Soil Organic Matter Impacts upon Fluxes of Cadmium in Soils Measured using Diffusive Gradients in Thin Films

Abstract

Classical analytical methods limit understanding of the dynamics of geochemical processes in soils. The technique of diffusive gradients in thin films (DGT) allows the quantification of the mobilization fluxes of traces metals in soils and more specifically the metal supply from the soil's solid phase. Diffusive gradients in thin films, measuring fluxes from soil solids to solutions, were reported in three different cadmium (Cd)–contaminated soils with different levels of soil organic matter (SOM). The soil solution concentration ratio between the labile Cd, determined using differential pulse anodic stripping voltammetry, and the total Cd obtained by inductively coupled plasma–atomic emission spectrometry was compared. The data suggest that SOM affected the complexation of Cd in the soil solution, and the values obtained by DGT also demonstrated that the sorption of the Cd to the solid phase was also affected. The fluxes of Cd into the DGT were decreased when organic matter was added to the soils but were also decreased when SOM was reduced using hydrogen peroxide (H₂O₂).     

Chemical speciation and bioavailability of Cd,Cu, Pb and Zn in Western Balkan soils

Abstract

Three thermal power plants in Serbia, Croatia and Bosnia of the Western Balkan region were expected to be metal polluting sources, and this study was performed to investigate the bioavailability and chemical speciation of trace metals in soils and soil water extracts, respectively. Surface (0–15 cm) soil samples along with maize and grass samples were collected at a gradient from the pollution source. The chemical speciation of metals was conducted using the Windereme Humic Aqueous Model (WHAM)/Model VI for water, whereas the Diffusion Gradient in Thin Films (DGT) technique was used to estimate plant availability. The chemical speciation indicated that more than 99% of all four metals in soil water extracts were complexed to fulvic acid. This is connected to relatively high soil pH (> 6.5) and high contents of soil organic matter in these soils. The accumulation of trace metals by DGT was not correlated to plant uptake. This is connected to the very low partitioning of free ions in solution, but also to the low variation in metal solubility and metal concentration in plant tissue between sites. In spite of active thermal power plants located in the areas, hardly any differences in concentration of soil metals between sites were seen and the partition of metals in soil waters was insignificant. The latter indicates that these soils have a large metal-retaining capacity. The only significant soil chemical variable affecting the variation in metal solubility was the soil pH. In a time with large infrastructure and industrial expansion in these areas, this investigation indicates the importance of protecting these high-quality soils from industrial use and degradation. High industrial activity has so far had insignificant effect on soil quality with respect to bioavailability of trace metals in these soils.     

Effect of biosolid application to Mollisol Chilean soils on the bioavailability of heavy metals (Cu,Cr, Ni,and Zn) as assessed by bioassays with sunflower (Helianthus annuus) and DGT measurements

Purpose

This study assessed the effect of biosolid application on the bioavailable fraction of some trace elements (Cu, Cr, Ni, and Zn) using a bioassay with sunflower (Helianthus annuus) and a chemical assay, diffusion gradient in thin films (DGT).

Materials and methods

Five surface soil samples (0–20 cm) were collected from an agricultural zone in Central Chile where biosolids are likely to be applied. Municipal biosolids were mixed with the soil at concentrations of 0, 30, 90, and 200 Mg ha^?1. The experiment to determine the bioavailability of metals in the soil using the bioassay was performed using sunflower. The DGT technique and Community Bureau of Reference (BCR) sequential extraction were used to determine the bioavailable fractions of the metals.

Results and discussion

The application of biosolids increased the phytoavailability of Zn, Ni, and Cr in most of the soils, as indicated by the increasing concentrations in sunflower plants as the biosolid application rate increased. In two of the soils, Codigua and Pelvín, this increase peaked at an application rate of 90 Mg ha^?1. Decreases in the bioavailable fractions of Zn, Ni, and Cr were observed with higher biosolid application rates. The bioavailability of metals was estimated through multiple linear regression models between the metals in the sunflower plants and the different chemical fractions of metals in the soils treated with different biosolid rates, which displayed a positive contribution of the labile (water soluble, carbonate, and exchangeable), oxide, and organic metal forms in the soil, particularly with respect to Ni and Zn at application rates of 30 and 90 Mg ha^?1. The bioavailable fraction of metals was determined in soils using the DGT technique. The effective concentration (C _E) results were compared with those in sunflower plants. The DGT technique could effectively predict the bioavailable fractions of Cr, Ni, and Zn in the Taqueral soil but only that of Zn in the Polpaico soil.

