Presence Of Non-aqueous Phase Liquids Research Articles

Influence of Residual Nonaqueous-Phase Liquids (NAPLs) on the Transport and Retention of Perfluoroalkyl Substances.

Per- and polyfluoralkyl substances (PFAS) are known to accumulate at interfaces, and the presence of nonaqueous-phase liquids (NAPLs) could influence the PFAS fate in the subsurface. Experimental and mathematical modeling studies were conducted to investigate the effect of a representative NAPL, tetrachloroethene (PCE), on the transport behavior of PFAS in a quartz sand. Perfluorooctanesulfonate (PFOS), perfluorononanoic acid (PFNA), a 1:1 mixture of PFOS and PFNA, and a mixture of six PFAS (PFOS, PFNA, perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorohexanesulfonate (PFHxS), and perfluorobutanesulfonate (PFBS)) were used to assess PFAS interactions with PCE-NAPL. Batch studies indicated that PFAS partitioning into PCE-NAPL (Knw < 0.1) and adsorption on 60-80 mesh Ottawa sand (Kd < 6 × 10-5 L/g) were minimal. Column studies demonstrated that the presence of residual PCE-NAPL (∼16% saturation) delayed the breakthrough of PFOS and PFNA, with minimal effects on the mobility of PFBS, PFHpA, PFHxS, and PFOA. Breakthrough curves (BTCs) obtained for PFNA and PFOS alone and in mixtures were nearly identical, indicating the absence of competitive adsorption effects. A mathematical model that accounts for NAPL-water interfacial sorption accurately reproduced PFAS BTCs, providing a tool to predict PFAS fate and transport in co-contaminated subsurface environments.

VARIATION IN RADON CONCENTRATION IN SOIL GASES TO DETECT THE NAPL PRESENCE

Non-Aqueous Phase Liquids (NAPLs) compounds are complex mixtures of organic liquids derived from petroleum and/or industrial activity. Contamination of soils and groundwater by NAPLs can generate health and economics problems by compromising water resources; restrict soils use; and cause damage to the public and private patrimony, and the environment. Today there is an increase in areas contaminated by different types of NAPLs, cause of great concern worldwide, due to the difficulty of locating and quantifying contamination, which is a major obstacle that prevents the cleaning of soils and groundwater in affected locations. This work aims to use the concentrations of the Radon gas in the soil as a way to determine areas contaminated by NAPL, using/prove the high affinity of the Radon for NAPLs, which causes the concentration of Radon in the soil to have a deficit in relation to that naturally observed in the studied region. After understanding the affinity of the Radon by the NAPLs, a gas station was located (with the contribution of the city hall of Belo Horizonte – Minas Gerais – Brazil), which went through a diesel oil leak from the storage tank making the area contaminated. Measurements of the Radon concentration were carried out with the AlphaGUARD® Radon monitor. These measurements confirmed the presence of a deficiency in the Radon concentration, which demonstrated its ability to be used as a marker for the presence of NAPL, contributing to future plans remediation and control of pollution, as well as studies of oil wells on-shore.

Symmetry between Theoretical and Physical Investigation of Water Contamination Using Amplitude Variation with Offset Analysis of Ground-Penetrating Radar Data

We evaluated the symmetry of theoretical and experimental analysis of water contamination such as non-aqueous phase liquid (NAPL) by using amplitude variations with offset analysis (AVO) of ground-penetrating radar (GPR) data. We used both theoretical and experimental approaches for AVO responses of GPR to small distributions of contamination. Theoretical modeling is a tool used to confirm the feasibility of geophysical surveys. Theoretical modeling of NAPL-contaminated sites containing wet sand—both with the water and light non-aqueous phase liquid—was applied by keeping in consideration the GPR AVO analysis in acquisition. Reflectivity was significantly altered with the changes in the contents of water and NAPL during modeling. The wet and dry sands introduced in our model changed two major phenomena: one, the wave pattern—implying a slight phase shift in the wave; and two, an amplitude jump with the dim reflection radar gram observed in the model. Experimental data were collected and analyzed; two observations were recorded during physical data analysis. First, relative permittivity confirmed the presence of NAPL in an experimental tank. Second, reflection patterns with jumps in amplitude and changes in polarity confirmed the theoretical investigation. Our results demonstrate that GPR AVO analysis can be as effective for detection of non-aqueous phase liquid (NAPLs) as it has been used to determine moisture contents in the past. The theoretical and experimental models were in symmetry, and both found a jump in reflection strength. The reflection pattern normally jumped with NAPL-intrusion. From the perspective of water contamination, this study emphasizes the need to take into account the impact of GPR AVO analyses along with the expert’s adaptive capacities.

