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.     

A Comparative Plume Study of DRO,GRO, Benzene,and MTBE: Implications for Risk Management

Groundwater remediation and no-further action decision making at petroleum underground storage tank (UST) sites has largely been based on an understanding of plume length, plume stability, and attenuation rates for key hydrocarbon constituents. Regulatory guidance to support and guide such decisions is based in part on plume studies involving individual hydrocarbon constituents, namely benzene and methyl tert-butyl ether (MTBE). Questions remain regarding whether current guidance is applicable to chemical mixtures such as gasoline range organics (GRO), diesel range organics (DRO), and oxygen containing organic compounds (OCOCs) resulting from hydrocarbon biodegradation. To help address this concern, data from California's GeoTracker database were used to estimate maximum plume lengths, plume stability, and attenuation rates of DRO (which can be used as an analytical surrogate for OCOCs) and GRO relative to benzene and MTBE. The distributions of maximum plume lengths were similar for the four constituents with medians ranging from 27 to 32 m. The fraction of monitoring wells with a decreasing concentration trend ranged from 19% for DRO to 40% for MTBE, while fewer than 7% of the wells had an increasing concentration trend for any of the constituents. Median attenuation rates ranged from 0.10% day⁻¹ for DRO to 0.17% day⁻¹ for MTBE. The results suggest attenuation based risk management is appropriate for DRO and GRO plumes at most petroleum UST sites.     

A simple method for calculating growth rates of petroleum hydrocarbon plumes

Consumption of aquifer Fe(III) during biodegradation of ground water contaminants may result in expansion of a contaminant plume, changing the outlook for monitored natural attenuation. Data from two research sites contaminated with petroleum hydrocarbons show that toluene and xylenes degrade under methanogenic conditions, but the benzene and ethylbenzene plumes grow as aquifer Fe(III) supplies are depleted. By considering a one-dimensional reaction front in a constant unidirectional flow field, it is possible to derive a simple expression for the growth rate of a benzene plume. The method balances the mass flux of benzene with the Fe(III) content of the aquifer, assuming that the biodegradation reaction is instantaneous. The resulting expression shows that the benzene front migration is retarded relative to the ground water velocity by a factor that depends on the concentrations of hydrocarbon and bioavailable Fe(III). The method provides good agreement with benzene plumes at a crude oil study site in Minnesota and a gasoline site in South Carolina. Compared to the South Carolina site, the Minnesota site has 25% higher benzene flux but eight times the Fe(III), leading to about one-sixth the expansion rate. Although it was developed for benzene, toluene, ethylbenzene, and xylenes, the growth-rate estimation method may have applications to contaminant plumes from other persistent contaminant sources.     

Exceptionally Long MTBE Plumes of the Past Have Greatly Diminished

Studies published in the late 1990s and early 2000s identified the presence of exceptionally long methyl tert‐butyl ether (MTBE) plumes (more than 600 m or 2000 feet) in groundwater and have been cited in technical literature as characteristic of MTBE plumes. However, the scientific literature is incomplete in regard to the subsequent behavior and fate of these MTBE plumes over the past decade. To address this gap, this issue paper compiles recent groundwater monitoring records for nine exceptional plumes that were identified in prior studies. These nine sites exhibited maximum historical MTBE groundwater plume lengths ranging from 820 m (2700 feet) to 3200 m (10,500 feet) in length, exceeding the lengths of 99% of MTBE plumes, as characterized in multiple surveys at underground storage tank sites across the United States. Groundwater monitoring data compiled in our review demonstrate that these MTBE plumes have decreased in length over the past decade, with five of the nine plumes exhibiting decreases of 75% or more compared to their historical maximum lengths. MTBE concentrations within these plumes have decreased by 93% to 100%, with two of the nine sites showing significant decreases (98% and 99%) such that the regulatory authority has subsequently designated the site as requiring no further action.     