Conclusions

The application of biosolids significantly increased the labile fraction of most of the metals in the studied soils, particularly at the highest biosolid application rate. C _E increased as the concentration of biosolids increased for most of the metals. The effectiveness of the DGT technique for predicting the bioavailability of metals was dependent on the soil type and the metal. However, the C _E for soil Cu was not related to plant Cu for all soils studied.     

Monitoring Metal Speciation in The rivers Meuse and Rhine Using DGT

Although a number of metal speciation methods are nowadays available, most water quality regulations are based on total metal concentrations. One of the main reasons for the ignorance of speciation is the lack of methods with potentiality for monitoring. Conditions that have to be met by such speciation methods are: simple performance, robust and sufficiently accurate. In this study the potential for monitoring purposes of Diffusive Gradients in Thin films (DGT) is investigated as part of a European project for sensor development for routine prediction of metal biouptake in natural waters. Performance characteristics of DGT have been assessed in experiments under controlled laboratory conditions and during in situ application over 4–9 months under different hydrological conditions in the rivers Meuse and Rhine. Results have been worked out for Cu, Ni and Pb. The study shows that DGT has sufficient potential as a robust tool in routine monitoring to observe trends in water quality. However, it appears that during in situ application of DGT the measurement uncertainty of the results is much larger than under laboratory conditions. The increase in measurement uncertainties will partially be due to uncertainties in some as constant considered factors in the calculation of the DGT concentration. For Cu and Ni, the average values for the reproducibility in the rivers Meuse and Rhine appeared to be 28% and 17%, respectively, whereas under laboratory conditions the reproducibilities for both metals were better than 10%. In the speciation of Cu, Ni and Pb in the rivers Meuse and Rhine, the labile fraction, determined using DGT, decreased in the series Ni, Cu, Pb. The ratio of the non-labile and labile fractions of the metals appeared to decrease with increasing content of Dissolved Organic Carbon (DOC).     

氧化节杆菌生物降解苯并芘

A pot experiment was conducted with multi-metal (Pb, Cd, Cu, and Zn) contaminated acidic soil to investigate changes in available metal burden resulting from the application of industrial wastes (fly ash and steel slag). The efficiency of amendments-induced metal stabilization was evaluated by diffusive gradients in thin films (DGT), sequential extraction, and plant uptake. The stability of remediation was assessed by an acidification test and by chemical equilibrium modeling. Addition of fly ash (20 g kg-1 ) and steel slag (3 g kg-1 ) resulted in similar increase in soil pH. Both amendments significantly decreased the concentrations of metals measured with DGT (C DGT) and the metal uptake by Oryza sativa L. Significant correlations were found between C DGT and the concentration of a combination of metal fractions (exchangeable, bound to carbonates, and bound to Fe/Mn oxides), unraveling the labile species that participate in the flux of metal resupply. The capability of metal resupply, as reflected by the R (ratio of C DGT to pore water metal concentration) values, significantly decreased in the amended soils. The C DGT correlated well with the plant uptake, suggesting that DGT is a good indicator for bioavailability. Acidification raised the extractable metal concentration in amended soil but the concentration did not return to the pre-amendment level. Equilibrium modeling indicated that the soil amendments induced the precipitation of several Fe, Al and Ca minerals, which may play a positive role in metal stabilization. Chemical stabilization with alkaline amendments could be an effective and stable soil remediation strategy for attenuating metal bioavailability and reducing plant metal uptake.     

