Rare earth element signature modifications induced by differential acid alteration of rocks in the Iberian Pyrite Belt.

The efficient use of REE as tracers of weathering processes requires further data acquisition to establish robust connections between mechanisms, mineral assemblages and REE concentration patterns. Here, results are provided corresponding to rocks from four locations in the Iberian Pyrite Belt that were altered with different intensity by sulfuric fluids. The acidic alteration was mild (pH 5–7) in Calañas and El Villar, while strong (pH below 3 to 5) in Quebrantahuesos and Tharsis. The main REE reservoir before alteration were phyllosilicates (and plagioclase/feldspar in El Villar only). Mild alteration generated mainly kaolinite while illite and some plagioclase/feldspar were preserved. Mildly altered rocks approximately preserved the relative REE concentrations of their precursors, interpreted as indicating a low fluid/rock ratio environment where binding sites in minerals outnumbered those in fluids. Strong acid alteration produced alunite, jarosite, beudantite and goethite, with partial illite preservation. Where illite and/or goethite were major minerals, this alteration generated REE patterns enriched in light REE over heavy REE or did not modify the relative REE concentrations of the original rock. However, samples where REE concentrations were controlled by alunite or jarosite had LREE > > HREE. In alunite the maximum concentration corresponded to Nd and Sm. In jarosite concentrations decreased from La to Lu, except that a positive Eu anomaly was preserved from the precursor. These REE concentration patterns are interpreted as due to crystallographic factors, controlled by the best fit of REE with charge 3+ in the 12-fold coordination site of K in jarosite and alunite. This site is larger in jarosite and fits La best, whereas the smaller site in alunite best fits Nd and Sm. Goethite REE signature is variable, perhaps due to two formation routes, (1) silicates ➔ goethite and (2) silicates ➔ jarosite ➔ goethite. Our interpretations of REE concentration in alunite, jarosite and goethite are novel and provide new routes to further develop REE as tracers of acid alteration processes. [Display omitted] • Eu anomaly was negative in altered volcanic rocks, positive in altered shales. • Kaolinite, formed at pH 5–7, inherited the REE pattern of precursor phyllosilicates. • Alunite (pH 3–5) and jarosite (pH < 3) had a modified REE pattern with LREE > > HREE. • REE signature in alunite and jarosite is controlled by the size of the K crystallographic site. • Goethite variable REE signature is caused by two formation routes, from silicates or from jarosite. [ABSTRACT FROM AUTHOR]