Residual Nonaqueous Phase Liquids Saturation Research Articles

Dynamics of microbial populations and diversity in NAPL contaminated peat soil under varying water table conditions

Despite the risks that hydrocarbon contamination from pipeline leaks or train derailments impose on the health of peatlands in hydrocarbon production areas and transportation corridors, assessing the effect of such contaminations on the health and sustainability of peatlands has received little attention. This study investigates the impacts of hydrocarbons on peat microbial communities. Column experiments were conducted on non-aqueous phase liquid (NAPL) contaminated undisturbed peat core (0–35 cm) under static and fluctuating water table conditions. Water table fluctuations reduced residual NAPL saturation from 8.1-11.3% to 7.7–9.5%. Biodegradation of n-C8 and n-C12 along with oxidation of CH4 together produced high CO2 concentrations in the headspace. Clear patterns in dynamics in the microbial community structure were observed, with a more pronounced population growth. However, a significant loss of microbial richness was observed in contaminated columns. The result indicates that the phylum Proteobacteria benefited most from NAPL; however, their families differed between static and fluctuating water table conditions. This study established strong evidence that peat microbes and water table fluctuation can be an excellent tool for hydrocarbon removal and its control in peatlands.

Impact of mineralogy and wettability on pore-scale displacement of NAPLs in heterogeneous porous media

Subsurface formations often contain multiple minerals with different wettability characteristics upon contact with nonaqueous-phase liquids (NAPLs). Constitutive relationships between microstructure heterogeneity and NAPL fate and transport in these formations are difficult to predict. Several studies have used pore-scale network models with faithful representations of rock pore space topology to predict macroscopic descriptors of two-phase flow, however wettability is usually considered as a spatially random variable. This study attempts to overcome this limitation by considering more realistic representations of rock mineralogy and wettability in these models. This is especially important for heterogeneous rocks where properties vary at the pore-scale. The work was carried out in two phases. First, pore-fluid occupancy maps during waterflooding were obtained by X-ray microtomography to elucidate the impact of pore wall mineralogy and wettability on water preferential flow paths and NAPL trapping within a heterogeneous aquifer sandstone (Arkose). Then, microtomography images of the rock were used to generate a hybrid pore network model (PNM) that incorporated both pore space topology and pore wall mineralogy. In-situ contact angles (CA) measured on the surface of different minerals were assigned to the network on a pore-by-pore basis to describe the exact wettability distribution of the rock (Pore-by-pore model). The equivalent network was used as input in a quasi-static flow model to simulate waterflooding, and the predictions of residual NAPL saturation and relative permeabilities were compared against their experimental counterparts. To examine the sensitivity of the model to the underlying fluid-solid interactions, we also used traditional methods of wettability characterization in the input data and assigned them randomly to the PNM. Wettability in this case was assessed from macroscale CA distribution of oil droplets on the surface of unpolished Arkose substrates released by spontaneous imbibition of water (Arkose model) and from pendant drop measurements on polished quartz (Quartz model). Our results revealed that the Pore-by-pore model predicted waterflooding with the highest accuracy among all three cases. The Arkose model slightly overestimated NAPL removal whereas the Quartz model failed to predict the experiments. More in-depth analysis of the Pore-by-pore and Arkose models showed that macroscopic transport quantities are less dependent to microstructure heterogeneity if minerals are distributed uniformly across the rock. The predictions herein indicate the importance of incorporating mineralogy and wettability maps to improve the prediction capabilities of PNMs especially in systems with high mineral heterogeneity, where minerals are nonuniformly distributed, or selective fluid-mineral interactions are targeted.

Experimentally based pore network modeling of NAPL dissolution process in heterogeneous porous media

Practical designs of non-aqueous phase liquids (NAPLs) remediation strategies require reliable modeling of interphase mass transfer to predict the retraction of NAPL during processes such as dissolution. In this work, the dissolution process of NAPL during two-phase flow in heterogeneous porous media is studied using pore-network modeling and micromodel experiments. A new physical-experimental approach is proposed to enhance the prediction of the dissolution process during modeling of interphase mass transfer. In this regard, the normalized average resident solute concentration is evaluated for describing the dissolution process at pore-level. To incorporate the effect of medium heterogeneities, a new experimental factor is considered for enhancing corner diffusion modeling. In addition, capillary desaturation curves (CDCs) are predicted during hydraulic flow modeling to estimate initial residual NAPL saturation. The developed network model can predict residual NAPL saturations and mass transfer rate coefficient for a NAPL-water system at different injection rates and fluid saturations. The evaluated mass transfer rate coefficients using the proposed physical-experimental approach show a significant improvement compared to either mechanistic or empirical methods. The proposed approach in this study can be attractive for possible applications in commercial simulators of contaminant transport in porous media.