Effect of Residual NAPLs on the Transport of Bisphenol A and Bisphenol S in Saturated Porous Media

Endocrine disrupter, like bisphenol A (BPA) and bisphenol S (BPS), is frequently detected in the subsurface environment, imposing threats to the groundwater quality and public health. However, current understanding of environmental fate and transport of BPA/BPS is still not clear, especially with respect to those in the subsurface media with trapped non-aqueous phase liquids (NAPLs). In this study, the effect of residual NAPLs on the retention and transport of BPA/BPS in the saturated sand and soil media was investigated using column experiments. The results showed that residual NAPLs (i.e., xylene and perchloroethylene (PCE)) inhibited the transport of BPA in the sand columns, and the inhibit effect of xylene was greater than that of PCE. While the presence of NAPLs showed little influence on the transport of BPS in the sand columns, in soil A (sandy soil), the residual NAPLs had similar effect on the retention and transport of BPA and BPS. Both BPA and BPS showed higher retention in the soil B columns than in the sand and soil A columns due to soil B’s higher organic matter contents, which can strongly sorb BPA/BPS. The presence of residual NAPLs reduced the retention of BPA/BPS in the soil B columns because the NAPLs blocked the sorption sites of the soil organic matter for BPA/BPS. This study demonstrates the importance of residual NAPLs, types of media, properties of contaminants, and their interactions to the fate and transport of BPA/BPS in saturated porous media.

A pore-scale investigation of heavy crude oil trapping and removal during surfactant-enhanced remediation

The presence of nonaqueous phase liquid (NAPL) in the subsurface presents significant challenges for soil and groundwater remediation. In particular, heavy crude oil, coal tar and/or bitumen present unique difficulties for removal and cleanup due to associated high viscosities, low aqueous solubilities, and limited mobility extraction potential. Although surfactant-enhanced aquifer remediation (SEAR) techniques have shown some promise for source removal, overall remediation (mobilization) performance will depend significantly on interfacial effects between the fluid and solid phases. A pore-scale study, implementing synchrotron X-ray microtomography (SXM), was conducted to understand and quantify the trapping and mobilization mechanisms and in-situ emulsification processes of heavy crude oil distributed within increasing complexity (i.e. physical heterogeneity) unconsolidated sands during surfactant flushing events. Pore-scale imaging analyses were conducted to quantify the changes in oil blob morphology before and after surfactant flushing events to assess the primary factors controlling the recovery. Results showed relatively low (10%) net recovery from the homogeneous sand after 5 pore volumes (PVs) of surfactant flushing and may be, in part, due to the more connected ganglia (i.e. single continuous) oil-phase. Such a condition may have limited the surfactant/oil contact resulting in relatively low interfacial activity and correspondingly inefficient oil mobilization and recovery. Negligible net oil recovery was achieved from the mildly-heterogeneous-sand and is likely due to the lower associated permeability of this particular porous medium. Furthermore, the oil-phase distribution within this medium primarily consisted of small disconnected blobs more readily exposed (in contact with) the surfactant solution. For the highly-heterogeneous-sand experiments, an average of 20% heavy-oil recovery resulted after each flushing event (total of ~37% after 5 PVs) and was attributed to more efficient reduction of interfacial tension associated with the increased surfactant-oil contact. The associated higher pH sand/fine‑carbonate system may have aided in maintaining a water-wet porous medium, a condition more conducive to higher oil recovery and displacement efficiency.

