the quantities of the studied metals leached in the two pyrolysis samples were lower than those in the untreated sediment. The amounts of metals leached from the pyrolysis residues correlated significantly with the first extracted fraction (exchangeable fraction).     

Lateral diffusion in a mixture of mobile and immobile particles. A Monte Carlo study.

The lateral diffusion coefficient for mixtures of mobile and immobile particles is obtained from Monte Carlo calculations of random walks by mobile tracers in the presence of immobile obstacles on a triangular lattice. The diffusion coefficient of the mobile species is obtained as a function of the area fractions of mobile and immobile species. The results are applied to diffusion of band 3 in the erythrocyte membrane, and indicate that obstruction of diffusion of mobile band 3 by band 3 and glycophorin attached to the membrane skeleton is not sufficient to explain the observed diffusion coefficient.     

Vertical distribution and chemical character of sediment phosphorus in two shallow estuaries in the Baltic Sea

The vertical distribution of various phosphorus (P) forms and their relation to physico-chemical properties of estuary sediment material were studied to better understand the potential release and burial of P. Core samples were taken from two dissimilar estuaries in the Baltic Sea: one in the Archipelago Sea (AS) and one in the Gulf of Finland (GoF). The P reserves were characterized by a sequential extraction procedure including the analysis of simultaneously dissolved elements in two extraction steps. The sediment material was also analysed for particle size distribution and total elements. In addition, several environmental variables were determined. The occurrence of the various forms of P varied with sediment depth among different sites. Reductant soluble, iron (Fe) bound P was the most dynamically changing P form in the sediment, while P bound to other metal oxides and apatite-P were the most stable fractions. High sedimentation rate was a dominating factor for sediment P burial. In addition, the content of organic matter, the amount of erosion-transported sorption components, and the oxygen (O₂) conditions in the near-bottom water were important determinants of the behaviour of sediment P. The results indicate that, over the long term, both estuaries have acted as sinks for deposited P and restricted the transport of P to the AS and the open GoF, thereby partly alleviating the eutrophication process.     

Solid-phase distribution of heavy metals as affected by single reagent extraction in dredged sediment derived surface soils

ABSTRACT

EDTA is useful to assess mobile metal pools in polluted soils and sediments. There is a need to enhance our understanding of the significance of metal fractions released. The impact of single reagent extraction with 0.05 mol L^?1 EDTA on the solid phase distribution of trace metals in surface soils sampled from confined dredged sediment disposal sites was investigated. Not extracted and EDTA extracted soils were subjected to sequential extraction to fractionate the total contents into: (1) easily exchangeable and carbonate bound fraction; (2) reducible fraction; (3) oxidisable fraction; and (4) residual fraction. With EDTA, significant portions of metals associated with the acid extractable and reducible fractions were released. The oxidisable and residual fractions remained unaffected for most of the investigated metals except for the organic matter associated metals (Cu and Pb). A decrease in the residual fraction after EDTA-extraction for Cu and Pb was attributed to artifacts of the sequential extraction procedure.     

Determination of concentrations of elements in the atmospheric aerosol of the urban and rural areas of beijing in winter

The proton-induced X-ray emission technique is one of the most suitable methods in the study of the multielement content of atmospheric aerosols. Atmospheric aerosol samples were collected in winter using an eight-stage cascade impactor at a site of the urban center and a rural site of Beijing. The aerosol samples collected were analyzed to determine maximum, minimum, and average concentrations of up to 20 elements and the ratios of the average element concentrations for the coarse to fine particles (C/F) by the PIXE technique. It has been found that the average elemental concentrations in the urban center are higher than those in the rural area, except S and Br. The concentrations for S and Pb in the atmospheric aerosols are found to be less than the results of previous measurement, but their concentrations in the fine particles increased in winter in the samples from the urban center. The deposition probability of the International Commission on Radiological Protection (ICRP) mode and the mass particle-size distributions of the elements determined in the urban center have been utilized to evaluate inhalable particulate matter fractions retained in the three regions of one’s respiratory tract and their harm to human health is discussed.     

