Non-aqueous Phase Liquid Removal Research Articles

Impact of Magnetic Fields on the Efficiency of Dense Non-Aqueous Phase Liquid Removal from Unsaturated Zones Using Steam Injection

Unsaturated zone is of great importance in providing water and nutrients that are vital to the biosphere and the main factor controlling water movement from the land surface to the aquifer. Contamination of unsaturated zone by Dense Non-Aqueous Phase Liquids (NAPLs) has becoming major threat to human environment as a result of increasing concern with industrialization. The use of steam injection for remediation of porous media which are contaminated by DNAPLs has not given the desire recovery efficiency, hence the need for improvement in recovery efficiency has been a subject of continuous study. This study investigated the effect of magnetic field on the removal of DNAPL from unsaturated zone using steam injection. An unsaturated zone of a sand box of interior dimensions 110 x 74 x 8.5 cm was polluted at different periods with 200 ml of Carbon tetrachloride. Steam injection experiment with flow rate of 0.01 m3/s was performed to determine the recovery efficiencies of Carbon tetrachloride in an unsaturated zone containing sand of porosity 0.42 and permeability of 0.001163779 cm/s. Magnetic field in step of 1 Tesla (T) was introduced from 1-3 Tesla (T) into experiment. The effects of magnetic field on removal of DNAPL from unsaturated zone using steam injection only and steam injection with magnetic field were compared using descriptive statistic. The recovery efficiency of Carbon tetrachloride using steam injection only was 82.05 %, while that with varying magnetic field at 1T, 2T and 3T were 89.45%, 94.95% and 95.35% respectively. The recovery efficiency of steam injection with varying magnetic field at 1T, 2T and 3T were 9.02, 15.72, 16.21% higher than the result of steam injection only for Carbon tetrachloride. The result demonstrated the ability of steam injection to recover contaminants from the subsurface. The application of magnetic field as an aid to facilitate system activities has been signifi-cantly effective due to its ability to overcome the constraints of conventional treatment processes. A combined application of steam injection with magnetic field appreciably enhances the removal of Non Aqueous phase liquids from Unsaturated Zone.

Effect of fracture distribution on extraction efficiency in low-permeability NAPL-contaminated formations

Hydraulic fracturing offers an effective solution to the challenge of remediating low-permeability contaminated formations by improving substance transport rates. In this study, COMSOL Multiphysics, a large-scale multi-physics coupled simulation software, was employed to simulate enhanced extraction and remediation of low permeability non-aqueous phase liquid (NAPL)-contaminated formations using hydraulic fractures. The results obtained indicate that fracturing and enhanced extraction can effectively improve the NAPL removal rate. The NAPL removal rate increased with increasing depth of the extraction well screens, fracture length, and fracture spacing. Through a coupling analysis of multiple factors and working conditions, the extraction well screens are suggested to be buried within the lower one-third of the low-permeability contaminated formation, and the length of a single fracture should be within 50%–80% of the extraction radius. When the distance between the two fractures was greater than 1.75 m, the enhancement effect of the fracture length was further promoted. Consequently, a reasonable configuration of fracture length, quantity, and spacing can effectively broaden the influence radius of extraction wells.

Understanding of Co-boiling between Organic Contaminants and Water during Thermal Remediation: Effects of Nonequilibrium Heat and Mass Transport.

In situ thermal desorption (ISTD) provides an efficient solution to remediation of soil and groundwater contaminated with nonaqueous phase liquids (NAPLs). Establishing a relationship between the subsurface temperature rise and NAPL removal is significant to reduce energy consumption of ISTD. However, the co-boiling phenomenon between NAPL and water poses a great challenge in developing this relationship due to the nonequilibrium heat and mass transport effects. We performed a systematic experimental investigation into the local temperature rise patterns at different distances from a NAPL pool and under different degrees of superheat by selecting four representative NAPLs (i.e., trichloroethylene, tetrachlorethylene, n-hexane, and n-octane) according to their density and boiling point relative to water. The patterns of temperature rise indicated that the underground temperature field can be divided into three zones: the zone of local thermal equilibrium, the nonequilibrium zone affected by co-boiling, and the zone unaffected by co-boiling. We developed a pattern-recognition-based approach, which considers the effects of local heat and mass transport to establish a qualitative correlation between the temperature rise and NAPL removal. Our results give deeper insights into the understanding of subsurface temperatures in ISTD practice, which can serve as the guideline for more accurate and sustainable remediation.

