Rapid Removal of Poly- and Perfluorinated Compounds from Investigation-Derived Waste (IDW) in a Pilot-Scale Plasma Reactor.

A pilot-scale plasma reactor installed into an 8 × 20 ft2 mobile trailer was used to rapidly and effectively degrade poly- and perfluoroalkyl substances (PFAS) from liquid investigation-derived waste (IDW; development and purge water from monitoring wells) obtained from 13 different site investigations at Air Force installations. In the raw water, numerous PFAS were detected in a wide concentration range (∼10-105 ng/L; total oxidizable precursors (TOP) ∼102-105 ng/L, total fluorine by combustion ion chromatography ∼102 to 5 × 106 ng F/L). The concentration of total PFAS (12 perfluorocarboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFSAs)) in the 13 samples ranged between 2.7 and 1440 µg/L and the concentration of perfluorooctane sulfonate (PFOS) plus perfluorooctanoic acid (PFOA) ranged between 365 and 73700 ng/L. Plasma-based water treatment resulted in rapid perfluoroalkyl acids (PFAAs) removal from 4 L individual IDW samples with faster rates for longer-chain PFCAs (C ≥ 8) and PFSAs (C ≥ 6) than for PFCAs and PFSAs of shorter chain length. In 9 of the 13 IDW samples, both PFOS and PFOA were removed to below United States Environmental Protection Agency's (USEPA's) health advisory concentration level (HAL) concentrations in <1 min, whereas longer treatment times (up to 50 min) were required for the remaining four IDW samples due to either extremely high solution electrical conductivity, which decreased the plasma-liquid contact area (one IDW sample) or high concentrations of PFAAs and their precursors; the latter was found to be converted to PFAAs during the treatment. Overall, 36-99% of the TOP concentration present in the IDWs was removed during the treatment. There was no effect of non-PFAS co-contaminants on the degradation efficiency. Overall, the results indicate that plasma-based water treatment is a viable technology for the treatment of PFAS-contaminated IDW.

Enhanced reductive dechlorination of trichloroethene in an acidic DNAPL impacted aquifer.

A field pilot test was conducted using an emulsified vegetable oil (EVO) and colloidal magnesium hydroxide [Mg(OH)2] formulation to enhance reductive dechlorination of dense non-aqueous phase liquid (DNAPL) trichloroethene (TCE) in an acidic (pH < 4), heterogeneous aquifer. The field test consisted of i) a single well injection test to evaluate Mg(OH)2 distribution and ii) installation of two EVO-Mg(OH)2 permeable reactive barriers (PRBs; PRB-1 & PRB-2) at varying distances downgradient of the DNAPL source area. Distribution of Mg(OH)2 was observed up to 2.3 m away from the injection point within a permeable coarse sand layer; however, Mg(OH)2 transport in the overlying clayey-silty sand was minimal. Downgradient of the PRBs, colloidal Mg(OH)2 increased the pH of the coarse sand to levels appropriate for biological reductive dechlorination (pH >∼5); however, some settling of Mg(OH)2 in the injection wells generated persistent high pH (∼9-10) within the PRBs. A redesigned suspension of colloidal Mg(OH)2 was tested and proved to be more effective at raising aquifer pH without an excessive rise in pH within the PRBs. At PRB-1 (located closest to the DNAPL source area), limited TCE biodegradation was observed due to the influx of high TCE concentrations (up to 400 mg/L) and inhibition of dechlorinating bacteria. At PRB-2 (located 25 m downgradient of the DNAPL source area), TCE concentrations were much lower (13-26 mg/L) and production of cis-1,2-dichloroethene (cDCE) and some vinyl chloride (VC) was observed. Subsequent bioaugmentation with a commercial dechlorinating culture at PRB-2 improved conversion of cDCE to VC and ethene at downgradient monitoring wells over the duration of the study. These results emphasize the importance of PRB location (relative to the DNAPL source), base selection for pH adjustment, source strength, and local heterogeneities for the design and long-term performance of ERD in acidic DNAPL-impacted aquifers.

Pyrosequence analyses of bacterial communities during simulated in situ bioremediation of polycyclic aromatic hydrocarbon-contaminated soil.