Phytoremediation removal rates of benzene, toluene, and chlorobenzene

ABSTRACTPhytoremediation is a sustainable remedial approach, although performance efficacy is rarely reported. In this study, we assessed a phytoremediation plot treating benzene, toluene, and chlorobenzene. A comparison of the calculated phytoremediation removal rate with estimates of onsite contaminant mass was used to forecast cleanup periods. The investigation demonstrated that substantial microbial degradation was occurring in the subsurface. Estimates of transpiration indicated that the trees planted were removing approximately 240,000 L of water per year. This large quantity of water removal implies substantial removal of contaminant due to large amounts of contaminants in the groundwater; however, these contaminants extensively sorb to the soil, resulting in large quantities of contaminant mass in the subsurface. The total estimate of subsurface contaminant mass was also complicated by the presence of non-aqueous phase liquids (NAPL), additional contaminant masses that were difficult to quantify. These uncertainties of initial contaminant mass at the site result in large uncertainty in the cleanup period, although mean estimates are on the order of decades. Collectively, the model indicates contaminant removal rates on the order of 10−2–100 kg/tree/year. The benefit of the phytoremediation system is relatively sustainable cleanup over the long periods necessary due to the presence of NAPL.

Mechanism for detecting NAPL using electrical resistivity imaging

The detection of non-aqueous phase liquid (NAPL) related impacts in freshwater environments by electrical resistivity imaging (ERI) has been clearly demonstrated in field conditions, but the mechanism generating the resistive signature is poorly understood. An electrical barrier mechanism which allows for detecting NAPLs with ERI is tested by developing a theoretical basis for the mechanism, testing the mechanism in a two-dimensional sand tank with ERI, and performing forward modeling of the laboratory experiment. The NAPL barrier theory assumes at low bulk soil NAPL concentrations, thin saturated NAPL barriers can block pore throats and generate a detectable electrically resistive signal. The sand tank experiment utilized a photographic technique to quantify petroleum saturation, and to help determine whether ERI can detect and quantify NAPL across the water table.This experiment demonstrates electrical imaging methods can detect small quantities of NAPL of sufficient thickness in formations. The bulk volume of NAPL is not the controlling variable for the amount of resistivity signal generated. The resistivity signal is primarily due to a zone of high resistivity separate phase liquid blocking current flow through the fully NAPL saturated pores spaces. For the conditions in this tank experiment, NAPL thicknesses of 3.3cm and higher in the formation was the threshold for detectable changes in resistivity of 3% and greater. The maximum change in resistivity due to the presence of NAPL was an increase of 37%. Forward resistivity models of the experiment confirm the barrier mechanism theory for the tank experiment.

Effect of low-concentration rhamnolipid biosurfactant on Pseudomonas aeruginosa transport in natural porous media.

The effect of low-concentrations of monorhamnolipid biosurfactant on transport of Pseudomonas aeruginosa ATCC 9027 in natural porous media (silica sand and a sandy soil) was studied with miscible-displacement experiments using artificial groundwater as the background solution. Transport of two types of cells was investigated, glucose- and hexadecane-grown cells with lower and higher cell surface hydrophobicity (CSH), respectively. The effect of hexadecane presence as a residual non-aqueous phase liquid (NAPLs) on transport was also examined. A clean-bed colloid deposition model was used to calculate deposition rate coefficients (k) for quantitative assessment. Significant cell retention was observed in the sand (81% and 82% for glucose- and hexadecane-grown cells, respectively). Addition of a low-concentration rhamnolipid solution enhanced cell transport, with 40 mg/L of rhamnolipid reducing retention to 50% and 60% for glucose- and hexadecane-grown cells, respectively. The k values for both glucose- and hexadecane-grown cells correlate linearly with rhamnolipid-dependent CSH represented as bacterial-adhesion-to-hydrocarbon rate of cells. Retention of cells by the soil was nearly complete (>99%). Addition of 40 mg/L rhamnolipid solution reduced retention to 95%. The presence of NAPLs in the sand increased the retention of hexadecane-grown cells with higher CSH. Transport of cells in the presence of the NAPL was enhanced by rhamnolipid at all concentrations tested, and the relative enhancement was greater than in was in the absence of NAPL. This study shows the importance of hydrophobic interaction on bacterial transport in natural porous media and the potential of using low-concentration rhamnolipid for facilitating the transport in subsurface for bioaugmentation efforts.