Forms and cycling of phosphorus in prairie and boreal forest soils

The distribution of soil P among inorganic and organic forms was examined in prairie and boreal forest soil profiles from Saskatchewan, Canada. A sequential extraction procedure was employed to separate P into labile and stable inorganic (P_i) and organic (P_o) fractions. Profile depth, climate, vegetation, and cultivation all had a major influence on the distribution of P which is attributed to differing intensities of pedogenic processes such as weathering and leaching, and their relationship to P transformations in the soil environment.     

The Concentration and Partitioning of Heavy Metals in Surface Sediments of the Maharlu Lake,SW Iran

In this study, an assessment is made of the environmental impacts of heavy metal concentration and fractionation in bed sediments of the saline Maharlu Lake, SW Iran. Total elemental analysis indicated that sediments were highly enriched in Pb and Cd. Sequential extraction analysis revealed that salt of the lake is probably highly contaminated with Cd, Pb, and Co. Due to the oxidizing conditions of the lake, the organic matter fraction of the elements was not significant. In all sediments, Cd, Pb, Co, Mn, and Zn were strongly associated with exchangeable plus carbonate fractions, with mean percentage of 76.4%, 65.3%, 56%, 40.9%, and 34.3%, respectively. On average, the percentage of Ni associated with the sum of the exchangeable and carbonate fractions was 19.8%. Cr, Fe, and Cu fractionation indicated that these metals are environmentally inert and immobile. Statistical relationships among metal fractions and sediment properties showed that Cd, Pb, Zn, Ni, Co, and Mn were mainly from recent anthropogenic sources, while such sources were less important for Cr, Cu, and Fe. The latter metals represented natural geochemical levels.     

Metal contents and fractionation in contaminated soil after column leaching using [S,S]-EDDS

Abstract

Column leaching using [S, S]-ethylene diamine disuccinate ([S, S]-EDDS) on copper tailing soils was carried out to investigate metal content and fractionation after leaching. The soil column was divided into four layers after leaching. Fractionation of Cu, Pb, Zn, and Mn in soil was analyzed using a modified BCR sequential extraction method. Metal contents (Cu, Pb, Ca, Mn) in soil layers increased with the depth of the soil column after leaching in the [S, S]-EDDS treatment. The cumulative extraction efficiency was approximately 43.1% for Cu, 26.8% for Zn, 19.5% for Pb, 10.5% for Ca, 2.07% for Mg, 58.5% for Mn, and 7.92% for Fe. The removal of the reducible fractions of Cu and Mn and the exchangeable fraction of Zn was the most significant in the treatment with [S, S]-EDDS. The exchangeable fraction of Pb was the main fraction that was affected by leaching using [S, S]-EDDS. Distribution of Cu and Mn were severely modified by leaching with [S, S]-EDDS. Percentages of residual fractions of the tested heavy metals in the treatment with [S, S]-EDDS after leaching were much higher than that in the control. Although column leaching using [S, S]-EDDS could remove target metals effectively and impaired their availability, it also dissolved large amounts of major elements and modified the distribution of Mn appreciably.     

The Use of a Five-stage Sequential Leaching Procedure for Risk Assessment of Heavy Metals in Waste Rock Utilized in Railway Ballast

A five-stage sequential leaching procedure was used to determine the distribution of 10 metals in three combination samples taken from waste rock material, originating from a Finnish zinc mine, and used as railway ballast in Northern Finland. The leaching procedure consists of the following five sequential fractions: a water-soluble fraction (H₂O), an exchangeable fraction (CH₃COOH), an easily reduced fraction (NH₂OH-HCl), an oxidizable fraction (H₂O₂ + CH₃COONH₄), and a residual fraction (HF + HNO₃ + HCl). The results show, in accordance with all earlier corresponding studies, that a sequential extraction procedure is very suitable for evaluating the effects of external conditions on the solubility of harmful heavy metals, and that external conditions have a large effect on their leachability/solubility, and therefore on their mobility, bioavailability, and environmental risk. In addition, the total concentration of each element is much larger than its solubility in each of the first four fractions (1)–(4) – the potential bioavailability fractions – because the highest concentrations of all metals occurred in the residual fraction (5). The conditions of this phase – three strong acids and strong, long-lasting shaking – are never possible in nature, and therefore the residual fraction is called the inert phase. Thus, the total concentrations of the heavy metals are poor measures of real environmental risk and give no information about the effect of external conditions on their solubility. In addition, the dependency of different elements on the external conditions differs.     