Barcoded amplicon pyrosequencing was used to generate libraries of partial 16S rRNA genes from two columns designed to simulate in situ bioremediation of polycyclic aromatic hydrocarbons (PAHs) in weathered, contaminated soil. Both columns received a continuous flow of artificial groundwater but one of the columns additionally tested the impact of biostimulation with oxygen and inorganic nutrients on indigenous soil bacterial communities. The penetration of oxygen to previously anoxic regions of the columns resulted in the most significant community changes. PAH-degrading bacteria previously determined by stable-isotope probing (SIP) of the untreated soil generally responded negatively to the treatment conditions, with only members of the Acidovorax and a group of uncharacterized PAH-degrading Gammaproteobacteria maintaining a significant presence in the columns. Additional groups of sequences associated with the Betaproteobacterial family Rhodocyclaceae (including those associated with PAH degradation in other soils), and the Thiobacillus, Thermomonas, and Bradyrhizobium genera were also present in high abundance in the biostimulated column. Similar community responses were previously observed during biostimulated ex situ treatment of the same soil in aerobic, slurry-phase bioreactors. While the low relative abundance of many SIP-determined groups in the column libraries may be a reflection of the slow removal of PAHs in that system, the similar response of known PAH degraders in a higher-rate bioreactor system suggests that alternative PAH-degrading bacteria, unidentified by SIP of the untreated soil, may also be enriched in engineered systems.

Evaluating the effects of bioremediation on genotoxicity of polycyclic aromatic hydrocarbon-contaminated soil using genetically engineered, higher eukaryotic cell lines.

Bioremediation is one of the commonly applied remediation strategies at sites contaminated with polycyclic aromatic hydrocarbons (PAHs). However, remediation goals are typically based on removal of the target contaminants rather than on broader measures related to health risks. We investigated changes in the toxicity and genotoxicity of PAH-contaminated soil from a former manufactured-gas plant site before and after two simulated bioremediation processes: a sequencing batch bioreactor system and a continuous-flow column system. Toxicity and genotoxicity of the residues from solvent extracts of the soil were determined by the chicken DT40 B-lymphocyte isogenic cell line and its DNA-repair-deficient mutants. Although both bioremediation processes significantly removed PAHs from the contaminated soil (bioreactor 69% removal, column 84% removal), bioreactor treatment resulted in an increase in toxicity and genotoxicity over the course of a treatment cycle, whereas long-term column treatment resulted in a decrease in toxicity and genotoxicity. However, when screening with a battery of DT40 mutants for genotoxicity profiling, we found that column treatment induced DNA damage types that were not observed in untreated soil. Toxicity and genotoxicity bioassays can supplement chemical analysis-based risk assessment for contaminated soil when evaluating the efficacy of bioremediation.

Long-term simulation of in situ biostimulation of polycyclic aromatic hydrocarbon-contaminated soil.

A continuous-flow column study was conducted to evaluate the long-term effects of in situ biostimulation on the biodegradation of polycyclic aromatic hydrocarbons (PAHs) in soil from a manufactured gas plant site. Simulated groundwater amended with oxygen and inorganic nutrients was introduced into one column, while a second column receiving unamended groundwater served as a control. PAH and dissolved oxygen (DO) concentrations, as well as microbial community profiles, were monitored along the column length immediately before and at selected intervals up to 534 days after biostimulation commenced. Biostimulation resulted in significantly greater PAH removal than in the control condition (73% of total measured PAHs vs. 34%, respectively), with dissolution accounting for a minor amount of the total mass loss (~6%) in both columns. Dissolution was most significant for naphthalene, acenaphthene, and fluorene, accounting for >20% of the total mass removed for each. A known group of PAH-degrading bacteria, 'Pyrene Group 2' (PG2), was identified as a dominant member of the microbial community and responded favorably to biostimulation. Spatial and temporal variations in soil PAH concentration and PG2 abundance were strongly correlated to DO advancement, although there appeared to be transport of PG2 organisms ahead of the oxygen front. At an estimated oxygen demand of 6.2 mg O(2)/g dry soil and a porewater velocity of 0.8 m/day, it took between 374 and 466 days for oxygen breakthrough from the 1-m soil bed in the biostimulated column. This study demonstrated that the presence of oxygen was the limiting factor in PAH removal, as opposed to the abundance and/or activity of PAH-degrading bacteria once oxygen reached a previously anoxic zone.

Recovery of phenanthrene-degrading bacteria after simulated in situ persulfate oxidation in contaminated soil.

A continuous-flow column study was conducted to investigate the long-term effects of persulfate oxidation on the abundance and activity of the indigenous microbial community and phenanthrene-degrading bacteria in contaminated soil from a former manufactured gas plant (MGP) site. Approximately six pore volumes of a 20 g/L persulfate solution were introduced into the column, followed by simulated groundwater for 500 days. Soil samples were collected from the surface of the soil bed and along the column length immediately before and after persulfate injection and up to 500 days following injection. Exposure to persulfate led to a 2- to 3-log reduction in total bacterial 16S rRNA genes, severe inhibition of (14)C-acetate mineralization (as a measure of general microbial activity), and a decrease in community diversity. However, relatively rapid recovery of both bacterial gene abundance and activity was observed within 30 days after persulfate exposure. Mineralization of (14)C-phenanthrene was also inhibited but did not recover until 100 days postoxidation. Known phenanthrene-degrading bacterial groups decreased to below detection limits throughout the column, with recovery times from 100 to 500 days after persulfate injection. These findings suggest that coupling biological processes with persulfate oxidation is possible, although recovery of specific contaminant degraders may occur much later than the general microbial community recovers. Furthermore, the use of total bacterial quantity or nonspecific measures of activity as a surrogate for the recovery of contaminant degraders may be inappropriate for evaluating the compatibility of chemical treatment with subsequent bioremediation.

