Soil Gas Sampling for 1,4‐Dioxane during Heated Soil Vapor Extraction

Soil gas sampling for 1,4‐dioxane at elevated soil temperatures, such as those experienced during in‐situ thermal treatment, has the potential to yield low results due to condensation of water vapor in the ambient temperature sampling vessel and the partitioning of 1,4‐dioxane into that condensate. A simple vapor/condensate sampling apparatus was developed to collect both condensate and vapor samples to allow for determination of a reconstituted effective soil gas concentration for 1,4‐dioxane. Results using the vapor/condensate sampling apparatus during a heated air injection SVE field demonstration are presented, along with those of a comparable laboratory system. Substantial 1,4‐dioxane mass was found in the condensate in both the lab and field (as high as ~50% in field). As soil temperatures increased, less 1,4‐dioxane mass was detected in field condensate samples than expected based on laboratory experiments. Extraction well effluent sampling at the wellhead by direct vapor canister sampling provided erratic results (several biased low by a factor of 5 or more) compared to those of the vapor/condensate apparatus. Direct vapor canister sampling of extraction well effluent after the air‐water separator, however, provided results reasonably comparable (within 35%) to those using the vapor/condensate apparatus at the wellhead. Soil gas sampling at elevated temperatures using the vapor/condensate apparatus alleviates potential low sampling bias due to condensation.     

1,4‐Dioxane Soil Remediation Using Enhanced Soil Vapor Extraction: I. Field Demonstration

1,4‐Dioxane is totally miscible in water, sequestering in vadose pore water that can serve as a source of long‐term groundwater contamination. Although some 1,4‐dioxane is removed by conventional soil vapor extraction (SVE), remediation is typically inefficient. SVE efficiency is hindered by low Henry’s Law constants at ambient temperature and redistribution to vadose pore water if SVE wells pull 1,4‐dioxane vapors across previously clean soil. It was hypothesized that heated air injection and more focused SVE extraction (“Enhanced SVE” or XSVE) could increase the efficiency of 1,4‐dioxane vadose treatment, and this new process was tested at former McClellan Air Force Base, CA. The XSVE system had four peripheral heated air injection wells surrounding a 6.1 m × 6.1 m × 9.1 m deep treatment zone with a central vapor extraction well. After 14 months of operation, soil temperatures reached as high as ~90 °C near the injection wells and the treatment zone was flushed with ~20,000 pore volumes of injected air. Post‐treatment sampling results showed reductions of ~94% in 1,4‐dioxane and ~45% in soil moisture. Given the simplicity of the remediation system components and the promising demonstration test results, XSVE has the potential to be a cost‐effective remediation option for vadose zone soil containing 1,4‐dioxane.     

Rapid Analysis of 1,4‐Dioxane in Groundwater by Frozen Micro‐Extraction with Gas Chromatography/Mass Spectrometry

An innovative micro‐extraction of aqueous samples coupled with gas chromatography/mass spectrometry in selected ion‐monitoring mode (GC/MS‐SIM) was developed to selectively analyze for 1,4‐dioxane with low part‐per‐billion detection sensitivity. Recoveries of 1,4‐dioxane ranged from 93% to 117% for both spiked laboratory reagent water and natural groundwater matrices, the later having elevated organic carbon content (8.34 ± 0.31 mg/L as total organic carbon). We observed that freezing the aqueous sample along with the extraction solvent enhanced the extraction efficiency, minimized physical interferences, and improved sensitivity resulting in a limit of detection for 1,4‐dioxane to approximately 1.6 μg/L. This method substantially reduces the labor, time, reagents and cost, and uses instruments that are commonly found in analytical laboratories. This method requires a relatively small sample volume (200 μL), and can be considered a green analytical method as it minimizes the use of toxic solvents and the associated laboratory wastes.     

Concurrent Treatment of 1,4‐Dioxane and Chlorinated Aliphatics in a Groundwater Recirculation System Via Aerobic Cometabolism

This research demonstrates that groundwater contaminated by a relatively dilute but persistent concentration of 1,4‐dioxane (1,4‐D), approximately 60 μg/L, and chlorinated aliphatic co‐contaminants (1.4 to 10 μg/L) can be efficiently and reliably treated by in situ aerobic cometabolic biodegradation (ACB). A field trial lasting 265 days was conducted at Operable Unit D at the former McClellan Air Force Base and involved establishing an in situ ACB reactor through amending recirculated groundwater with propane and oxygen. The stimulated indigenous microbial population was able to consistently degrade 1,4‐D to below 3 μg/L while the co‐contaminants trichloroethene (TCE) and 1,2‐dichloroethane (1,2‐DCA) were decreased to below 1 μg/L and 0.18 μg/L, respectively. A stable treatment efficiency of more than 95% removal for 1,4‐D and 1,2‐DCA and of more than 90% removal for TCE was achieved. High treatment efficiencies for 1,4‐D and all co‐contaminants were sustained even without propane and oxygen addition for a 2‐week period.     

