Sequential extraction of labile elements and chemical characterization of a basaltic soil from Mt. Meru,Tanzania

We conducted a modified Bureau Commun Reference (BCR) sequential extraction on a basaltic soil (phono-tephrite) from Mt. Meru in Northern Tanzania in order to determine the relative contribution of water soluble, carbonate and exchangeable, oxide and organic fractions to the bulk composition of the soil. Elemental compositions were determined by ICP-MS and corrected for loss on ignition. Relatively immobile elements, such as Zr, Hf and Al, are enriched by 10–30% compared to the unweathered protolith, consistent with soil formation being accompanied by mass loss due to chemical weathering. However, superimposed on this mass loss appears to be enrichment of elements such as Fe, Ca and Mg, especially towards the surface. In some cases, the bulk concentrations of these elements at the surface exceed that of the protolith. These data suggest that the surface of the Meru soil columns may have experienced “re-fertilization” by the deposition of volcanic ash. From the carbonate and exchangeable extraction, we found evidence of clay rich horizons which may sequester as much as 5% of the bulk K. The concentration of calcium carbonate appears to decrease with depth, but the largest incorporation of Sr and Ba into carbonates occurs below 114 cm. Fe and Mn oxides scavenge more than 10–20% of total Ti, V, Co, Cu, Zr and Pb below 114 cm. The organic fraction sequestered significant fractions of total Al, Cu, REE’s and Pb throughout the soil column.     

Metal mobility by de-icing salt from an infiltration trench for highway runoff

Soil from an infiltration trench for highway runoff was leached in columns alternately with NaCl and de-ionised water to simulate the runoff of de-icing salt into the trench followed by snowmelt or rainwater. Simultaneously, two columns with the same soil were leached with de-ionised water throughout the experiment. In addition, the groundwater below the infiltration trench was sampled on some occasions. The column leachate and groundwater were split into two sub samples, one was filtered though a 0.45 μm filter; both were analysed for Pb, Cd, Zn, Fe and total organic carbon (TOC). The column experiment showed clearly that an extensive mobilisation of Pb occurred in low electrolyte water leaching following NaCl leaching. The high Pb concentration coincided with peaks in Fe and TOC concentrations and implied colloid-assisted transport. Conversely, Cd and Zn concentrations were raised in the NaCl leachate and a high correlation with Cl showed that Cl complexes are important for the mobilisation, although a pH effect and ionic exchange cannot be excluded. Only 0.15% and 0.06% of the total amount of Pb was leached from the columns leached with alternating NaCl and deionised water confirming the usual hypotheses about the high immobility of Pb in soils. However, on one occasion when the ionic strength and pH was the lowest measured the concentration of Pb in groundwater sampled from 2.5 m depth was 27 μg L⁻¹ in the dissolved phase (<0.45 μm) and 77 μg L⁻¹ in the particle phase (>0.45 μm). These Pb concentrations are almost 3 and 8 times above the Swedish limit for drinking water quality. Accordingly, in spite of the immobility of Pb the accumulation in roadside soils is so large that groundwater quality is threatened. In conclusion, the study suggests that roadside soils impacted by NaCl from de-icing operations contribute Pb to groundwater by colloid-assisted transport.     

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

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

Metal mobility due to storm events on an impacted hillslope in Palmerton,PA

Water samples were collected continuously from perennial springs on a hillslope impacted by historical metal deposition to study the hydrologic and geochemical behavior of a watershed during storm events, and assess the natural attenuation of metals in soil. Water samples were collected throughout storm hydrographs for inorganic chemistry analyses, and a sequential extraction was performed on watershed soil samples. Despite 30 a of natural attenuation at the site, Zn is mobilized into streamwater during storm events, with concentrations ranging from 18 to 452 μg/L. While Cd and Pb concentrations in water samples remained relatively constant, Zn concentration increased corresponding with the peak in the hydrograph indicating this metal is being released from adsorption sites located in an unsaturated zone that is temporarily inundated during storm events. Zinc is held on exchangeable, water and acid soluble sites, and in the reducible fraction, further indicating Zn may be released as a result of the downward movement of water through the soil profile. Equilibrium geochemical modeling predicts Zn desorption with a decrease in pH, which may occur as a result of site re-vegetation. The long legacy of metal emissions from a historical smelting operation will continue to limit the attenuating ability of this site.     

