Increasing the Knowledge of Heavy Metal Contents and Sources in Agricultural Soils of the European Mediterranean Region

This paper contributes to increase the knowledge of the contents and sources of heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) to agricultural soils in Castellón province (Spain), a representative area of the European Mediterranean region. The surface horizons of 77 agricultural soils under vegetable crops were sampled and heavy metals were analysed by atomic absorption spectroscopy (AAS) after microwave extraction using the USEPA 3051A method. Mean heavy metal contents were similar to those obtained in other areas of this region. However, heavy metal contents (e.g. Cr, Pb) in some soils were above the maximum limit set in the 86/278/CEE Directive. Multivariate analysis (correlation analysis and principal component analysis - PCA) was performed so as to identify the sources of heavy metals to soils. Co, Fe and Ni were highly correlated amongst them (r > 0.800; p < 0.01), whereas Cr and Mn were less correlated with Co, Fe and Ni (r > 0.500; p < 0.01). Other relationships among heavy metals (i.e. Cu, Pb and Zn) were also identified, although correlation coefficients were not so high as those among Co, Fe and Ni (r < 0.500; p < 0.01). Contents of Co, Fe, Mn and Ni were interpreted to be mainly associated with parent rocks corresponding to the first principal component (PC1). On the other hand, Cd, Cu, Pb and Zn were interpreted to be mainly related to anthropogenic activities and comprised the second (Pb and Zn) and the third (Cd and Cu) principal components (PC2 and PC3, respectively), designated as anthropogenic components. Remarkably, Cr appears to be related in the study area to both the lithogenic and the anthropogenic components. Lithogenic elements were highly correlated with soil properties. Positive relationships with CEC (r > 0.200; p < 0.05) and clay (r > 0.400; p < 0.01), and negative relationships with carbonates (r > -0.400; p < 0.01) and sand (r > -0.300; p < 0.01) were observed. Anthropogenic elements were less correlated with soils properties, since these elements are generally more mobile because they form more soluble chemical species associated to anthropogenic sources. Particularly, no correlation was found between Cd and Zn and soil properties. These findings extend results achieved in other parts of the region, highlighting the need to set soil quality standards in order to declare soils affected by anthropogenic pollution, particularly in the case of anthropogenic metals such as Cd, Cu and Pb, and also Cr and Zn in some areas. Further knowledge from other areas in this region would improve the basis for proposing such standards at regional level, which is a priority objective in Europe according to the European Thematic Strategy for Soil Protection.