Mobility and fractionation of rare earth elements during supergene weathering and gossan formation and chemical modification of massive sulfide gossan

Abstract

Primary massive sulfide gossans (MSG) in the Bathurst Mining Camp (BMC), New Brunswick, Canada, are characterized by relative enrichment of Au, Sb, and As, formation of jarosite group minerals (jarosite, plumbojarosite, and argentojarosite) and little or no fractionation in the rare earth elements (REE), including preservation of large positive Eu anomalies (average [Eu/Eu*] NASC = 4.14 in MSG; 6.61 in massive sulfide mineralization; 0.60 in host rocks). The chemical and mineralogical characteristics of MSG (e.g., Halfmile Lake deposit) imply low pH (<3) and relatively oxidizing conditions during gossan formation; oxidation of a volcanogenic massive sulfide body (comprising pyrite, pyrrhotite, sphalerite, galena, and chalcopyrite) with a falling water table. The lack of light REE or heavy REE fractionation and preservation of positive Eu anomalies characteristic of the original (465 Ma) hydrothermal fluid is consistent with relatively large water–rock ratios during massive sulfide mineralization oxidation, and removal of the REE predominantly as sulfate complexes (LnSO 4 +, Ln(SO 4) 2 −). Low pH groundwaters recovered from past producing mines in the BMC display REE patterns reflecting those inferred to have occurred during gossan formation. Gossan at the Restigouche deposit, in contrast to the Halfmile Lake deposit, displays mineralogical and chemical evidence for having been chemically reworked since primary gossan formation. Evidence for chemical reworking includes loss of primary massive sulfide mineralization textures, replacement of plumbojarosite with anglesite, almost complete removal of jarosite minerals, loss of Au, Sb, and As and apparent preferential removal of Eu, resulting in loss of positive Eu anomalies for most samples (average [Eu/Eu*] NASC = 1.21 in the gossan, with many displaying strong negative anomalies; 3.65 in massive sulfide mineralization; 0.54 in host rocks). Based on geochemical modeling, conditions inferred for the chemical reworking of the Restigouche deposit include near neutral conditions and either relatively oxidizing conditions with Eu 2+ hosted in a preferentially weathered mineral host (possibly through substitution for Pb in plumbojarosite and beudantite) or cycling between reduced and oxidized conditions during gossan reworking.