Antonio Violante

MOBILITY AND BIOAVAILABILITY OF HEAVY METALS AND METALLOIDS IN SOIL ENVIRONMENTS

In soil environments, sorption/desorption reactions as well as chemical complexation with inorganic and organic ligands and redox reactions, both biotic and abiotic, are of great importance in controlling their bioavailability, leaching and toxicity. These reactions are affected by many factors such as pH, nature of the sorbents, presence and concentration of organic and inorganic ligands, including humic and fulvic acid, root exudates, microbial metabolites and nutrients. In this review, we highlight the impact of physical, chemical, and biological interfacial interactions on bioavailability and mobility of metals and metalloids in soil. Special attention is devoted to: i) the sorption/desorption processes of metals and metalloids on/from soil components and soils; ii) their precipitation and reduction-oxidation reactions in solution and onto surfaces of soil components; iii) their chemical speciation, fractionation and bioavailability.

Sorption/desorption of arsenate on/from Mg–Al layered double hydroxides: Influence of phosphate

We have studied: (i) the sorption of arsenate on Mg-Al layered double hydroxides (LDHs) containing chloride (LDH-Cl) or carbonate (LDH-CO(3)) in the absence or presence of phosphate; (ii) the competitive sorption of arsenate and phosphate as affected by reaction time and pH and; (iii) the desorption of arsenate previously sorbed on the LDH by phosphate. The LDH samples were uncalcined (LDH-Cl-20 and LDH-CO(3)-20) or calcined at 450 degrees C (LDH-Cl-450 and LDH-CO(3)-450). More phosphate than arsenate was sorbed onto all the minerals but LDH-Cl-450 sorbed much lower amounts of both the ligands than LDH-Cl-20; vice versa LDH-CO(3)-450 showed a capacity to sorb arsenate and phosphate much greater than LDH-CO(3)-20. XRD analysis showed that arsenate was included into the layer spaces of LDH-Cl-20, but not in those of LDH-CO(3)-20. Competition in sorption between arsenate and phosphate was affected by pH, reaction time, surface coverage and sequence of addition of the ligands. Phosphate showed a greater affinity for LDHs than arsenate. The final arsenate sorbed/phosphate sorbed molar ratio increased with reaction time or by adding arsenate before phosphate, but decreased by increasing pH and by adding phosphate before arsenate. The effect of reaction time on the desorption of arsenate by phosphate was also studied.

Sorption of arsenite and arsenate on ferrihydrite: Effect of organic and inorganic ligands

We studied the sorption of As(III) and As(V) onto ferrihydrite as affected by pH, nature and concentration of organic [oxalic (OX), malic (MAL), tartaric (TAR), and citric (CIT) acid] and inorganic [phosphate (PO(4)), sulphate (SO(4)), selenate (SeO(4)) and selenite (SeO(3))] ligands, and the sequence of anion addition. The sorption capacity of As(III) was greater than that of As(V) in the range of pH 4.0-11.0. The capability of organic and inorganic ligands in preventing As sorption follows the sequence: SeO(4) ≈ SO(4) < OX < MAL ≈ TAR < CIT < SeO(3) ≪ PO(4). The efficiency of most of the competing ligands in preventing As(III) and As(V) sorption increased by decreasing pH, but PO(4) whose efficiency increased by increasing pH. In acidic systems all the competing ligands inhibited the sorption of As(III) more than As(V), but in alkaline environments As(III) and As(V) seem to be retained with the same strength on the Fe-oxide. Finally, the competing anions prevented As(III) and As(V) sorption more when added before than together or after As(III) or As(V).

Adsorption of heavy metals on mixed Fe-Al oxides in the absence or presence of organic ligands