Effect of Biofuels on Biodegradation of Benzene and Toluene at Gasoline Spill Sites

The risk that benzene and toluene from spills of gasoline will impact drinking water wells is largely controlled by the natural anaerobic biodegradation of benzene and toluene. Benzene and toluene, as well as ethanol and other biofuels, are degraded under anaerobic conditions to the same pool of degradation products. Biodegradation of biofuels may produce concentrations of degradation products that make the thermodynamics for degradation of benzene and toluene infeasible under methanogenic conditions and produce larger plumes of benzene and toluene. This study evaluated the concentrations of fuel alcohols that are necessary to inhibit the anaerobic degradation of benzene and toluene under methanogenic conditions. At two ethanol spill sites, concentrations of ethanol greater ≥42 mg/L inhibited the anaerobic degradation of toluene. The pH and concentrations of acetate, dissolved inorganic carbon, and molecular hydrogen were used to calculate the Gibbs free energy for the biodegradation of toluene. In general, the anaerobic biodegradation of toluene was not thermodynamically feasible in water with ≥42 mg/L ethanol. In a microcosm study, when the concentrations of ethanol were ≥14 mg/L or the concentrations of n‐butanol were ≥16 mg/L, the biodegradation of the alcohols consistently produced concentrations of hydrogen, dissolved inorganic carbon, and acetate that would preclude natural anaerobic biodegradation of benzene and toluene by syntrophic organisms. In contrast, iso‐butanol and n‐propanol only occasionally produced conditions that would preclude the biodegradation of benzene and toluene.     

Monitored Natural Attenuation of Manufactured Gas Plant Tar Mono- and Polycyclic Aromatic Hydrocarbons in Ground Water: A 14-Year Field Study

Site 24 was the subject of a 14-year (5110-day) study of a ground water plume created by the disposal of manufactured gas plant (MGP) tar into a shallow sandy aquifer approximately 25 years prior to the study. The ground water plume in 1988 extended from a well-defined source area to a distance of approximately 400 m down gradient. A system of monitoring wells was installed along six transects that ran perpendicular to the longitudinal axis of the plume centerline. The MGP tar source was removed from the site in 1991 and a 14-year ground water monitored natural attenuation (MNA) study commenced. The program measured the dissolved mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs) periodically over time, which decreased significantly over the 14-year period. Naphthalene decreased to less than 99% of the original dissolved mass, with mass degradation rates of 0.30 per year (half-life 2.3 years). Bulk attenuation rate constants for plume centerline concentrations over time ranged from 0.33 ± 0.09 per year (half-life 2.3 ± 0.8 years) for toluene and 0.45 ± 0.06 per year (half-life 1.6 ± 0.2 years) for naphthalene. The hydrogeologic setting at Site 24, having a sandy aquifer, shallow water table, clay confining layer, and aerobic conditions, was ideal for demonstrating MNA. However, these results demonstrate that MNA is a viable remedial strategy for ground water at sites impacted by MAHs and PAHs after the original source is removed, stabilized, or contained.     

Land Application of Sulfate Salts for Enhanced Natural Attenuation of Benzene in Groundwater: A Case Study

Sulfate reducing conditions are widely observed in groundwater plumes associated with petroleum hydrocarbon releases. This leads to sulfate depletion in groundwater which can limit biodegradation of hydrocarbons (usually benzene, toluene, ethylbenzene, xylenes [BTEX] compounds) and can therefore result in extended timeframes to achieve groundwater cleanup objectives by monitored natural attenuation. Under these conditions, sulfate addition to the subsurface can potentially enhance BTEX biodegradation and facilitate enhanced natural attenuation. However, a delivery approach that enables effective contact with the hydrocarbons and is able to sustain elevated and uniform sulfate concentrations in groundwater remains a key challenge. In this case study, sulfate addition to a groundwater plume containing predominantly benzene by land application of agricultural gypsum and Epsom salt is described. Over 4 years of groundwater monitoring data from key wells subjected to pilot‐scale and site‐wide land application events are presented. These are compared to data from pilot testing employing liquid Epsom salt injections as an alternate sulfate delivery approach. Sulfate land application, sulfate retention within the vadose zone, and periodic infiltration following ongoing precipitation events resulted in elevated sulfate concentrations (>150 mg/L) in groundwater that were sustained over 12 months between application events and stimulated benzene biodegradation as indicated by declines in dissolved benzene concentration, and compound‐specific isotope analysis data for carbon in benzene. Long‐term groundwater benzene concentration reductions were achieved in spite of periodic rebounds resulting from water table fluctuations across the smear zone. Land application of gypsum is a potentially cost‐effective sulfate delivery approach at sites with open, unpaved surfaces, relatively permeable geology, and shallow hydrocarbon impacts. However, more research is needed to understand the fate and persistence of sulfate and to improve the likelihood of success and effectiveness of this delivery approach.     

