Tracking NSZD mass removal rates over decades: Site-wide and local scale assessment of mass removal at a legacy petroleum site.

Long-term estimates of natural source zone depletion (NSZD) rates for petroleum LNAPL (light non-aqueous phase liquid) sites are not available. One-off measurements are often thought valid over the lifetime of LNAPL sites. In the context of site-wide LNAPL mass estimates, we report site-specific gasoline and diesel NSZD rates spanning 21-26 years. Using depth profiles of soil gases (oxygen, carbon dioxide, methane, volatiles) above LNAPL, NSZD rates were estimated in 1994, 2006 and 2020 for diesel and 1999, 2009 and 2020 for gasoline. Each date also had soil-core mass estimates, which together with NSZD rates allow estimation of the longevity for LNAPL presence. Site-wide coring (in 1992, 2002, 2007) estimated LNAPL mass reductions of 12,000 t. For diesel NSZD, the ratio of NSZD rates for 2006 (16,000-49,000 L/ha/y) to those in 2020 (2600-14,000 L/ha/y) was ~3-6. By 2020, the 1994 diesel NSZD rates would have predicted the entire removal of measured mass (16-42 kg/m2). For gasoline, NSZD rates in 1999 were extremely high (50,000-270,000 L/ha/y) but 9-27 times lower (5800-10,000 L/ha/y) a decade later. The gasoline NSZD rates in 1999 predicted near complete mass removal in 2-12 years, but 10-11 kg/m2 was measured 10 and 21 years later which is 26% of the initial mass in 1999. The outcomes substantiate the need to understand NSZD rate changes over the lifetime of LNAPL-impacted sites.

A practical tool for estimating subsurface LNAPL distributions and transmissivity using current and historical fluid levels in groundwater wells: Effects of entrapped and residual LNAPL.

A model is presented to account for elevation-dependent residual and entrapped LNAPL above and below, respectively, the water-saturated zone when predicting subsurface LNAPL specific volume (fluid volume per unit area) and transmissivity from current and historic fluid levels in wells. Physically-based free, residual, and entrapped LNAPL saturation distributions and LNAPL relative permeabilities are integrated over a vertical slice of the subsurface to yield the LNAPL specific volumes and transmissivity. The model accounts for effects of fluctuating water tables. Hypothetical predictions are given for different porous media (loamy sand and clay loam), fluid levels in wells, and historic water-table fluctuations. It is shown the elevation range from the LNAPL-water interface in a well to the upper elevation where the free LNAPL saturation approaches zero is the same for a given LNAPL thickness in a well regardless of porous media type. Further, the LNAPL transmissivity is largely dependent on current fluid levels in wells and not historic levels. Results from the model can aid developing successful LNAPL remediation strategies and improving the design and operation of remedial activities. Results of the model also can aid in accessing the LNAPL recovery technology endpoint, based on the predicted transmissivity.

Effect of compositional heterogeneity on dissolution of non-ideal LNAPL mixtures.

The extent of dissolution of petroleum hydrocarbon fuels into groundwater depends greatly on fuel composition. Petroleum fuels can consist of thousands of compounds creating different interactions within the non-aqueous phase liquid (NAPL), thereby affecting the relative dissolution of the components and hence a groundwater plume's composition over long periods. Laboratory experiments were conducted to study the variability in the effective solubilities and activity coefficients for common constituents of gasoline fuels (benzene, toluene, p-xylene and 1,2,4-trimethylbenzene) (BTX) in matrices with an extreme range of molar volumes and chemical affinities. Four synthetic mixtures were investigated comprising BTX with the bulk of the NAPL mixtures made up of either, ethylbenzene (an aromatic like BTX with similar molar volume); 1,3,5-trimethylbenzene (an aromatic with a greater molar volume); n-hexane (an aliphatic with a low molar volume); and n-decane (an aliphatic with a high molar volume). Equilibrium solubility values for the constituents were under-predicted by Raoult's law by up to 30% (higher experimental concentrations) for the mixture with n-hexane as a filler and over-predicted by up to 12% (lower experimental concentrations) for the aromatic mixtures with ethylbenzene and 1,3,5-trimethylbenzene as fillers. Application of PP-LFER (poly-parameter linear free energy relationship) model for non-ideal mixtures also resulted in poor correlation between experimentally measured and predicted concentrations, indicating that differences in chemical affinities can be the major cause of deviation from ideal behavior. Synthetic mixtures were compared with the dissolution behavior of fresh and naturally weathered unleaded gasoline. The presence of lighter aliphatic components in the gasoline had a profound effect on estimating effective solubility due to chemical affinity differences (estimated at 0.0055 per percentage increase in the molar proportion of aliphatic) as well as reduced molar volumes (estimated at -0.0091 in the activity coefficient per unit increase in molar volume, mL/mol). Previously measured changes in activity coefficients due to natural weathering of 0.25 compares well to 0.27 calculated here based on changes in the chemical affinity and molar volumes. The study suggests that the initial estimation of the composition of a fuel is crucial in evaluating dissolution processes due to ideal and non-ideal dissolution, and in predicting long term dissolution trends and the longevity of NAPL petroleum plume risks.