Enhanced mass transfer of residual NAPL by convection in stagnant zone

Cosolvent flushing is a promising method to improve NAPLs (non-aqueous phase liquids) removal. Nevertheless, the removal performance is undermined by the tailing phenomenon, i.e., the contaminant concentration tends to remain unchanged in later period as NAPL is residually trapped in the stagnant zone. High proportion of stagnant zone leads to more severe tailing phenomenon and how to accelerate dissolution of NAPL in the stagnant zone is important for NAPL remediation. However, few work has studied the remediation process at pore-scale due to limited observation techniques. As a result, the fundamental process of convection enhancement remains unclear. In this work, dynamics of NAPL removal in the stagnant zone is quantitatively investigated in transparent micromodels via the use of Raman spectroscopy. Impacts of injection condition and properties of the porous media are systematically investigated. Results indicate that convection dominants the mass transfer in aqueous phase and enhances the NAPL dissolution. Increasing the flushing velocity can enhance convection, but when the flushing velocity exceeds 3 cm/min, convection in the region away from the dominant channel is little affected by the flushing velocity. Differently, increasing the pore throat size will enhance convection in the entire stagnant zone and accelerate the whole dissolution process.

Enhanced NAPL Removal and Mixing With Engineered Injection and Extraction

AbstractAquifer remediation with in‐situ soil washing techniques and enhanced oil removal typically involves the injection of liquid solutions into the geological formation to displace and mobilize non‐aqueous phase liquids (NAPLs). The efficiency of these systems is oftentimes low because the displacing fluid bypasses large quantities of NAPL due to the inherent complexity of a heterogeneous natural system. Here, engineered injection and extraction (EIE) generated by rotating periodic injection is proposed as a method to enhance NAPL removal and mixing. To evaluate the method, we perform two‐phase flow simulations in multiple realizations of random permeability fields with different correlation structures and connectivity between injection and extraction wells embedded in a five‐spot pattern. Results show that EIE can significantly improve removal efficiency and mixing depending on several controlling factors. The effects of EIE are more significant under unfavorable conditions, that is, when injection and extraction wells are well‐connected through preferential channels, permeabilities are highly heterogeneous, and/or the mobility ratio between the wetting and the non‐wetting fluids is larger than one. Removal efficiency reaches its maximum value when the Kubo number is close to one, that is, when the saturation front travels one range of the permeability field in an injection pulse. These effects can develop in just a few cycles. However, removal efficiency should undergo first an early stage with detrimental effects in order to maximize removal in the long term. EIE not only enhances NAPL removal and mixing but also reduces the uncertainty, making the system more reliable and less dependent on heterogeneity.

Mechanistic modeling and measurement of foamed gas flow resistance in fractures

Geologic heterogeneity is one of the important factors controlling migration and distribution of nonaqueous phase liquids in the subsurface. Heterogeneity, such as fractures, complicates the effectiveness of environmental remediation, and uncharacterized aquifer heterogeneity causes significant uncertainties in the removal of nonaqueous phase liquids. Foaming an injection gas is an effective method to alleviate the challenges in accessing heterogeneous media during remediation processes because foam is nonNewtonian and redirects gas and liquid flow. Foamed gas may also assist in increasing the storage of carbon dioxide in saline formations. This paper investigates foam flow behavior in microscale fractures and develops a mechanistic transient foam flow model using the population balance method. Microscale experiments in fractures with apertures of 25 and 88 μm are used to validate the model for pressure drop, gas saturation, and bubble texture. Key differences related to modeling foam in fractures are the potential for continuously varying gas–liquid curvature in fractures and the relationship of this curvature to apparent foam viscosity. Incorporation of a local foam flow resistance factor is important to representing flow physics accurately. Hence, the results of this study provide foundational understanding for upscaling foam rheology in different sized fractures to ensure successful operations in soil/aquifer remediation and CO2 storage in saline formations.