Enhancement of In Situ Bioremediation of BTEX-Contaminated Ground Water by Oxygen Diffusion from Silicone Tubing

A field study of oxygen-enhanced biodegradation was carried out in a sandy iron-rich ground water system contaminated with gasoline hydrocarbons. Prior to the oxygen study, intrinsic microbial biodegradation in the contaminant plume had depleted dissolved oxygen and created anaerobic conditions. An oxygen diffusion system made of silicone polymer tubing was installed in an injection well within an oxygen delivery zone containing coarse highly permeable sand. During the study, this system delivered high dissolved oxygen (DO) levels (39 mg/L) to the ground water within a part of the plume. The ground water was sampled at a series of monitors in the test zone downgradient of the delivery well to determine the effect of oxygen on dissolved BTEX, ground water geochemistry, and microbially mediated biodegradation processes. The DO levels and Eh increased markedly at distances up to 2.3 m (7.5 feet) downgradient. Potential biofouling and iron precipitation effects did not clog the well screens or porous medium. The increased dissolved oxygen enhanced the population of aerobes while the activity of anaerobic sulfate-reducing bacteria and methanogens decreased. Based on concentration changes, the estimated total rate of BTEX biodegradation rose from 872 mg/day before enhancement to 2530 mg/day after 60 days of oxygen delivery. Increased oxygen flux to the test area could account for aerobic biodegradation of 1835 mg/day of the BTEX. The estimated rates of anaerobic biodegradation processes decreased based on the flux of sulfate, iron (II), and methane. Two contaminants in the plume, benzene and ethylbenzene, are not biodegraded as readily as toluene or xylenes under anaerobic conditions. Following oxygen enhancement, however, the benzene and ethylbenzene concentrations decreased about 98%, as did toluene and total xylenes.     

Modeling of Plume Capture by Continuous, Low-Permeability Barriers

Modeling was performed to simulate ground water flow through reactive barriers of lower hydraulic conductivity than the surrounding aquifer to determine the plume capture widths. As a plume approaches such a barrier, it spreads laterally. Therefore, to intercept an entire plume, the barrier must be wider than the upgradient width of the undisturbed plume. The results indicate that, for practical values of barrier thickness and plume width, hydraulic conductivities ten-fold less than that of the aquifer can be accommodated by making the width of the barrier approximately 20% greater than the upgradient width of the plume. Barrier hydraulic conductivities one-hundred-fold less than that of the aquifer may require barrier widths up to twice the width of the upgradient plume for plumes 100 feet wide (33 m) and as little as 1.1 times for plumes 1000 feet wide (325 m). The results presented here lend support to the view that novel emplacement methods that create zones of slightly lower hydraulic conductivity than the native aquifer may be viable alternatives to the excavation-and-backfill approaches which have thus far been used for installing permeable reactive barriers.     

Methane Production and Isotopic Fingerprinting in Ethanol Fuel Contaminated Sites

Biodegradation of organic compounds in groundwater can be a significant source of methane in contaminated sites. Methane might accumulate in indoor spaces posing a hazard. The increasing use of ethanol as a gasoline additive is a concern with respect to methane production since it is easily biodegraded and has a high oxygen demand, favoring the development of anaerobic conditions. This study evaluated the use of stable carbon isotopes to distinguish the methane origin between gasoline and ethanol biodegradation, and assessed the occurrence of methane in ethanol fuel contaminated sites. Two microcosm tests were performed under anaerobic conditions: one test using ethanol and the other using toluene as the sole carbon source. The isotopic tool was then applied to seven field sites known to be impacted by ethanol fuels. In the microcosm tests, it was verified that methane from ethanol (δ¹³C = −11.1‰) is more enriched in ¹³C, with δ¹³C values ranging from −20‰ to −30‰, while the methane from toluene (δ¹³C = −28.5‰) had a carbon isotopic signature of −55‰. The field samples had δ¹³C values varying over a wide range (−10‰ to −80‰), and the δ¹³C values allowed the methane source to be clearly identified in five of the seven ethanol/gasoline sites. In the other two sites, methane appears to have been produced from both sources. Both gasoline and ethanol were sources of methane in potentially hazardous concentrations and methane could be produced from organic acids originating from ethanol along the groundwater flow system even after all the ethanol has been completed biodegraded.     