Fate and transport of free-phase and dissolved-phase hydrocarbons in peat and peatlands: developing a conceptual model

Physical and chemical, and pore-scale to field-scale properties of peat soil affect the migration of non-aqueous phase liquids (NAPLs) and dissolved-phase solutes in contaminated peatlands in a way not anticipated based on the current understanding derived from their behavior in mineral soil systems. Peat pore surface wettability, which is determined by pore surface chemistry, has strong hysteresis and shows hydrophilic and hydrophobic behaviors during water drainage from and water imbibition into pore spaces. This leads to high residual NAPL saturation in pore spaces. Systematic reduction of pore radius size with depth associated with greater peat decomposition in a typical peat profile leads to an increase in NAPL-entry capillary pressure and a reduction in peat permeability with increasing depth. The former leads to stronger capillarity in deeper peat horizons, causing resistance to NAPL percolation compared to that in shallow ones; along with decreased permeability with depth, this results in higher NAPL mobility in shallower peat. The cumulative effect is preferential horizontal migration of NAPL in shallow less decomposed peat horizons. Occupation of peat macro-pores by NAPL dramatically decreases the effective water permeability and leads to lower rates of water infiltration and groundwater discharge in the contaminated area. With respect to dissolved-phase hydrocarbons, the dual porosity structure of peat soil, which exhibits larger pores and higher effective porosity near the surface, also favours preferential transport in the surface peat layer, and leads to increasing solute retardation with depth. In addition, adsorption of hydrocarbon solutes onto natural dissolved organic carbon present in peat pore water influences the effective adsorption of hydrocarbon solutes onto peat by reducing the apparent adsorption partitioning coefficient. The concepts and evidence presented in this manuscript suggest both free-phase and dissolved-phase hydrocarbon have restricted mobility in peatlands. On this basis, in large peatlands where ecological function is not notably impacted, a case can be made for allowing natural processes to degrade the hydrocarbon, rather than the common response of digging up and disposing of contaminated soils, which destroys the ecosystem function.

Measurement of NAPL-water interfacial areas and mass transfer rates in two-dimensional flow cell.

The nonaqueous-phase liquid (NAPL)-water interfacial area and the mass transfer rate across the NAPL and water interface are often key factors in in situ groundwater pollution treatment. In this study, the NAPL-water interfacial area and residual NAPL saturation were measured using interfacial and partitioning tracer tests in a two-dimensional flow cell. The results were compared with previous column and field experiment results. In addition, the mass transfer rates at various NAPL-water interfacial areas were investigated. Fe2+-activated persulfate was used for in situ chemical oxidation remediation to remove NAPL gradually. The results showed that the reduction of NAPL-water interfacial areas as well as NAPL saturation by chemical oxidation caused a linear decrease in the interphase mass transfer rates (R2 = 0.97), revealing the relationship between mass transfer rates and interfacial areas in a two-dimensional system. The NAPL oxidation rates decreased with the reduction of interfacial areas, owing to the control of NAPL mass transfer into the aqueous phase.

Surface and Interfacial Properties of Nonaqueous‐Phase Liquid Mixtures Released to the Subsurface at the Hanford Site