Determination of High Resolution Pore Water Profiles of Trace Metals in Sediments of the Rupel River (Belgium) using Det (Diffusive Equilibrium in Thin Films) and DGT (Diffusive Gradients in Thin Films) Techniques

The techniques of diffusional equilibrium in thin films (DET) and diffusional gradients in thin films (DGT) were used to obtain high resolution pore water profiles of total dissolved and labile trace (mobilizable) metals in the sediments of the Rupel River, Belgium. DGT measures labile metal species in situ by immobilizing them on a resin gel after diffusion through a diffusive gel whereas for DET an equilibrium is established between the DET gel and the pore water. Concentrations of Pb and Zn obtained by DGT were in good agreement with the results obtained by centrifugation, and thus were well buffered by rapid equilibrium with the solid phase, whereas Fe, Mn and Cd were very tightly bound to the sediment phase and large differences were observed between the labile and the total metal concentrations. Cu, Zn, Co and Ni show intermediated behavior. Good correlations were found between the profiles of As and Fe and Mn and Co for DET as well as DGT showing a close link between the geochemical behavior of these elements. Cu, Zn, Pb and Cd are also influenced by the reductive mobilization of Fe and Mn oxides but are also closely linked to the bacterial degradation of organic matter in the surface sediments as to the precipitation of metal sulfides in the deeper layers.     

The Monitoring of Cr(III) and Cr(VI) in Natural Water and Synthetic Solutions: An Assessment of the Performance of the Dgt and Dpc Methods

The technique of diffusive gradients in thin films or diffusive gradient in thin films (DGT) has been used in this work for the in situ measurement of labile Cr(III) and Cr(VI) species. Direct measurement of Cr(VI) was also carried out in parallel with a field-based colourimetric technique based on the EPA 7196 diphenyl-carbohydrazide (DPC) method. The efficiency of the DGT and DPC methods were tested (a) in the laboratory, using synthetic solutions in the presence of realistic concentrations of Cr, humic substances (HS), and ethylenediaminetetraacetic acid (EDTA), and (b) in the field, in river water affected by effluents discharged by the tannery industry. The main advantage of the DGT method is that it allows the in situ separation of labile species of Cr(III) and Cr(VI), though there are still uncertainties about its performance in field conditions. The DPC method proved to be a fast, accurate, and relatively economical option for the field-based determination of Cr(VI). Sample acidification and ageing of unacidified samples from contaminated aquatic environments, produced significant errors in the determination of ‘dissolved’ Cr. The concentration of Cr(VI) determined by either the DGT or the DPC method exceeds recommended international guidelines.     

A New Method of Preparing Gel for DGT Technique and Application to the Soil Phosphorus Availability Test

There are different methods for soil phosphorus (P) availability assessment. Researchers have recently introduced a new method called diffusive gradients in thin films (DGT) to evaluate P availability in soils. The aim of this study was manufacturing DGT gel using copolymerization of acrylamide and allylic double bonds agarose to replace the patented agarose as a cross-linker. We evaluated the efficacy of the prepared gel and used the assembled DGT with that gel in 10 calcareous soils. We compared the available P measured with the assembled DGT in those soils to Olsen’s P measured in the same soils. Corn plant (Zea mays L.) was also grown in those soils in a greenhouse for two months. Results showed that the diffusion coefficient of P ions in the gel with 0.3% of allylagarose at 25 °C was 6.9 * 10^–6 cm².s^?1, implying that P ions were allowed to diffuse freely through the prepared diffusive gel. Measured P by the assembled DGT showed a close linear correlation (r² = 0.98) with the P concentrations measured in soil solutions extracted by the Olsen method. This demonstrates the prepared allylagarose cross-linked gels’ efficiency and thus the reliability of the assembled DGT in easily and rapidly measuring the soil’s available P. The P, as measured by the assembled DGT in the examined soils, indicated a little lower correlation coefficient (r = 0.77) than those measured by the Olsen method (r = 0.88). However, the CE values measured by DGT showed a good correlation with P uptake by the roots (r = 0.88, p ≤ 0.01). The best correlation between CE and P content in corn occurred for the measurements made after 48 h of DGT placement in soils. The 20-h measurements had about the same r value, indicating that 20 h is sufficient for the placement of DGT assembly in the soil before its removing and measuring the available P. According to our findings, acrylamide—allylagarose gel as a diffusive gel in DGT was found to be suitable for P measurements in both aqueous solutions and soil.     

