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.

Variability in As, Ca, Cr, K, Mn, Sr, and Ti concentrations among humic acids isolated from peat using NaOH, Na4P2O7 and NaOH+Na4P2O7 solutions.

Sphagnum peat has been found to efficiently remove heavy metals, oil, detergents, dyes, pesticides and nutrients from contaminated waters since its major constituents, i.e., unesterified polyuronic acids, cellulose, and fulvic and humic acids (HA), show functional groups (e.g., alcohols, aldehydes, carboxylic acids, ketones and phenolic hydroxides) which may adsorb pollutant species. The influence of the extractant on the analytical characteristics of HA is an old but still open topic that should be studied in relation to the nature of the matrix from which they originate. While a number of works have been published on the effects of different reagents on the extraction yields and structural properties of HA from soils, relatively little attention has been devoted to peat HA. In this work, the contents of some major and trace elements (As, Ca, Cr, K, Mn, Sr, and Ti) in five Sphagnum-peat samples and in their corresponding HA fractions isolated using three common extractant solutions, i.e., 0.5M NaOH, 0.1M Na(4)P(2)O(7), and 0.5M NaOH+0.1M Na(4)P(2)O(7), where investigated by X-ray fluorescence spectroscopy. In general, Cr, Mn, and Ti concentrations of bulk peat samples were higher than those of the corresponding HA fractions regardless of the extractant used. Arsenic, Ca, K, and Sr concentrations in the HA fractions were affected by the extraction procedure, although at different extents depending on the extractant utilized. In particular, compared to both NaOH and NaOH+Na(4)P(2)O(7), the Na(4)P(2)O(7) extractant yielded HA generally richer in As, Ca, K, and Sr, and poorer in Ti. These results may be related to both the nature of each HA fraction and the physical and chemical form of each element supplied to the studied bog via atmospheric deposition.

Influence of extractant on quality and trace elements content of peat humic acids.

Among several extractants used to isolate humic acids (HA) from terrestrial environments, sodium hydroxide (NaOH) and sodium pyrophosphate (Na(4)P(2)O(7)) are the most utilized. In order to evaluate the influence of these different extractant solutions on the HA quality and on their trace elements content, HA were isolated from five Sphagnum-peat samples using three different solutions: (a) 0.5M NaOH; (b) 0.1M Na(4)P(2)O(7); (c) 0.5M NaOH+0.1M Na(4)P(2)O(7). The obtained HA have been analyzed with respect to ash content, elemental composition, main atomic ratios and characterized by FT-IR and total luminescence (TL) spectroscopies. In addition, both raw peat and HA have been analyzed using X-ray fluorescence in order to determine the Br, Cu, Fe, Ni, Pb and Zn contents. Results showed that HA extracted with NaOH and NaOH+Na(4)P(2)O(7) are quite similar with respect to ash, elemental contents and spectroscopic characteristics, while Na(4)P(2)O(7) solution, which in general reduces the extraction yield, seems to affect the nature of HA, featuring a more complex and aromatic character. With respect to the contents in the corresponding raw peat samples, the HA fractions were richer in Br, Cu and Ni, regardless of the extractant used, and poorer in Fe, Pb and Zn. Further, Br, Cu, Ni and Zn were more concentrated in HA extracted with Na(4)P(2)O(7) than in those extracted with NaOH and NaOH+Na(4)P(2)O(7), probably because of the greater affinity of these elements for these more aromatic humic molecules.