Sorption of cadmium in some arable and forest soils

The sorption of cadmium labeled with ¹⁰⁹Cd in nitrate form, from aqueous solutions in different horizons of some arable and forest soils was studied under static (batch) conditions. Before sorption, a method of sequential soil treatment was applied, which consist in the consecutive removal of individual soil components by the use of appropriate reagents and procedures. Three sorption isotherms were tested. Kinetic studies showed that the sorption of cadmium is rather rapid and it can be well described by a Freundlich or a linear isotherm, whereas the closeness of Langmuir isotherm to the experimental results is lower. From the different sorption isotherms, it would also be possible to estimate the effect of individual components on the sorption of cadmium in soils. It was found that the untreated soils exhibit the highest sorption and the sorption decreases in the order of untreated > acetate treated > water treated > peroxide treated > dithionite treated soil. Sorption of cadmium increases with the depth of the studied soils disregarding their chemical treatment.This revised version was published online in November 2005 with corrections to the Cover Date.     

Sorption, desorption and extraction of cadmium from some arable and forest soils

Summary The behavior of cadmium labeled with ¹⁰⁹Cd in different depth horizons of arable and forest soils were studied under static (batch) conditions in three interconnected processes, which consist of sorption, desorption and extraction. In the sorption, Cd²⁺ was applied in the aqueous calcium nitrate solution. Both untreated soils and peroxide treated soils were used in order to remove organic matter from some of the soil samples used in parallel. The influence of the V/m ratio on the sorption coefficients was investigated in preliminary experiments with untreated soils. Contrary to the usually short-term sorption, a long-term sorption of cadmium was investigated in untreated and treated soil horizons, which lasted more than fortnight. Kinetic studies of sorption were carried out and cadmium concentration dependence in aqueous phase of the second order kinetic constants was observed. For evaluation of sorption and desorption processes Freundlich isotherms were used. It was found that the Freundlich adsorption intensity coefficient is more time dependent than the absorption capacity coefficient, and the sorption itself consists of rapid and slow processes according to the soil constituents. Desorption and extraction processes revealed the possibility of cadmium recovery from various soil horizons. Based on the obtained results two- or three-stage theory of cadmium retention in soils was proposed. Some new insight into the role of organic matter in the sorption/desorption process of cadmium is also presented.     

Use of the diffusive gradients in thin films technique (DGT) with various diffusive gels for characterization of sewage sludge-contaminated soils

The diffusive gradients in thin film technique (DGT) was used for characterization of South Moravian arable soils (sampling sites Zlín, Tuřany, and Chrlice) amended by sewage sludge in the 1980s. Two types of polyacrylamide diffusive gel with different pore size (APA gels—cross-linked with agarose and RG gels—cross-linked with bis-acrylamide) were employed. The (bio)available parts of Cd, Cu, and Ni and the proportions of inorganically and organically complexed species of these metals were assessed. The degree of metal resupply from the soil solid phase to the soil solution was also determined. Metal concentrations obtained by the DGT technique were lower by almost 4 to 5 orders of magnitude in comparison with those obtained by extraction with aqua regia. DGT concentrations of metals were also lower by approximately 1 to 2 orders of magnitude in comparison with those obtained by extraction with sodium nitrate (commonly used for assessment of the (bio)available part of metals). Results obtained by DGT measurement were expected to be closer to the actual content of available metal species than results obtained by extraction with sodium nitrate. Using RG gels together with APA gels provided resolution of inorganically and organically complexed metal species and their proportional representation. Inorganic metal species (particles smaller than 1 nm) formed a predominant part of assessed metal content in all studied soil samples and horizons. However, there was the exception of the cadmium content in the middle profile of Chrlice sandy soil sample. Ratio R values indicated that resupply of Cd, Cu, and Ni from the solid phase to the soil solution varied for individual soil samples and individual depth profiles. Mobile and labile species of Cd, Cu, and Ni were much more closely related to upper rather than deeper horizons. This observation correlates very well with the mechanical treatment and amendment of the studied soils.     

