Evaluation of volatilization as a natural attenuation pathway for MTBE

Volatilization and diffusion through the unsaturated zone can be an important pathway for natural attenuation remediation of methyl tert-butyl ether (MTBE) at gasoline spill sites. The significance of this pathway depends primarily on the distribution of immiscible product within the unsaturated zone and the relative magnitude of aqueous-phase advection (ground water recharge) to gaseous-phase diffusion. At a gasoline spill site in Laurel Bay, South Carolina, rates of MTBE volatilization from ground water downgradient from the source are estimated by analyzing the distribution of MTBE in the unsaturated zone above a solute plume. Volatilization rates of MTBE from ground water determined by transport modeling ranged from 0.0020 to 0.0042 g m(-2)/year, depending on the assumed rate of ground water recharge. Although diffusive conditions at the Laurel Bay site are favorable for volatilization, mass loss of MTBE is insignificant over the length (230 m) of the solute plume. Based on this analysis, significant volatilization of MTBE from ground water downgradient from source areas at other sites is not likely. In contrast, model results indicate that volatilization coupled with diffusion to the atmosphere could be a significant mass loss pathway for MTBE in source areas where residual product resides above the capillary zone. Although not documented, mass loss of MTBE at the Laurel Bay site due to volatilization and diffusion to the atmosphere are predicted to be two to three times greater than mass loading of MTBE to ground water due to dissolution and recharge. This result would imply that volatilization in the source zone may be the critical natural attenuation pathway for MTBE at gasoline spill sites, especially when considering capillary zone limitations on volatilization of MTBE from ground water and the relative recalcitrance of MTBE to biodegradation.     

MTBE and gasoline hydrocarbons in ground water of the United States

The occurrence of methyl tert-butyl ether (MTBE) and gasoline hydrocarbons was examined in three types of studies of ground water conducted by the U.S. Geological Survey: major aquifer surveys, urban land-use studies, and agricultural land-use studies. The detection frequency of MTBE was dependent on the study type, with the highest detection frequency in urban land-use studies. Only 13 ground water samples from all study types, or 0.3%, had concentrations of MTBE that exceeded the lower limit of the U.S. EPA's Drinking-Water Advisory. The detection frequency of MTBE was highest in monitoring wells located in urban areas and in public supply wells. The detection frequency of any gasoline hydrocarbon also was dependent on study type and generally was less than the detection frequency of MTBE. The probability of detecting MTBE in ground water was strongly associated with population density, use of MTBE in gasoline, and recharge. Ground water in areas with high population density, in areas where MTBE is used as a gasoline oxygenate, and in areas with high recharge rates had a greater probability of MTBE occurrence. Also, ground water from public supply wells and shallow ground water underlying urban land-use areas had a greater probability of MTBE occurrence compared to ground water from domestic wells and ground water underlying rural land-use areas. The probability of detecting MTBE in ground water was weakly associated with the density of leaking underground storage tanks, soil permeability, and aquifer consolidation, and only concentrations of MTBE >0.5 microg/L were associated with dissolved oxygen.     

The acute toxicity of motor fuels to brackish water organisms

The addition of synthetic additives, such as methanol and methyl tertiary butyl ether (MTBE) to the base fuel, with the aim of raising the octane content of motor fuel, is currently of special interest in Sweden. A question, which has to be solved, is whether it is preferable to carry the additives by ship in separate tanks, because of the probable enhanced toxicity of the motor fuels by the addition of solvents, or not. The acute toxicity of these blend fuels has been compared with the acute toxicity of base fuel, gasoline and low leaded gasoline. As test organisms, two representative species of the Baltic Sea have been used, the harpacticoid Nitocra spinipes and the bleak, Alburnus alburnus. The results of the tests show that the acute toxicity of base fuel to aquatic organisms is not increased by the addition of 15% methanol or 5% MTBE.     