A Study of Diffusive Gradients in Thin Films for the Chemical Speciation of Zn(II), Cd(II), Pb(II), and Cu(II): The Role of Kinetics

The lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes were studied using diffusive gradients in thin films (DGT). A unique feature of this research was (1) the use of DGTs with diffusive layer thicknesses ranging from 0.4 to 2.0 mm to study lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes, combined with (2) the application of a competing ligand exchange (CLE) method using Chelex 100, the same chelating resin that is used in DGT, to study the kinetic speciation. The CLE experiments were run immediately after the completion of the DGT experiments, thereby allowing effects of the competing ligand to be separated from the effects introduced by the use of the polyacrylamide gel that is used in DGT. The results indicate that Zn(II) and Cd(II) tend to form more labile and more mobile complexes with humic acid than Pb(II) or Cu(II). The dissociation rate constants of Zn(II), Cd(II), and Pb(II) were found to increase with the ionic potential of the metal, suggesting that the binding between some trace metals and humic acid has a significant covalent component. Furthermore, the results suggest that the Eigen mechanism may not be strictly obeyed for metals such as Cu(II) which have high rate constants of water exchange, k _w. Consequently, the markedly slow kinetics of Cu(II)-HA species suggests that the usual equilibrium assumption may not be valid in freshwaters.     

Partitioning of metals (Cd, Co, Cu, Ni, Pb, Zn) in soils: concepts, methodologies, prediction and applications – a review

Prediction of the fate of metals in soil requires knowledge of their solid–liquid partitioning. This paper reviews analytical methods and models for measuring or predicting the solid–liquid partitioning of metals in aerobic soils, and collates experimental data. The partitioning is often expressed with an empirical distribution coefficient or K_d, which gives the ratio of the concentration in the solid phase to that in the solution phase. The K_d value of a metal reflects the net effect of various reactions in the solid and liquid phases and varies by orders of magnitude among soils. The K_d value can be derived from the solid–liquid distribution of added metal or that of the soil‐borne metal. Only part of the solid‐phase metal is rapidly exchangeable with the solution phase. Various methods have been developed to quantify this ‘labile’ phase, and K_d values based on this phase often correlate better with soil properties than K_d values based on total concentration, and are more appropriate to express metal ion buffering in solute transport models. The in situ soil solution is the preferred solution phase for K_d determinations. Alternatively, water or dilute‐salt extracts can be used, but these may underestimate in situ concentrations of dissolved metals because of dilution of metal‐complexing ligands such as dissolved organic matter. Multi‐surface models and empirical models have been proposed to predict metal partitioning from soil properties. Though soil pH is the most important soil property determining the retention of the free metal ion, K_d values based on total dissolved metal in solution may show little pH dependence for metal ions that have strong affinity for dissolved organic matter. The K_d coefficient is used as an equilibrium constant in risk assessment models. However, slow dissociation of metal complexes in solution and slow exchange of metals between labile and non‐labile pools in the solid phase may invalidate this equilibrium assumption.     

Evaluation of Different Extraction Methods for the Assessment of Heavy Metal Bioavailability in Various Soils

The main objective of this study was to compare the effectiveness of different methods (heavy metals in pore water (PW), diffusive gradients in thin films (DGT), diethylene triamine pentaacetic acid (DTPA) extraction, and total heavy metals (THM) in soil) for the assessment of heavy metal bioavailability from soils having various properties and heavy metal contents. The effect of soil heavy metal pollution on shoot yield and sulfatase enzyme activity was also studied. Wheat (Triticum aestivum) was grown in different soils from Spain (n?=?10) and New Zealand (n?=?20) in a constant environment room for 25 days. The bioavailabilities of Cd, Cr, Cu, Ni, Pb, and Zn were assessed by comparing the metal contents extracted by the different methods with those found in the roots. The most widely applicable method was DGT, as satisfactory Cu, Ni, Pb, and Zn root concentrations were obtained, and it was able to distinguish between low and high Cr values. The analysis of the metal concentrations in PW was effective for the determination of Cr, Ni, and Zn content in root. Copper and Pb root concentrations were satisfactorily assessed by DTPA extraction, but the method was less successful with determining the Ni and Cr contents and suitable just to distinguish between high and low concentrations of Zn. The THM in soil method satisfactorily predicted Cu and Pb root concentrations but could only be used to distinguish between low and high Cr and Zn values. The Cd root concentration was not successfully predicted for any of the used methods. Neither shoot yield nor sulfatase enzyme activity was affected by the metal concentrations.     