Effect of addition of ameliorative materials on the distribution of As,Cd, Pb,and Zn in extractable soil fractions

The effects of lime, limestone, and zeolite addition on the availability of As, Cd, Pb, and Zn in three contaminated soils were investigated in a pot experiment after four vegetation periods of spring wheat, spring barley, and oat. The results showed different responses of extractable element portions to soil amendment when 0.01 mol dm⁻³ aqueous CaCl₂ was applied as a soil extraction agent. Substantial differences were evident among the investigated elements as well as among the individual soil treatments. Except natural zeolite, the ability of ameliorative materials to redistribute cadmium and zinc from a soil solution into less mobile but labile soil fractions was observed. The lead availability was less affected and the extractability of arsenic even increased in some of the treated pots. Moreover, the availability of arsenic was more affected by different characteristics of experimental soils than by individual soil treatments. It was found that these treatments can be applied neither for multicontaminated nor for all the soil types. The soil treatments had a lower effect on the less mobile soil fractions. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Determination of cadmium in Bentonite clay mineral using a carbon paste electrode

Sodium activated Bentonite, a sodium modified Montmorillonite, was submitted to cadmium sorption from nitrate solutions in order to simulate a cadmium polluted clay mineral. The remaining cadmium concentration in solution was analyzed at equilibrium by means of Differential Pulse Polarography (DPP) in order to calculate the cadmium concentration sorbed by the clay. The cadmium distribution between clay mineral and solution was observed for different concentrations, showing a Freundlich sorption profile. The clay mineral, previously submitted to the cadmium sorption procedure, was included in a carbon paste in order to investigate the cadmium content by voltammetric determination. For cadmium detection in Bentonite, a linear response of the carbon paste electrode (CPE) was observed in the 5 · 10^–5– 1.8 · 10^–4 mol/g range with good reproducibility. Received: 23 July 1998 / Revised: 19 November 1998 / Accepted: 26 November 1998     

Determination of cadmium in Bentonite clay mineral using a carbon paste electrode

Sodium activated Bentonite, a sodium modified Montmorillonite, was submitted to cadmium sorption from nitrate solutions in order to simulate a cadmium polluted clay mineral. The remaining cadmium concentration in solution was analyzed at equilibrium by means of Differential Pulse Polarography (DPP) in order to calculate the cadmium concentration sorbed by the clay. The cadmium distribution between clay mineral and solution was observed for different concentrations, showing a Freundlich sorption profile. The clay mineral, previously submitted to the cadmium sorption procedure, was included in a carbon paste in order to investigate the cadmium content by voltammetric determination. For cadmium detection in Bentonite, a linear response of the carbon paste electrode (CPE) was observed in the 5 · 10^–5– 1.8 · 10^–4 mol/g range with good reproducibility. Received: 23 July 1998 / Revised: 19 November 1998 / Accepted: 26 November 1998     

Removal of Mn(II) and Cd(II) from wastewaters by natural and modified clays

The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents, by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q ₀ parameter, which is related to the sorption capacity, corresponding to 6.3 mg g^{− 1} for K-10/Cd(II), 4.8 mg g^{− 1} for K-10/Mn(II), 11.2 mg g^{− 1} for NT-25/Cd(II) and 6.0 mg g^{− 1} for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction, a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L^{− 1} solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent.     

A comparison of sequential extraction procedures for fractionation of arsenic,cadmium, lead,and zinc in soil

Twelve soil samples differing in physicochemical properties and total element contents were extracted by three sequential extraction procedures to determine As, Cd, Pb, and Zn bound to individual soil fractions and are defined by individual operational procedures. In the case of arsenic, two additional sequential extraction schemes were designed entirely for fractionation of soil containing arsenic were tested. The results confirmed that determination of element proportions bound to individual soil fractions is strongly dependent on the extracting agent and/or procedure applied within individual extracting schemes. As expected, absolute values of the elements released among the individual extracting procedures are weakly comparable. More reliable results were determined for the more mobile soil elements i.e. cadmium and zinc, in the fractions characterizing the most mobile proportions of investigated elements where significant correlations with basic soil characteristics were observed. In contrast, ambiguous results were observed for As and Pb, for both the individual extraction procedures and the effect of the soil characteristics. Regardless of the studied element, the poorest results were determined for reducible and oxidizable soil fractions. The application of at least two independent procedures or modification of the extraction scheme according to element investigated and/or particular soil characteristics can also be helpful in definition of element pattern in soils in further research.     

Relationships of labile pool of Mn with some general soil properties and extractable soil Mn contents

Labile pool (E-value) of Mn and extractable soil Mn content using six multinutrient extractants were estimated in fifty surface (0–15 cm) soil samples. Labile pool of Mn was poorly correlated to the general soil properties and modified Olsen’s-; 0.01 M CaCl₂- and 1 M MgCl₂-extractable Mn contents but it was positively and significantly correlated to diethylene triamine pentaacetic acid (DTPA), pH 7.3; ammonium bicarbonate + DTPA (pH 7.6); and Mehlich-3-extractable soil Mn contents. The multinutrient extractants involving only simple salt solutions were not useful to assess the availability of Mn in soils.     