Surface and interfacial tensions are key parameters affecting nonaqueous‐phase liquid (NAPL) movement and redistribution in the subsurface after spill events. In this study, the impact of major additive components on surface and interfacial tensions for organic mixtures and wastewater was investigated. Organic mixture and wastewater compositions were based on CCl4 mixtures released at the U.S. Department of Energy's Hanford site, where CCl4 was discharged simultaneously with dibutyl butyl phosphonate, tributyl phosphate, dibutyl phosphate, and a machining lard oil. A considerable amount of wastewater consisting primarily of nitrates and metal salts was also discharged. The measured tension values revealed that the addition of these additive components caused a significant lowering of the interfacial tension with water or wastewater and the surface tension of the wastewater phase in equilibrium with the organic mixtures, compared with pure CCl4, but had minimal effect on the surface tension of the NAPL itself. These results led to large differences in spreading coefficients for several mixtures, where the additives caused both a higher (more spreading) initial spreading coefficient and a lower (less spreading) equilibrium spreading coefficient. This indicates that if these mixtures migrate into uncontaminated areas, they will tend to spread quickly but will form a higher residual NAPL saturation after equilibrium than pure CCl4 With time, CCl4 probably volatilizes more rapidly than other components in the originally disposed mixtures and the lard oil and phosphates would become more concentrated in the remaining NAPL, resulting in a lower interfacial tension for the mixture. These results show that the behavior of organic chemical mixtures should be accounted for in flow and transport models.

Use of optimization to develop a correlation model for predicting residual NAPL saturation

Predicting the residual saturation of a trapped non-aqueous phase liquid (NAPL) contaminant is critical to estimate the region of contamination, the design of remediation strategies, and risk assessment. Models were developed to predict residual NAPL saturation utilizing optimization and non-linear functions, consequently allowing for a broader mathematical approach to model development. The input parameters evaluated represent soil and fluid properties; the uniformity coefficient (C u), the coefficient of gradation, the capillary number (Nc), the bond number (Nc), and the total trapping number (Nt). Overall, the model that performed the best was based on a second-order equation with the independent variables C u and Nt1 using the sum of the squares of the errors. The non-linear error function based on a derivative of Marquardt's percent standard deviation performed the best for three other cases.

Characterization of pore scale NAPL morphology in homogeneous sands as a function of grain size and NAPL dissolution

In this study, we investigate pore scale morphology of nonaqueous phase liquids (NAPLs) trapped in different pore sizes using tracer techniques. Specific interfacial area and saturation of NAPL trapped in homogeneous sands were measured using the interfacial and partitioning tracer techniques. The observed NAPL–water interfacial areas increased in a log-linear fashion with decreasing sand grain size, but showed no clear trend with residual NAPL saturation formed in the various grain sizes. The measured values were used to calculate the NAPL morphology index, which characterizes the spatial NAPL distribution within the pore space. The NAPL morphology indices, increased exponentially with decreasing grain size, indicating that the NAPL becomes smaller, but more blobs. For a fixed grain size, the specific interfacial area and saturation of the NAPL were measured following changes caused by dissolution using alcohol. The observed interfacial areas showed a decrease linearly as a function of the NAPL saturation.

Simple screening models of NAPL dissolution in the subsurface

Three simple screening models of nonaqueous phase liquid (NAPL) dissolution in the subsurface are proposed based on the NAPL mass conservation and the assumption of proportionality between the residual NAPL source zone concentration and the remaining residual NAPL mass. The purpose of the proposed models is to predict the solute concentration in the zone of the residual NAPL as a result of dissolution. The predicted source zone concentration decrease is used to simulate and account for the decrease of dissolution rate with time. The proposed simple NAPL dissolution models enable the pseudo-equilibrium formulation to be used and therefore the numerical simulations for field application problems can be simplified compared to the non-equilibrium counterpart. With proper choice of empirical parameters, the proposed simple screening models can work as well as more complex dissolution rate correlation models, such as that of Imhoff et al. [Water Resour. Res. 30 (1994) 307–320]. It is found that the proposed models are very good for quantifying non-equilibrium dissolution, which is characterized by tailing of breakthrough curves. The models are especially useful for situations of small residual NAPL saturation, which are typical for many field applications.

Magnetic resonance imaging of nonaqueous phase liquid during soil vapor extraction in heterogeneous porous media