The applicability of accelerated solvent extraction (ASE) to extract lipid biomarkers from soils

We investigated the ability of accelerated solvent extraction (ASE) to extract selected lipid biomarkers (C₁₉–C₃₄ n-alkanes, n-alcohols and n-fatty acids as well as dehydroabietic acid and β-sitosterol) from a sandy soil profile under Corsican pine. Two organic layers (moss and F1) as well as two mineral soil horizons (EA and C1) were sampled and extracted with DCM/MeOH (93:7 v/v) by ASE at 75 °C and a pressure of 6.9 × 10⁶ Pa or 17 × 10⁶ Pa. Soxhlet extractions were used as the established reference method. After clean-up and derivatization with BSTFA, the extracts were analyzed on GC/MS.Using Soxhlet as a reference, we found ASE to extract all compounds adequately. The n-alkanes, especially, were found to be extracted very efficiently from all horizons studied. Only the n-fatty acids and β-sitosterol from the organic layers seemed to be extracted at a slightly lower efficiency by ASE. In all but two instances the relative abundance of extracted lipids within a component class was the same regardless of the extraction method used.Using a higher pressure in the ASE extractions significantly increased the extraction efficiency for all component classes in the moss layer, except β-sitosterol. The effect was most pronounced for the n-alkanes. In the EA horizon, a higher pressure slightly reduced the extraction efficiency for dehydroabietic acid. The observed differences between ASE and Soxhlet extractions as well as the pressure effect can be explained by a decrease in polarity of the extractant due to the elevated pressure and temperature applied during ASE extractions as compared to Soxhlet extractions. This would mainly increase the extraction efficiency of the least polar biomarkers: the n-alkanes as was observed. In addition, a better penetration of still partially water-filled micro pores under elevated pressure and temperature may have played a role.     

The nature and distribution of Cu,Zn, Hg,and Pb in urban soils of a regional city: Lithgow,Australia

This study investigates the concentration and spatial distribution of Cu, Zn, Hg and Pb in the surface (0–2 cm) soils of a regional city in Australia. Surface soils were collected from road sides and analysed for their total Cu, Zn, Hg and Pb concentrations in the <180 μm and <2 mm grain size fractions. The average metal concentration of surface soils, relative to local background soils at 40–50 cm depth, are twice as enriched in Hg, more than three times enriched in Cu and Zn, and nearly six times as enriched in Pb. Median surface soil metal concentration values were Cu – 39 mg/kg (682 mg/kg max), Zn – 120 mg/kg (4950 mg/kg max), Hg – 44 μg/kg (14,900 μg/kg max) and Pb – 46 mg/kg (3490 mg/kg max). Five sites exceeded the Australian NEPC (1999) 300 mg/kg guideline for Pb in residential soils. Strong positive correlations between Cu, Zn and Pb, coupled with the spatial distribution of elevated soil concentrations towards the city centre and main roads suggest traffic and older housing as major sources of contamination. No spatial relationships were identified between elevated metal loadings and locations of past or present industries.     

A revised method for determining existing acidity in re-flooded acid sulfate soils