A study was carried out on the adsorption of Co2+, Cu2+, Pb2+, and Zn2+ ions on mixed Fe-Al oxides inthe absence or presence of increasing concentrations of oxalate or tartrate. Mixed Fe-Al oxides were prepared by precipitating at pH 5.5 mixtures of Fe and Al ions at initial Fe/Al molar ratios (R) of 0, 1, 2, 4, 10 and ∞ (R0, R1, R2, R4, R10 and R∞).The oxides aged 7 days at 20 °C or 30 days at 50 °C showed different chemical composition and physico-chemical and mineralogical properties. All the mixed Fe-Al oxides showed presence of poorly crystalline materials (ferrihydrite) even after prolonged aging. The heavy metals wereselectively adsorbed on the oxides. For all the precipitates aged7 days at 20 °C, the selectivity sequence wasPb2+> Cu2+ > Zn2+ > Co2+, but the pH at which 50% ofeach cation was adsorbed (pH50) was different from sample tosample. It was found that usually the greater the amounts of Fe in Fe-Al gels the lower the pH50 for each metal, but the adsorption of a heavy metal was not linearly related to Fe content. The pH50 usually did not change significantly when the oxides were aged 30 days at 50 °C. Competitive adsorption of Cu and Zn on ferrihydrite (R∞) showed thatCu strongly prevented Zn adsorption even at an initial Zn/Cu molar ratio of 8, whereas Cu sorption was not inhibited. In thepresence of oxalate (OX) or tartrate (TR) (organic ligand/Pb molar ratio (rL) from 0 to 7) the quantities of Pb adsorbedon the Fe-Al oxides usually increased with increasing rL. The adsorption increase of Pb was particularly high on the oxidesricher in Fe (R4-R∞), but a significant increase was also observed on R0-R2 samples. The adsorption of Pb on the oxides hasbeen influenced not only by the presence and concentration of organic ligands but also by the sequence of addition of Pb and tartrate on the sorbents. It has been ascertained that on each oxide the greater amounts of Pb were adsorbed when tartrate wasadded before Pb and usually according to the following sequence: Tr before Pb > Pb before Tr > Pb + Tr > Pb.

Total arsenic, inorganic arsenic, and other elements concentrations in Italian rice grain varies with origin and type.

Rice is comparatively efficient at assimilating inorganic arsenic (Asi), a class-one, non-threshold carcinogen, into its grain, being the dominant source of this element to mankind. Here it was investigated how the total arsenic (Ast) and Asi content of Italian rice grain sourced from market outlets varied by geographical origin and type. Total Cr, Cd Se, Mg, K, Zn, Ni were also quantified. Ast concentration on a variety basis ranged from means of 0.18 mg kg(-1) to 0.28 mg kg(-1), and from 0.11 mg kg(-1) to 0.28 mg kg(-1) by production region. For Asi concentration, means ranged from 0.08 mg kg(-1) to 0.11 mg kg(-1) by variety and 0.10 mg kg(-1) to 0.06 mg kg(-1) by region. There was significant geographical variation for both Ast and Asi; total Se and Ni concentration; while the total concentration of Zn, Cr, Ni and K were strongly influenced by the type of rice.

EFFECTS OF PHOSPHORUS FERTILIZATION ON ARSENIC UPTAKE BY WHEAT GROWN IN POLLUTED SOILS

In this study we have examinated the results of two experiments on the uptake and distribution of arsenic (As) in roots, shoots, and grain of wheat grown in As-polluted soils and in an unpolluted soil irrigated with As-contaminated water in absence or presence of phosphorus (P) fertilization. Arsenic concentrations in wheat samples of the two experiments are higher than those in the plants grown on uncontaminated soil. In the experiments showed in this work, it is highlighted the role of P fertilization in preventing As uptake and translocation in wheat plants. These findings could have important implications to reduce the potential risk posed to human health by As entering the food-chain.

Sorption of Cu, Pb and Cr on Na-montmorillonite: competition and effect of major elements.

The competitive sorption among Cu, Pb and Cr in ternary system on Na-montmorillonite at pH 3.5, 4.5 and 5.5 and at different heavy metal concentrations, and the effect of varying concentrations of Al, Fe, Ca and Mg on the sorption of heavy metals were studied. Competitive sorption of Cu, Pb and Cr in ternary system on montmorillonite followed the sequence of Cr≫Cu>Pb. Moreover, the competition was weakened by the increase of pH while was intensified by the increase of heavy metal concentration. The sorption of heavy metal on montmorillonite was inhibited by the presence of Ca and Mg, while Al and Fe showed different patterns in affecting heavy metal sorption. Aluminum and Fe generally inhibited the sorption of heavy metal when the pH and/or concentration of major elements were relatively low. However, promoting effects on heavy metal sorption by Al and Fe were found at relatively high pH and/or great concentration of major elements. The inhibition of major elements on heavy metal sorption generally followed the order of Al>Fe>Ca⩾Mg, while Fe was more efficient than Al in promoting the sorption of heavy metals. These findings are of fundamental significance for evaluating the mobility of heavy metals in polluted environments.