The problem of arsenic interference in the analysis of Cd to evaluate its extractability in soils contaminated by arsenic

The arsenic (As) spectral interference observed in the determination of cadmium (Cd) by inductively coupled plasma atomic emission spectrometry (ICP-AES) was studied in atomic absorption spectrometry (AAS) using flame (FAAS) and graphite furnace (GFAAS) as atomizers. The soils of 15 kitchen gardens located near two smelters in the North of France were selected according the ratio As/Cd. Four different extracting solutions usually used to evaluate the mobility of Cd were chosen to extract Cd from these soil samples: citric acid 0.11 M, acetic acid 0.11 M, calcium chloride 0.01 M and water. The quantitative determinations of Cd in the 15 soils for each solvent were investigated by ICP-AES at two lines (228.802 and 214.438 nm) and by FAAS or GFAAS with two-way background compensation. Compared to the Cd concentrations measured in the acid solutions and in the CaCl₂ solution after the addition of a chemical modifier, it was clearly demonstrated that the high-speed self-reversal background compensation (HSSR-method) was the method of choice to eliminate the spectral interference of As during Cd determination by FAAS and by GFAAS. In water, it was shown that the deuterium lamp used for the background compensation (D₂-method) was able to eliminate the most of the As interference. In comparison with Cd concentrations in water after adding a chemical modifier, those obtained with the HSSR-method were similar and a very good correlation was obtained between these two methods (R² = 0.995). It was therefore established that the HSSR-method would be able to replace the chemical modifiers to eliminate As interference in the determination of Cd-extractable from As contaminated soils.     

Characterization of high molecular weight cadmium species in contaminated vegetable food

Spinach and radish grown from seeds were each contaminated with 4 different amounts of cadmium. After a cell breakdown of the eatable parts and centrifugation of the resulting homogenates all supernatants (cytosols) were separated by gel permeation chromatography (GPC). The size-range of the GPC method used was about 20–8000 kDa for globular proteins. The high molecular weight (HMW-Cd-SP, 150–700 kDa) and the low molecular weight Cd species (LMW-Cd-SP, < 150 kDa) in all plant cytosols eluted at about the same retention volume by GPC. The most important Cd binding form in the cytosols of all plants was found to be HMW-Cd-SP. The Cd elution maxima were detected in the range of about 200 kDa. The Cd determinations were performed with ET-AAS by means of matrix modifier. By incubating chosen cytosols with a proteinase before the GPC it was verified that the HMW-Cd-SP in both vegetables are Cd proteins. The molar proportions protein/Cd were about 2–6 in the respective GPC fractions of the HMW-Cd-SP of the highest contaminated plants. The GPC fractions of the HMW-Cd-SP of spinach and radish were further separated by a preparative, native and continuous polyacrylamide gel electrophoresis (PAGE) method. At pH 8 the species were negatively charged, had only a small UV-absorption at 280 nm and showed a very similar elution behavior in all analyzed cytosols. Therefore, we suppose that the HMW-Cd-SP of these two different vegetable foodstuffs have a very similar chemical structure. Received: 2 February 2000 / Revised: 24 March 2000 / Accepted: 28 March 2000     

The sequential analytical procedure as a tool for evaluation of As, Cd and Zn mobility in soil

The BCR EUR 14763 EN sequential extraction method, developed for the analysis of heavy metals in sediments, was applied to 35 soil samples covering the area of the Czech Republic. The soils varied in their physical-chemical properties and total element contents. While the residual fraction in the case of cadmium was only 18% of total Cd, for Zn and As the residual fraction was dominant (55 and 75%, respectively). The decreasing concentrations of extractable elements in the order Cd > Zn > As correspond to their availability in plants. The influence of selected soil properties (pH, sorption capacity, organic matter, and clay-silt-sand content) on the distribution of As, Cd and Zn was evaluated. Received: 3 August 1998 / Revised: 18 November 1998 / Accepted: 20 November 1998     

Comparative study of methods for evaluating the mobility of element species in contaminated soil and technogenic sand under batch and dynamic extraction