1,4‐Dioxane Soil Remediation Using Enhanced Soil Vapor Extraction (XSVE): II. Modeling

1,4‐Dioxane is a volatile organic compound that is fully miscible in water, allowing it to sequester in vadose zone pore water and serve as a long‐term source of groundwater contamination. Conventional soil vapor extraction (SVE) removes 1,4‐dioxane; however, substantial 1,4‐dioxane can remain even after other colocated chlorinated solvents have been remediated. A field demonstration of “enhanced SVE” (XSVE) with focused extraction and heated injection was conducted at former McClellan AFB, CA, achieving 94% reduction in soil concentrations. A screening‐level tool, HypeVent XSVE, was created to assist in system design and data reduction and to anticipate how operating factors affect XSVE performance (e.g., cleanup level, remediation time, etc.). It assumes well‐mixed conditions, and combines an energy balance, mass balances for water and contaminant, and a temperature‐dependent 1,4‐dioxane Henry's Law constant. User inputs include the target treatment zone size, initial 1,4‐dioxane and soil moisture concentrations, and ambient site and injection/extraction conditions (temperature, humidity). Projections based on inputs representative of demonstration site conditions adequately anticipated the observed macroscopic field results. Sensitivity analyses show that removal increases with increasing heated air injection temperature and relative humidity and decreasing initial soil moisture content.     

Monitoring In Situ Biodegradation of MTBE Using Multiple Rounds of Compound‐Specific Stable Carbon Isotope Analysis

At a large industrial facility, methyl tert‐butyl ether (MTBE) was released to the subsurface and dispersed into the light, non‐aqueous phase liquids (LNAPL), in the first aquifer, with the LNAPL serving as a continuous source of MTBE in groundwater. Compound‐specific isotope analysis was conducted on both MTBE and tert‐butyl alcohol (TBA) in groundwater samples collected in 2008, 2011, and 2013 from wells located along and off the center line of the MTBE plume. The study demonstrated the onset and progress of biodegradation of MTBE between 2008 and 2013. The TBA observed in 2008 appears to be derived only in part from MTBE transformation while a significant portion of TBA might be contributed directly from LNAPL sources. In 2011 to 2013, the dominant source of TBA in the mid‐gradient plume was MTBE transformation. A contribution of an offsite LNAPL source, in particular to the down‐gradient area of the plume, is possible but could not be unequivocally confirmed. The time series provided direct evidence for MTBE biodegradation, but also a valuable insight on the sources of TBA.     

Temperature‐Activated Auto‐Decomposition Reactions: An Under‐Utilized In Situ Remediation Solution

The remediation industry has witnessed multiple innovations arising from a greater understanding of the physical, chemical, and biological processes that control the fate and transport of chemicals in the subsurface environment. In addition, increasing emphasis is being placed on remediation solutions that are greener, simpler, and more resource efficient. The positive impacts that can be derived from this emphasis include reduced energy consumption, reduced waste emissions, and lower costs. Temperature‐activated auto‐decomposition reactions represent a potentially underutilized option for the in situ remediation of certain organic contaminants, and an option that can be both highly effective and greener than other available technologies.     

A Low‐Cost,In Situ Resistivity and Temperature Monitoring System

We present a low‐cost, reliable method for long‐term in situ autonomous monitoring of subsurface resistivity and temperature in a shallow, moderately heterogeneous subsurface. Probes, to be left in situ, were constructed at relatively low cost with an electrode spacing of 5 cm. Once installed, these were wired to the CR‐1000 Campbell Scientific Inc. datalogger at the surface to electrically image infiltration fronts in the shallow subsurface. This system was constructed and installed in June 2005 to collect apparent resistivity and temperature data from 96 subsurface electrodes set to a pole‐pole resistivity array pattern and 14 thermistors at regular intervals of 30 cm through May of 2008. From these data, a temperature and resistivity relationship was determined within the vadose zone (to a depth of ~1 m) and within the saturated zone (at depths between 1 and 2 m). The high vertical resolution of the data with resistivity measurements on a scale of 5‐cm spacing coupled with surface precipitation measurements taken at 3‐min intervals for a period of roughly 3 years allowed unique observations of infiltration related to seasonal changes. Both the vertical resistivity instrument probes and the data logger system functioned well for the duration of the test period and demonstrated the capability of this low‐cost monitoring system.     

