Geochemistry and behavior of REE in stream sediments close to an old Sn-W mine, Ribeira, Northeast Portugal

Abstract

The abandoned Sn-W Ribeira mine, northeast of Portugal, contained quartz veins with cassiterite, wolframite, scheelite, pyrite, arsenopyrite, sphalerite, chalcopyrite, manganocolumbite, bismuthinite, native bismuth, phosphates and carbonates. The exploration took place on the northern slope of the Viveiros stream, which is an affluent of the Sabor River. The waste-rock dumps and tailings were deposited on the hillside, close to the mine and are nowadays exposed to significant weathering and erosion, as they are not vegetated. The eroded material is transported by the Viveiros stream toward the Sabor River. A seasonal stream drains the tailings. The stream sediments samples were collected along the Viveiros stream, in the seasonal stream, in a seasonal spring at the bottom of the tailings, in the Sabor River and in other streams not affected by mine workings, following the mine influence along the Viveiros stream and in the Sabor River (1.2km away from the mine workings). The data show that the degree of pollution increases along the Viveiros stream, especially in winter. The highest degree of pollution is for As, In, W, Sn and Bi. The sediments from the drainage of the main tailings are particularly polluted during winter, by Bi, In and Sn. The sedimentary precipitate from the spring is polluted in Cu, As, In, Sn, Ta, W, Bi, Zn, Nb, Ag, Sb and Ta. The sediments from the Sabor River are significantly polluted by As, Ag, In, Sn, W and Bi. The sediments from the regional streams, Viveiros stream and Sabor River have similar REE (NASC normalized) patterns (ΣREE=131.7–185.9mg/kg, LaN/LuN=1.23–1.42 and Eu/Eu*=1.02), while those from the seasonal stream, crossing the main tailings, are enriched in REE (ΣREE=250.3–283.6mg/kg, LaN/LuN=1.6–2.09 and Eu/Eu*=0.96). The general decrease in LaN/LuN values with increase in total Fe2O3 can be explained by the partitioning of HREE to the solid Fe-oxides phase. The sedimentary precipitate and coatings, which are mainly formed by Fe-oxy-hydroxides, but also contain jarosite, are impoverished in all REE. The impoverishment can be explained by the release of REE from the surface of the Fe-oxy-hydroxides, which occurs due to a local lowering of pH, caused by jarosite dissolution. During successive alternate cycles of wet and dry conditions, takes place the formation of Fe-oxy-hydroxides and jarosite in the sedimentary precipitate and coatings. The subsequent dissolution of jarosite releases acidity, thus promoting de-sorption of REE from the Fe-oxy-hydroxides mineral phases.