Modeling the effects of nonlinear equilibrium sorption on the transport of solute plumes in saturated heterogeneous porous media

Transport of sorbing solutes in 2D steady and heterogeneous flow fields is modeled using a particle tracking random walk technique. The solute is injected as an instantaneous pulse over a finite area. Cases of linear and Freundlich sorption isotherms are considered. Local pore velocity and mechanical dispersion are used to describe the solute transport mechanisms at the local scale. This paper addresses the impact of the degree of heterogeneity and correlation lengths of the log-hydraulic conductivity field as well as negative correlation between the log-hydraulic conductivity field and the log-sorption affinity field on the behavior of the plume of a sorbing chemical. Behavior of the plume is quantified in terms of longitudinal spatial moments: center-of-mass displacement, variance, 95% range, and skewness. The range appears to be a better measure of the spread in the plumes with Freundlich sorption because of plume asymmetry. It has been found that the range varied linearly with the travelled distance, regardless of the sorption isotherm. This linear relationship is important for extrapolation of results to predict behavior beyond simulated times and distances. It was observed that the flow domain heterogeneity slightly enhanced the spreading of nonlinearly sorbing solutes in comparison to that which occurred for the homogeneous flow domain, whereas the spreading enhancement in the case of linear sorption was much more pronounced. In the case of Freundlich sorption, this enhancement led to further deceleration of the solute plume movement as a result of increased retardation coefficients produced by smaller concentrations. It was also observed that, except for plumes with linear sorption, correlation between the hydraulic conductivity and the sorption affinity fields had minimal effect on the spatial moments of solute plumes with nonlinear sorption.     

Field Treatment of MTBE‐Contaminated Groundwater Using Ozone/UV Oxidation

Methyl‐tertiary butyl ether (MTBE) is often found in groundwater as a result of gasoline spills and leaking underground storage tanks. An extrapolation of occurrence data in 2008 estimated at least one detection of MTBE in approximately 165 small and large public water systems serving 896,000 people nationally (United States Environmental Protection Agency [U.S. EPA] 2008). The objective of this collaborative field study was to evaluate a small groundwater treatment system to determine the effectiveness of ultraviolet (UV)/ozone treatment in removing MTBE from contaminated drinking water wells. A pilot‐scale advanced oxidation process (AOP) system was tested to evaluate the oxidation efficiency of MTBE and intermediates under field conditions. This system used ozone as an oxidizer in the presence of UV light at hydraulic retention times varying from 1 to 3 min. MTBE removal efficiencies approaching 97% were possible with this system, even with low retention times. The intermediate t‐butyl alcohol (TBA) was removed to a lesser extent (71%) under the same test conditions. The main intermediate formed in the oxidation process of the contaminated groundwater in these studies was acetone. The concentrations of the other anticipated intermediates t‐butyl formate (TBF), isopropyl alcohol (IPA), methyl acetate (MAc), and possible co‐occurring aromatics (BTEX) in the effluent were negligible.     

Long-term reactive solute transport in an aquitard using a centrifuge model

Characterizing and predicting reactive solute transport in low hydraulic conductivity ( K ) clay-rich media is challenging because the very long transport time for solutes renders conventional column tests impractical. In this study, a centrifugation technique was developed to assess the transport of a simple aqueous solution (NaCl) by accelerating flow by centrifugal force through low K (1.1 × 10⁻¹¹ m/s) core samples. Duplicate cores (52-mm length × 33-mm diameter) were centrifuged at 330 × g for 90 d to model the migration of saline pore water (0.5 M NaCl) under in situ conditions through an approximately 17-m-thick clay prototype over approximately 24,000 years. A PHREEQC one-dimensional reactive solute transport code simulated effluent breakthrough of the NaCl during centrifugation, with best-fit cation exchange coefficients similar to batch tests. The calibrated code was used to predict solute profile development over the long term in the prototype or simulated field-scale conditions. Chromatographic separation of solutes due to ion exchange was evident over several meters in the simulated prototype and the field profile. The applicability of centrifugation methods to predict transport of more complex suites of reactive solutes over the long term is yet to be verified.     

