Solid speciation and fractionation of rare earth elements in a spodosol profile from northern Sweden as revealed by sequential extraction

Abstract

A sequential extraction has been carried out on seven soil samples from a spodosol profile in till with granitic composition. The soil profile was sampled in northern Sweden. Five fractions were selected for extraction: (A) CH 3COONa-extractable (exchangeable/adsorbed/carbonate); (B) Na 4P 2O 7-extractable (labile organics); (C) 0.25 M NH 2OH⋅HCl-extractable (amorphous Fe-oxyhydroxides/Mn-oxides); (D) 1 M NH 2OH⋅HCl-extractable (crystalline Fe-oxides); and (E) KClO 3/HCl-extractable (organics and sulphides). Extracted rare earth elements (REE) were determined with High Resolution ICP-MS. In addition to the soil, stream water suspended particulate matter was also analysed for REE. Total concentrations in the soil samples show that the REE have been fractionated during weathering. In the acidic (pH 4.28) E-horizon all REE are depleted relative to the unweathered till. The depletion decreases with increasing atomic number. Also in the B-horizon (pH 5.86) the REE are depleted, although to a lesser extent compared to the E-horizon. Secondary phases in the B-horizon fractionate the REE in different ways. Rare earth elements extracted in extractions A and C were enriched in the intermediate REE relative to heavy and light REE if normalized to local till. In extractions B and D, the heavy REE were enriched relative to the light REE, and in extraction E a large enrichment of light REE relative to heavy REE was found. Stream water suspended particulate matter is enriched in all REE relative to local till. The light REE are more enriched than the heavy REE. Normalized La/Lu ratios in the suspended matter ranged from 1.5 to 2.4, and were negatively correlated with stream water discharge as well as with content of detrital inorganic matter in the suspended load. The only extracted phase that potentially can explain the high normalized La/Lu ratio in the suspended matter is the phase extracted in extraction E, which has a ratio of 2.0–4.2. The normalized La/Lu ratio for the rest of the extractions ranged from 0.5 to 1.2. It is concluded that organic matter seems to be important for the particulate transport of REE in northern coniferous areas.