Non-electrostatic surface complexation models for protons and lead(II) sorption onto single minerals and their mixture

Potentiometric titrations and lead sorption tests were conducted using muscovite, clinochlore, hematite, goethite, quartz, and a mixture of these same minerals. Mechanistic models were developed to represent and interpret these data. The aim was isolating the specific contribution of each mineral in proton and lead binding. Acid-base properties of each single mineral as well as their mixture were represented by discrete models, which consider the dissociation of n monoprotic sites (n-site/n-K(H) models). A one-site/one-K(H) model (logK(H1) = 10.69) was chosen for quartz (dissociation of SiOH edge hydroxyl groups). Goethite and hematite (FeOH groups) were represented by the same one-site/one-K(H) model (logK(H1) = 10.35). Three-site/three-K(H) models were used for muscovite (logK(H1) = 4.18; logK(H2) = 6.65; logK(H3) = 9.67) and clinochlore (logK(H1) = 3.84; logK(H2) = 6.57; logK(H3) = 9.71) assuming that SiOH and AlOH of the aluminosilicate matrix dissociate in the acid-neutral pH range while SiOH groups of quartz inclusions dissociate in the basic range. Similarly, the mixture of these minerals was represented by a three-site/three-K(H) model (logK(H1) = 3.39; logK(H2) = 6.72; logK(H3) = 10.82). According to crossed comparisons with single minerals, the first two sites of the mixture were associated with the aluminosilicate matrix (SiOH and AlOH respectively) and the third site with iron oxides (FeOH) and quartz groups. Additivity of proton binding in the mixture was demonstrated by simulating the mixture's titration curve. A unified model for the entire set of titration curves (single minerals and mixture) was also developed introducing a three-peak distribution function for proton affinity constants. Experimental data for lead sorption onto the mixture and individual minerals in 3-5 pH range denoted the competition between protons and metallic ions. The entire set of lead isotherms (individual mineral and mixture data) was represented adequately by a unified model taking into account both monodentate and bidentate complexes with the three active sites (additivity of lead binding). Experimental data of metal distribution in solid and liquid phases were successfully simulated by implementing the protonation and the surface complexation constants into the database of a dedicated software for chemical equilibria.     

Heavy metal ion influence on the photosynthetic growth of Rhodobacter sphaeroides

The potential of purple non-sulphur bacteria for bioremediation was assessed by investigating the ability of Rhodobacter sphaeroides strain R26.1 to grow photosynthetically in heavy metal contaminated environments. Bacterial cultures were carried out in artificially polluted media, enriched with the transition metal ions Hg2+, Cu2+, Fe2+, Ni2+, Co2+, MoO4(2-), and CrO4(2-) in millimolar concentration range. For each investigated ion the effect on growth parameters was evaluated. The analysis of concentration-effect curves revealed a differentiated response, indicating that diverse mechanisms of tolerance and/or resistance are involved. Adaptation or selection procedures were not applied, leading to assess intrinsic abilities of coping with these contaminants. The microorganism proved to be highly tolerant to heavy metal exposure, especially towards Co2+, Fe2+ and MoO4(2-). In addition Ni2+ and Co2+ were found to decrease the cellular content of light harvesting complexes. A characteristic behavior was observed with mercuric ions, which produced a significant increase of the lag-phase.     

Integrating methods for the environmental sustainability: the SPIn-Eco Project in the Province of Siena (Italy)

This paper shows how different methods can be integrated in order to provide an organic evaluation of the environmental sustainability at the territorial level. A territory is a complex, dynamic and open system where a population develops, uses resources, produces goods and services, consumes, depletes and finally obtains economic results. All these elements characterise human behaviour, which can be monitored, measured and compared to the capacity of the environment to sustain it in the long run. The SPIn-Eco Project for the Province of Siena (Italy) is described as an example of an environmental sustainability assessment of an area, and its methods (Ecological Footprint, Greenhouse Gas Inventory, Extended Exergy Analysis, Emergy Evaluation, Life Cycle Assessment (LCA) and Remote Sensing) are briefly introduced. This Project has been proposed and funded by the most important provincial administrative and financial institutions in the territory (the Administration of the Province of Siena and the Monte dei Paschi Foundation, respectively), and was designed and realised in 4 years (2001-2004) by a research team coordinated by the University of Siena.     

Metal contamination in urban street sediment in Pisa (Italy) can affect the production of antioxidant metabolites in Taraxacum officinale Weber

Taraxacum officinale Weber (dandelion) is a very ubiquitous species, and it can grow in urban environments on metal-polluted sediments deposited in the gutters. This study represents a preliminary step to verify the presence of metals in sediments collected in urban streets in Pisa and to assess the alteration in dandelion metabolites in order to understand its adaptation to polluted environments. The soil and sediments were collected at three urban streets and analyzed for total and extractable Cr, Pb, Cu, Ni, and Zn. The total values of Pb and Zn in street sediments exceeded the limits for residential areas of soils. Zn was the most mobile of the metals analyzed. Floating cultivations trials were set up with dandelion seedlings and street sediments. The metals were analyzed in roots and leaves. Antioxidant power, anthocyanins, polyphenols, non-protein thiols (NP-TH) and chlorophylls were measured in dandelion leaves. The first two parameters (anthocyanins and antioxidant power) were higher in the polluted samples compared to the control; chlorophyll content was lower in the treated samples, whereas NP-TH showed no differences. NP-TH groups determined in roots were associated with the root content of Zn and Pb. These results indicate that dandelion can tolerate plant stress by altering its metabolite content.