Progress in Remediation of Groundwater at Petroleum Sites in California

Quantifying the overall progress in remediation of contaminated groundwater has been a significant challenge. We utilized the GeoTracker database to evaluate the progress in groundwater remediation from 2001 to 2011 at over 12,000 sites in California with contaminated groundwater. This paper presents an analysis of analytical results from over 2.1 million groundwater samples representing at least $100 million in laboratory analytical costs. Overall, the evaluation of monitoring data shows a large decrease in groundwater concentrations of gasoline constituents. For benzene, half of the sites showed a decrease in concentration of 85% or more. For methyl tert‐butyl ether (MTBE), this decrease was 96% and for TBE, 87%. At remediation sites in California, the median source attenuation rate was 0.18/year for benzene and 0.36/year for MTBE, corresponding to half‐lives of 3.9 and 1.9 years, respectively. Attenuation rates were positive (i.e., decreasing concentration) for benzene at 76% of sites and for MTBE at 85% of sites. An evaluation of sites with active remediation technologies suggests differences in technology effectiveness. The median attenuation rates for benzene and MTBE are higher at sites with soil vapor extraction or air sparging compared with sites without these technologies. In contrast, there was little difference in attenuation rates at sites with or without soil excavation, dual phase extraction, or in situ enhanced biodegradation. The evaluation of remediation technologies, however, did not evaluate whether specific systems were well designed or implemented and did not control for potential differences in other site factors, such as soil type.     

Mass and flux distributions from DNAPL zones in sandy aquifers

At three industrial sites in Ontario, New Hampshire, and Florida, tetrachloroethylene (PCE) and trichloroethylene (TCE), released decades ago as dense nonaqueous phase liquids (DNAPLs), now form persistent source zones for dissolved contaminant plumes. These zones are suspended below the water table and above the bottoms of their respective, moderately homogeneous, unconfined sandy aquifers. Exceptionally detailed, depth-discrete, ground water sampling was performed using a direct-push sampler along cross sections of the dissolved-phase plumes, immediately downgradient of these DNAPL source zones. The total plume PCE or TCE mass-discharge through each cross section ranged between 15 and 31 kg/year. Vertical ground water sample spacing as small as 15 cm and lateral spacing typically between 1 and 3 m revealed small zones where maximum concentrations were between 1% and 61% of solubility. These local maxima are surrounded by much lower concentration zones. A spacing no larger than 15 to 30 cm was needed at some locations to identify high concentration zones, and aqueous VOC concentrations varied as much as four orders of magnitude across 30 cm vertical intervals. High-resolution sampling at these sites showed that three-quarters of the mass-discharge occurs within 5% to 10% of the plume cross sectional areas. The extreme spatial variability of the mass-discharge occurs even though the sand aquifers are nearly hydraulically homogeneous. Depth-discrete field techniques such as those used in this study are essential for finding the small zones producing most of the mass-discharge, which is important for assessing natural attenuation and designing remedial options.     

Impact of Temperature on Groundwater Source Attenuation Rates at Hydrocarbon Sites