Multivariate relationships and spatial distribution of geochemical features of soils in Jamaica

Abstract

Concentrations of 31 chemical elements in 165 soil samples from the tropical island of Jamaica were analyzed during the island-wide soil survey. Multivariate outliers were detected and remedied for quality control of the database. Multivariate analyses including principal component analysis (PCA), cluster analysis, and analysis of variance (ANOVA), and a geographic information system (GIS) were applied to study the geochemical features of element associations and sample clusters. The results show that rare earth elements, most of the heavy metals and trace elements (including As, Al, Cd, Ce, Co, Cr, Dy, Eu, Fe, Hf, Hg, La, Lu, Mn, Pb, Sb, Sc, Sm, Th, Ti, U, V, Yb, Zn) are enriched in the bauxitic soils relative to the non-bauxitic soils, and closely correlated with one another. Negative correlations between the bauxite-enriched elements and the mobile alkali and alkaline earth elements including Ca, Sr, Mg and Na are observed, showing the opposite tendencies of enrichment of the immobile elements and leaching of the mobile elements during the soil formation processes. The halogen elements of Br and I are also relatively enriched in the bauxitic soils, but they appear to be rather affected by sea-spray. Copper has poor correlations with all the other elements, which is likely to be related to mineralization. Significantly different concentrations of the bauxite-enriched elements are observed between the bauxitic and non-bauxitic soils.     

Leaching of Trace Elements from Biological Tissue by Formalin Fixation

In studies of trace elements in biological tissue, it is imperative that sample handling does not substantially change element concentrations. In many cases, fresh tissue is not available for study, but formalin-fixed tissue is. Formalin fixation has the potential to leach elements from the tissue, but few studies have been published in this area. The concentrations of 19 elements were determined by high-resolution inductively coupled plasma mass spectrometry in formalin in which human and rat brain samples had been stored for different time durations ranging from weeks up to several years. Additional analysis was carried out in fixed brain samples. There was substantial leaching of elements from the tissue into the formalin, and the leaching varied considerably between different elements. For example, formalin concentrations of As, Cd, Mg, Rb, and Sb increased more than 100-fold upon long-term (years) storage, while for Ni and Cr, the leaching was negligible. The degree of leaching was strongly time-dependent. In conclusion, formalin fixation and storage of biological tissue has the potential to leach substantial fractions of several trace elements from the tissue. The potential of leaching must be critically considered when using formalin-fixed biological tissue in trace metal analysis.     

Distribution of extractable heavy metals in different soil fractions

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.     

Variation of Cu and Zn Fractionation and Mobility in Mine Tailing Soil Due to Experimental Leaching

The aims of this paper were to assess the variation of heavy metal (Cu and Zn) fractions and mobility in abandoned metal mine soil due to batch experimental leaching. Four solutions with different pH levels were used in the experiments. The total and fractional concentrations of heavy metals in untreated and leached soils were determined. The Kruskal–Wallis test was applied to verify the differences in the Cu and Zn distribution in soils before and after leaching. In order to assess the mobility of heavy metals, mobility factors (MFs) were calculated. The research results showed that the original/untreated soil was mainly of a sandy texture and acidic in character. After batch leaching for 7 days, the distribution of heavy metals was dominant in the residual fraction (F5). Heavy metal fractions in F1, F2, F3, and F5 showed a decreasing trend, but an increasing trend in F4 was observed. Among the solutions applied having different pH values, HCl (pH 3) illustrated the strongest effect on decreasing heavy metals in short-term mobile fractions (F1 and F2). The MF of Zn decreased more than that of Cu after 7-day batch leaching.     

Identification of Pt and Pd bound to humic acid species in spiked soils and street dusts by size exclusion chromatography and ICP-MS