A comparative study of the batch and dynamic extraction methods used to evaluate the physicochemical “mobility” of element species in environmental samples was carried out using samples of contaminated soils and technogenic sands of the Dzhida Tungsten–Molybdenum Factory. In determining the total concentration of mobile species of Cu, Zn, Pb, Cd, Mn, and Mo, they were extracted with an acetate–ammonium buffer solution (pH 4.8) in the batch mode. Fractionation of the most mobile and environmentally relevant element species, that is, exchange and acid-soluble, was carried out in a dynamic extraction mode in a rotating coil column using calcium nitrate and acetic acid. Element concentrations in the initial samples and extracts were determined by inductively coupled plasma atomic emission spectrometry and mass spectrometry. It is shown that the concentrations of mobile species of Cd, Mn, and Mo, isolated with an acetate–ammonium buffer solution, correspond to the sum of these elements in the exchange and acid-soluble fractions, while the concentration of lead in the acetate–ammonium extract is 2–4 times higher. The convergence of the results of dynamic and batch extraction of copper and zinc depends on the type of sample: for sand, the results are in satisfactory agreement, while for soil, the concentration of copper and zinc in the acetate–ammonium extract is 2–4 times lower than their concentration in the exchange and acid-soluble forms. Nevertheless, the data obtained confirm that the conventional method of batch extraction with an acetate–ammonium buffer solution (pH 4.8) can be considered acceptable for the rapid assessment of the physicochemical mobility and potential bioavailability of elements in soil and technogenic sand. For a more detailed study of highly contaminated samples and the assessment of their danger to the environment, it is advisable to separate exchange and acid-soluble fractions.     

A simple optical sensor for cadmium ions assay in water samples using spectrophotometry

A new simple and inexpensive optical chemical sensor for cadmium(II) ions is presented. The cadmium sensing system was prepared by incorporating 2-amino-cyclopentene-1-dithiocarboxylic acid (ACDA) on a triacetylcellulose membrane. The absorption spectra of the optical sensor membrane in Cd(II) solution showed a maximum peak at 430 nm. The proportionality in intensity of the membrane color on the optode to varying amounts of Cd(II) suggests its potential applications for screening Cd(II) in aqueous samples by visual colorimetry. The sensor provided a wide concentration range of 3.0 × 10⁻⁶–3.4 × 10⁻⁴ M of Cd(II) ions with a detection limit of 1.0 × 10⁻⁶ M (0.2 μg/mL). The relative standard deviations for eight replicate measurements of 8.0 × 10⁻⁶ and 5.0 × 10⁻⁵ M Cd(II) were 2.7 and 2.3%, respectively. The response time of the optode was 6 min. The influence of interfering ions on the determination of 1.0 × 10⁻⁵ M Cd(II) was studied and the main interferences were removed by extraction method. The sensor was applied to the determination of Cd(II) in water samples.     

Evaluation of methods to measure differential 15N labeling of soil and root N pools for studies of root exudation

To study patterns of root exudation, the effectiveness of different techniques for in situ 15N labeling of Brassica napus, Centaurea jacea and Lolium perenne with ammonium nitrate was tested. Stem infiltration was found to effectively label plants with thicker stems, whereas, for grass species, cutting and immersing the leaf tips into 15N solution proved to be most effective. A microdiffusion technique to isolate ammonium, combined with conventional cation-exchange chromatography to separate nitrate from amino-N compounds thereafter, was found suitable for separation of the N fractions of plant and soil extracts for 15N determination. All three species were then cultivated in nutrient solution and labeled with 15NH4 15NO3 by stem feeding for 42 hours. Kinetics of 15N labeling of bulk roots and shoots as well as hot water extractable material were assessed, and up to 1.1 at% 15N excess (APE) was found in nutrient solutions. The main amino acids exuded by L. perenne were glycine, serine, alanine and aspartic acid. To assess the suitability of this set of methods to study root exudation in field settings, L. perenne was grown without fertiliser addition in pots containing low-nutrient soil. Plants were 15N labeled via tip immersion and 15N and N concentrations were analysed in shoots, roots and soils during a 48-h interval. Shoots reached 1.25 APE, roots and soil 0.10 and 0.005 APE, respectively. Between 4% (48 h) and 6% (24 h) of total plant 15N was exuded by roots into the soil. In roots amino acids comprised the largest proportion of the soluble 15N pool, whereas soil 15N levels were similar for amino acids and ammonium, exceeding those of nitrate. Mechanisms for the shift within N fractions from roots to soils are briefly discussed.     

The effect of sorption properties of soil minerals on the vertical migration rate of cesium in soil

The vertical distribution of¹³⁷Cs is shown for two types of soil: silly loamy “supposed” soil and silly lessive one, slightly eroded, occuring in the vicinity of Lublin (Eastern Poland). Based on the distribution data the vertical migration rates of¹³⁷Cs are calculated for both soils. These rates are found to be 0.045 and 0.3 cm/year respectively. The percent contribution of¹³⁷Cs originating from the damaged reactor in Chernobyl is also calculated. The kinetics of cesium adsorption and its adsorption isotherms on minerals separated from the tested soils are also studied. The sorption of Cs on soil minerals markedly affects the migration rate of¹³⁷Cs in soil. The experimental results indicate that, among the extracted mineral fractions, the largest adsorption takes place on marls from the silly loamy soil. This work is supplemented by results of a physicochemical analysis of the studied soils.     