The temperature sensitivity of microbial populations is reflected in measured source attenuation rates at hydrocarbon‐impacted sites. The objective of this study was to evaluate the correlation between temperature and source attenuation rates (concentration vs. time attenuation rate over many years) of benzene and toluene by analyzing groundwater monitoring data from >2000 hydrocarbon sites. Historical monitoring records were obtained from three databases, processed to yield long‐term multiyear source attenuation rates, and then compared with representative temperatures at each site. Statistically significant and positive relationships between temperature and source attenuation rates were established for benzene and toluene, indicating that temperature does impact hydrocarbon degradation, but is one of many factors that contribute to source attenuation. There was an observed 1.1 to 1.6 times increase in attenuation rates per 10 °C increase in temperature, which is less than the rate increases predicted by the Arrhenius equation. The temperature dependence on attenuation rate is consistent with several lines of evidence that methanogenesis plays a key role in the rate of hydrocarbon source zone attenuation rather than being controlled strictly by the availability of electron acceptors. First, methanogenesis is known to be strongly influenced by temperature, with significantly higher rates up to about 35 °C. Second, the temperature‐degradation rate relationship was stronger at sites with deeper water tables (>30 ft) that are less susceptible to oxygen influx than sites with shallow water tables (<15 ft). Third, dissolved methane concentrations were higher at sites with warmer temperatures. Overall, these results provide indirect support for a conceptual model where methanogenesis is a key degradation process at hydrocarbon sites, and that attenuation of these source zones is temperature‐sensitive.     

Modeling the Potential Effect of Additives on Enhancing the Solubility of Aromatic Solutes Contained in Gasoline

The potential effect of two common gasoline additives, ethanol and methyl tertiary-butyl ether (MTBE), on enhancing the solubility of the aromatic solutes benzene, toluene, ethylbenzene, and o-, m-, and p-xylene, was examined using a computer model, ARSOL. Aqueous solute systems containing cosolvents ethanol and MTBE at 0, 0.1, 1, and 4.3 percent were modeled for both ethanol and MTBE systems. Five- and 10-percent ethanol systems were also modeled. Little solubility enhancement was predicted by modeling at cosolvent levels less than 1 percent. At cosolvent levels greater than 1 percent, predicted solute solubility increased curvilinearly with an increase in percent cosolvent; a 10 percent cosolvent system increased aromatic hydrocarbon solubility by approximately 100 percent. According to the model predictions, MTBE enhanced solute solubility more than ethanol, with enhancement by MTBE being approximately 10 percent greater than enhancement by ethanol at 4.3 percent cosolvent. Other concerns regarding gasoline additives are the observed reduction in partitioning of solutes to soils and sediments and the contamination of water supplies due to the high water solubility of the additives.     

Estimation of anaerobic biodegradation rate constants at MGP sites

Field data at six former manufactured gas plant sites in New Jersey were used to estimate the biodegradation rate constants for the anaerobic processes naturally occurring within the ground water contaminant plumes (primarily iron and sulfate reduction). Those rate constants turned out to be about an order of magnitude smaller than values reported for the same contaminants (primarily benzene and naphthalene) at fuel sites. At four of the sites, there appeared to be sufficient electron acceptor present to eventually degrade the contaminants in the plume. However, the presence of nonaqueous phase liquids tends to offset that capacity by continuing to act as a source of contaminants that can dissolve in the ground water.     

Enhanced attenuation of septic system phosphate in noncalcareous sediments

Review of phosphate behavior in four mature septic system plumes on similar textured sand has revealed a strong correlation between carbonate mineral content and phosphate concentrations. A plume on calcareous sand (Cambridge site, 27 wt % CaCO3 equiv.) has proximal zone PO4 concentrations (4.8 mg/L P average) that are about 75% of the septic tank effluent value, whereas three plumes on noncalcareous sand (Muskoka, L. Joseph, and Nobel sites, <1 wt % CaCO3 equiv.) have proximal zone phosphate concentrations (<0.1 mg/L P) that are consistently less than 2% of the effluent values. Phosphate attenuation at the noncalcareous sites appears to be an indirect result of the development of acidic conditions (site average pH 3.5 to 5.9) and elevated Al concentrations (up to 24 mg/L), which subsequently causes the precipitation of Al-P minerals such as variscite (AlPO4 x 2H2O). This is supported by scanning electron microscope analyses, which show the widespread occurrence of (Al+P)--rich secondary mineral coatings on sand grains below the infiltration beds. All of these septic systems are more than 10 years old, indicating that these attenuation reactions have substantial longevity. A field lysimeter experiment demonstrated that this reaction sequence can be readily incorporated into engineered waste water treatment systems. We feel this important P removal mechanism has not been adequately recognized, particularly for its potential significance in reducing P loading from septic systems in lakeshore environments.     