Pyrosequence analysis of bacterial communities in aerobic bioreactors treating polycyclic aromatic hydrocarbon-contaminated soil.

Two aerobic, lab-scale, slurry-phase bioreactors were used to examine the biodegradation of polycyclic aromatic hydrocarbons (PAHs) in contaminated soil and the associated bacterial communities. The two bioreactors were operated under semi-continuous (draw-and-fill) conditions at a residence time of 35 days, but one was fed weekly and the other monthly. Most of the quantified PAHs, including high-molecular-weight compounds, were removed to a greater extent in the weekly-fed bioreactor, which achieved total PAH removal of 76%. Molecular analyses, including pyrosequencing of 16S rRNA genes, revealed significant shifts in the soil bacterial communities after introduction to the bioreactors and differences in the abundance and types of bacteria in each of the bioreactors. The weekly-fed bioreactor displayed a more stable bacterial community with gradual changes over time, whereas the monthly-fed bioreactor community was less consistent and may have been more strongly influenced by the influx of untreated soil during feeding. Phylogenetic groups containing known PAH-degrading bacteria previously identified through stable-isotope probing of the untreated soil were differentially affected by bioreactor conditions. Sequences from members of the Acidovorax and Sphingomonas genera, as well as the uncultivated "Pyrene Group 2" were abundant in the bioreactors. However, the relative abundances of sequences from the Pseudomonas, Sphingobium, and Pseudoxanthomonas genera, as well as from a group of unclassified anthracene degraders, were much lower in the bioreactors compared to the untreated soil.

A review of physical, chemical, and hydrogeologic characteristics of stray gas migration: Implications for investigation and remediation.

Releases of natural gas into groundwater from oil and gas exploration, production, or storage (i.e., "stray gas") can pose a risk to groundwater users and landowners in the form of a fire or explosive hazard. The acute nature of stray gas risk differs from the long-term health risks posed by the ingestion or inhalation of other petroleum hydrocarbons (e.g., benzene). Stray gas also exhibits different fate and transport behaviors in the environment from other hydrocarbon contaminants, including the potential for rapid and extensive transport of free-phase gas through preferential pathways, and the resulting variable and discontinuous spatial distribution of free and dissolved gas phases. While there is extensive guidance on response actions for releases of other hydrocarbons such as benzene, there are relatively few examples available in the technical literature that discuss appropriate response measures for the investigation and remediation of stray gas impacts. This paper describes key considerations in the physical, chemical, and hydrogeological characteristics of stray gas releases and implications for the improved investigation and mitigation of associated risks.

Oxidative mutagenicity of polar fractions from polycyclic aromatic hydrocarbon-contaminated soils.

Soils at hazardous waste sites contain complex mixtures of chemicals and often are difficult to characterize in terms of risk to human and ecological health. Over time, biogeochemical processes can decrease the apparent concentrations of pollutants but also can lead to accumulation of new products for which toxicity and behavior in the environment are largely unknown. A bioassay-directed fractionation technique was used to assess the contribution of redox-active bacterial metabolites to the toxicity of soil contaminated with polycyclic aromatic hydrocarbons (PAHs). A reverse mutation assay with Escherichia coli WP2 uvrA/pKM101 (IC188) and E. coli WP2 uvrA oxyR/pKM101 (IC203) was used to screen fractions for genotoxicity. Strain IC203 carries the delta oxyR30 mutation, which prevents the expression of antioxidant proteins in response to oxidative stress and increases its reversion by compounds that generate reactive oxygen species (ROS). Polar fractions of PAH-contaminated soil extracts were mutagenic to strain IC203 but not to strain IC188, suggesting the involvement of ROS in genotoxicity. Genotoxic potencies ranged from 300 to 1700 revertants per milligram of fraction. Catalase was able to decrease IC203 reversion, implicating the involvement of hydrogen peroxide as a key ROS. Oxidized PAH compounds, including quinones, were identified in the mutagenic fractions but were not by themselves mutagenic. Deasphalted whole extracts and recombined fractions were not mutagenic, indicating that interactions between compounds in different fractions can mitigate genotoxicity.

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas, Eastern Kentucky.

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ13 C-CH4 and δ2 H-CH4 ) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ13 C-CH4 and δ2 H-CH4 ranged from -84.0‰ to -58.3‰ and from -246.5‰ to -146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO2 reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region.

Purging and other sampling variables affecting dissolved methane concentration in water supply wells.