Soil vapor extraction (SVE) is commonly used to remediate nonaqueous phase liquids (NAPLs) from the vadose zone. This paper aims to determine the effect of grain size heterogeneity on the removal of NAPL in porous media during SVE. Magnetic resonance imaging (MRI) was used to observe and quantify the amount and location of NAPL in flow-through columns filled with silica gel grains. MRI is unique because it is nondestructive, allowing three-dimensional images to be taken of the phases as a function of space and time. Columns were packed with silica gel in three ways: coarse grains (250–550 μm) only, fine grains (32–63 μm) only, and a core of fine grains surrounded by a shell of coarse grains. Columns saturated with water were drained under a constant suction head, contaminated with decane, and then drained to different decane saturations. Each column was then continuously purged with water-saturated nitrogen gas and images were taken intermittently. Results showed that at residual saturation, a sharp volatilization front moved through the columns filled with either coarse-grain or fine-grain silica gel. In the heterogeneous columns, the volatilization front in the core lagged just behind the shell because gas flow was greater through the shell and decane in the core diffused outward to the shell. When decane saturation in the core was above residual saturation, decane volatilization occurred near the inlet, the relative decane saturation throughout the core dropped uniformly, and decane in the core flowed in the liquid phase to the shell to replenish volatilized decane. These results indicate that NAPL trapped in low-permeability zones can flow to replenish areas where NAPL is lost due to SVE. However, when residual NAPL saturation is reached, NAPL flow no longer occurs and diffusion limits removal from low-permeability zones.

Flow behavior and residual saturation formation of liquid carbon tetrachloride in unsaturated heterogeneous porous media

The formation of residual, discontinuous nonaqueous phase liquids (NAPLs) in the vadose zone is a process that is not well understood. To obtain data that can be used to study the development of a residual NAPL saturation in the vadose zone and to test current corresponding models, detailed transient experiments were conducted in intermediate-scale columns and flow cell. The column experiments were conducted to determine residual carbon tetrachloride (CCl 4) saturations of two sands and to evaluate the effect of CCl 4 vapors on the water distribution. In the intermediate-scale flow cell experiment, a rectangular zone of the fine-grained sand was packed in an otherwise medium-grained matrix. A limited amount of CCl 4 was injected from a small source and allowed to redistribute until a pseudo steady state situation had developed. A dual-energy gamma radiation system was used to determine fluid saturations at numerous locations. The experiments clearly demonstrated the formation of residual CCl 4 saturations in both sands. Simulations with an established multifluid flow simulator show the shortcomings of current relative permeability–saturation–capillary pressure ( k– S– P) models. The results indicate that nonspreading behavior of NAPLs should be implemented in simulators to account for the formation of residual saturations.

Carbon Tetrachloride Flow Behavior in Unsaturated Hanford Caliche Material: An Investigation of Residual Nonaqueous Phase Liquids

At many contaminated sites, nonaqueous phase liquids (NAPLs) persist in the vadose zone for long periods of time. This occurs because the permeability of the NAPL becomes negligible at some saturation and downward movement ceases, resulting in residual NAPL. To obtain data that can be used to study the development of a residual NAPL saturation and to test corresponding models, a detailed transient experiment was conducted in a 170 cm long by 90 cm high by 5.5 cm wide flow cell. Fluid saturation measurements were obtained with a dual-energy γ radiation system. The experimental conditions reflected those at the Hanford Site in Washington State, where an estimated 363 to 580 m 3 of carbon tetrachloride (CCl 4 ) was disposed to the subsurface. A key subsurface feature at the Hanford Site is a sloped Plio-Pleistocene caliche layer, which was reproduced in the experiment as a sloped lens in a medium-grained, uniform, sand matrix. The caliche contains considerable amounts of CaCO 3 and may have fluid wettability properties other than strongly water wet. A total of 800 mL of CCl 4 was injected into the experimental domain at a rate of 0.5 mL min −1 from a small source area located at the surface. After apparent static conditions were obtained with respect to CCl 4 redistribution, saturation measurements indicated that all of the dense nonaqueous phase liquids (DNAPL) that had initially moved into the caliche remained in this layer. Water was subsequently applied to the surface at a constant rate over the full length of the caliche layer to study CCl 4 displacement as a result of changing water saturations. Water saturation in the caliche layer rose to as high as 0.91 during water infiltration. Results show that 25% of the DNAPL present in the caliche migrated from this layer as a consequence of water infiltration, while 75% remained in the caliche layer. The experimental results could not be reproduced with numerical multifluid flow simulations based on common constitutive theory. This indicates that improvements in constitutive theory may be needed to accurately model air−DNAPL−water flow behavior.