Titratable actual acidity (TAA) is a technique commonly used to estimate the existing pool of exchangeable H⁺ in acid sulfate soils (ASS). A widely adopted version of the TAA method involves titrating a 1M KCl suspension of oven-dry soil (1:40) with NaOH to a known pH endpoint. However, when ASS are subject to long term re-flooding during wetland remediation, former sulfuric horizons can develop substantial quantities of porewater Fe²⁺, non-sulfidic solid-phase Fe(II) and a variety of reduced inorganic sulfur (RIS) species (e.g. pyrite, mackinawite, greigite and elemental sulfur). For these sediments, an oven-drying approach may induce oxidation of the abundant Fe(II) and/or reactive RIS species, thereby generating H⁺ and leading to overestimation of existing in situ exchangeable H⁺. In this study, we compare TAA via the standard approach (1M KCl; 1:40; oven-dry soil, 4 hr extract; TAA_D) with an identical O₂-free extraction approach using wet-sediment (TAA_W). We apply both methods to former sulfuric horizon sediments from freshwater re-flooded ASS wetlands. There are significant (α = 0.01) differences (up to 12×) between TAA measured by the two methods, with the oven-dried standard approach overestimating TAA relative to the wet, O₂-free approach in 85% of cases. Despite the fact that all AVS-S and some S(0) was oxidised during the oven-drying process, the increases in TAA (TAA_D–TAA_W) show very weak correlation(s) with corresponding losses in RIS species or increases in water soluble sulfate and KCl extractable sulfate. However, oven-drying caused substantial loss of 1M KCl exchangeable Fe(II) and 1 M HCl-extractable Fe(II) and led to large increases in 1 M HCl-extractable Fe(III). These changes in Fe fractions displayed strong positive linear correlation (α = 0.01) with increases in TAA. Although this is not evidence of causality, it suggests that oxidation of Fe(II) species are playing an important role in the development of additional exchangeable H⁺ and may be largely responsible for the contrasting TAA derived by the two methods. The differences in TAA between the two methods are greatest in organic-rich surface sediments and are significantly positively correlated with total organic carbon content. These findings have major implications for accurately assessing TAA in re-flooded ASS wetlands.     

Geochemical associations for evaluating the availability of potentially harmful elements in urban soils: Lessons learnt from Athens,Greece

The estimation of potentially harmful element (PHE) availability in urban soil is essential for evaluating impending risks for human and ecosystem health. In the present study five single extraction procedures were evaluated based on the analysis of 45 urban top-soil samples from Athens, Greece. The pseudototal (aqua regia), potentially phytoavailable (0.05 M EDTA), mobilizable (0.43 M HAc), bioaccessible (0.4 M glycine) and reactive pools (0.43 M HNO₃) of PHEs were determined. In general, geogenic elements in Athens soil (Ni, Cr, Co, As) are relatively less available than typical tracers of anthropogenic contamination (Pb, Zn, Cu, Cd). Results of principal component analysis (PCA) indicate an association between available fractions of Pb, Cu, Zn, Cd and amorphous Fe oxides, whereas amorphous Mn oxides account for the available concentrations of Mn, Ni and Co. Empirical multiple linear regression models demonstrate that pseudototal concentration is the predominant explanatory factor of variability for the available pools of the anthropogenic elements. Major elemental composition and total organic carbon (TOC) improve the predictions for the geogenic group of elements, although the explained variability remains low. Dilute HNO₃ is a better predictor of Zn, Ni, As and Mn availability, whereas Pb and Cu available fractions are predicted more accurately by the classical aqua regia protocol. This study contributes to the international database on the environmental behavior of PHEs and provides additional knowledge that can be used toward the harmonization of chemical extraction methodology in urban soil.     

Geochemistry of radium in soils of the Eastern United States

The abundance and chemical/mineralogical form of ²²⁶Ra, ²³⁸U and ²³²Th were determined on samples of soil and associated vegetation at 12 sites in the eastern United States. Progressive, selective chemical extraction plus size fractionation determined the abundance and radiometric equilibrium condition of these nuclides in 6 operationally defined soil fractions: exchangeable cations, organic matter, “free” Fe-oxides, sand, silt, and clay.In soils, profile-averaged ²²⁶Ra/²³⁸U activity ratios (AR) are within 10% of unity for most sites, implying little fractionation of U and Ra when the entire soil profile is considered. However, ²²⁶Ra greatly exceeds ²³⁸U activity in most surface soil (AR up to 1.8, av 1.22), in vegetation (AR up to 65, av. 2.8), in the exchangeable+organic fraction (AR up to 30, av. 13), in some soil Fe oxides (AR up to 3.5, av. 0.83) and in the C horizons of deeply weathered soils (AR up to 1.5).A major factor in Ra behavior is uptake by vegetation, which concentrates Ra>U and moves Ra from deeper soil to surface soil. Vegetation is capable of creating the observed Ra excess in typical surface soil horizons (AR up to 1.8, av. 1.22) in about 1000 a. Of the total Ra in an average A horizon, 42% occurs as exchangeable ions and in organic matter, but only 6–8% of the parent U and Th occur in these soil forms. In contrast, U is slightly enriched relative to Ra in Fe-oxides of A horizons, implying rapid chemical partition of vegetation-cycled U and Ra.In deeper horizons, transfer by vegetation and/or direct chemical partitioning of Ra into organic and exchangeable forms provides a source for unsupported ²²⁶Ra in Ra-rich organic matter, and leaves all soil minerals Ra-poor (AR=0.73). Organic matter evidently has a strong affinity for Ra.The phenomena discussed above are relevant to evaluation of indoor Rn hazard, and behavior of Ra at sites affected by radioactive waste disposal, phosphate tailings, Ra-rich brine, and uraniferous fertilizer.     

