Controls on the stable Mo isotopic composition of inner-continental precipitation

Abstract

The molybdenum (Mo) isotope budget of the surface environment has been well characterized in recent decades, facilitating accurate mass balance modeling of the ancient redox-driven Mo cycle. One yet unresolved component is the range of possible processes and sources that result in isotopically heavy river waters relative to continental sources. Following a recent hypothesis that isotopically heavy δ⁹⁸Mo of precipitation may control the final δ⁹⁸Mo of river water relative to its continental source bedrock, we investigated the δ⁹⁸Mo composition of 19 snow samples from three locations in Central Europe: the Swiss Alps (“Alpine” samples) from the Hochalpine Forschungsstation Jungfraujoch (HFSJ) in both summer and winter, the Swiss Jura Mountains in winter and the French Vosges Mountains in winter. Stream waters from two snowmelt-fed streams were additionally collected from the Alpine site. Snow sample δ⁹⁸Mo compositions were highly variable, ranging from −0.03 to +1.93 ‰, with no clear mixing trends indicating complex sources, source pathways, or post-depositional processing. Only the winter snow samples from the high-altitude HFSJ site had δ⁹⁸Mo values consistently heavier than typical continental crust. The δ⁹⁸Mo results were coupled with radiogenic Sr isotopic, major ion, and trace element compositions as tracers for three major sources of airborne ion inputs: sea salt, mineral dust, and anthropogenic aerosols. We found that the most likely source of Mo to precipitation in the lower elevation Vosges and Jura Mountains samples was isotopically light soil mineral dust, which reflected the underlying bedrock sources, with a likely additional anthropogenic component. The isotopically heavy winter snow samples at the elevated HFSJ site were attributed to a higher input of carbonate mineral dust from long-distance transport of carbonate-rich Saharan dust, which was overwritten in the summer by an influx of low elevation sources transported upwards during higher vertical thermal mixing. Finally, we concluded that precipitation has a negligible direct effect on the overall Mo content and isotopic composition of inner continental European streams and rivers relative to other sources, such as bedrock weathering. Future time-series studies may augment these conclusions to show possible heterogeneity of precipitation as well as the addition of sample sites closer to marine sources, where a larger flux of isotopically heavy marine aerosols to streams might be expected.