Evaluation of a permeable reactive barrier to capture and degrade hydrocarbon contaminants.

A permeable reactive barrier (PRB) was installed during 2005/2006 to intercept, capture and degrade a fuel spill at the Main Power House, Casey Station, Antarctica. Here, evaluation of the performance of the PRB is conducted via interpretation of total petroleum hydrocarbon (TPH) concentrations, degradation indices and most probable number (MPN) counts of total heterotroph and fuel degrading microbial populations. Results indicate that locations which contained the lowest TPH concentrations also exhibited the highest levels of degradation and numbers of fuel degrading microbes, based on the degradation indices and MPN methods selected. This provides insights to the most appropriate reactive materials for use in PRB's in cold and nutrient-limited environments.

Hydraulic performance of a permeable reactive barrier at Casey Station, Antarctica.

A permeable bio-reactive barrier (PRB) was installed at Casey Station, Antarctica in 2005/06 to intercept, capture and degrade petroleum hydrocarbons from a decade old fuel spill. A funnel and gate configuration was selected and implemented. The reactive gate was split into five separate cells to enable the testing of five different treatment combinations. Although different treatment materials were used in each cell, each treatment combination contained the following reactive zones: a zone for the controlled release of nutrients to enhance degradation, a zone for hydrocarbon capture and enhanced degradation, and a zone to capture excess nutrients. The materials selected for each of these zones had other requirements, these included; not having any adverse impact on the environment, being permeable enough to capture the entire catchment flow, and having sufficient residence time to fully capture migrating hydrocarbons. Over a five year period the performance of the PRB was extensively monitored and evaluated for nutrient concentration, fuel retention and permeability. At the end of the five year test period the material located within the reactive gate was excavated, total petroleum hydrocarbon concentrations present on the material determined and particle size analysis conducted. This work found that although maintaining media reactivity is obviously important, the most critical aspect of PRB performance is preserving the permeability of the barrier itself, in this case by maintaining appropriate particle size distribution. This is particularly important when PRBs are installed in regions that are subject to freeze thaw processes that may result in particle disintegration over time.

Effectiveness of in situ air sparging for removing NAPL gasoline from a sandy aquifer near Perth, Western Australia.

In situ air sparging has the potential to augment the removal of nonaqueous phase liquid (NAPL) contaminants in soil vapour extraction (SVE) systems when the NAPL is present in the capillary fringe or below the water table. NAPL removal can also be enhanced from above the water table by improving air access. Results are presented from a pilot-scale field trial aimed at evaluating the performance of such a remediation strategy where in situ air sparging was used in conjunction with a soil vapour extraction system to remove weathered gasoline NAPL from an unconfined sandy aquifer. A simple analysis that partitions extracted soil vapour between air injected through the sparge well and air drawn from the atmosphere across the soil surface, together with petroleum hydrocarbon concentrations in the extracted soil vapour, was used to interpret the effectiveness of air sparging. The composition and mass of the NAPL in the aquifer were also monitored along with observations on the distribution of air in the aquifer. Results showed that sparged air constituted 42% of the extracted soil vapour but contributed the majority of the petroleum hydrocarbons removed. For the first 5 days of sparging, hydrocarbon concentrations in the sparged air were in equilibrium with the NAPL in the aquifer leading to total petroleum hydrocarbon concentrations in the combined system being three to four times greater than for soil vapour extraction alone. Petroleum hydrocarbon concentrations in the extracted soil vapour decreased over time as a result of the depletion of the more volatile constituents from the NAPL, possible development of mass transfer limitations and increased fraction of clean air from depleted zones. Overall, 65% of the 673 kg of petroleum hydrocarbons extracted in soil vapour over a period of 30 days was carried in sparged air from the single sparge well. Percentages of the mass carried in the sparged air were even higher (median 70%) for individual aromatic hydrocarbons. Inclusion of air sparging increased the mass extracted by a factor of 1.9 (more for individual petroleum hydrocarbons) over and above that for soil vapour extraction alone for the 30 days of sparging. Air sparging was also effective in removing residual NAPL from below the water table. The mass of petroleum hydrocarbons removed from the site was not reflected in changes to the mass of NAPL in the aquifer. This result is apparently due to lateral inflow of NAPL to the site although evidence of a depleted source of volatilised hydrocarbons suggests the possible development of mass transfer limitations.