Annual estimates of water and solute export from 42 tributaries to the Yukon River

Annual export of 11 major and trace solutes for the Yukon River is found to be accurately determined based on summing 42 tributary contributions. These findings provide the first published estimates of tributary specific distribution of solutes within the Yukon River basin. First, we show that annual discharge of the Yukon River can be computed by summing calculated annual discharges from 42 tributaries. Annual discharge for the tributaries is calculated from the basin area and average annual precipitation over that area using a previously published regional regression equation. Based on tributary inputs, we estimate an average annual discharge for the Yukon River of 210 km³ year^–1. This value is within 1% of the average measured annual discharge at the U.S. Geological Survey gaging station near the river terminus at Pilot Station, AK, for water years 2001 through 2005. Next, annual loads for 11 solutes are determined by combining annual discharge with point measurements of solute concentrations in tributary river water. Based on the sum of solutes in tributary water, we find that the Yukon River discharges approximately 33 million metric tons of dissolved solids each year at Pilot Station. Discharged solutes are dominated by cations calcium and magnesium (5.65 × 10⁹ and 1.42 × 10⁹ g year^–1) and anions bicarbonate and sulphate (17.3 × 10⁹ and 5.40 × 10⁹ g year^–1). These loads compare well with loads calculated independently at the three continuous gaging stations along the Yukon River. These findings show how annual solute yields vary throughout a major subarctic river basin and that accurate estimates of total river export can be determined from calculated tributary contributions. Copyright © 2011. This article is a U.S. Government work and is in the public domain in the USA.     

A Comparison of Benzene and Toluene Plume Lengths for Sites Contaminated with Regular vs. Ethanol-Amended Gasoline

This article describes various statistical analyses of plume-length data to evaluate the hypothesis that the presence of ethanol in gasoline may hinder the natural attenuation of hydrocarbon releases. Plume dimensions were determined for gasoline-contaminated sites to evaluate the effect of ethanol on benzene and toluene plume lengths. Data from 217 sites in Iowa (without ethanol; set 1) were compared to data from 29 sites in Kansas that were contaminated by ethanol-amended gasoline (10% ethanol by volume; set 2). The data were log-normally distributed, with mean benzene plume lengths (± standard deviation) of 193 ± 135 feet for set 1 and 263 ± 103 feet for set 2 (36% longer). The median lengths were 156 feet and 263 feet (69% longer), respectively. Mean toluene plume lengths were 185± 131 feet for set 1 and 211 ±99 feet for set 2 (14% longer), and the median lengths were 158 feet and 219 feet (39% longer), respectively. Thus, ethanol-containing BTEX plumes were significantly longer for benzene (p < 0.05), but not for toluene. A Wilcoxon signed rank test showed that toluene plumes were generally shorter than benzene plumes, which suggests that toluene was attenuated to a greater extent than benzene. This trend was more pronounced for set 2 (with ethanol), which may reflect that benzene attenuation is more sensitive to the depletion of electron acceptors caused by ethanol degradation. These results support the hypothesis that the presence of ethanol in gasoline can lead to longer benzene plumes. The importance of this effect, however, is probably site-specific, largely depending on the release scenario and the available electron acceptor pool.     

Predicting high-frequency variation in stream solute concentrations with water quality sensors and machine learning

Stream solute monitoring has produced many insights into ecosystem and Earth system functions. Although new sensors have provided novel information about the fine-scale temporal variation of some stream water solutes, we lack adequate sensor technology to gain the same insights for many other solutes. We used two machine learning algorithms – Support Vector Machine and Random Forest – to predict concentrations at 15-min resolution for 10 solutes, of which eight lack specific sensors. The algorithms were trained with data from intensive stream sensing and manual stream sampling (weekly) for four full years in a hydrologic reference stream within the Hubbard Brook Experimental Forest in New Hampshire, USA. The Random Forest algorithm was slightly better at predicting solute concentrations than the Support Vector Machine algorithm (Nash-Sutcliffe efficiencies ranged from 0.35 to 0.78 for Random Forest compared to 0.29 to 0.79 for Support Vector Machine). Solute predictions were most sensitive to the removal of fluorescent dissolved organic matter, pH and specific conductance as independent variables for both algorithms, and least sensitive to dissolved oxygen and turbidity. The predicted concentrations of calcium and monomeric aluminium were used to estimate catchment solute yield, which changed most dramatically for aluminium because it concentrates with stream discharge. These results show great promise for using a combined approach of stream sensing and intensive stream discrete sampling to build information about the high-frequency variation of solutes for which an appropriate sensor or proxy is not available.     

