Fracture zone-scale variation of trace elements and stable isotopes in calcite in a crystalline rock setting

Abstract

With an aim to increase the understanding about the isotopic and chemical heterogeneity of calcites in water-conducting fracture zones with different crystalline wall rock compositions at different depths, we present trace element chemistry, isotopic composition (delta O-18, delta C-13, Sr-87/Sr-86) and biomarkers of euhedral low-temperature fracture-coating calcite. Paleohydrogeological fluctuations and wall rock influence on the hydrochemistry in the deep groundwater are explored. Samples are from several fracture zone sub-fractures (at -360 to -740 m), retrieved during an extensive core drilling campaign in Sweden. Calcite generally showed fracture zone specific values of delta C-13,delta O-18 and Sr-87/Sr-86, which indicates precipitation from relatively homogeneous fluid (similar to the modern groundwater at the site) at the same event in each fracture zone. delta O-18 and delta C-13 in the different fracture zones were consistent with precipitation from waters of different salinity and decreasing organic input with depth, respectively. The latter is also supported by biomarkers showing clear indications of SRB-related organic compounds (e. g. iso- and anteiso-C-17:0-branched fatty acids), except in the deepest zone. In contrast to the isotopes, variation in trace elements within the fracture zones was generally up to several orders of magnitude. Manganese and REE, as oppose to the other metals, were higher in the shallow fracture zones (112-1130 and 44-97 ppm, respectively) than in the deeper (28-272 and 5-11 ppm, respectively), in agreement with the groundwater composition. Although the rock types varied between and within the different fracture zones, this had insignificant influence on the trace element chemistry of the calcites. Co-variation was generally relatively large for many trace elements, with isometric logratio correlation generally better than 0.75, which indicates that their variation in the calcites is due to variation of Ca in the fracture water, but other local factors, especially uptake in co-precipitating minerals (clay minerals, barite, pyrite and zeolites), but also microbial activity and metal speciation may have influenced the metal incorporation into calcite. These detailed studies of fracture calcite are of importance for the understanding of variation in fluid chemistry and trace metal uptake in fracture zones, adding together with hydrochemical studies detailed information optimal for site characterisation. (c) 2013 Elsevier Ltd. All rights reserved.