LC-MS/MS quantitative analysis of reducing carbohydrates in soil solutions extracted from crop rhizospheres

A simple, sensitive, and specific analytical method has been developed for the quantitative determination of 15 reducing carbohydrates in the soil solution of crop rhizosphere. Reducing carbohydrates were derivatized with 1-phenyl-3-methyl-5-pyrazolone, separated by reversed-phase high-performance liquid chromatography and detected by electrospray ionization tandem mass spectrometry. Lower limits of quantitation of 2 ng/mL were achieved for all carbohydrates. Quantitation was performed using peak area ratios (analyte/internal standard) and a calibration curve spiked in water with glucose-d₂ as the internal standard. Calibration curves showed excellent linearity over the range 2–100 ng/mL (10–1,000 ng/mL for glucose). The method has been tested with quality control samples spiked in water and soil solution samples obtained from the rhizosphere of wheat and canola and has been found to provide accurate and precise results.     

The influence of humic acid on the pH-dependent sorption of americium(III) onto kaolinite

This work investigates the sorption of americium [Am(III)] onto kaolinite and the influence of humic acid (HA) as a function of pH (3–11). It has been studied by batch experiments (V/m = 250:1 mL/g, C _Am(III) = 1 × 10⁻⁵ mol/L, C _HA = 50 mg/L). Results showed that the Am(III) sorption onto the kaolinite in the absence of HA was typical, showing increases with pH and a distinct adsorption edge at pH 3–5. However in the presence of HA, Am sorption to kaolinite was significantly affected. HA was shown to enhance Am sorption in the acidic pH range (pH 3–4) due to the formation of additional binding sites for Am coming from HA adsorbed onto kaolinite surface, but reduce Am sorption in the intermediate and high pH above 6 due to the formation of aqueous Am-humate complexes. The results on the ternary interaction of kaolinite–Am–HA are compared with those on the binary system of kaolinite–HA and kaolinite–Am and adsorption mechanism with pH are discussed. Effect of different molecular weight of HA, with three HA fractions separated by ultrafiltration techniques, on the Am sorption to kaolinite were also studied. The results showed that the enhancement of the sorption of Am onto kaolinite at the acidic pH conditions (pH 3–4) was higher with HA fractions of higher molecular weight. Also, the Am sorption over a pH range from 6 to 10 decreased with decreasing molecular weight of HA.     

Comparison of palladium-magnesium nitrate and ammonium dihydrogenphosphate modifiers for cadmium determination in honey samples by electrothermal atomic absorption spectrometry

The occurrence of certain trace elements, such as cadmium, in honey bee can be considered as an indication of environmental pollution. In the present work, two methods for Cd determination in honey by electrothermal atomic absorption spectrometry, using palladium-magnesium nitrate and ammonium dihydrogenphosphate as chemical modifiers, have been developed. In none of these cases honey samples required pretreatment. Honey was diluted in water (20% w/v), and hydrogen peroxide, nitric acid, and Triton X-100 were added to minimize the matrix effect. For the first method, 21.6 μg of palladium and 4.5 μg of magnesium were added as chemical modifier; for the second method, 60 μg of ammonium dihydrogenphosphate were employed. The limits of detection obtained were 0.32 ng g⁻¹ for ammonium dihydrogenphosphate method and 0.54 ng g⁻¹ for palladium-magnesium nitrate method. The characteristic mass was 0.7 and 1.0 pg for ammonium dihydrogenphosphate and palladium-magnesium nitrate methods, respectively. The relative standard deviation (<10%) and the analytical recovery (98-105%) were comparable in both methods. The optimised methods were applied to the determination of the cadmium content in unpolluted Galician honey samples. Cd has been detected the analysed samples in the range (n.d.—4.3 ng g⁻¹).     

Characterization of soil particle surfaces using adsorption excess isotherms

Measurement of adsorption excess isotherms of methanol-benzene mixtures was applied to the characterization of soil particle surfaces. The sorption capacity and Gibbs energy of sorption of the solid-liquid interface were determined for montmorillonite, three types of soil, and their humin fractions. The soils were found to be less polar or less hydrophilic than the clay, and the humin fraction of soils was found to be less hydrophilic than the whole soils. The soil and humin samples have heterogeneous surfaces which can be divided in two regions on the basis of their relative polarity. The x-axis intersection of the straight section of isotherm assigns the relative proportions of the hydrophilic and hydrophobic regions of the surface.