Seasonal riverine barium isotopic variation in the middle Yellow River: Sources and fractionation

Barium (Ba) isotopes have been used to trace water mass mixing and export productivity in the oceans. However, the sources, isotopic signature and seasonal variation of dissolved Ba in large rivers remain poorly constrained. In order to improve our understanding of sources and fractionation of riverine Ba isotopes at the continental scale, weekly sampling of river water was carried out in the middle Yellow River over the full hydrological year of 2013. Dissolved Ba was mainly sourced from silicate dissolution, whose flux was correlated with physical erosion rate in this arid to semi-arid basin, largely covered by loess. More than half of the annual dissolved Ba flux was transported during the monsoon season (June to mid-September), in particular during a storm event period (accounting for 4% of the annual dissolved Ba flux in 4 days). The dissolved Ba isotopic composition (δ¹³⁸Ba_rw) ranged from +0.17‰ to +0.46‰, all higher than δ¹³⁸Ba of loess (0.00 ± 0.04‰). The seasonal variation in δ¹³⁸Ba_rw is best explained via an adsorption model of light Ba isotopes onto solids in the river, which is sensitive to erosion of loess, in particular during the storm event and the spring-time ice melting intervals, with a potential role of barite precipitation in groundwater during the dry seasons. With one to three orders of magnitude higher particulate matter fluxes during the monsoon seasons in rivers such as the Yellow River, desorption of Ba could result an unaccounted strong variation of Ba concentration and isotopic composition in coastal environments, which further study requires.