Occurrence of MTBE in Heating Oil and Diesel Fuel in Connecticut

The objective of this study was to confirm if MTBE, which is not intentionally added to fuels other than gasoline, is a contaminant in heating oil and diesel fuel. The study entailed conducting a statewide sampling program of heating oil and diesel fuel in Connecticut. An analytical method was developed to conduct analyses of heating oil and diesel fuel for MTBE in the milligram per liter (mg/L) range. The method involved equilibrating product with water to extract MTBE followed by static head-space analysis on aliquots of the water. Analyses were conducted using a gas chromatograph with a MTBE specific column. The statewide sampling program confirmed the widespread occurrence of MTBE in heating oil and diesel fuel. MTBE was detected in all samples collected during our sampling program at concentrations ranging from 9.7 to 906 mg/L in heating oil (26 samples), and from 74 to 120 mg/L in diesel fuel (five samples). Based on these ranges. MTBE concentrations in ground water in the vicinity of heating oil and diesel fuel releases could exceed thousands of micrograms per liter. Our analysis would suggest that the levels of heating oil and diesel fuel contamination observed could result from the commingling of only a few parts gasoline with thousands of parts of these fuels. The extent to which MTBE occurs in heating oil and diesel fuel nationwide is not known, but our data suggests that it may be widespread.     

Review of Quantitative Surveys of the Length and Stability of MTBE,TBA, and Benzene Plumes in Groundwater at UST Sites

Quantitative information regarding the length and stability condition of groundwater plumes of benzene, methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) has been compiled from thousands of underground storage tank (UST) sites in the United States where gasoline fuel releases have occurred. This paper presents a review and summary of 13 published scientific surveys, of which 10 address benzene and/or MTBE plumes only, and 3 address benzene, MTBE, and TBA plumes. These data show the observed lengths of benzene and MTBE plumes to be relatively consistent among various regions and hydrogeologic settings, with median lengths at a delineation limit of 10 µg/L falling into relatively narrow ranges from 101 to 185 feet for benzene and 110 to 178 feet for MTBE. The observed statistical distributions of MTBE and benzene plumes show the two plume types to be of comparable lengths, with 90th percentile MTBE plume lengths moderately exceeding benzene plume lengths by 16% at a 10‐µg/L delineation limit (400 feet vs. 345 feet) and 25% at a 5‐µg/L delineation limit (530 feet vs. 425 feet). Stability analyses for benzene and MTBE plumes found 94 and 93% of these plumes, respectively, to be in a nonexpanding condition, and over 91% of individual monitoring wells to exhibit nonincreasing concentration trends. Three published studies addressing TBA found TBA plumes to be of comparable length to MTBE and benzene plumes, with 86% of wells in one study showing nonincreasing concentration trends.     

An Empirical Evaluation of the Influence of Ethanol on Natural Attenuation of Gasoline Constituents