Influence of non-aqueous phase liquid configuration on induced polarization parameters: Conceptual models applied to a time-domain field case study

Resistivity and induced polarization (IP) measurements on soil contaminated with non-aqueous phase liquids (NAPLs) show a great variety in results in previous research. Several laboratory studies have suggested that the presence of NAPLs in soil samples generally decrease the magnitude of the IP-effect, while others have indicated the opposite. A number of conceptual models have been proposed suggesting that NAPLs can alter the pore space in different ways, e.g. by coating the grain surfaces and thus inhibiting grain polarization, or by changing the pore throat size and thus affecting the membrane polarization mechanism. The main aim of this paper is to review previously published conceptual models and to introduce some new concepts of possible residual NAPL configurations in the pore space. Time domain induced polarization measurements were performed at a NAPL contaminated field site, and the data were inverted using the Constant Phase Angle (CPA) model and the Cole–Cole model respectively. No significant phase anomalies were observed in the source area of the contamination when the CPA inverted profiles were compared with soil sampling results of free-phase contaminant concentrations. However, relatively strong phase and normalized phase anomalies appeared next to the source area, where residual free-phase presence could be expected according to the chemical data. We conclude that depending on the NAPL configuration, different spectral IP responses can be expected. In previous research, the NAPL configurations in different samples or field sites are often unknown, and this may to some extent explain why different results have been achieved by different authors. In our field case, we believe that the NAPL forms a more or less continuous phase in the pore space of the source zone leading to an absence of IP anomalies. The increase in phase and normalized phase angle observed next to the source zone is interpreted as a degradation zone. The ongoing biodegradation may have led to a fractionation of the continuous NAPL in the outer part of the original source zone, leading to residual presence of isolated NAPL droplets in the soil pores. With such NAPL configurations, an increased polarization can be expected according to the electrochemical- and membrane polarization mechanisms. More research is needed to confirm the effects of different NAPL configuration on spectral IP parameters.

Oxygen Mass Transfer in Biological Treatment System in the Presence of Non-aqueous Phase Liquid

Oxygen mass transfer is an important phenomenon in any biological treatment systems, fermentation reactors and other biochemical reactors. In biological treatment processes, aeration and agitation is carried out to enhance the oxygen mass transfer in the system, which in turn enhances the fermentation or treatment efficiency. In case of wastewater treatment plant, this process takes around 45-50% of the total energy requirement of the treatment plant. This paper proposes a new method for enhancing an oxygen mass transfer phenomenon in biological treatment processes by introducing non-aqueous phase liquids in the treatment system.

Time domain reflectometry-measuring dielectric permittivity to detect soil non-acqeous phase liquids contamination-decontamination processes

Contamination of soils with non-aqueous phase liquids (NAPL) constitutes a serious geo-environmental problem, given the toxicity level and high mobility of these organic compounds. To develop effective decontamination methods, characterisation and identification of contaminated soils are needed. The objective of this work is to explore the potential of dielectric permittivity measurements to detect the presence of NAPLs in soils. The dielectric permittivity was measured by Time Domain Reflectometry method (TDR) in soil samples with either different volumetric content of water (􀀅w) and NAPL (􀀅NAPL) or at different stages during immiscible displacement test carried out with two different flushing solutions. A mixing model proposed by Francisca and Montoro, was calibrated to estimate the volume fraction of contaminant present in soil. Obtained results, showed that soil contamination with NAPL and the monitoring of immiscible fluid displacement, during soil remediation processes, can be clearly identified from dielectric measurements.

Effects of hydroxypropyl-β-cyclodextrin and β-cyclodextrin on the distribution and biodegradation of phenanthrene in NAPL-water system

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) in contaminated sites is often limited by the presence of nonaqueous-phase liquids (NAPLs). To increase the bioavailability of PAHs in NAPLs, we investigated the effect of cyclodextrins (CDs) [including hydroxypropyl-β-cyclodextrin (HPCD) and β-cyclodextrin (β-CD)] on the equilibrium partitioning and biodegradation of phenanthrene (Phe) dissolved in two NAPLs, hexadecane and di-2-ethylhexyl phthalate (DEHP). The result showed that the extent of β-CD- or HPCD-mediated phenanthrene partitioning from NAPL into the aqueous phase increased with increasing concentrations of the CD in the aqueous phase and the relative abundance of phenanthrene in NAPL. Overall, the capacity of HPCD to partition phenanthrene was higher compared to β-CD, as confirmed by molecular docking. The effect of CD on the apparent concentration of phenanthrene in the hexadecane-water system was about twice that in the DEHP-water system. As a result of the increased partitioning of phenanthrene into the aqueous phase by CD, the biodegradation of phenanthrene was enhanced, and was influenced by the type and concentration of CD as well as the and type of NAPL used. When the concentration of β-CD was increased from 0.72 mM to 7.2 mM, it was found that there was a linear correlation between apparent equilibrium concentrations and biodegradation rates of phenanthrene (R2 > 0.97). At the same time, increases in the concentration of CD led to increases in competition between CD and the phenanthrene-degraders for phenanthrene. When the concentration of HPCD was increased beyond 3.6 mM, the enhancing effect of HPCD on the biodegradation rate of phenanthrene was not obvious. Thus, although CD appeared to be a promising agent for promoting bioremediation, the concentration and type of CD should be carefully chosen for different areas to reflect its ability to enhance the biodegradation.