An Overview of Chemical Oxidation Based Remediation technologies for Non-Aqueous Phase Liquids Removal from Soil

<p>This review provides a general overview of the application of chemical oxidation to hydrophobic contaminants in the form of non-aqueous phase liquids (NAPLs). Three types of chemical oxidation processes, conventional activated persulfate, permanganate, and ozonation, along with three advanced oxidation processes (AOPs), the Fenton process, photocatalysis, and plasma oxidation are presented discussed. In addition, this paper provides a brief insight into the combination of chemical oxidation with other remediation technologies for the efficient removal of NAPLs. The common and wide use of activated persulfate for soil remediation is hindered by the fact that it needs heat activation, whereas the main drawback of using permanganate is the precipitation of manganese oxide at the NAPLs face. In addition, the high cost of equipment at the site restricts the ozone application for in-suit soil remediation. The application of AOPs processes such as Fenton and plasma oxidation has received great attention due to its high removal efficiency. However, photocatalysis technology in the field is difficult because it needs photo energy to run the oxidation process. Although plasma oxidation can degrade contaminants in minutes, some active species have short-lived time that could disappear before entering the soil layer. Ozonation is efficient in treat soils with low moisture and large pore spaces. Nevertheless, the optimal pH for ozonation oxidation is 3, which is hard to achieve in real-world applications. Combining chemical oxidation with other remediation technology is a valuable technique of soil remediation as the synergetic effects may increase the sustainability of the applied process towards green technology for soil remediation.</p>

Experimental investigation on light non-aqueous phase liquids removal from groundwater using steam injection technique

Groundwater pollution by Non-Aqueous Phase Liquids (NAPLs) has become an increasing threat. This article studied the steam injection efficiency in the groundwater remediation contaminated with non-aqueous phase liquid (diesel) through a bench-scale laboratory experiment. The experimental set up consists of a steam boiler and sandbox. Steam, which was generated from the steam boiler was supplied to the sandbox at injection rate of 0.14m3/s, pressure of 1.5bar and temperature of 150°C. The initial volume of diesel used was 500ml. At the supply of the steam to the sandbox, it was observed that the mixture of groundwater and diesel was heated and at a temperature above their boiling points, the mixture change phase and vaporized from the chamber through the outlet or recovery side into the condenser and were separated on cooling using phase separator. The remediation time was from 0 to 6 hours and it was showed that as the time increases, the recovered volume of diesel increases as 66.04% of diesel was recovered after the allowed 6hours. Therefore, it was evident that the steam injection technique is efficient in the removal of light non-aqueous phase liquids in groundwater.

Nonaqueous Phase Liquid Removal by Postconventional Techniques

AbstractNonaqueous phase liquids (NAPL) tend to be trapped within aquifers. The review first covers conventional technologies that rely on pumping water, hot water, and/or air sparging with vapor e...

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.

Unifying NAPL Drawdown and Transmissivity Testing in Unconfined, Confined, Perched, and Fractured Settings using the Z‐Factor and MH Principles

AbstractLight nonaqueous phase liquid (LNAPL) flow in in fractured rock is governed by the same physics as porous media, but LNAPL discharge to a well from fractured rock is subject to the unique geometry of the fractures within the rock and the degree of interconnectivity between the factures. Previous conceptualization and definition of drawdown of nonaqueous phase liquids (NAPL) has employed a single drawdown value to represent the entire vertical interval of mobile NAPL. Application of the single drawdown model may result in erroneous calculation of NAPL transmissivity in fractured rock settings. This work illustrates how drawdown in multiphase systems can be variable over the vertical interval of mobile NAPL. In settings with discrete fracture networks, it is clear that consistently applying a single drawdown value will not accurately represent the pressure gradients. This work presents the multiphase head (MH) model, which is proposed as a comprehensive methodology for evaluating NAPL drawdown in fractured rock, and unconsolidated porous media. The MH model utilizes fluid statics and physical principles to accurately represent pressure differences in the formation and convert those into NAPL drawdown for discrete elevations. This first principles approach to describing how drawdown varies with NAPL‐production zone elevations and fluid levels, resulting in a more accurate representation of discharge vs. fluid elevation behavior. Application of the MH model to various scenarios has identified that dissimilar scenarios can represent similar behavior during recovery from a NAPL removal event or baildown test. The resulting understanding improves the selection of representative portions of baildown test data to use in NAPL transmissivity analysis. Proper conceptualization of drawdown in bedrock identifies an alternate analysis method, the Z‐factor, to estimate NAPL transmissivity. The resulting drawdown calculations and transmissivity analysis method result in a comprehensive approach to calculating NAPL transmissivity in both bedrock and unconsolidated porous media.

