Ornella Abollino

Adsorption of heavy metals on Na-montmorillonite. Effect of pH and organic substances

Clays (especially montmorillonite and bentonite) are widely used as barriers in landfills to prevent contamination of subsoil and groundwater by leachates containing heavy metals. For this reason it is important to study the adsorption of metals by these clays. The sorption of seven metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) on Na-montmorillonite was studied as a function of pH and in the presence of ligands, forming complexes of different stabilities with the metals of interest. The continuous column method was used as it better simulates natural conditions. The total capacity of Na-montmorillonite towards these metals was determined. The pH variations influence to a higher extent the concentrations of Cu, Pb and Cd in the effluent. Moreover the results suggest that complex formation hinders the sorption of the metals on the clay, with an increasing influence in the order: Mn < or = Pb < or = Cd < or = Zn < Ni < Cu < Cr. The evaluation of the total capacity of Na-montmorillonite shows that this clay is a good sorbent towards all examined metals.

Heavy metals in agricultural soils from Piedmont, Italy. Distribution, speciation and chemometric data treatment.

The distribution and speciation of heavy metals in five agricultural soils of Piedmont Region (north-western Italy) were investigated. Ten metals, namely Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti and Zn were considered. Analytical determinations were performed by atomic emission or atomic absorption spectroscopy after microwave sample dissolution in acid solution. Total metal concentrations fit in the typical concentration ranges for unpolluted soils, with the exception of cadmium and lead content in some horizons. The effect of sampling depth on concentrations was discussed. Speciation studies were carried out by applying Tessiers procedure, which allows to subdivide the total metal content into five fractions, representing portions bound to different components of the soil. Moreover, the element labilities in two soils were evaluated by extraction with EDTA. Correlations among the variables and/or similarities among the sampling points were identified by principal component analysis and hierarchical cluster analysis.

Distribution and mobility of metals in contaminated sites. Chemometric investigation of pollutant profiles

The distribution and mobility of heavy metals in the soils of two contaminated sites in Piedmont (Italy) was investigated, evaluating the horizontal and vertical profiles of 15 metals, namely Al, Cd, Cu, Cr, Fe. La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr. The concentrations in the most polluted areas of the sites were higher than the acceptable limits reported in Italian and Dutch legislations for soil reclamation. Chemometric elaboration of the results by pattern recognition techniques allowed us to identify groups of samples with similar characteristics and to find correlations among the variables. The pollutant mobility was studied by extraction with water, dilute acetic acid and EDTA and by applying Tessiers procedure. The fraction of mobile species, which potentially is the most harmful for the environment, was found to be higher than the one normally present in unpolluted soils, where heavy metals are, to a higher extent, strongly bound to the matrix.

Accumulation of heavy metals from contaminated soil to plants and evaluation of soil remediation by vermiculite

We evaluated the distribution of 15 metal ions, namely Al, Cd, Cu, Cr, Fe, La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr, in the soil of a contaminated site in Piedmont (Italy). This area was found to be heavily contaminated with Cu, Cr and Ni. The availability of these metal ions was studied using Tessiers sequential extraction procedure: the fraction of mobile species, which potentially is the most harmful for the environment, was much higher than that normally present in unpolluted soils. This soil was hence used to evaluate the effectiveness of treatment with vermiculite to reduce the availability of the pollutants to two plants, Lactuca sativa and Spinacia oleracea, by pot experiments. The results indicated that the addition of vermiculite significantly reduces the uptake of metal pollutants by plants, confirming the possibility of using this clay in amendment treatments of metal-contaminated soils. The effect of plant growth on metal fractionation in soils was investigated. Finally, the sum of the metal percentages extracted into the first two fractions of Tessiers protocol was found to be suitable in predicting the phytoavailability of most of the pollutants present in the investigated soil.

Parameters affecting the determination of mercury by anodic stripping voltammetry using a gold electrode.

The electrochemical determination of aqueous Hg(II) by anodic stripping voltammetry (ASV) at a solid gold electrode is described. The aim of this work is to optimise all factors that can influence this determination. Potential wave forms (linear sweep, differential pulse, square wave), potential scan parameters, deposition time, deposition potential and surface cleaning procedures were examined for their effect on the mercury peak shape and intensity. Five supporting electrolytes were tested. The best responses were obtained with square wave potential wave form and diluted HCl as supporting electrolyte. Electrochemical and mechanical surface cleaning, aimed at removing the amount of mercury deposited onto the gold surface, were necessary for obtaining a good performance of the electrode. Response linearity, repeatability, accuracy and detection limit were also evaluated.