Determination of the Bioavailable Fraction of Cu and Zn in Soils Amended with Biosolids as Determined by Diffusive Gradients in Thin Films (DGT), BCR Sequential Extraction, and Ryegrass Plant

This study assessed the effect of biosolids applied at rates, 0, 30, 45, and 60?Mg?ha^?1 on the chemical associations and bioavailability of Cu and Zn in soils from an important agricultural zone of the Metropolitan Region in Central Chile. Three methods were used to determine the bioavailability of Cu and Zn in soils: ryegrass (Lolium perenne) plants, diffusive gradients in thin films (DGT) technique, and Community Bureau of Reference (BCR) sequential extraction. The DGT effective concentration (C _E) and sequential extract acid soluble fraction of the BCR extraction (most labile fraction of the soils, normally associated with bioavailability) were compared with total metal concentration in ryegrass plants as a means to compare the chemical and biological measures of bioavailability. Total Zn was higher in comparison to Cu for all treatments. Concentrations were within the limits set by the Chilean regulations for land-applied biosolids. Metals in the control soil were primarily found in the residual fraction of soils. Biosolids application generally decreased this fraction, with a subsequent increase observed mainly in the acid soluble fraction. The contents of Cu and Zn in ryegrass plants increased with increasing rates of biosolids. Comparison of the Cu and Zn content in ryegrass plants with C _E, showed a good correlation for Zn. However, the C _E for soil Cu was only related to plant Cu for some of the soils studied. Correlation between Zn in ryegrass plants and the labile fraction of Zn as measured by the sequential extraction was excellent, with correlation coefficients >0.9, while for Cu, correlation coefficients were lower.     

Using diffusive gradients in thin films technique for in-situ measurement of labile phosphorus around Oryza sativa L. roots in flooded paddy soils

Behavior of phosphorus(P) in flooded rice soil is controlled by iron(Fe) redox cycling in root-zone. In this study, we applied a novel approach—the diffusive gradients in thin films(DGT) technique—for investigating the in-situ distribution of labile phosphorus(P) and Fe in close proximity to Asian rice(Oryza sativa L.) roots at submillimeter to millimeter spatial resolutions during the seedling and booting stages. We conducted a seven-year field experiment under rice-wheat rotation with different P fertilizer treatments. The results showed a significant and strong positive relationship of the average DGT-labile P concentration with soil Olsen P(R2= 0.77, P < 0.01) and with rice total P concentration(R²= 0.62, P < 0.05). Furthermore, results on one-and two-dimensional changes of DGT-labile P indicated that fertilization only in the wheat season produced sufficient amounts of labile P in the flooded paddy soils, similar to when fertilizer was applied only in the rice season;dissolved P concentrations, however, were lower. A co-occurrence and significant positive correlation(P < 0.01) between DGT-labile P and Fe indicated Fe-coupled mobilization of P in flooded paddy soils. These results collectively indicated that the DGT technique provided information on in-situ distribution of labile P and its variability in close proximity to rice roots. This suggests that the DGT technique can improve our understanding of in-situ and high-resolution labile P processes in paddy soils and can provide useful information for optimizing P fertilization.     

Soil solution concentration of Cd and Zn canbe predicted with a CaCl2 soil extract

Risk assessment of heavy metals in soil requires an estimate of the concentrations in the soil solution. In spite of the numerous studies on the distribution of Cd and Zn in soil, few measurements of the distribution coefficient in situ, K_d, have been reported. We determined the K_d of soils contaminated with Cd and Zn by measuring metal concentrations in the soil and in the soil solution and attempted to predict them from other soil variables by regression. Soil pH explained most of the variation in logK_d (R² = 0.55 for Cd and 0.70 for Zn). Introducing organic carbon content or cation exchange capacity (CEC) as second explanatory variable improved the prediction (R² = 0.67 for Cd and 0.72 for Zn), but these regression models, however, left more than a factor of 10 of uncertainty in the predicted K_d. This large degree of uncertainty may partly be due to the variable degree of metal fixation in contaminated soils. The labile metal content was measured by isotopic dilution (E value). The E value ranged from 18 to 92% of the total metal content for Cd and from 5 to 68% for Zn. The prediction of K_d improved when metals in solution were assumed to be in equilibrium with the labile metal pool instead of the total metal pool. It seems necessary therefore to discriminate between ‘labile’ and ‘fixed’ pools to predict K_d for Cd and Zn in field contaminated soils accurately. Dilute salt extracts (e.g. 0.01 m CaCl₂) can mimic soil solution and are unlikely to extract metals from the fixed pool. Concentrations of Cd and Zn in the soil solution were predicted from the concentrations of Cd and Zn in a 0.01 m CaCl₂ extract. These predictions were better correlated with the observations for field contaminated soils than the predictions based on the regression equations relating logK_d to soil properties (pH, CEC and organic C).     