Pore-scale dynamics of nanofluid-enhanced NAPL displacement in carbonate rock

This study presents a pore-scale investigation of two-phase flow dynamics during nanofluid flooding in subsurface formations containing non-aqueous phase liquids (NAPLs) such as crude oils. The goal was to gain fundamental understanding of the dominant displacement mechanisms of NAPL at different stages of nanofluid injection in a carbonate rock using x-ray microtomography integrated with a miniature core-flooding system. The nanofluid consisted of surfactant-based microemulsions with in-situ synthesized silica nanoparticles. After establishing its initial wettability state, the carbonate core sample was subjected to various pore volumes (PV) of nanofluid flooding (from 0.5 to 10) to examine the impact on NAPL flow dynamics. We found that most NAPL mobilization occurred within the first PV of injection, removing nearly 50% of NAPL from the rock. The nanofluid invaded into larger pores first due to a sharp decrease in NAPL/brine interfacial tension (from 14 to 0.5 mN/m) and contact angle (from 140 to 88°). With higher amount of nanofluid delivered into the pores through advection, over 90% of NAPL droplets were emulsified and their size decreased from 9 to 3 μm. Subsequent nanofluid injection could further remove NAPL from the smaller pores by altering the thickness of NAPL layers adsorbed on the rock. This dynamic solubilization process reached equilibrium after 5 PV of injection, leading to a reduced layer thickness (from 12 to 0.2 μm), a narrower in-situ contact angle distribution around 81°, and an additional 16% of NAPL removal.

Synergistic effects of surfactant mixtures on the displacement of nonaqueous phase liquids in porous media

Binary surfactant mixtures have often been used to enhance the recovery or cleanup of nonaqueous phase liquids (NAPLs) such as crude oil from subsurface formations. Through synergistic effects, these mixtures further promoted NAPL mobilization and solubilization by lowing NAPL/brine interfacial tension (IFT) and desorbing NAPL from mineral surfaces, thereby altering their wettability. While the impact of mixing synergy on IFT has been well documented, its effect on wettability alteration in rocks under different test conditions (i.e., mineralogy and pore topology) is still unclear. The objective of this study was to establish structure-function relationships in these systems and identify the test conditions under which binary mixtures outperform single surfactants. Four different nonionic surfactants (alkyl glucosides, linear/branched alcohol ethoxylates) were selected with a hydrophile-lipophile balance number of ˜13. We used IFT, contact angle (CA), and spontaneous imbibition tests with NAPL-aged cores to understand the mechanisms of interaction and examine the efficiency of surfactants and their mixtures in promoting NAPL displacement in three sedimentary rocks with different mineralogy and pore topology. Synergistic effects were investigated by calculating cross-sectional areas and interaction parameters of surfactant mixtures and relating them to IFT and CA. Alkylphenol ethoxylates with relatively short aliphatic tails could fill the gaps between the large sugar-based heads of alkyl glucosides and enhance their geometrical packing at NAPL/brine interfaces. The denser interfacial layer formed by these mixtures led to the largest decrease in IFT and promoted the highest NAPL mobilization in low permeability sandstone and carbonate samples. The ability of nonionic surfactants to restore the wettability of oil-wet mineral surfaces was a function of their molecular structure and rock topology. In homogeneous sandstones, alkyl glucosides with their strong hydrogen bonding ability with silanol groups of quartz, could restore the wettability to a greater extent and consequently exhibited the highest NAPL removal. However, they were ineffective in altering the wettability of carbonates due to their strong self-association tendency into large micelles which prevented them from penetrating rough and nanoporous regions. The synergistic mixing of alkyl glucosides with alkylphenol ethoxylates could overcome these limitations as they exhibited a complementary mechanism of action with respect to IFT reduction and wettability alteration, recovering the largest amounts of NAPL in carbonate-bearing rocks.

Numerical modelling of the impact of surfactant partitioning on surfactant-enhanced aquifer remediation

The partitioning of surfactants into non-aqueous phase liquids (NAPLs) during Surfactant-Enhanced Aquifer Remediation (SEAR) is potentially an important and non-negligible phenomenon that can strongly impact remediation efficiency. This paper numerically investigates the impact of surfactant partitioning on the enhanced NAPL dissolution and mobilization mechanisms and the overall NAPL removal from the subsurface. For demonstration, a multiphase model is used to simulate a hypothetical SEAR consisting of Triton X100 surfactant solution for the removal of perchloroethylene (PCE) entrapped in contaminated porous medium at the core/column scale. The simulations are conducted for two-dimensional homogenous and three-dimensional heterogeneous systems. By simultaneously incorporating spatial heterogeneity of porous media, injection rate, and endpoint mobility ratio into the model, we delineate the interplay of surfactant partitioning with flow and transport dynamics. Our results show that surfactant partitioning from the aqueous phase across the interface to the NAPL phase can undermine both efficiency of the enhanced dissolution and mobilization of NAPL species. This undermining is more pronounced for when aqueous phase mobility is less than the mobility of the NAPL phase. For such conditions interfacial tension between the two phases is reduced less for partitioning than non-partitioning cases (due to loss of surfactant into NAPL phase) and a secondary water front is formed due to partitioning that makes aqueous phase breaks through earlier.