Subsurface Transport Potential of Perfluoroalkyl Acids at Aqueous Film-Forming Foam (AFFF)-Impacted Sites

Subsurface transport potential of a suite of perfluoroalkyl acids (PFAAs) was studied in batch sorption experiments with various soils and in the presence of co-contaminants relevant to aqueous film-forming foam (AFFF)-impacted sites. Specifically, PFAA sorption to multiple soils in the presence of nonaqueous phase liquid (NAPL) and nonfluorinated AFFF surfactants was examined. This study is the first to report on sorption of perfluorobutanoate (PFBA) and perfluoropentanoate (PFPeA) (log Koc = 1.88 and 1.37, respectively) and found that sorption of these compounds does not follow the chain-length dependent trend observed for longer chain-length PFAAs. Sorption of PFBA was similar to that of perfluorooctanoate (PFOA, log Koc = 1.89). NAPL and nonfluorinated AFFF surfactants all had varying impacts on sorption of longer chain (>6 CF2 groups) PFAAs. The primary impact of NAPL was observed in low foc soil (soil A) where Freundlich n-values increased when NAPL was present. Impacts of nonfluorinated AFFF surfactants varied with surfactant and soil. The anionic surfactant sodium decyl sulfate (SDS) illicited PFAA chain-length dependent impacts in two negatively charged soils with varying foc. In soil A, Kd values for perfluoroheptanoate (PFHpA) increased 91% with SDS, whereas values for perfluorodecanoate (PFDA) increased only 28%. An amphoteric surfactant, n,n-dimethyldodecylamine n-oxide (AO), had the most notable impact on PFAA sorption to a positively charged soil (soil C). In this soil, AO oxide significantly increased sorption for the longer chain PFAAs (i.e., 528% increase in Kd for PFDA). Changes in sorption caused by SDS and AO may be due to mixed hemimicelle formation, competitive sorption, or changes to PFAA solubility. Short-chain PFAA behavior in the presence of NAPL, SDS, and AO was again notable. Co-contaminants generally increased the sorption of these compounds to all soils. Log Kd values of PFBA in soil A increased 85%, 372%, and 32% in the presence of NAPL, SDS, and AO, respectively. Use of Kd values to calculate retardation factors (Rf) of PFAAs demonstrates the variability of co-contaminant impacts on PFAA transport. Whereas NAPL and nonfluorinated surfactants decreased the sorption of perfluorooctanesulfonate (PFOS) at lower PFOS concentrations (1 μg/L), they led to increases in sorption at higher PFOS concentrations (500 μg/L). These results demonstrate that PFAA groundwater transport will depend on the solid phase characteristics as well as PFAA concentration and chain length. Detailed site-specific information will likely be needed to accurately predict PFAA transport at AFFF-impacted sites.

Measuring the dielectric properties of soil–organic mixtures using coaxial impedance dielectric reflectometry

Abstract Contamination of soils with non-aqueous phase liquids (NAPLs) is frequently produced by accidental spills and storage tanks or pipes leakage. The main goals dealing with soil and groundwater contamination include determining the extension of the affected zone, monitoring the contaminant plume and quantifying the pollution degree. The objective of this work is to evaluate the potential of dielectric permittivity measurements to detect the presence of NAPLs in sands. Tested samples were fine, medium, coarse and silty sand with different volumetric contents of water and paraffin oil. The dielectric permittivity was measured by means of a Coaxial Impedance Dielectric Reflectometry method in specimens with either known fluid content or at different stages during immiscible displacement tests. A simplified method was developed to quantify the amount of oil from dielectric permittivity measurements and effective mixture media models. Obtained results showed that groundwater contamination with NAPL and the monitoring of immiscible fluid displacement in saturated porous media can be clearly identified from dielectric measurements. Finally, very accurate results can be obtained when computing the contamination degree with the proposed method in comparison with the real volumetric content of NAPL (r 2 > 90%).