Metal contamination and solid phase partitioning of metals in the stream and bottom sediments in a reservoir receiving mine drainage

This study was conducted to assess the anthropogenic impact on metal concentrations in the bottom sediments of the Juam reservoir, Korea, and in stream sediments in its catchment, and to estimate the potential mobility of selected metals (Fe, Mn, Cu, Ni, Pb and Zn) using sequential extraction. A comparison of the metal concentrations in the stream sediments with mean background values in sediments collected from first- or second-order creeks shows that Pb, Cu and Ni are the most affected by anthropogenic inputs. The ²⁰⁶Pb/²⁰⁷Pb ratios of the bottom and core sediments (means: 1.2320 ± 0.0502 and 1.2212 ± 0.0040, respectively) suggest that Pb contamination is mainly due to the waste discharge of abandoned coal and metal mines rather than industrial and airborne sources. Considering the proportion of metals bound to the exchangeable, carbonate and reducible fractions, the comparative mobility of metals is suggested to decrease in the order Mn > Pb > Zn > Ni > Fe ≫ Cu.     

Anthropogenic Pb accumulation in forest soils from Lake Clair watershed: Duchesnay experimental forest (Québec, Canada)

Mineral soil horizons (Ae, Bhf1, Bhf2, Bf, BC and C) were carefully collected from two podzolic soil profiles in the Lake Clair watershed (Québec) in order to assess anthropogenic trace metal accumulation. Petrographic and selective analyses were performed to establish the soil mineralogy and properties. Furthermore, a complete sequential extraction procedure has been applied to help understanding the complex chemical speciation of Pb in forest soils. Chemical speciation of Pb showed a strong vertical gradient: 85% of this metal is mainly partitioned in refractory minerals in the C-horizon whereas in the upper Bhf1 and Ae-horizons, less than 50% of Pb is associated with this fraction. In the Ae-horizon, for example, 35%, 30% and 12% of total Pb, respectively, is associated with the exchangeable, labile organic matter and amorphous Fe-Mn oxides fractions. The distribution of Pb and Cr in the studied forest soils mainly reflects progressive contamination of the watershed by anthropogenic atmospheric sources. The anthropogenic source is indicated by elevated Cr and Pb concentrations in the topsoil (Bhf and Ae) horizons and by strong negative correlation between ²⁰⁶Pb/²⁰⁷Pb ratios and total Pb concentrations. According to these isotopic values, penetration of anthropogenic Pb does not exceed 10 cm in both soil profiles. Below this depth, both Pb concentrations and isotopic ratios remain nearly constant and similar to values observed in pre-anthropogenic sediments from Lake Clair. These values are interpreted as the natural geochemical backgrounds of the watershed. Based on that behaviour, calculated anthropogenic Pb net inputs amounted to between 1.24 and 1.8 g/m².     

