Transport of road salt contamination in karst aquifers and soils over multiple timescales.

Road deicing has caused widespread environmental Na+ and Cl- release for decades, yet the transport and retention of these contaminants in karst aquifers and soils are poorly understood. We examined the transport dynamics of Na+ and Cl- from road salt in shallow groundwater during flooding and over seasonal timescales by intensively monitoring an urban and a rural karst spring over approximately 2 years. Furthermore, we used a 20-year dataset for the rural spring to determine how salt retention affected long-term geochemical trends in the shallow groundwater. Salt transport was governed by hydrologic pathways through karst aquifers: during winter and early spring floods, flow through preferential pathways rapidly transported salty meltwater or stormwater over hours to days, while the remaining salt-contaminated water moved diffusely through the rock matrix on timescales of months to years. Flood hydrograph separations revealed that event water constituted 61.2% of stormflow on average at the urban spring, leading to more extreme variability in salt concentrations during flooding and throughout the year. This variability indicates that baseflow contributions to urban streams overlying karst aquifers with preferential flowpaths are likely less effective at buffering salt concentrations. In contrast, salt concentrations were less variable in the baseflow-dominated rural spring (28.7% event water). Furthermore, salt was episodically released from soils to shallow groundwater throughout the year during first flush events. A Cl- mass balance indicates that Cl- applied during previous winters persists within the springs' recharge basins for more than a year, raising baseline concentrations as road salt is introduced faster than it can be flushed from the basin. Inter-annual salt retention by soils or slow groundwater movement likely caused significant Cl- and specific conductivity (SpC) increases at the rural spring from 1996 to 2016. Accumulation of salt in shallow groundwater can elevate baseflow concentrations in surface waters, where it threatens aquatic organisms.