Cerium Sequestration in Fractures in the Upper Kilometer of Granitoids, SE, Sweden

This study seeks to define geochemical processes governing the accumulation and sequestration of Ce in granitoidic fractures down to >700 m depth, revealing past intrusions of oxygenated waters. The fracture coatings (secondary mineral precipitates in open fractures) gathered from the study area (Laxemar, SE Sweden) are characterized by high levels of Ce (Fig. 1b) compared to host rock cocentration (average: 86 ppm, n=65) and show a striking feature of distinct positive Ce anomalies (CeWN*=1.21-3.95, n=8) in the uppermost 20 m of the bedrock (Fig. 1a). Cerium and Mn X-ray absorption spectroscopy (XAS) of selected fracture coatings, together with existing data (e.g. fracture mineralogy and groundwater chemistry), indicate that: (1) Ce(IV) occurs down to c.a. 70 m depth and is exclusively associated with Mn oxides which occur as todorokite and triclinic birnessite as suggested by Mn EXAFS spectra; (2) Since Mn is largely speciated as Mn2+ in the present bedrock groundwaters, the Ce(IV)-bearing Mn oxides most probably resulted from oxidative weathering of wall rock and fracture coating minerals when oxygenated waters intruded into the bedrock (down to several hundred meters depth) during deglacation events (>13000 BP); (3) Unlike other samples, clear XAS features of a poorly-crystalline hexagonalbirnessite-like phase and larger proportion of aqueous Mn2+ were observed in the sample with strikingly positive Ce anomaly (CeWN* = 3.95) (Fig. 1b) at the depth of 0.87 m, suggesting an ongoing dynamic accumulatinon of Ce(IV), i.e. dissolution and reprecipiation of Mn oxides while Ce(IV)- enriched residue largely remained