Mercury speciation in soils of the industrialised Thur River catchment (Alsace,France)

Methylmercury (MeHg) and total Hg (THg) concentrations in soil profiles were monitored in the Thur River basin (Alsace, France), where a chlor-alkali plant has been located in the city of Vieux-Thann since the 1930s. Three soil types were studied according to their characteristics and location in the catchment: industrial soil, grassland soil and alluvial soil. Contamination of MeHg and THg in soil was important in the vicinity of the plant, especially in industrial and alluvial soil. Concentrations of MeHg reached 27 ng g⁻¹ and 29,000 ng g⁻¹ for THg, exceeding the predictable no effect concentration. Significant ecotoxicological risk exists in this area and remedial actions on several soil types are suggested. In each type of soil, MeHg concentrations were highest in topsoil, which decreased with depth. Concentrations of MeHg were negatively correlated with soil organic matter and total S, particularly when MeHg concentrations exceeded 8 ng g⁻¹. Under these conditions, MeHg concentrations in soil seemed to be influenced by THg, soil organic matter and total S concentrations. It was found that high MeHg/THg ratios (near 2%) in soil were mainly related to the combined soil environmental conditions such as low THg concentrations, low organic C/N ratios (<11) and relatively low pH (5–5.5). Nevertheless, even when the MeHg/THg ratio was low (∼0.04%), MeHg and THg concentrations were elevated, up to 13 ng g⁻¹ and to 29,000 ng g⁻¹, respectively. Thus, both THg and MeHg concentrations should be taken into account to assess potential environmental risks of Hg.     

OSL ages and possible bioturbation signals at the Upper Paleolithic site of Lagoa do Bordoal,Algarve, Portugal

Three sediment samples were collected from a soil profile at the Lagoa do Bordoal site, Algarve, Portugal. Quartz extracted from soil horizons within the profile, was optically dated using the single-aliquot regenerative-dose (SAR) protocol outlined by Murray and Wintle (Radiation Measurements 5 (2000) 523). The optically stimulated luminescence (OSL) emitted by quartz within the 90–150 μm size range was measured using three aliquot sizes. The equivalent doses (D_E) that were obtained show an asymmetric distribution. As the numbers of grains in each aliquot are reduced, the distribution of doses is clearly shifted to lower D_E values including zero doses on single grain aliquots. This shift is accompanied by an increase in the asymmetry of the distribution. These patterns indicate that as the aliquot size decreases, the distributions are increasingly characterized by aliquots with lower D_E's. With respect to the present day modern surface, this shift is most evident in the sample collected from a depth of 37 cm, within an ancient B-horizon. It is least evident in the sample located only 10 cm below it, within a sand unit. An asymmetric distribution of D_E's can be a result of a large number of grains that were well bleached at burial being mixed with a small number of grains that were partially bleached at that time (Radiation Measurements 30 (1999) 207). However, the shift in D_E's that is seen in the Lagoa East samples is most likely due to the postburial downward movement of fully and partially bleached grains from the surface, with possible contributions from the downward movement of grains that received low doses while buried in overlying horizons. The simplest explanation for our results is that grains carrying zero or small D_E's have been moved downward during bioturbation events. These results suggest that downward bioturbation in ancient soil profiles can be identified based on the OSL characteristics of quartz grains. We are also able to provide a minimum age of 24.4±3.2 ka for the Upper Palaeolithic lithic assemblage at the site.     

Element fractionation by sequential extraction in a soil with high carbonate content

