Earth and Atmospheric Sciences, Department of


Date of this Version



Published in Water Resources Research (2009) v. 45, 17 p. W00A18, doi:10.1029/2008WR006963. Copyright 2009, the American Geophysical Union. Used by permission.


Unsaturated zone salt reservoirs are potentially mobilized by increased groundwater recharge as semiarid lands are cultivated. This study explores the amounts of pore water sulfate and fluoride relative to chloride in unsaturated zone profiles, evaluates their sources, estimates mobilization due to past land use change, and assesses the impacts on groundwater quality. Inventories of water-extractable chloride, sulfate, and fluoride were determined from borehole samples of soils and sediments collected beneath natural ecosystems (N = 4), nonirrigated ("rain-fed") croplands (N = 18), and irrigated croplands (N = 6) in the southwestern United States and in the Murray Basin, Australia. Natural ecosystems contain generally large sulfate inventories (7,800-120,000 kg/ha) and lower fluoride inventories (630-3,900 kg/ha) relative to chloride inventories (6,600-41,000 kg/ha). Order-of-magnitude higher chloride concentrations in precipitation and generally longer accumulation times result in much larger chloride inventories in the Murray Basin than in the southwestern United States. Atmospheric deposition during the current dry interglacial climatic regime accounts for most of the measured sulfate in both U.S. and Australian regions. Fluoride inventories are greater than can be accounted for by atmospheric deposition in most cases, suggesting that fluoride may accumulate across glacial/interglacial climatic cycles. Chemical modeling indicates that fluorite controls fluoride mobility and suggests that water-extractable fluoride may include some fluoride from mineral dissolution. Increased groundwater drainage/recharge following land use change readily mobilized chloride. Sulfate displacement fronts matched or lagged chloride fronts by up to 4 m. In contrast, fluoride mobilization was minimal in all regions. Understanding linkages between salt inventories, increased recharge, and groundwater quality is important for quantifying impacts of anthropogenic activities on groundwater quality and is required for remediating salinity problems.