The retention of metal species by different solid sorbents: Mechanisms for heavy metal speciation by sequential three column uptake

An apparatus consisting of three columns packed with different substrates, namely an anion exchange resin, a reversed phase sorbent and a chelating ion exchange resin, was developed. The retention of cadmium, copper and lead onto the substrates at different pH conditions was investigated, first by considering each column separately, then by connecting them in series. The aim of the study is to distinguish among species with different charge or chemical behaviour. Experiments were performed with the free metal ions, their anionic complexes with EDTA and 8-hydroxyquinoline-5-sulphonic acid, and their neutral complexes with 8-hydroxyquinoline. The results obtained were compared with those computed according to the theoretical species distribution of all species as a function of pH. The applicability of the technique to seawater was demonstrated.

The use of mosses as environmental metal pollution indicators

The possibility of using mosses as environmental indicators of metal pollution has been investigated. Mosses of the species Bryum argenteum were collected from different parts of Piedmont (Italy), ranging from highly polluted areas to nearly uncontaminated mountain areas. Periodical samplings were planned in every site on a monthly base, in order to check variations of metal uptake throughout one year; correlations with pluviometric and thermal patterns were investigated for all sampling stations. On every moss sample 20 elements, ranging from major (K, P, Al, Ca, Fe and Mg) to minor (Mn, Na, Ti and Zn) and trace (As, Ba, Cd, Co, Cr, Cu, Li, Ni, Pb and Sr), were quantitatively determined by inductively coupled plasma-atomic emission spectrometry or graphite furnace-atomic absorption spectrometry, depending on the needed sensitivity. Statistical analyses, carried out with principal component analysis and cluster analysis methods, revealed that a good correlation exists between metal content in mosses and pollution degree in the areas sampled.

Determination of metals in wine with atomic spectroscopy (flame-AAS, GF-AAS and ICP-AES); a review

Metals in wine occur at the mg l-1 level or less and, though not directly related to the taste of the final product, their content should be determined because excess is undesirable, and in some cases prohibited, due to potential toxicity. Lead content in wine, for example, is restricted in several states by legislation to guarantee consumer health protection. Of several methods for metal determination, techniques of atomic spectroscopy are the most sensitive and rapid. Most of the elements present in wine can be determined with these techniques, at concentrations ranging from the mg l-1 to the μg l-1 level. Here, inductively coupled plasma-atomic emission spectrometry (ICP-AES), flame atomic absorption spectrometry (flame-AAS) and graphite furnace-atomic absorption spectrometry (GF-AAS) are compared for their characteristics as employed in metal determination in wine.

Speciation of copper and manganese in milk by solid-phase extraction/inductively coupled plasma-atomic emission spectrometry

A speciation method was developed to study distribution of copper and manganese species in cow milk. The method is based upon solid-phase extraction of selective fractions of the analytes, followed by elution and determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES), using it as a flow-injection detector. Fractions detected were cationic, anionic, neutral and casein-bound. A different behaviour is observed for the two metals.

The role of chemometrics in single and sequential extraction assays: A review: Part I. Extraction procedures, uni- and bivariate techniques and multivariate variable reduction techniques for pattern recognition

Element mobility and availability in natural solid matrices can be studied with single and sequential extraction procedures; such procedures provide reliable and useful information only if the experiments are correctly planned and executed and the results are properly interpreted. Chemometrics can be a valuable tool for these aims, especially taking into account the large amounts of data generated with extraction essays and the complexity of the processes under investigation. This review deals with the application of chemometrics in research studies involving single and sequential extractions on soils or sediments, for several purposes: the development and optimization of the extraction conditions, the calculation of element fractionation, the visual illustration of the experimental results, the acquisition of different areas of information, including relationships among variables, similarities and differences among samples, causes of the observed behaviour (e.g. source identification), risk assessment, models and predictions of future events. In Part I of the review, following an overview on extraction procedures, the applications of univariate and bivariate chemometric methods are reported; then the principles of multivariate techniques for pattern recognition based on variable reduction, their applications and the main findings obtained are addressed.