Carbon Tetrachloride Flow Behavior in Unsaturated Hanford Caliche Material: An Investigation of Residual Nonaqueous Phase Liquids

At many contaminated sites, nonaqueous phase liquids (NAPLs) persist in the vadose zone for long periods of time. This occurs because the permeability of the NAPL becomes negligible at some saturation and downward movement ceases, resulting in residual NAPL. To obtain data that can be used to study the development of a residual NAPL saturation and to test corresponding models, a detailed transient experiment was conducted in a 170 cm long by 90 cm high by 5.5 cm wide flow cell. Fluid saturation measurements were obtained with a dual‐energy γ radiation system. The experimental conditions reflected those at the Hanford Site in Washington State, where an estimated 363 to 580 m3 of carbon tetrachloride (CCl4) was disposed to the subsurface. A key subsurface feature at the Hanford Site is a sloped Plio‐Pleistocene caliche layer, which was reproduced in the experiment as a sloped lens in a medium‐grained, uniform, sand matrix. The caliche contains considerable amounts of CaCO3 and may have fluid wettability properties other than strongly water wet. A total of 800 mL of CCl4 was injected into the experimental domain at a rate of 0.5 mL min−1 from a small source area located at the surface. After apparent static conditions were obtained with respect to CCl4 redistribution, saturation measurements indicated that all of the dense nonaqueous phase liquids (DNAPL) that had initially moved into the caliche remained in this layer. Water was subsequently applied to the surface at a constant rate over the full length of the caliche layer to study CCl4 displacement as a result of changing water saturations. Water saturation in the caliche layer rose to as high as 0.91 during water infiltration. Results show that 25% of the DNAPL present in the caliche migrated from this layer as a consequence of water infiltration, while 75% remained in the caliche layer. The experimental results could not be reproduced with numerical multifluid flow simulations based on common constitutive theory. This indicates that improvements in constitutive theory may be needed to accurately model air−DNAPL−water flow behavior.

A proposed model to include a residual NAPL saturation in a hysteretic capillary pressure–saturation relationship

A residual non-aqueous phase liquid (NAPL) present in the vadose zone can act as a contaminant source for many years as the compounds of concern partition to infiltrating groundwater and air contained in the soil voids. Current pressure–saturation–relative permeability relationships do not include a residual NAPL saturation term in their formulation. This paper presents the results of series of two- and three-phase pressure cell experiments conducted to evaluate the residual NAPL saturation and its impact on the pressure–saturation relationship. A model was proposed to incorporate a residual NAPL saturation term into an existing hysteretic three-phase parametric model developed by Parker and Lenhard [Water Resour. Res. 23(12) (1987) 2187], Lenhard and Parker [Water Resour. Res. 23(12) (1987) 2197] and Lenhard [J. Contam. Hydrol. 9 (1992) 243]. The experimental results indicated that the magnitude of the residual NAPL saturation was a function of the maximum total liquid saturation reached and the water saturation. The proposed model to incorporate a residual NAPL saturation term is similar in form to the entrapment model proposed by Parker and Lenhard, which was based on an expression presented by Land [Soc. Pet. Eng. J. (June 1968) 149].

Correlation model to predict residual immiscible organic contaminants in sandy soils

Researchers in both environmental and petroleum engineering have conducted studies in one-dimensional columns to quantify the amount of residual nonaqueous phase liquids (NAPL) trapped in the porous media as a function of capillary, viscous and buoyancy forces. From these previous studies, it is proven that significant amounts of the original NAPL spill remain as a trapped residual. The objective of this research was to extend this body of work and to develop a correlation model that could predict residual NAPL saturation as a function of common soil characteristics and fluid properties. These properties include parameters derived from sieve analysis, namely, the uniformity coefficient ( C u), the coefficient of gradation ( C c), as well as fluid properties (interfacial tension, viscosity and density). Over 100 column experiments were conducted across a range of nine different soil gradations. The data produced by these tests, along with measured soil and fluid properties, were used to generate correlation models to predict residual NAPL saturation ( S rn). The first correlation model predicts S rn for the region where residual NAPL saturation is independent of the capillary number, and dependent on C u, C c and the Bond number. The second correlation model predicts S rn for the region where residual NAPL saturation is dependent on capillary number, as well as C u, C c and the Bond number. The third correlation model predicts S rn over the entire region as a function of C u, C c and the total trapping number. The correlation models have a R 2 value of 0.972, 0.934 and 0.825, respectively. Hence, the models may potentially be integrated into site characterization approaches.

