Improved Darcian streambed measurements to quantify flux and mass discharge of volatile organic compounds from a contaminated aquifer to an urban stream

Abstract

Quantifying VOC transport from contaminated groundwater to streams is challenging and important for understanding off-site migration of VOCs, cross-media contamination (groundwater to surface water and eventually air), and potential impacts on downstream ecosystems and human populations. A streambed point sampling approach was used to quantify fluxes of water and 14 VOCs from groundwater to an urban stream in North Carolina, USA, during summer (June 2015) and winter (January 2016). The approach is unique in coupling measurements of vertical hydraulic conductivity, vertical hydraulic head gradient, and groundwater VOC concentration at each individual sampling point, reducing or eliminating some potential concerns with other Darcian methods for quantifying VOC inputs to streams. Most results were consistent with discharge of two main VOC plumes on opposite sides of the stream. Plume 1 from the west side was dominated by cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) at mean concentrations of 19 and 11 μg L^-1, respectively. Plume 2 from the east side was dominated by benzene (mean concentration 56 μg L^-1). Plume 2 was not previously known, and the improved sampling approach allowed VOC discharge from both plumes to be quantified simultaneously. For 13 of the 14 detected VOCs, the mean VOC flux from groundwater to the stream (f_VOC) was higher in January 2016 than in June 2015, mainly because groundwater flux was higher in January. The only exception was cDCE, the most abundant VOC in Plume 1, which had mean f_VOC values of 9.8 and 9.5 mg m^-2 d^-1 in June 2015 and January 2016, respectively. Benzene was the most abundant VOC in Plume 2 and had mean f_VOC values of 11 and 37 mg m^-2 d^-1 in June 2015 and January 2016, respectively. High groundwater flux drove almost all the occurrences of high VOC flux. For a given VOC, the flow-weighted mean concentration (with each VOC concentration weighted by the upward groundwater flux at the VOC sampling point) was generally larger than the unweighted mean concentration. Thus, flow-weighting of concentrations gave a more accurate indication of the average VOC concentration in net groundwater discharge to the stream. An estimate of total VOC mass discharge from groundwater to the study reach of the stream, 3.6 kg of VOC per year, was based on the f_VOC results and streambed area in the reach. The bulk of this discharge was due to benzene, cDCE, and VC, with individual mass discharges of 2.1, 0.83, and 0.40 kg yr^-1, respectively. Estimates of maximum potential VOC degradation in the streambed suggest that the 3.6 kg yr^-1 estimate of mass discharge was not sensitive to potential degradation of VOCs in the streambed sediments above the groundwater sampling depth.

Keywords: Contaminant flux; Groundwater; Stream; VOC.