The influence of carbonate and other buffering substances in soils on the results of a 3-step sequential extraction procedure (BCR) used for metal fractionation was investigated. Deviating from the original extraction scheme, where the extracts are analysed only for a limited number of metals, almost all elements in the soils were quantified by X-ray fluorescence spectroscopy, in the initial samples as well as in the residues of all extraction steps. Additionally, the mineral contents were determined by X-ray diffractometry. Using this methodology, it was possible to correlate changes in soil composition caused by the extraction procedure with the release of elements. Furthermore, the pH values of all extracts were monitored, and certain extraction steps were repeated until no significant pH-rise occurred. A soil with high dolomite content (27%) and a carbonate free soil were extracted. Applying the original BCR-sequence to the calcareous soil, carbonate was found in the residues of the first two steps and extract pH-values rose by around two units in the first and second step, caused mainly by carbonate dissolution. This led to wrong assignment of the carbonate elements Ca, Mg, Sr, Ba, and also to decreased desorption and increased re-adsorption of ions in those steps. After repetition of the acetic acid step until extract pH remained low, the carbonate was completely destroyed and the distributions of the elements Ca, Mg, Sr, Ba as well as those of Co, Ni, Cu, Zn and Pb were found to be quite different to those determined in the original extraction. Furthermore, it could be shown that the effectiveness of the reduction process in step two was reduced by increasing pH: Fe oxides were not significantly attacked by the repeated acetic acid treatments, but a 10-fold amount of Fe was mobilized by hydroxylamine hydrochloride after complete carbonate destruction. On the other hand, only small amounts of Fe were released anyway. Even repeated reduction steps did not destroy the amorphous Fe oxides completely, showing that 0.1 mol L⁻¹ hydroxylamine hydrochloride was not strong enough to attack these oxides effectively.The extraction sequences were carried out not only on the soil samples, but also on their coarse and fine fractions (> or <2 μm). The fine fraction of the calcareous soil contained only 10% dolomite, but was enriched in organic matter and clay minerals, which also resulted in increased extract pH-values during the sequential extraction. Hence, the effects on ion release in the fine fraction were similar to those of the whole soil. Since the destruction of the organic matter was incomplete after regular oxidation, the H₂O₂-treatment of the fine fraction had to be repeated. The addition of the extractable amounts of the two fractions showed good agreement to the results obtained for extraction of the whole soils. Likewise the pH-values of the carbonate-free soil extracts did not increase significantly, therefore it was concluded that repetitions of extraction steps for this soil were not necessary.Extract-pHs should always be controlled so that extraction conditions are comparable; to be able to use the BCR extraction scheme or similar ones for carbonate- and organic-rich samples this is mandatory. Single extraction steps should be repeated if pH rises too much; additionally the oxidizing step should be performed more than twice for samples rich in organic substances, depending upon the violence of the reaction with H₂O₂. If these precautions are neglected the validity of the extraction data is likely to be questionable.     

Assessing soil erosion and control factors by radiometric technique in the source region of the Yellow River,Tibetan Plateau

Measurements of ¹³⁷Cs concentration in soils were made in a representative catchment to quantify erosion rates and identify the main factors involved in the erosion in the source region of the Yellow River in the Tibetan Plateau. In order to estimate erosion rates in terms of the main factors affecting soil loss, samples were collected taking into account the slope and vegetation cover along six selected transects within the Dari County catchment. The reference inventory for the area was established at a stable, well-preserved, site of small thickness (value of 2324 Bq·m^− 2). All the sampling sites had been eroded and ¹³⁷Cs inventories varied widely in the topsoil (14.87–25.56 Bq·kg^− 1). The effective soil loss values were also highly variable (11.03–28.35 t·km^− 1·yr^− 1) in line with the vegetation cover change. The radiometric approach was useful in quantifying soil erosion rates and examining patterns of soil movement.     

Leaching of metals from copper smelter flue dust (Mufulira,Zambian Copperbelt)

The leaching behaviour of electrostatic precipitator dust from the Mufulira Cu smelter (Copperbelt, Zambia) was studied using a 48-h pH-static leaching experiment (CEN/TS 14997). The release of metals (Cd, Co, Cu, Ni, Pb and Zn) and changes in mineralogical composition using X-ray diffraction and PHREEQC-2 modelling were investigated in the pH range of 3–7. The highest concentrations of metals were released at pH 3–4.5, which encompasses the natural pH of the dust suspension (～4.3). About 40% of the total Cu was leached at pH 3, yielding 107 g/kg. Chalcanthite (CuSO₄·5H₂O), magnetite (Fe₃O₄) and delafossite (CuFeO₂) represented the principal phases of the studied dust. In contact with water, chalcanthite was dissolved and hydrated Cu sulphates precipitated at pH 4–7. Gypsum (CaSO₄·2H₂O) and secondary Fe or Al phases were observed in the leached residues. Serious environmental impact due to leaching may occur in dust-contaminated soil systems in the vicinity of the smelting plants.     