Since the 1990s, questions have arisen as to whether the release of ethanol‐blended fuel will inhibit natural attenuation of other gasoline constituents in groundwater. This study evaluated the hypothesis that ethanol affects hydrocarbon attenuation and whether the use of ethanol‐blended fuel alters the applicability of monitored natural attenuation (MNA) as an approach for managing risks at fuel‐release sites. Groundwater data from California's GeoTracker database were used to compare attenuation of benzene, toluene, methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) at sites with and without detections of ethanol. Excel‐based tools were developed to conduct attenuation evaluations on thousands of wells simultaneously. Ethanol was detected at least once in 4.5% of the wells and 0.6% of the samples of which it was analyzed. The distribution of Mann‐Kendall concentration trend analysis results and first‐order attenuation rates were essentially the same at sites with or without ethanol detections. Median plume lengths were shorter at sites where ethanol had not been detected compared to sites where ethanol was detected (36 vs. 43 m for benzene; 36 vs. 42 m for toluene; 43 vs. 52 m for MTBE; and 44 vs. 59 m for TBA). However, the distribution of plume lengths was similar irrespective of ethanol concentrations, suggesting other factors may influence plume elongation. Finally, while anaerobic ethanol degradation can result in methane generation, the distributions of methane concentrations were the same at sites with and without ethanol detections. These results suggest that the use of ethanol‐blended fuel should not limit the application of MNA at most biodegrading fuel‐release sites.     

Do conservative solutes migrate at average pore-water velocity?

According to common understanding, the advective velocity of a conservative solute equals the average linear pore-water velocity. Yet direct monitoring indicates that the two velocities may be different in heterogeneous media. For example, at the Camp Dodge, Iowa, site the advective velocity of discrete Cl- plumes was less than one tenth of the average pore-water velocity calculated from Darcy's law using the measured hydraulic gradient, effective porosity, and hydraulic conductivity (K) from large-scale three-dimensional (3D) techniques, e.g., pumping tests. Possibly, this difference reflects the influence of different pore systems, if the K relevant to transient solute flux is influenced more by lower-K heterogeneity than a steady or quasi-steady water flux. To test this idea, tracer tests were conducted under controlled laboratory conditions. Under one-dimensional flow conditions, the advective velocity of discrete conservative solutes equaled the average pore-water velocity determined from volumetric flow rates and Darcy's law. In a larger 3D flow system, however, the same solutes migrated at approximately 65% of the average pore-water velocity. These results, coupled with direct observation of dye tracers and their velocities as they migrated through both homogeneous and heterogeneous sections of the same model, demonstrate that heterogeneity can slow the advective velocity of discrete solute plumes relative to the average pore-water velocity within heterogeneous 3D flow sytems.     

Fate of MTBE Relative to Benzene in a Gasoline-Contaminated Aquifer (1993–98)

Methyl tert -butyl ether (MTBE) and benzene have been measured since 1993 in a shallow, sandy aquifer contaminated by a mid-1980s release of gasoline containing fuel oxygenates. In wells downgradient of the release area, MTBK was detected before benzene, reflecting a chromatographic-like separation of these compounds in the direction of ground water flow. Higher concentrations of MTBE and benzene were measured in the deeper sampling ports of multilevel sampling wells located near the release area, and also up to 10 feet (3 m) below the water table surface in nested wells located farther from the release area. This distribution of higher concentrations at depth is caused by recharge events that deflect originally horizontal ground water flowlines. In the laboratory, microcosms containing aquifer material incubated with uniformly labeled ¹⁴C-MTBE under aerobic and anaerobic. Fe(III)-reducing conditions indicated a low but measurable biodegradation potential (<3%¹⁴C-MTBW as ¹⁴CO₂) after a seven-month incubation period, Tert -butyl alcohol (TBA), a proposed microbial-MTBE transformation intermediate, was detected in MTBE-contaminated wells, but TBA was also measured in unsaturated release area sediments. This suggests that TBA may have been present in the original fuel spilled and does not necessarily reflect microbial degradation of MTBE. Combined, these data suggest that milligram per liter to microgram per liter decreases in MTBE concentrations relative to benzene are caused by the natural attenuation processes of dilution and dispersion with less-contaminated ground water in the direction of flow rather than biodegradation at this point source gasoline release site.     

