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 (7800-120,000 kg/ha) and lower fluoride inventories
(630-3900 kg/ha) relative to chloride inventories (6600-41,000 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.
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