Bioavailability as a Factor in Risk Assessment of Metal-Contaminated Soil

To accurately assess the risks of metal contaminants in soil, the bioavailability of the metals need to be considered. The bioavailable concentrations determined from homogenized, dried soils are not necessarily representative of in situ conditions of undisturbed field soils. In this study, we investigated the accumulation of metals in wheat (Triticum aestivum) grown in undisturbed contaminated (Pb, Zn, Cu, and Cd) soil cores, in relation to total soil, leachate, and diffusive gradients in thin films (DGT)-labile metal concentrations. Despite the fact that many of the samples contained metal concentrations above guideline values, no significant effects were observed on wheat growth. The bioavailability of metals in the most contaminated samples was estimated to be medium to low, possibly explaining why few effects were observed in the bioassay. For Cu, Zn, and especially for Pb, leachate and DGT-labile concentrations were better predictors of uptake by wheat than total concentrations based on correlations. It is suggested that DGT and leachate concentrations in combination with bioassays in undisturbed soil cores can be used to account for metal bioavailability in soil. These tests could be used during the ecological risk screening stage, in conjunction with total concentrations and guideline values to better estimate receptor exposure.     

Assessment of trace element phytoavailability in compost amended soils using different methodologies

Purpose

This study evaluates the effects of two soil amendments and the growth of two plant species on labile trace element (TE) fractions in two different contaminated soils.

Materials and methods

We studied the effects of two organic amendments (biosolid compost and alperujo compost) and two plant species (Medicago polymorpha and Poa annua) on pH, total organic carbon (TOC), and TE availability, by three extraction methods (CaCl₂ aqueous solution, soil pore water (SPW), and diffusive gradient in thin film (DGT)), in two contaminated soils with contrasting pH values (Aznalcázar, 6.53, and Vicario, 3.48) in a 118-day pot experiment. The effects of the composts on labile TE fractions were compared with element concentrations in plants.

Results and discussion

No relevant effects of amendments and plants were found on the physical and chemical characteristics of the Aznalcázar soil. However, the addition of amendments was essential for plant species growing in the acid Vicario soil. In this soil, amendments and plant growth increased pH and TOC and reduced substantially TE bioavailability. Although absolute values of bioavailable TE contents obtained by the three methods were very different and followed the trend CaCl₂ extraction?>?SPW?>?DGT, these values follow a similar behavior in the two studied soils and for the two species.

Conclusions

The results demonstrate that the application of organic amendments are suitable for remediating acid TE-contaminated soils, for the establishment of a vegetation cover on previously bare soils for reducing wind and water erosion and for reducing labile TE fractions to prevent leaching of pollutants into subsoil or groundwater layers. Moreover, the results obtained in this study pointed out that under microcosm conditions, the three methods tested (CaCl₂ extraction, SPW, and DGT) to predict TE bioavailability were highly correlated.

     

Changes in Cd and Cr fluxes during the bioremediation of phenanthrene

Abstract. Different types of contaminants such as polycyclic aromatic hydrocarbons (PAHs) and metals coexist in different chemical forms in soil. Although bioremediation of organics has been widely studied, little attention has been paid to changes in metal behaviour during the bioremediation process. In this study, the diffusion gradient in thin-film (DGT) technique was used to assess changes in potentially bioavailable Cd and Cr fluxes in soil during the bioremediation of phenanthrene. Fluxes of Cd were low (< 0.2pgcm⁻² s⁻¹) and increased to 0.4–0.9 pg cm⁻² s⁻¹, while Cr(III) fluxes showed an approximately tenfold increase. Results showed that there was increased mobilization of metals associated with the fungal reduction of phenanthrene concentrations by Penicillium frequentans.     