The role of eddies in solute transport and recovery in rock fractures: Implication for groundwater remediation

A better understanding of solute transport and retention mechanism in rock fractures has been challenging due to difficulty in their direct observations in microscale rough‐walled fractures. Six representative troughs in a rough‐walled fracture were selected for microscale observations of eddy formation with increasing flow velocity and its effect on spatiotemporal changes of solute concentration. This experimental study was enabled by a microscale visualization technique of micro particle image velocimetry. With increasing flow velocity (Re ≤ 2.86), no eddies were generated, and solutes along the main streamlines transported rapidly, whereas those near the wall moved slowly. A larger amount of solutes remained trapped at all troughs at Re = 2.86 than Re < 1. For Re = 8.57, weak eddies started to be developed at the troughs on the lee side, which little contributed to overall solute flushing in the fracture. Accordingly, a large of amount of water was needed for solute flushing. The flow condition of 1 < Re < 10, before a full development of eddies, was least favourable in terms of time and amount of remediation fluid required to reach a target concentration. After large eddies were fully developed at troughs on the lee side for Re = 17.13, solutes were substantially reduced by eddies with less amount of water. Fully developed eddies were found to enhance solute transport and recovery, as opposed to a general consensus that eddies trap and delay solutes. Direct inflow into troughs on the stoss side also made a great contribution to solute flushing out of the troughs. This study indicates that fully developed eddies or strong inflows at troughs are highly possible to form for Re > 10 and this flow range could be favourable for efficient remediation.     

The Role of Bioattenuation in the Management of Aromatic Hydrocarbon Plumes in Aquifers

Ground water scientists have made significant advances in understanding the soil interactions, hydrogeology, fate and transport, and subsurface microbiology of aromatic hydrocarbons (BTEX) in aquifer systems. It is now generally recognized that a major factor responsible for the attenuation and mass reduction of BTEX in plumes is the widespread occurrence of hydrocarbon biodegradation by indigenous soil microorganisms in aquifer material. Most well-studied BTEX plumes that develop from the accidental release of gasoline fuels contain low levels of soluble hydrocarbons (< 1 to 5000 ppb) and have been shown to be spatially confined because of natural biotransformation mechanisms. These in situ processes are controlled by source and aquifer characteristics, permeability, sorption, and geochemical properties of the aquifer. Many laboratory subsoil-ground water microcosms and field studies (10 to 20 C) have demonstrated the rapid biodecay (1 to SO percent/day for microcosms and 0.5 to 1.5 percent/day for plumes) of these aromatic compounds under primarily aerobic conditions (i.e., those with sufficient dissolved oxygen). The ability to implement ground water bioremediation will depend upon our understanding of source control and aquifer recharge effects on the spatial distribution of plumes. In addition, estimating the biodegradation of sorbed BTEX, determining limits and potential for in situ biostimulation of soluble plumes, and establishing data requirements for predictive modeling of natural attenuation will be useful for this remediation technology. The use of these tools to manage ground water quality appears to represent the most practical alternative, particularly for low-risk ground water supplies.     

Used Motor Oil as a Source of MTBE, TAME, and BTEX to Ground Water

Methyl tert-butyl ether (MTBE), the widely used gasoline oxygenate, has been identified as a common ground water contaminant, and BTEX compounds (benzene, toluene, ethylbenzene, and xylenes) have long been associated with gasoline spills. Because not all instances of ground water contamination by MTBE and BTEX can be attributed to spills or leaking storage tanks, other potential sources need to be considered. In this study, used motor oil was investigated as a potential source of these contaminants. MTBE in oil was measured directly by methanol extraction and gas chromatography using a flame ionization detector (GC/FID). Water was equilibrated with oil samples and analyzed for MTBE, BTEX, and the oxygenate tert-amyl methyl ether (TAME) by purge- and-trap concentration followed by GC/FID analysis. Raoult's law was used to calculate oil-phase concentrations of MTBE, BTEX, and TAME from aqueous-phase concentrations. MTBE, TAME, and BTEX were not detected in any of five new motor oil samples, whereas these compounds were found at significant concentrations in all six samples of the used motor oil tested for MTBE and all four samples tested for TAME and BTEX. MTBE concentrations in used motor oil were on the order of 100 mg/L. TAME concentrations ranged from 2.2 to 87 mg/L. Concentrations of benzene were 29 to 66 mg/L, but those of other BTEX compounds were higher, typically 500 to 2000 mg/L.     

