Search

The isotopic compositions of alkali metal elements are powerful tracers of various geological processes. Coupled K and Rb isotopic studies can potentially yield new clues on the mechanisms responsible for the depletions in moderately volatile elements in planetary objects, global surface geochemical cycles, and mechanistic aspects of water–rock interactions. Rubidium isotopic studies have however been hampered by difficulties in purifying Rb from rocks, notably due to its similar chemical behavior to K. Here we characterize the properties of three different types of resins (AMP-PAN resin; AG50W-X8 and AG50W-X12 cation-exchange resins; Sr resin) for Rb and K purification. We show that AMP-PAN resin and Sr resin can readily separate Rb from K and other matrix elements. However, AMP-PAN resin has a high Rb blank (∼80 ng) and is cumbersome to use, which limits its applicability. For cation resins, we test the effects of column length, acid molarity, temperature, pressure drop (flow rate), and resin cross-linkage on the Rb separation using a Fluoropolymer Pneumatic Liquid Chromatography (FPLC) unit built in our laboratory. Increasing column length or resin cross-linkage has a positive effect on the separation, while increasing acid molarity, temperature, or pressure drop (flow rate) has negative impacts. Gravity-driven cation-exchange resin columns fail to cleanly separate Rb from K, but an AG50W-X12 resin column of 150 cm length and 0.16 cm inner diameter installed on a FPLC unit can cleanly separate Rb from K. We separated Rb from synthetic and natural rock samples using three different purification schemes designed based on the three types of resins, and measured the Rb isotopic compositions of the Rb separates by MC-ICPMS. The three methods yielded consistent results, demonstrating the efficacy of our Rb separation and the accuracy of our Rb isotopic analyses. The Rb isotopic compositions of several geostandards were analyzed (BCR-2, BHVO-2, BE-N, AGV-2, GS-N, G-3, a

The transition from an anoxic to oxygenated atmosphere was arguably the most dramatic change in the history of the Earth. This “Great Oxidation Event” (Holland 2006) transformed the biogeochemical cycles of the elements by imposing an oxidative step in the cycles, creating strong redox gradients in the terrestrial and marine realms that energised microbial metabolism. Although much past research was focused on establishing when the rise of atmospheric oxygen took place, recognition that substantial mass-independent fraction (MIF) of the sulphur isotopes is restricted to the time interval before 2.45 Ga and requires an anoxic atmosphere (Farquhar et al. 2000, 2007; Mojzsis et al. 2003; Ono et al. 2003; Bekker et al. 2004) argues the atmosphere became permanently oxygenated at this time (Pavlov and Kasting 2002). A false-start to the modern aerobic biosphere and a “whiff” of atmospheric oxygen (Anbar et al. 2007) may have occurred in the latest Archaean, as reflected in a transient enrichment in the redox-sensitive element molybdenum in marine shales and a reduction in the extent of MIF precisely coincident with the peak in Mo and FeS_2 enrichment (Kaufman et al. 2007). Geochemical proxies are imperfect, and an earlier (c. 3 Ga) appearance of atmospheric oxygen is possible (Ohmoto et al. 2006) but disputed (Farquhar et al. 2007; Buick 2008).