Sequestering ability of landfill leachate towards toxic metal ions

The great part of municipal solid wastes is worldwide stored in sanitary landfills. The interaction of organic and inorganic wastes with rainwater produces in the landfill a leachate of extremely variable composition. It depends on several variables such as the type of wastes, the age of landfill, the pH, the redox potential, etc [1-2]. Four are the recognized categories of pollutants in landfill leachate: inorganic macrocomponents, dissolved organic matter (DOM), heavy metals and xenobiotic organic compounds [3]. In particular, heavy metals (arsenic, cadmium, copper, lead, mercury, etc.) are usually present at concentration of few ppb and up to some ppm. A variable but consistent fraction of DOM is constituted by humic and fulvic-like compounds, formed through a series of biological and chemical processes that involve DOM, especially during the methanogenic phase of wastes decomposition [3]. The great number of binding sites in humic like substances, mainly carboxylic and phenolic groups, are responsible of the high sequestering ability of leachate towards metal ions. As consequence, the speciation scheme of all the toxic metal ions contained in the landfill is strictly influenced by the amount and composition of DOM fraction in leachate. Due to the imperfections or the possible damages of landfill liners, the leachate can contaminate superficial and ground waters in proximity of the landfill causing serious environmental pollution and human health risks. In a previous study the presence and the amount of landfill leachate, also in trace, on some groundwater samples collected in proximity of Bellolampo landfill was evaluated [4]. The obtained results showed a leachate concentration of ~ 130 μg L-1. Landfill of Bellolampo is a solid waste sanitary landfill near Palermo (Sicily). The landfill has been created in 1960s and become a controlled dump site in 1980s. Previous ICP-OES measurements on Bellolampo leachate have been shown a Pb, Cd and Cu concentrations in the ranges 0.05 - 2.3, 0.02 - 0.12 and 0.02 - 0.6 mg L-1 respectively. The environmental and health risks related to the presence of toxic heavy metal ions in leachate depends on the species that metals form with the other components and at the conditions of the contaminated groundwater, with particular attention to the amount of free metal ions, the most dangerous among their possible species in aqueous solution. For this reason, the study of the sequestering ability of landfill leachate towards toxic metal ions is of fundamental importance to establish the environmental impact of leachate contamination. Here we present a potentiometric and voltammetric (Differential Pulse Anodic Stripping Voltammetry, DP-ASV) study on the acid-base properties and on the sequestering ability of leachate samples collected in Bellolampo landfill towards Cd(II), Pb(II) and Cu(II) ions. The voltammetric and potentiometric titrations were carried out in NaCl aqueous solution, at I = 0.1 mol L-1 in order to simulate the mean experimental conditions typical of groundwaters. The acid – base properties of the filtered leachate were compared to those of the soluble fraction of humic substances, with carboxylic and phenolic groups as main binding sites of the macromolecules. Two units namely leach1 and leach2 containing COOH and phenol OH groups, respectively were considered and the Diprotic Like model has been used to process the ISE-H+ potentiometric data [5]. The voltammetric titrations of toxic metal ions solutions with leachate (diluted or as it is) were carried out adjusting the pH of titrand solutions at 5. The results shown an appreciable sequestering ability of leachate towards the heavy metal ions considered and an estimation of the metal complexes stability has been done by calculating rough metal – leachate formation constants