Abstract

The formation of PGE-humic acid (HA) complexes in soil and street dust samples was investigated. In order to assess the distribution of Pt and Pd among molecular weight fractions of humic substances, the HA extracts (extracted by 0.1 mol L^?1 sodium pyrophosphate) were analysed by size exclusion chromato-graphy coupled on-line with UV-Vis detection. Similar chromatograms were obtained for soils and street dust samples (254 nm, 280 nm) and two size fractions were operationally defined as high (1600–5000 Da) and low molecular (< 1600 Da) HA fractions. The concentration of Pt and Pd in the separated extracts was determined by ICP-MS. The results indicate that up to 43% of Pt is in the high molecular and up to 52% in the low molecular HA fraction. In both type of soil samples, Pd is preferentially bound to the low molecular HA fraction. Dependence of Pd–HA and Pt–HA formation on the sample type both in the soils and in the street dust sample as well as on Pt oxidation state was established. Metallic Pt shows a tendency for complexation with the fractions of HA higher than 5000 Da. In the street dust samples, the distribution of Pt and Pd is similar and is strongly dependent on the sample type, being bound mainly to the fractions: higher than 5000 Da, 1600–5000 Da and the fraction lower than 1600 Da.     

Methodological aspects of moss sample preparation. Effects of freezing and duration of washing on the cellular distribution of elements in Fontinalis squamosa Hedw.

Aquatic bryophytes are widely used in biomonitoring studies, mainly because of their capacity to act as bioaccumulators. As different methods can be used to preserve and process moss samples, the results of elemental analyses may also vary, particularly if the contents of different cellular compartments are analyzed separately. In the present study, we compared the total concentrations of some elements and the concentrations of these in different cellular locations in frozen-thawed and fresh samples of the aquatic moss Fontinalis squamosa that were also washed for different lengths of time before analysis. We used the sequential elution technique (SET) to extract the different fractions, and we determined the concentrations of K, Mg, Ca, Cd, Co, Cu, Al and Zn in the extracts. The results varied depending on the element, cellular location and moss sampling site. In the moss samples processed after freezing, the greatest differences were in the intracellular concentrations of K, Mg and Cd, which were lower than in the fresh samples. Minor differences were found in the concentrations of elements in other cellular locations and in the total concentrations of elements. The increase in the duration of the initial washing step, carried out to remove soluble and particulate intercellular elements, may also cause the release of elements (e.g. K and Mg) bound to extracellular exchange sites. The concentrations in the other cellular fractions and the total concentrations were less affected by the washing duration. Neither freezing nor the use of long washing times are recommended for processing moss samples prior to extraction of elements by the SET. Further studies are needed to confirm and clarify the observations.     

Trace Metal Fractionation by the Sequential Extraction Method in Sediments from the Lis River (Portugal)

The extractable contents of Zn, Pb, Cu, Cr, Mn, Ni, Fe and Al were evaluated in sediments from the Lis River (Portugal) using the three-step sequential extraction procedure described by Community Bureau of Reference (BCR, now the Standards, Measurement and Testing Programme) of the European Union. The distribution of trace metals among the exchangeable, water and acid soluble, reducible, oxidizable and residual fractions was determined. The highest metal concentrations were observed in samples collected at the most polluted river sites (animal husbandry, domestic, industrial and agricultural wastes). Pb, Cu, Cr, Ni, Fe and Al were found mainly associated with the residual and organic fractions. High concentrations of Zn and Mn were found in the exchangeable/acid soluble fraction.     

Fluorescence fluctuation spectroscopy in the presence of immobile fluorophores

Fluorescence contributions from immobile sources present a challenge for fluorescence fluctuation spectroscopy (FFS) because the absence of signal fluctuations from stationary fluorophores leads to a biased analysis. This is especially of concern for cellular FFS studies on proteins that interact with immobile structures. Here we present a method that correctly analyzes FFS experiments in the presence of immobile sources by exploiting selective photobleaching of immobile fluorophores. The fluorescence decay due to photobleaching of the immobile species is modeled taking into account the nonuniform illumination volume. The experimentally observed decay curve serves to separate the mobile and immobile fluorescence contribution, which is used to calculate the molecular brightness from the FFS data. We experimentally verify this approach in vitro using the fluorescent protein EGFP as our immobilized species and a diffusing dye of a different color as the mobile one. For this special case, we also use an alternative method of determining the brightness by spectrally resolving the two species. By conducting a dilution study, we show that the correct parameters are obtained using either technique for a wide range of mobile fractions. To demonstrate the application of our technique in living cells, we perform experiments using the histone core protein H2B fused with EGFP expressed in COS-1 cells. We successfully recovered the brightness of the mobile fraction of H2B-EGFP.     

The distribution and bioavailability of Cd and Zn in cultivated soil of Henan Province

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.