Analytical Integration Procedures for the Derivation of Risk-Based Generic Assessment Criteria for Soil

ABSTRACT Risk assessment models commonly used in contaminated sites employ a simple integration procedure by only partially combining exposure pathways from surface soil with vapor pathways from subsurface soil being excluded in the combination. The simplified approach can approximate the integrated generic assessment criteria only when there is a dominant exposure pathway. But these models are often based on a simple partitioning of a chemical in soil between the sorbed, dissolved, and vapor phases without consideration of the presence of non-aqueous phase liquid, and critically fail to consider non-soil background exposure for non-carcinogenic compounds. As a result, the generic assessment criteria derived may not be considered protective of human health. This article describes analytical integration procedures for the derivation of the generic assessment criteria that consider non-soil background exposure while limiting the average daily exposure for vapor pathways calculated from soil saturation limits. Significance of consideration of soil saturation limits for the derivation of the generic assessment criteria using an integrated approach is illustrated for organic compounds having varied levels of background exposure and soil saturations. The analytical integration procedures for the derivation of the soil generic assessment criteria under the linear chemical partition approach are also reviewed aiming to provide a single source of complete integration procedures for the derivation of the integrated generic assessment criteria.

Effects of growth conditions and NAPL presence on transport of Pseudomonas saccharophilia P15 through porous media

Extensive research has been done to characterize transport of bacteria in porous media; however, little is understood on how the presence of non-aqueous phase liquids (NAPLs) coupled with the growth state and carbon source of bacteria affect bacterial transport. The objective of this research is to quantify the bacterial adhesion of Pseudomonas saccharophilia P15 (P15), which is known to biodegrade polycyclic aromatic hydrocarbons (PAH) and to interact with coal tars, within a NAPL–water–mineral system. Through a series of short-pulse column experiments, the transport and deposition of P15 in porous media (quartz sand) as a function of growth state and carbon sources (peptone and naphthalene), and in the presence and absence of residual NAPL (hexadecane), is measured and evaluated. Coating 20% of the quartz grain with hexadecane as a model NAPL increased the retention of P15 by as much as a factor of 26 as compared to the retention exhibited in quartz sand with no NAPL present. P15 grown on peptone and in the late exponential growth state exhibited a greater amount of deposition within the hexadecane column than when it was grown on naphthalene or was in early exponential growth phase. During early growth stage P15 grown on naphthalene adhered stronger to the porous media compared to when grown on peptone. Results were compared with results of MATH assays, where P15 partitioning to hexadecane was evaluated as a function of carbon source and growth state.

Avaliação do desempenho de surfactantes para a solubilização de fases líquidas não aquosas em meio aquoso

The presence of non-aqueous phase liquids (NAPLs) in the subsurface is a threat to public health as well as a serious environmental issue. NAPLs may remain adsorbed or form lenses floating on aquifers causing long-term contaminations. Surfactants may increase NAPLs solubility, enhancing the pump-and-treatment performance. Size, shape, hydration and ionization degree of the micelles define the affinity and the space available for the solubilization of a particular contaminating agent. The tests carried out at laboratory scale, taking into account the NAPL to be removed and the medium characteristics were useful to select surfactants and evaluate their efficiency as NAPLs solubilizers.

Diffusive partitioning tracer test for the quantification of nonaqueous phase liquid (NAPL) in the vadose zone: Performance evaluation for heterogeneous NAPL distribution