Optimal estimation of residual non–aqueous phase liquid saturations using partitioning tracer concentration data

Stochastic methods are applied to the analysis of partitioning and nonpartitioning tracer breakthrough data to obtain optimal estimates of the spatial distribution of subsurface residual non–aqueous phase liquid (NAPL). Uncertainty in the transport of the partitioning tracer is assumed to result from small‐scale spatial variations in a steady state velocity field as well as spatial variations in NAPL saturation. In contrast, uncertainty in the transport of the nonpartitioning tracer is assumed to be due solely to the velocity variations. Partial differential equations for the covariances and cross cpvariances between the partitioning tracer temporal moments, nonpartitioning tracer temporal moments, residual NAPL saturation, pore water velocity, and hydraulic conductivity fields are derived assuming steady flow in an infinite domain [Gelhar, 1993] and the advection‐dispersion equation for temporal moment transport [Harvey and Gorelick, 1995]. These equations are solved using a finite difference technique. The resulting covariance matrices are incorporated into a conditioning algorithm which provides optimal estimates of the tracer temporal moments, residual NAPL saturation, pore water velocity, and hydraulic conductivity fields given available measurements of any of these random fields. The algorithm was tested on a synthetically generated data set, patterned after the partitioning tracer test conducted at Hill AFB by Annable et al. [1997]. Results show that the algorithm successfully estimates major features of the random NAPL distribution. The performance of the algorithm, as indicated by analysis of the “true” estimation errors, is consistent with the theoretical estimation errors predicted by the conditioning algorithm.

Dissolution Fingering During the Solubilization of Nonaqueous Phase Liquids in Saturated Porous Media: 1. Model Predictions

The dissolution of nonaqueous phase liquids (NAPLs) trapped at residual saturation is an important problem at many contaminated groundwater sites. It is well known that NAPL ganglia trapped within the pore space reduce the permeability of the medium to aqueous phase flow. When fluid flow is imposed on such a system, the aqueous phase may interact with the dissolution‐induced permeability changes, leading to fingered patterns. This mechanism is very similar to that of mineral dissolution instabilities, which are a particular example of reactive infiltration instabilities. Extending that literature, we present a nonlinear model describing the dissolution of NAPL ganglia and perform a linear stability analysis of the resultant moving free boundary problem, demonstrating that instabilities may develop from a planar dissolution front. Predicted finger wavelengths are a function of both residual NAPL saturation and the imposed aqueous phase flow rate; they range from centimeters to meters. Experimental observations of dissolution fingering are presented in a companion paper [Imhoff et al., this issue] and are compared with predictions from this model. Dissolution fingering may affect the solubilization of NAPL ganglia in natural environments and in experimental studies of NAPL dissolution intended to quantify mass transfer rates.

Dissolution Fingering During the Solubilization of Nonaqueous Phase Liquids in Saturated Porous Media: 2. Experimental Observations

Nonaqueous phase liquids (NAPLs) are a common source of contamination at polluted groundwater sites, where they frequently remain trapped within the pore space at residual saturation and reduce the permeability of the medium to aqueous phase flow. The model presented in a companion paper [Imhoff and Miller, this issue] suggested that when fluid flow is imposed on such a system, the aqueous phase may interact with dissolution‐induced permeability changes, and lead to fingered patterns. In this investigation, a two‐dimensional flow cell was used to study the effects of porous medium structure, Darcy flux, initial residual NAPL saturation, median particle diameter, gravity, and NAPL composition on dissolution fingering. Fingering occurred when two conditions were met: (1) 11 to 80 e‐fold times had elapsed, where e‐fold time is the time required for the instability to grow by a factor e and was predicted from the linear stability analysis in the companion paper; and (2) the length of the dissolution front before finger development was smaller than the zone of NAPL residual. Where fingers formed, finger structure was similar and showed no systematic variation within the parameters investigated. Observed finger wavelengths compared well with model predictions. A single experiment in a three‐dimensional cell, 1 m long, demonstrated that fingers can grow to at least 30 cm in length. When experimental observations in this cell were compared with predictions of NAPL dissolution based on models that did not include fingering, the measurements of changing NAPL saturation differed significantly from model predictions.