Total concentration,speciation and mobility of potentially toxic elements in soils around a mining area in central Iran

The current study was designed to investigate the extent and severity of contamination as well as the fractionation of potentially toxic elements (As, Cd, Cr, Cu, Pb, Zn, Ni) in minesoils and agricultural soils around a Pb–Zn mine in central Iran. For this purpose, 20 agricultural soils and eight minesoils were geochemically characterized. Results showed that minesoils contained elevated concentrations of As (12.9–254 mg kg⁻¹), Cd (1.2–55.1 mg kg⁻¹), Pb (137–6239 mg kg⁻¹) and Zn (516–48,889 mg kg⁻¹). The agricultural soils were also polluted by As (5.5–57.1 mg kg⁻¹), Cd (0.2–8.5 mg kg⁻¹), Pb (22–3451 mg kg⁻¹) and Zn (94–9907 mg kg⁻¹). The highest recorded concentrations for these elements were in soils influenced directly by tailing ponds. Chromium, Cu and Ni content in agricultural soils (with average value of 74.1, 34.6 and 50.7 mg kg⁻¹, respectively) were slightly higher than the minesoils (with average value of 54.5, 33.1 and 43.4 mg kg⁻¹, respectively). Sequential extraction data indicated that there were some differences between the speciation of PTEs in soil samples. In the agricultural soils, Zn and Cd were mainly associated with carbonate bound fraction, As and Pb with reducible fraction, Cu with oxidisable fraction and Cr and Ni with residual phase. With respect to mobility factor values, Zn and Cd in the agricultural soils have been found to be the most mobile while As mobility is negligible. Also, the mobility factor of As, Cd and Pb in agricultural soils adjoining tailing ponds was high. In minesoil sample Cd was most abundant in the carbonate form, whereas other studied elements were mainly present in the reducible and residual fractions; therefore, despite the high total concentrations of As, Pb and Zn in the minesoils, the environmental risk of these elements was low. Based on the obtained data, a portion of Cu, Cr and Ni input was from agricultural activities.     

137Cs and 90Sr mobility in soils and transfer in soil–plant systems in the Novozybkov district affected by the Chernobyl accident

The Chernobyl radionuclides distribution and mobility in soils and uptake by plants have been studied in seminatural and agricultural moraine and in fluvioglacial landscapes typical for the areas of the Bryansk region affected by the accident.The major part of the Chernobyl ¹³⁷Cs accumulated in the topsoil is insoluble in water, 40 to 93% of this radionuclide is strongly fixed by soil, while 70 to 90% of the ⁹⁰Sr is present in water soluble, exchangeable and weak-acid soluble forms. Radionuclide vertical migration is most pronounced in local depressions with organic and gley soils in which both radionuclides are detected to the depth of 30–40 cm.In woodlands, most of the ¹³⁷Cs is still fixed in litter and the upper mineral soil layer. The concentration peak in litter has moved to the lower AOF layer. Concentration in topsoil leads to high radionuclide uptake by forest species with shallow root systems (bilberry, mushrooms, fern). Contaminated forest products may contribute considerably to the internal irradiation doses of the local population. On flood plain grasslands traditionally used by local populations for haycrops and grazing, radionuclides are more strongly fixed in soils with fine texture. Radioisotope uptake by plants decreases in the order: legumes>herbs>grasses. Transfer to grasses in local depressions is usually higher compared with the dry levees. Observed exclusions are assumed to be due to comparatively low mobility of ¹³⁷Cs and relatively high K content in soil. ¹³⁷Cs accumulation in potato tubers grown on sandy soddy podzolic watershed soils mainly corresponds to its total amount in soils; uptake of ⁹⁰Sr depends upon the percentage of its most mobile fraction.Pronounced relief is proved to cause different patterns in distribution and migration of radionuclides in soils and local food chains. The study showed it to be true for private farms situated in different landscape positions within the same settlement.The forest litter, topsoil and products, and flood plain pastures, especially localities in depressions are critical materials for the long-term radioecological monitoring of the contaminated landscapes of the study area and those of similar conditions. Population of the areas within the zone of contamination exceeding 15Ci/km² (555kBq/m²) should be recommended to exclude local forest products from their diets and to avoid cattle grazing on wet flood plain meadows without remediation.     

