Accurate characterization of contaminant mass in zones of low hydraulic conductivity (low k) is essential for site management because this difficult-to-treat mass can be a long-term secondary source. This study developed a protocol for the membrane interface probe (MIP) as a low-cost, rapid data-acquisition tool for qualitatively evaluating the location and relative distribution of mass in low-k zones. MIP operating parameters were varied systematically at high and low concentration locations at a contaminated site to evaluate the impact of the parameters on data quality relative to a detailed adjacent profile of soil concentrations. Evaluation of the relative location of maximum concentrations and the shape of the MIP vs. soil profiles led to a standard operating procedure (SOP) for the MIP to delineate contamination in low-k zones. This includes recommendations for: (1) preferred detector (ECD for low concentration zones, PID or ECD for higher concentration zones); (2) combining downlogged and uplogged data to reduce carryover; and (3) higher carrier gas flow rate in high concentration zones. Linear regression indicated scatter in all MIP-to-soil comparisons, including R(2) values using the SOP of 0.32 in the low concentration boring and 0.49 in the high concentration boring. In contrast, a control dataset with soil-to-soil correlations from borings 1-m apart exhibited an R(2) of ≥ 0.88, highlighting the uncertainty in predicting soil concentrations using MIP data. This study demonstrates that the MIP provides lower-precision contaminant distribution and heterogeneity data compared to more intensive high-resolution characterization methods. This is consistent with its use as a complementary screening tool.

Petroleum liquids, referred to as light non-aqueous phase liquids (LNAPLs), are commonly found beneath petroleum facilities. Concerns with LNAPLs include migration into clean soils, migration beyond property boundaries, and discharges to surface water. Single-well tracer dilution techniques were used to measure LNAPL fluxes through 50 wells at 7 field sites. A hydrophobic tracer was mixed into LNAPL in a well. Intensities of fluorescence associated with the tracer were measured over time using a spectrometer and a fiber optic cable. LNAPL fluxes were estimated using observed changes in the tracer concentrations over time. Measured LNAPL fluxes range from 0.006 to 2.6 m/year with a mean and median of 0.15 and 0.064 m/year, respectively. Measured LNAPL fluxes are two to four orders of magnitude smaller than a common groundwater flux of 30 m/year. Relationships between LNAPL fluxes and possible governing parameters were evaluated. Observed LNAPL fluxes are largely independent of LNAPL thickness in wells. Natural losses of LNAPL through dissolution, evaporation, and subsequent biodegradation, were estimated using a simple mass balance, measured LNAPL fluxes in wells, and an assumed stable LNAPL extent. The mean and median of the calculated loss rates were found to be 24.0 and 5.0 m3/ha/year, respectively. Mean and median losses are similar to values reported by others. Coupling observed LNAPL fluxes to observed rates of natural LNAPL depletion suggests that natural losses of LNAPL may be an important parameter controlling the overall extent of LNAPL bodies.

This article explores the hypothesis that natural losses of light nonaqueous phase liquids (LNAPLs) through dissolution and evaporation can control the overall extent of LNAPL bodies and LNAPL fluxes observed within LNAPL bodies. First, a proof-of-concept sand tank experiment is presented. An LNAPL (methyl tert-butyl ether) was injected into a sand tank at five constant injection rates that were increased stepwise. Initially, for each injection rate the LNAPL bodies expanded quickly. With time the rate of expansion of the LNAPL bodies slowed and at extended times the extent of the LNAPL became constant. Attainment of a stable LNAPL extent is attributed to rates of LNAPL addition being equal to rates of LNAPL losses through dissolution and evaporation. Secondly, analytical solutions are developed to extrapolate the processes observed in the proof-of-concept experiment to dimensions and time frames that are consistent with field-scale LNAPL bodies. Three LNAPL body geometries that are representative of common field conditions are considered including one-dimensional, circular, and oblong shapes. Using idealized conditions, the solutions describe volumetric LNAPL fluxes as a function of position in LNAPL bodies and the overall extent of LNAPL bodies as a function of time. Results from both the proof-of-concept experiment and the mathematical developments illustrate that natural losses of LNAPL can play an important role in governing LNAPL fluxes within LNAPL bodies and the overall extent of LNAPL bodies.

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