Mass Discharge in a Tracer Plume: Evaluation of the Theissen Polygon Method

A tracer plume was created within a thin aquifer by injection for 299 d of two adjacent “sub‐plumes” to represent one type of plume heterogeneity encountered in practice. The plume was monitored by snapshot sampling of transects of fully screened wells. The mass injection rate and total mass injected were known. Using all wells in each transect (0.77 m well spacing, 1.4 points/m² sampling density), the Theissen Polygon Method (TPM) yielded apparently accurate mass discharge (M_d) estimates at three transects for 12 snapshots. When applied to hypothetical sparser transects using subsets of the wells with average spacing and sampling density from 1.55 to 5.39 m and 0.70 to 0.20 points/m², respectively, the TPM accuracy depended on well spacing and location of the wells in the hypothesized transect with respect to the sub‐plumes. Potential error was relatively low when the well spacing was less than the widths of the sub‐plumes (>0.35 points/m²). Potential error increased for well spacing similar to or greater than the sub‐plume widths, or when less than 1% of the plume area was sampled. For low density sampling of laterally heterogeneous plumes, small changes in groundwater flow direction can lead to wide fluctuations in M_d estimates by the TPM. However, sampling conducted when flow is known or likely to be in a preferred direction can potentially allow more useful comparisons of M_d over multiyear time frames, such as required for performance evaluation of natural attenuation or engineered remediation systems.     

Diffusive Oxygen Emitters for Enhancement of Aerobic In Situ Treatment

Aerobic biodegradation can be enhanced within contaminant plumes by elevating typically low dissolved oxygen (D.O.) levels using materials or devices that passively release oxygen. We have developed passive devices that provide a uniform, steady, long-term source of oxygen by diffusion from pressurized polymeric tubing and report test results under lab and field conditions. Lab flow-through reactor tests were conducted to determine the diffusion coefficient (D) of oxygen through four readily available tubing materials. Oxygen diffusion was greatest through Tygon® 3350 platinum-cured silicone (D = 6.67 ± 10^-7 cm²/sec), followed by 2075 Ultra Chemical Resistant Tygon (1.59 ± 10^-7 cm²/sec), 2275 High Purity Tygon (5.11 ± 10^-8 cm²/sec), and low-density polyethylene (LDPE; 1.73 ± 10^-8 cm²/sec). Variable-pressure release tests with LDPE resulted in very close estimates of D, which confirmed that mass transfer is controlled by diffusion and that the concentration gradient is a valid approximation of the chemical potential driving diffusion. LDPE emitter devices were designed and installed in seven 8-inch-diameter well screens across a portion of a gasoline plume at a former service station. With the devices pressurized to 620.5 kPag (kilopascals gauge) late in the test, steady-state D.O. concentrations reached as high as 25 mg/L, comparing favorably to the value predicted using the mass-transfer coefficient estimated from the lab test (26.3 mg/L). The method can also be used to release other gases for other reasons: gaseous tracers (i.e., sulphur hexafluoride, helium, and argon), hydrogen (for reductive dechlorination), or light alkanes (for cometabolic biodegradation of methyl tertiary butyl ether [MTBE] or chlorinated solvents).     

Crude Oil Metabolites in Groundwater at Two Spill Sites

Two groundwater plumes in north central Minnesota with residual crude oil sources have 20 to 50 mg/L of nonvolatile dissolved organic carbon (NVDOC). These values are over 10 times higher than benzene and two to three times higher than Diesel Range Organics in the same wells. On the basis of previous work, most of the NVDOC consists of partial transformation products from the crude oil. Monitoring data from 1988 to 2015 at one of the sites located near Bemidji, MN show that the plume of metabolites is expanding toward a lakeshore located 335 m from the source zone. Other mass balance studies of the site have demonstrated that the plume expansion is driven by the combined effect of continued presence of the residual crude oil source and depletion of the electron accepting capacity of solid phase iron oxide and hydroxides on the aquifer sediments. These plumes of metabolites are not covered by regulatory monitoring and reporting requirements in Minnesota and other states. Yet, a review of toxicology studies indicates that polar metabolites of crude oil may pose a risk to aquatic and mammalian species. Together the results suggest that at sites where residual sources are present, monitoring of NVDOC may be warranted to evaluate the fates of plumes of hydrocarbon transformation products.