Biodegradation of Herbicide Propanil and Its Subproduct 3,4‐Dichloroaniline in Water

The rational use of pesticides generates an impact which is normally reversed and eliminated by the environment itself. However, the indiscriminate use of pesticides makes its natural degradation rhythm difficult, prolonging their presence in the soil for a great deal of time. Aiming towards a decrease in the environmental impact of pesticides, soil microorganisms capable of degrading pesticides, such as propanil, were investigated. An Enterobacter cloacae strain, isolated from rice field soil, was exposed to the herbicide propanil alone and in a mixture containing also bentazone, clomazone, quinclorac, and 2,4‐D. This bacterium was able to eliminate 100% of the applied propanil in 28 days. Propanil degradation in the 5‐herbicide mixture was much lower than that of individual pesticide degradation. The aeration of the system helped to degrade propanil and its subproduct 3,4‐dichloroaniline much faster. LC with UV detection was used to determine the remaining concentrations of the herbicides and their subproducts.     

Estimation of Biodegradation Rates Using Respiration Tests During In Situ Bioremediation of Weathered Diesel NAPL

Respiration tests were carried out during a seven month bioremediation field trial to monitor biodegradation rates of weathered diesel non-aqueous phase liquid (NAPL) contaminating a shallow sand aquifer. Multiple depth monitoring of oxygen concentrations and air-filled porosity were carried out in nutrient amended and nonamended locations to assess the variability of degradation rate estimates calculated from respiration tests.
The field trial consisted of periodic addition of nutrients (nitrogen and phosphorus) and aeration of a 100 m² trial plot. During the bioremediation trial, aeration was stopped periodically, and decreases in gaseous oxygen concentrations were logged semi-continuously using data loggers attached to recently developed in situ oxygen probes placed at multiple depths above and within a thin NAPL-contaminated zone. Oxygen usage rate coefficients were determined by fitting zero-and first-order rate equations to the oxygen concentration reduction curves, although only zero-order rates were used to calculate biodegradation rates. Air-filled porosity estimates were found to vary by up to a factor of two between sites and at different times.
NAPL degradation rates calculated from measured air-filled porosity and oxygen usage rate coefficients ranged up to 69 mg kg^-1 day^-1. These rates are comparable to and higher than rates quoted in other studies, despite the high concentrations and weathered state of the NAPL at this test site. For nutrient-amended sites within the trial plot, estimates of NAPL degradation rates were two to three times higher than estimates from nonamended sites. Rates also increased with depth.     

In Situ Bioremediation of Toluene‐Polluted Vadose Zone: Integrated Column and Wetland Study

A vertical soil column setup integrated with wetlands is developed to study the biodegradation and transport of toluene, a light non‐aqueous phase liquid (LNAPL), in the subsurface environment. LNAPL‐contaminated water is applied to infiltrate from the top of the soil column. The observed and simulated breakthrough curves show high equilibrium concentration at top ports rather than at lower ports, indicating effective toluene biodegradation with soil depth. The observed equilibrium concentration of toluene is higher in the case of unplanted wetland, asserting an accelerated biodegradation rate in the planted case. A difference in the relative concentration of toluene between input and output fluxes at 100 h is found as 13.34% and 30.86% for planted and unplanted wetland setups, respectively. Estimated biodegradation rates show that toluene degradation is 2.5 times faster in the planted wetland setup. In addition, the difference in the observed bacterial count and dissolved oxygen prove that toluene degraded aerobically at a faster rate in the planted setup. Simulations show that as time reached 80–100 h, there is no significant change in concentration profile, thereby confirming the equilibrium condition. The results of this study will be useful to frame plant‐assisted bioremediation techniques for LNAPL‐contaminated soil–water resources in the field.     

A Proposed Method to Estimate In Situ Dissolved Gas Concentrations in Gas‐Saturated Groundwater

Gas‐saturated groundwater forms bubbles when brought to atmospheric pressure, preventing precise determination of its in situ dissolved gas concentrations. To overcome this problem, a modeling approach called the atmospheric sampling method is suggested here to recover the in situ dissolved gas concentrations of groundwater collected ex situ under atmospheric conditions at the Horonobe Underground Research Laboratory, Japan. The results from this method were compared with results measured at the same locations using two special techniques, the sealed sampler and pre‐evacuated vial methods, that have been developed to collect groundwater under its in situ conditions. In gas‐saturated groundwater cases, dissolved methane and inorganic carbon concentrations derived using the atmospheric sampling method were mostly within ±4 and ±10%, respectively, of values from the sealed sampler and pre‐evacuated vial methods. In gas‐unsaturated groundwater, however, the atmospheric sampling method overestimated the in situ dissolved methane concentrations, because the groundwater pressure at which bubbles appear (P_critical) was overestimated. The atmospheric sampling method is recommended for use where gas‐saturated groundwater can be collected only ex situ under atmospheric conditions.