Effect of hydroxy-aluminium species on the sorption and interlayering of albumin onto montmorillonite

Abstract Proteins interact with soluble OH–Al species or Al precipitation products forming organo-mineral complexes with different chemical and physico-chemical properties. We studied the effect of pH, cation saturating the clays, presence of OH–Al species and order of component (OH–Al species, albumin and montmorillonite) addition on the amounts of proteinic molecules adsorbed on montmorillonite and the possible interlayering of OH–Al–protein complexes. Albumin molecules were very well intercalated into the interlayers of Na-montmorillonites, but very poor or no intercalation was observed for Mg-saturated montmorillonite and for an Al(OH) x -montmorillonite (chlorite-like) complex. We have found that the amount of albumin sorbed on the external and interlamellar spaces of montmorillonite in the presence of OH–Al species was influenced by the sequence of addition of albumin (Alb), OH–Al species (Al) and montmorillonite (Mt). Complexes were prepared by mixing: (i) Al+Mt before Alb; (ii) Al+Alb before Mt; and (iii) Alb+Mt before Al. When albumin was added to montmorillonite before OH–Al species (Alb+Mt before Al complexes) proteinic molecules were able to penetrate more easily into the interlayers of montmorillonite. On the contrary, when OH–Al species were initially added to the clay (Al+Mt before Alb complexes), they were previously interlayered and consequently prevented the intercalation of the proteinic molecules. Finally, when OH–Al species and proteins were added to the clay as a mixture (Al+Alb before Mt complexes), large OH–Al–protein polymers formed, which were only partially intercalated into the interlamellar spaces of the clay. In all the complexes, the amounts of proteinic molecules sorbed usually increased by increasing the pH.

Effect of inorganic and organic ligands on the sorption/desorption of arsenate on/from Al-Mg and Fe-Mg layered double hydroxides.

This paper describes the sorption of arsenate on Al-Mg and Fe-Mg layered double hydroxides as affected by pH and varying concentrations of inorganic and organic ligands, and the effect of residence time on the desorption of arsenate by ligands. The capacity of ligands to inhibit the fixation of arsenate followed the sequence: nitrate<nitrite<sulphate<selenite<tartrate<oxalate≪phosphate on Al-Mg-LDH and nitrate<sulphate≈nitrite<tartrate<oxalate<selenite≪ phosphate on Fe-Mg-LDH. The inhibition of arsenate sorption increased by increasing the initial ligand concentration and was greater on Al-Mg-LDH than on Fe-Mg-LDH. The longer the arsenate residence time on the LDH surfaces the less effective the competing ligands were in desorbing arsenate from sorbents. A greater percentage of arsenate was removed by phosphate from Al-Mg-LDH than from Fe-Mg-LDH, due to the higher affinity of arsenate for iron than aluminum.

Fate of herbicides influenced by biotic and abiotic interactions

The interactions between 2,4-D and simazine with inorganic and organic soil colloids affected by adsorption (abiotic) and enzymatic mechanisms (biotic) were investigated. Complex model systems which closely simulate those encountered in soils [i.e. pure montmorillonite, montmorillonite covered by different amounts of OH-Al species (chlorite-like complexes)], were used as adsorbents. 2,4-D gave a negligible adsorption on pure montmorillonite, whereas it was significantly adsorbed on chlorite-like complexes. The larger the OH-Al amounts on clay surfaces, the greater the quantity of 2,4-D adsorbed. An opposite behaviour was observed with simazine, which adsorbed much more on montmorillonite than on chlorite-like complexes. A well characterised laccase from the fungal strain Cerrena unicolor was used as biotic catalyst. The enzyme displayed a lower ability to oxidise 2,4-D and simazine whereas it was extremely efficient in the oxidation of 2,4-DCP (a derivative of 2,4-D) and catechol. The presence of soil colloids or reactive co-substrates differently influenced the enzymatic transformation of 2,4-DCP. The results obtained in this study provided useful information for predicting the behaviour of a xenobiotic substance when entered into soil.