Complex patterns of catchment solute–discharge relationships for coastal plain rivers

Riverine solute versus discharge (C–Q) relationships provide information about the magnitude and dynamics of material fluxes from landscapes. We analysed long‐term patterns of C–Q relationships for 44 rivers in Florida across a suite of geogenic, nutrient, and organic solutes and investigated land cover, watershed size, and surficial geology as controls on these patterns. Solute concentrations generally exhibited far less variability than did discharge, with coherent solute‐specific behaviours repeated across watersheds. Geogenic solutes generally diluted with increasing discharge, whereas organic solutes generally enriched; patterns for nutrients were highly variable across watersheds, but on average exhibited chemostasis. Despite strong evidence of both geologic and land cover controls on solute flow‐weighted concentrations, these variables were poor predictors of C–Q slopes (β) or relative coefficients of variation (CV_C:CV_Q). CV_C:CV_Q generally increased with watershed size, and wetland area appeared to influence C–Q patterns for base cations and organic solutes. Perhaps most importantly, we observed significant slope breaks in C–Q association in approximately half of our observations, challenging the generality of using single power functions to describe catchment solute export patterns. For all solutes except phosphorus (P), C–Q slopes decreased above statistically identified breaks (slopes for P increased), with breaks consistently at or near median flow (i.e., 50% flow exceedance probability). This common pattern significantly impacts solute load estimates; failing to account for slope breaks overestimates nitrate and total organic carbon loads as much as 125% and underestimates P loads as much as 35%. In addition to challenging generic power‐law characterization of C–Q relationships for these coastal plain rivers, and exploring the load estimate consequences thereof, our study supports emerging insights about watershed hydrochemical behaviours across a wide array of solutes.     

Influence of conduit network geometry on solute transport in karst aquifers with a permeable matrix

In karst aquifers with significant matrix permeability, water and solutes are exchanged between the conduits and carbonate matrix. Transport through the matrix increases the spread of solutes and increases travel times. This study numerically evaluates advective solute transport in synthetic karst systems that contain 3D branching conduit networks. Particle tracking is performed to analyze the spatial and temporal transport history of solute that arrives at the conduit outlet. Three measures of transport connectivity are used to quantify the solute migration behavior: the skewness of the particle arrival time distribution, the normalized fifth percentile of arrival times, and the fraction of the total travel time that occurs within conduits. All three of these metrics capture the influence of conduit network geometry on solute transport. A more tortuous network leads to enhanced conduit-matrix mixing, which reduces the transport connectivity and yields a broader distribution of solute arrival times. These results demonstrate that the conduit network geometry is an important control on solute transport in karst systems with a permeable matrix.     

DNAPL to LNAPL Transitions During Horizontal Cosolvent Flooding

Cosolvent flooding is a technology with the potential to remove nonaqueous phase liquid (NAPL) sources from the subsurface. It can be used to initiate separate phase mobilization, which allows removal of NAPL within very few pore volumes. Mobilization may result in a sinking DNAPL bank during horizontal flooding of NAPLs denser than water. Reversal of phase density difference between aqueous and DNAPL phases could potentially avoid this downward migration of mobilized DNAPLs. We achieved phase density difference reversal and made DNAPLs float using two components in the cosolvent flooding solution. A low-density cosolvent partitions preferentially into the DNAPL and swells it, which causes a reduction in density of the DNAPL and reversal of the density difference between the NAPL and aqueous phases. A highdensity additive that remains in the aqueous phase allows the cosolvent flooding solution overall to have a density greater than that of water and permits control of the flooding instability. This study focused on tert-butanol as the swelling cosolvent and tetrachloroethylene as the contaminant. In batch tests with sucrose and glycerol as dense additives, phase density difference reversal occurred. To investigate the applicability of phase density difference reversal as a remediation technology, horizontal column and sandbox experiments were performed. These experiments demonstrated the occurrence of phase density difference reversal and effective remediation in horizontal cosolvent floods.