Removal of non-aqueous phase liquids (NAPLs) from TPH-saturated sandy aquifer sediments using in situ air sparging combined with soil vapor extraction

Contamination in coastal aquifer plains is of great concern in many countries given that non-aqueous phase liquids (NAPLs) have polluted numerous sites through accidental oil spills or improper disposal. We have developed a method to remove pollutants such as NAPLs from sandy sediment samples collected from the Mandol area of Gomso Bay in western South Korea. The sediments were collected from around the diffuser in a two-dimensional (2D) acrylic reaction apparatus, and these contained a total petroleum hydrocarbon (TPH) concentration of 89.3 ppm (mg/kg media). The maximum perchloroethylene (PCE) concentration was 398.51 ppm in the unsaturated zone and 0.77 ppm in the saturated zone. Volatile organic compounds (VOCs) were detected between 20 and 44 hour. However, non-volatile contaminants remained in the sediments after treatment. In situ air sparging (IAS) combined with soil vapor extraction (SVE), transformation from sorbed and nonaqueous phases to the vapor phase, is incomplete when treatment is performed using a pervasive air flow for sediments such as the sand of Mandol. During air transformation, the groundwater flow conditions increased the rate of contaminant removal. Although pilot-scale testing in the field site was fluctuated due to the heterogeneous of sediments condition, this 2D study found that the proposed method can alter the measurable geophysical properties of NAPLs. These findings demonstrate that IAS combined with SVE in the saturated zone is an effective technology for aquifer remediation high applicability of sandy coastal sediments contaminated by NAPLs.

Laboratory study of creosote removal from sand at elevated temperatures

In situ thermal treatment (ISTT) technologies have been applied at sites impacted by non-aqueous phase liquids (NAPLs). There is a need to establish expectations for the treatment of semi-volatile NAPLs, including those consisting primarily of polycyclic aromatic hydrocarbons (PAHs), and the potential benefits and limitations of partial NAPL removal. A series of laboratory experiments was conducted to investigate NAPL removal and soil concentrations during the heating of creosote-impacted sand, as well as aqueous concentrations during post-heating dissolution. The results showed co-boiling near the water boiling temperature due to the low volatility of most creosote components, with limited decreases in NAPL saturation (from 30% to 21% of the pore space). Decreases in soil concentration were more substantial than decreases in NAPL saturation (by a factor of 2–180), with greater removal for higher-volatility components at higher treatment temperatures. Results of the dissolution experiments showed mixed results, with decreases in the aqueous concentrations for 12 of 15 components, but increases in aqueous concentrations for phenanthrene, fluoranthene and pyrene after heating to 205 °C or 320 °C. Overall, the results illustrate the utility of bench-scale treatability tests in helping to establish ISTT goals and expectations.

A mobile, modular and rapidly-acting treatment system for optimizing and improving the removal of non-aqueous phase liquids (NAPLs) in groundwater.

Non-aqueous phase liquids (NAPLs) in pumped groundwater are highly variable, challenging the selection of above-ground treatment strategies in pump-and-treat system. Adjustable systems with multiple treatment units are urgently required. In the present study, a mobile, modular and rapidly-acting treatment system was developed to treat groundwater contaminated by NAPLs at a chemical industrial site. The system integrated four units of coagulation sedimentation, air flotation, air stripping and chemical oxidation. During a 3-month onsite operation, the composition of groundwater NAPLs had huge fluctuations and different treatment units had unique advantages in eliminating some components. For instance, air stripping exhibited satisfactory removal efficiencies (>80%) for short-chain petroleum hydrocarbons and chloroalkanes, but poor performance for others comparing to other units. A decision-making tool and a central control system were further developed to combine and adjust the four units in proper orders, achieving satisfied removal efficiency (70-90%) for multi-component NAPLs, regardless of composition fluctuation. These findings raise the state-of-the-art modular and rapidly-acting groundwater treatment system to clean up NAPLs contaminated groundwater through pump-and-treat strategy, help in better understanding on the decision and management to improve the treatment performance, and provide guidelines for its implication at other sites contaminated with multi-component NAPLs or undergoing accidental contamination.

