Evaluating natural and anthropogenic inputs on the distribution of potentially toxic elements in urban soil of Valdivia, Chile.

The increasing population in urban areas in the last decades requires an effort to understand the geochemistry of contaminant elements in urban soil. Topsoil plays a crucial role in the exposure of Potentially Toxic Elements (PTEs) to humans through ingestion, dermal contact, and inhalation. In Chile, the last census revealed that 88.6% of people live in cities or towns and only 11.4% in rural areas. This study presents the first systematic geochemical survey of urban soil in the city of Valdivia, in the South of Chile. Topsoil samples (0-10 cm depth) were collected in less disturbed locations within the city at 130 sampling sites using a grid of 0.25 km2 squares covering a total area of approximately 30 km2. The concentrations of Al, Fe, Na, Ca, Mg, K, Ti, Be, V, Cr, Mn, Co, Ni, Cu, Zn, As, Mo, Sn, Cd, Se, Pb and Hg were measured. The results showed that high concentrations of Cu, V, Zn and Pb are located mainly in the city's northern area and exceed international soil quality legislation for agricultural use. Data processing comprised plotting of individual spatial distribution maps and the use of a combination of multivariate statistical methods. Hierarchical cluster analysis and principal component analysis identified three element associations. The two element groups V-Al-Ti-Fe-Cr-Co-Mn-Be-Ni and Ca-Na-K-As-Mg are interpreted as a dominant lithological origin related to the most pristine soil conditions in less populated areas. By contrast, the Sn-Pb-Zn-Mo-(Cu-Hg) association presents a significant correlation with urbanization indicators, including vehicular traffic and industrial activities developed since the end of the nineteenth century in Valdivia.

Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules.

We studied the electronic and conductance properties of two thiophene-curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO-LUMO band gap energies, showing that molecule 1 has lower values than 2. Theoretical calculations show the same trend. Self-assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO-LUMO gap in both molecules to almost the same value. Single-molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.