Heavy metal concentrations in soils as determined by laser-induced breakdown spectroscopy (LIBS), with special emphasis on chromium.

Soil is unanimously considered as one of the most important sink of heavy metals released by human activities. Heavy metal analysis of natural and polluted soils is generally conducted by the use of atomic absorption spectroscopy (AAS) or inductively coupled plasma optical emission spectroscopy (ICP-OES) on adequately obtained soil extracts. Although in recent years the emergent technique of laser-induced breakdown spectroscopy (LIBS) has been applied widely and with increasing success for the qualitative and quantitative analyses of a number of heavy metals in soil matrices with relevant simplification of the conventional methodologies, the technique still requires further confirmation before it can be applied fully successfully in soil analyses. The main objective of this work was to demonstrate that new developments in LIBS technique are able to provide reliable qualitative and quantitative analytical evaluation of several heavy metals in soils, with special focus on the element chromium (Cr), and with reference to the concentrations measured by conventional ICP spectroscopy. The preliminary qualitative LIBS analysis of five soil samples and one sewage sludge sample has allowed the detection of a number of elements including Al, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Si, Ti, V and Zn. Of these, a quantitative analysis was also possible for the elements Cr, Cu, Pb, V and Zn based on the obtained linearity of the calibration curves constructed for each heavy metal, i.e., the proportionality between the intensity of the LIBS emission peaks and the concentration of each heavy metal in the sample measured by ICP. In particular, a triplet of emission lines for Cr could be used for its quantitative measurement. The consistency of experiments made on various samples was supported by the same characteristics of the laser-induced plasma (LIP), i.e., the typical linear distribution confirming the existence of local thermodynamic equilibrium (LTE) condition, and similar excitation temperatures and comparable electron number density measured for all samples. An index of the anthropogenic contribution of Cr in polluted soils was calculated in comparison to a non-polluted reference soil. Thus, the intensity ratios of the emission lines of heavy metal can be used to detect in few minutes the polluted areas for which a more detailed sampling and analysis can be useful.

Trace element inputs into soils by anthropogenic activities and implications for human health.

Trace element definition and functions, and inputs into soils from the most important anthropogenic sources, related and not related to agricultural practices, of general and local or incidental concern, are discussed in the first part of this review. Trace element inputs include those from commercial fertilizers, liming materials and agrochemicals, sewage sludges and other wastes used as soil amendments, irrigation waters, and atmospheric depositions from urban, industrial, and other sources. In the second part of the review, the most important ascertained effects of soil trace elements on human health are presented. The possible relations found between some specific soil trace elements, such as Cd, Se, As and others, and cancer incidence and mortality, and diffusion of other important human diseases are reviewed. Brief conclusions and recommendations conclude this review.