Carbonate weathering, phosphate fertilizer, and hydrologic controls on dissolved uranium in rivers in the US Corn Belt: Disentangling seasonal geogenic- and fertilizer-derived sources.

Soil and bedrock weathering and phosphate (P) fertilizers may both contribute to the uranium (U) load of rivers in agricultural regions, but controls over their relative influence are not well known. This study investigates the U sources to rivers in Ohio, United States, part of the Eastern Corn Belt in the Mississippi River watershed. We present a regional picture of seasonal U sources to rivers based on four analyses: 1) a spatial analysis of legacy soil and water data, 2) new measurements of U and carbonate weathering products from rivers at 50 locations across the state collected seasonally over two years, 3) a weekly time series with additional 234U/238U (n = 5) and 87Sr/86Sr (n = 5) measurements from an agricultural river, and 4) a mass-balance approach to U addition to the landscape based on reported P fertilizer use. Uranium concentrations in surface waters collected statewide ranged 0.1-21 nM (n = 132), with significantly higher concentrations in the glaciated agricultural portion of the state (mean = 7.3 nM; n = 105) than the non-glaciated portion (mean = 2.0 nM; n = 24). Concentrations in the glaciated region were highest during the spring and summer and decreased during baseflow. In the time-series, concentrations were ~7 nM during baseflow and ~14 nM during intermediate seasonal discharge conditions, indicating a second more surficial endmember source of U in addition to bedrock weathering that is well correlated with other carbonate weathering products. Systematic increases in 87Sr/86Sr and decreases in 234U/238U with increasing discharge confirm a changing source of carbonate and U weathering and a third surficial endmember during high discharge events. Our mass balance approach and geochemical analysis suggest that elevated U concentrations are the result of carbonate weathering deep in the soil column during elevated seasonal flow. Further work on U dynamics in agricultural rivers is required to understand mechanism controlling seasonal changes in U concentrations and 234U/238U in downstream rivers and U flux.