Application of nanotechnology in removal of NAPLs from contaminated aquifers: a source clean-up experimental study

This work investigates the removal of non-aqueous phase liquids (NAPLs) from groundwater resources using nanotechnology. We present results of a series of multiphase fluid displacement experiments conducted in a naturally occurring sandstone rock. These experiments involve injection of an aqueous suspension of silica nanoparticles to remove a trapped NAPL phase. Specifically, the effect of nanoparticle concentration on the efficiency of the NAPL removal is studied. Our results show that silica nanoparticles successfully remobilised the trapped NAPL phase and resulted in 13% increase in its removal efficiency. The optimal concentration for NAPL removal efficiency is found to be 0.3 wt%.

Micro-scale displacement of NAPL by surfactant and microemulsion in heterogeneous porous media

Industrial processes such as remediation of oil-contaminated aquifers and enhanced oil recovery (EOR) often utilize chemical additives to increase the removal of non-aqueous phase liquids (NAPLs) from subsurface formations. Although the majority of crude oils are classified as LNAPLs, they often contain heavy molecules (DNAPLs) such as asphaltenes that tend to adsorb on minerals and alter their wettability. Effective additives are therefore those that can reduce the threshold capillary pressure, thus mobilizing LNAPL inside pore spaces and solubilizing DNAPL from rock surfaces. Nonionic surfactants in brine have often been injected to oil or contaminated aquifer formations in order to enhance NAPL displacement through IFT reduction. Recent studies revealed that surfactant-based microemulsions have a higher tendency to alter the wettability of surfaces, compared to surfactants alone, leading to more effective NAPL removal. However, the impact of these additives on pore-scale displacement mechanisms and multi-phase fluid occupancy in porous media is, to date, still unclear. In this study, x-ray microtomography experiments were performed to investigate the impact of surfactants and microemulsions on the mobilization and solubilization of NAPL in heterogeneous rocks. Saturation profiles indicated that an incremental NAPL removal was attained by addition of microemulsion to brine, compared with surfactant. Residual cluster size distributions revealed that microemulsions could break up large clusters into smaller disconnected ones, improving their mobilization in the rock. In-situ contact angle measurements showed that microemulsions could reverse the wettability of rough contaminated surfaces to a higher extent than surfactants. Unlike surfactant alone, the surfactant-solvent blend in the carrier fluid of microemulsions was able to penetrate rough grain surfaces, particularly those of dolomite cement, and desorb asphaltenes in the form of small-emulsified NAPL droplets, which were eventually washed away by the continuous flow process. The greater wettability alteration caused by microemulsions resulted in a lower threshold capillary pressure, which in turn promoted the mobilization of NAPL ganglia more than surfactant alone.

Enhanced removal of NAPL constituent from aquifer during surfactant flushing with aqueous hydraulic barriers of high viscosity

ABSTRACTThis study examines the effect of controlled groundwater flow paths induced by hydraulic barriers on the removal of NAPL constituent. An aqueous solution of thickener [0.05% (w/v) sodium carboxymethyl cellulose, SCMC] was continuously injected into a horizontally set two-dimensional physical model (sand-packed), forming aqueous plume(s) of high viscosity. The water flux at the down gradient of the model was measured using a flux tracer (n-octanol) and passive flux meter (PFM, packs of granular activated carbon). A non-reactive tracer (pentafluorobenzoic acid, PFBA) was used to identify the plume of high viscosity (hydraulic barrier) and ambient groundwater. When the barrier of high viscosity was formed, the plume was separated from the background water with little mixing, which was confirmed by the concentration profile of PFBA; whereas, the measured flux of ambient groundwater showed a distinctive distribution, due to the hydraulic barrier. When two barriers were set, the ambient water flux was enhanced in the middle, and the removal rate of PCE from the non-aqueous phase liquid (NAPL), measured by PFM, was found to improve by 26% during three hours of water flushing. When an aqueous solution of surfactant [0.37% (w/v), sodium dodecyl sulfate, SDS] was applied instead of water into the domain with two barriers set around the NAPL-contaminated spot, the removal of PCE from the NAPL increased by 101% for a three-hour time period. Based on the observations made in this study, hydraulic barriers formed by continuous injection of thickener solution change the flow direction of groundwater, and may increase the flux of groundwater (or aqueous solution of remediation agent) through a NAPL-contaminated region, improving the removal of NAPL.