Chemical changes in the rhizosphere of metal hyperaccumulator and excluder Thlaspi species

Rhizosphere processes involved in hyperaccumulation and exclusion of metals are still largely unknown. Therefore, we conducted a rhizobag experiment on contaminated and non‐contaminated soils to investigate the chemical changes in the rhizosphere of the hyperaccumulators Thlaspi goesingense and T. caerulescens, and the metal‐excluder T. arvense. Root growth was restricted to the rhizobags separated by a nylon membrane (7 μm \x 25 μm mesh size) from surrounding bulk soil. Depletion of labile Zn in rhizosphere could not explain the amount of metals accumulated in T. caerulescens, whereas the difference in EDTA‐extractable Zn even exceeded total plant uptake. Substantially increased DOC in T. arvense rhizosphere indicates alleviation of phytotoxicity by formation of metal‐organic complexes. Hyperaccumulation and depletion of labile Zn in the rhizosphere was observed for T. goesingense grown on contaminated soil. On non‐contaminated soil, Zn was accumulated but labile Zn in rhizosphere was not changed. Nickel present in background concentrations in both soils was accumulated by T. goesingense only when grown on non‐contaminated soil. In contrast, labile Ni in the rhizosphere was increased in both soils, suggesting a general tendency of Ni mobilization by T. goesingense.     

Bioavailability of Metals at a Southeastern Brazilian Coastal Area of High Environmental Concern Under Anthropic Influence: Evaluation Using Transplanted Bivalves (<Emphasis Type="Italic">Nodipecten nodosus</Emphasis>) and the DGT Technique

Metals are commonly determined in aquatic organisms, primarily using bivalves to provide important data on their bioavailability. The technique of diffusive gradients in thin films (DGTs) has also been employed to assess the concentration of metals in freshwater and marine environments, determining their lability. The present work evaluated and compared the labile and bioavailable concentrations of Cd, Co, Cu, Mn, Ni and Pb in seawater from Ilha Grande Bay, RJ, using DGT and transplanted bivalves (Nodipecten nodosus), respectively. The scallops and DGTs were immersed in water at three sampling locations within the bay from July to September 2012 (winter campaign) and from December 2012 to February 2013 (summer campaign). The metals were determined by inductively coupled plasma-mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES). DGT technique was successfully used to determine the concentrations of metals in waters, except for Pb when short deployment times were used. All metals were determined using transplanted bivalves (N. nodosus), but pre-exposure to Cd was evident, which made the interpretation of the data for this analyte difficult. The data on metal lability in Ilha Grande Bay waters obtained from the DGT technique were correlated with the metal bioavailability determined in the soft tissues of the transplanted N. nodosus for Co, Cu, Mn, Ni and Pb. This is the first evaluation of this type for this area of high environmental concern. Both techniques revealed that Náutico was the location with the highest concentration of metals in the study area.     

Radio-labile cadmium and zinc in soils as affected by pH and source of contamination

The determination of radio‐labile metals in soil has gained renewed interest for predicting metal availability. There is little information on to what extent the fraction of labile metal is affected by the soil properties and the source of metal contamination. The radio‐labile content (E value) of Cd and Zn was measured in field‐collected soils with Cd and Zn originating from different sources. The E values were erratic and sometimes even exceeded total metal content when the concentration in the soil extract was less than 8 μg Zn l^?1 or less than 3 μg Cd l^?1. Addition of EDTA (0.1 mm ) to the radio‐labelled soil suspension resulted in larger concentrations of Cd and Zn in solution and smaller E values for these soils. The E values were, however, unaffected by the presence of EDTA (0.1 mm ) in soils with larger concentrations of Cd and Zn in solution. The %E values (E value relative to metal soluble in aqua regia) ranged from 9% to 92% (mean 61%) for Cd and from 3% to 72% (mean 33%) for Zn. No correlation between soil properties and %E was observed for Cd, and the %E of Zn was negatively correlated with soil pH (r = ?0.65). There was a strong negative correlation between pH and %E in soils enriched with metals in soluble form (e.g. metal salts, corrosion of galvanized structures). In soils where Cd or Zn were added in a less soluble form, no such correlation was found, and %E values were generally less than in soils spiked with metal salts, suggesting that the source of the contamination controls mainly the labile fractions of Cd and Zn.