Inhomogeneous lithospheric thinning in the central North China Craton: Zircon U–Pb and S–He–Ar isotopic record from magmatism and metallogeny in the Taihang Mountains

The large scale Mesozoic magmatism and related metallogeny in the Taihang Mountains (TM) provide important clues for the lithospheric thinning of the North China Craton (NCC). Among the ore deposits, the vein gold mineralization of Shihu in the Fuping region and the skarn ore deposit of Xishimen in the Wu'an region represent typical Mesozoic metallogeny in the TM. In the Shihu gold mine, the Mapeng batholith is dominantly composed of monzogranite and granodiorite, whereas, the Wu'an pluton in the Xishimen iron mine mainly comprises monzonite and diorite. Here we present zircon LA–ICP-MS U–Pb data from 8 samples which reveal the timing of magmatism in the TM as ca. 130 Ma, which is contemporaneous with the large-scale metallogeny in the margins of the NCC. The δ³⁴S values recorded in the sulfide minerals from the Shihu gold deposit and the Xishimen skarn iron deposit show a range of 2.2‰–5.0‰, and 11.6‰–18.7‰, respectively. Helium isotopic compositions of fluid inclusions in pyrite from the Shihu gold deposit vary from 0.12 to 1.98 Ra (where Ra is the ³He/⁴He ratio of air = 1.39 × 10^? 6), with calculated mantle helium values of 1.4%–25%, whereas, those of the Xishimen skarn iron deposit range from 0.06 to 0.19 Ra, with calculated mantle helium of 0.7%–2.2%. The S–He–Ar isotopic data suggest a lower crustal origin for the ore-forming components, with variable inputs of mantle source. The large population of inherited zircons in our samples, with ²⁰⁷Pb/²⁰⁶Pb ages ranging between 2500 Ma and 1800 Ma, also supports crustal participation. Our data reveal that the Shihu gold deposit witnessed greater mantle input than the Xishimen skarn iron deposit, suggesting that the continental lithosphere is markedly thinner under the Fuping region than that under the Wu'an region. Our interpretation is also supported by published data from two ultra-broadband high-precision magnetotelluric sounding profiles across the TM region showing a variation in the lithosphere thickness from 155 km to 70 km while moving from the south (Wu'an region) to the north (Fuping region). Our study suggests that inhomogeneous lithospheric thinning in the central NCC occurred at least as early as ca. 130 Ma ago.     

The use of vetiver grass (Vetiveria zizanioides) in the phytoremediation of soils contaminated with heavy metals

Recent research has shown that phytoextraction approaches often require soil amendments, such as the application of EDTA, to increase the bioavailability of heavy metals in soils. However, EDTA and EDTA–heavy metal complexes can be toxic to plants and soil microorganisms and may leach into groundwater, causing further environmental pollution. In the present study, vetiver grass (Vetiveria zizanioides) was studied for its potential use in the phytoremediation of soils contaminated with heavy metals. In the pot experiment, the uptake and transport of Pb by vetiver from Pb-contaminated soils under EDTA application was investigated. The results showed that vetiver had the capacity to tolerate high Pb concentrations in soils. With the application of EDTA, the translocation ratio of Pb from vetiver roots to shoots was significantly increased. On the 14th day after 5.0 mmol EDTA kg⁻¹ of soil application, the shoot Pb concentration reached 42, 160, 243 mg kg⁻¹ DW and the root Pb concentrations were 266, 951, and 2280 mg kg⁻¹ DW in the 500, 2500 and 5000 mg Pb kg⁻¹ soils, respectively. In the short soil leaching column (9.0-cm diameter, 20-cm height) experiment, about 3.7%, 15.6%, 14.3% and 22.2% of the soil Pb, Cu, Zn and Cd were leached from the artificially contaminated soil profile after 5.0 mmol EDTA kg⁻¹ of soil application and nearly 126 mm of rainfall irrigation. In the long soil leaching experiment, soil columns (9.0-cm diameter, 60-cm height) were packed with uncontaminated soils (mimicking the subsoil under contaminated upper layers) and planted with vetiver. Heavy metal leachate from the short column experiment was applied to the surface of the long soil column, the artificial rainwater was percolated, and the final leachate was collected at the bottom of the soil columns. The results showed that soil matrix with planted vetiver, could re-adsorb 98%, 54%, 41%, and 88% of the initially applied Pb, Cu, Zn, and Cd, respectively, which may reduce the risk of heavy metals flowing downwards and entering the groundwater.