Geogenic versus anthropogenic geochemical influence on trace elements contents in soils from the Milazzo Peninsula

Milazzo Peninsula soils and substrates are extremely variable, composed of acidic, mafic and ultramafic metamorphic rocks, carbonatic sedimentary rocks, and sometimes volcanic rocks, thus contributing to a mixed influence on their chemical composition. Moreover, the region is highly polluted due to atmospheric releases from anthropogenic activities, such as refinery industry. In addition, emissions of airborne particles from volcanic eruptions are also likely to fall to the ground and provide trace elements to the soils. The purpose of this study is to distinguish between anthropogenic and geogenic sources contributing to the concentrations of metals in soils by studying their distribution in major and trace elements in relation to substrates. As regards geogenic sources, the major elements composition of soils comes firstly from metamorphic rocks, secondly from carbonates, and to a minor extent from volcanic rocks. Enrichment factors calculations relative to substrate rocks, and using Th as reference element, show that the soils are enriched in As, Pb, Zn, and Ni. Rare earth elements (REEs) patterns normalized to substrate rocks exhibit enrichment in light REEs and a positive anomaly in Gd, indicating anthropogenic contributions in the soil composition. REE ratios and trace elements were plotted to investigate the relationships between anthropogenic sources and substrates in soils compositions. The graphs of La/Ni vs La/Gd and La/Ce vs La/Nd show that soils plot on a line toward substrate rocks on one side, and toward an end member which is represented by a spent catalyst and atmospheric particles emitted by refinery activities. Plots of La vs Cr, and V vs La show similar trends, whereas plots of Zn vs Ni and Pb vs V suggest that another end member, which is unidentified, contributes to soil enrichment in Zn and Pb. A binary mixing model applied to the most Zn enriched soil suggests that anthropogenic inputs from refinery emissions may have contributed to 16% of the anomalies in La/Gd. These results suggest that the trace element composition of Milazzo's peninsula soils partly bears the signature of atmospheric emissions of the refinery.