Soil REE patterns as tracers of the emplacement of metal-rich anthropogenic materials. A case study in Moa (Cuba)

Abstract

PURPOSE: Are rare earth element (REE) patterns employable as tracers in human interventions of bulk soil disturbances, when high concentrations of metals are involved in the in situ soil disturbance? In terms of bulk soil disturbance, it is difficult to distinguish between bulk soil disturbances and emplacement of new earthen material. Chemical fingerprinting, in particular REE plus yttrium, is applied across many fields, but predominantlyin tracking the sources of potential environmental contaminants. MATERIALS AND METHODS: The REE normalised patterns (HNO₃:HF:HCl 3:1:1 digestion, ICP-MS) of two Calcaric Cambisols were compared with those of a Geric Ferralsol (Novic, Technic) originated from selective overburden of nickel mining (20°40′ N, 75°35′ W). RESULTS AND DISCUSSION: The sum of REE, including Y and Sc, ranged between 48 and 101 mg kg⁻¹. Principal component analysis (PCA) shows a discriminant role of REE. REE signature normalised to the upper continental crust shows slight positive Eu and negative Ce anomalies in the case of both Calcaric Cambisols, while the Geric Ferralsol shows anomalous patterns with the same anomalies plus a slight positive anomaly of Y, as a consequence of the addition of mining by-products. CONCLUSIONS: Here, we show that REE patterns of the individual horizons of a soil have characteristics that allow us to distinguish undisturbed from soils mixed with other soil materials, including those with different pH values and high metal contents (e.g. Cr, Mn, and Ni ≥ 0.5%, Fe ≫ 5 wt%). Our results demonstrate, by using soils with contrasting characteristics, that their origins can be traced via the patterns of their REEs, even in the presence of high concentrations of other metals. In perspective, when background maps of all REE elements in soils are available worldwide on an appropriate scale, this enables us to obtain a level of discriminatory detail on a local scale.