A partitioning tracer test based on gas-phase diffusion in the vadose zone yields estimates of the residual nonaqueous phase liquid (NAPL) saturation. The present paper investigates this technique further by studying diffusive tracer breakthrough curves in the vadose zone for a heterogeneous NAPL distribution. Tracer experiments were performed in a lysimeter with a horizontal layer of artificial kerosene embedded in unsaturated sand. Tracer disappearance curves at the injection point and tracer breakthrough curves at some distance from the injection point were measured inside and outside of the NAPL layer. A numerical code was used to generate independent model predictions based on the physicochemical sand, NAPL, and tracer properties. The measured and modeled tracer breakthrough curves were in good agreement confirming the validity of important modeling assumptions such as negligible sorption of chlorofluorocarbon (CFC) tracers to the uncontaminated sand and their fast reversible partitioning between the soil air and the NAPL phase. Subsequently, the model was used to investigate different configurations of NAPL contamination. The experimental and model results show that the tracer disappearance curves of a single-well diffusive partitioning tracer test (DPTT) are dominated by the near-field presence of NAPL around the tip of the soil gas probe. In contrast, breakthrough curves of inter-well tracer tests reflect the NAPL saturation in between the probes, although there is no unique interpretation of the tracer signals if the NAPL distribution is heterogeneous. Numerical modeling is useful for the planning of a DPTT application. Simulations suggest that several cubic meters of soil can be investigated with a single inter-well partitioning tracer test of 24-hour duration by placing the injection point in the center of the investigated soil volume and probes at up to 1 m distance for the monitoring of gaseous tracers.

Aerobic bioremediation of 1,2 dichloroethane and vinyl chloride at field scale

Aerobic bioremediation of 1,2 dichloroethane (1,2 DCA) and vinyl chloride (VC) was evaluated at field scale in a layered, silty and fine-sand anaerobic aquifer. Maximum concentrations of 1,2 DCA (2 g/L) and VC (0.75 g/L) in groundwater were within 25% and 70% of pure compound solubility, respectively. Aerobic conditions were induced by injecting air into sparging wells screened 20.5–21.5 m below ground (17–18 m below the water table). Using a cycle of 23 h of air injection followed by three days of no air injection, fifty days of air injection were accumulated over a 12 month period which included some longer periods of operational shutdown. Oxygen and volatile organic compound probes, and multilevel samplers were used to determine changes of the primary contaminants and the associated inorganic chemistry at multiple locations and depths. Air (oxygen) was distributed laterally up to 25 m from the sparge points, with oxygen partial pressures up to 0.7 atmospheres (28–35 mg/L in groundwater) near to the sparge points. The dissolved mass of 1,2 DCA and VC was reduced by greater than 99% over the 590 m 2 trial plot. Significantly, pH declined from nearly 11 to less than 9, and sulfate concentrations increased dramatically, suggesting the occurrence of mineral sulfide (e.g., pyrite) oxidation. Chloride and bicarbonate (aerobic biodegradation by-products) concentration increases were used to estimate that 300–1000 kg of chlorinated hydrocarbons were biodegraded, although the ratio of 1,2 DCA to VC that was biodegraded remained uncertain. The mass biodegraded was comparable but less than the 400–1400 kg of chlorinated compounds removed from the aqueous phase within a 10,000 m 3 volume of the aquifer. Due to the likely presence of non-aqueous phase liquid, the relative proportion of volatilisation compared to biodegradation could not be determined. The aerobic biodegradation rates were greater than those previously estimated from laboratory-based studies.

ALTERED MOBILITY OF BENZ[a]ANTHRACENE IN THE PRESENCE OF p-XYLENE AND ITS IMPACT ON RISK IN THE SUBSURFACE

Concerns over soil and groundwater contamination by PAHs have been raised as they are often introduced into the subsurface as nonaqueous-phase liquid (NAPL) mixtures. However, characterizing the risk posed by a mixture of chemicals is a challenging task due to its uncertainty in quantifying the effects of the interaction between substances. This study focuses on the effects of phase-transforming interaction on the fate, transport, and risk assessment of a PAH in a PAH - NAPL mixture. The cell test was carried out using benz[a]anthracene (BaA) and p-xylene to verify the increased mobility of highly sorbed pollutants in the presence of less sorbed, mobile liquid pollutants. The experimental results showed that BaA had greater mobility in the presence of p-xylene than in its absence. The main transport mechanisms in the vadose zone were by dissolution into p-xylene or water. The developed model showed that transport of BaA was significantly faster in the presence of NAPL, but needs improvement. As well, risk assessment indicated that the oral carcinogenic risk of BaA calculated with the concentration in groundwater was 15∼ 87 times larger when mixed with NAPL than when present as a single contaminant. This study demonstrated that consideration of phase-transforming interaction is necessary to analyze the risk of a PAH - NAPL mixture. The improvement of the transport model will be the topic of our continuing research.