Determining whether changes in groundwater methane concentration are naturally occurring or related to oil and gas operations can be complicated by numerous sources of variability. This study of 10 residential water supply wells in Northeastern Pennsylvania evaluates how i) sampling from different points within the water well system, ii) purging different water volumes prior to sampling, and ii) natural variation over time, affects concentrations of naturally occurring dissolved methane and other water quality parameters. Among the population of wells, all had dissolved methane concentrations >1mg/L. Regardless of the volume of water purged or the timing between events, the maximum change in methane concentration (ratio of maximum to minimum concentration) among samples from a single well was 3.2, with eight out of ten wells exhibiting a maximum change less than a factor of two (i.e., <±100%). Among water wells where methane concentration changed by ±50% or more, there was a strong correlation with changes in the concentrations of sodium, chloride, and other salinity indicators such as specific conductivity and TDS. This suggests that significant variability in methane concentration is predominantly related to changes in the relative volumes of sodium-rich fluids feeding the wellbore at any given time. Among study well locations with bladder and diaphragm pressure tanks, there was no significant difference in dissolved methane concentrations between samples collected either upstream or downstream of a pressure tank. There appears to be little benefit to purging multiple casing volumes of water from a well prior to sampling because such volumes tend to be much larger than those representative of normal residential use. We recommend purging a volume sufficient to remove standing water in the pressure tank and lines above the pump intake. This article culminates with additional recommendations for improving sample collection methods and interpreting sampling data.

Environmental Factors Associated With Natural Methane Occurrence in the Appalachian Basin.

The recent boom in shale gas development in the Marcellus Shale has increased interest in the methods to distinguish between naturally occurring methane in groundwater and stray methane associated with drilling and production operations. This study evaluates the relationship between natural methane occurrence and three principal environmental factors (groundwater redox state, water type, and topography) using two pre-drill datasets of 132 samples from western Pennsylvania, Ohio, and West Virginia and 1417 samples from northeastern Pennsylvania. Higher natural methane concentrations in residential wells are strongly associated with reducing conditions characterized by low nitrate and low sulfate ([NO3- ] < 0.5 mg/L; [SO42- ] < 2.5 mg/L). However, no significant relationship exists between methane and iron [Fe(II)], which is traditionally considered an indicator of conditions that have progressed through iron reduction. As shown in previous studies, water type is significantly correlated with natural methane concentrations, where sodium (Na) -rich waters exhibit significantly higher (p<0.001) natural methane concentrations than calcium (Ca)-rich waters. For water wells exhibiting Na-rich waters and/or low nitrate and low sulfate conditions, valley locations are associated with higher methane concentrations than upland topography. Consequently, we identify three factors ("Low NO3- & SO42- " redox condition, Na-rich water type, and valley location), which, in combination, offer strong predictive power regarding the natural occurrence of high methane concentrations. Samples exhibiting these three factors have a median methane concentration of 10,000 µg/L. These heuristic relationships may facilitate the design of pre-drill monitoring programs and the subsequent evaluation of post-drill monitoring results to help distinguish between naturally occurring methane and methane originating from anthropogenic sources or migration pathways.

Effect of Different Sampling Methodologies on Measured Methane Concentrations in Groundwater Samples.

Analysis of dissolved light hydrocarbon gas concentrations (primarily methane and ethane) in water supply wells is commonly used to establish conditions before and after drilling in areas of shale gas and oil extraction. Several methods are currently used to collect samples for dissolved gas analysis from water supply wells; however, the reliability of results obtained from these methods has not been quantified. This study compares dissolved methane and ethane concentrations measured in groundwater samples collected using three sampling methods employed in pre- and post-drill sampling programs in the Appalachian Basin. These include an open-system collection method where 40 mL volatile organic analysis (VOA) vials are filled directly while in contact with the atmosphere (Direct-Fill VOA) and two alternative methods: (1) a semi-closed system method whereby 40 mL VOA vials are filled while inverted under a head of water (Inverted VOA) and (2) a relatively new (2013) closed system method in which the sample is collected without direct contact with purge water or the atmosphere (IsoFlask® ). This study reveals that, in the absence of effervescence, the difference in methane concentrations between the three sampling methods was relatively small. However, when methane concentrations equaled or exceeded 20 mg/L (the approximate concentration at which effervescence occurs in the study area), IsoFlask® (closed system) samples yielded significantly higher methane concentrations than Direct-Fill VOA (open system) samples, and Inverted VOA (semi-closed system) samples yielded lower concentrations. These results suggest that open and semi-closed system sample collection methods are adequate for non-effervescing samples. However, the use of a closed system collection method provides the most accurate means for the measurement of dissolved hydrocarbon gases under all conditions.

Use of Rhodamine water tracer in the marshland upwelling system.

Rhodamine water tracer (RWT) was used to characterize the migration of waste water within the saline subsurface of a marshland upwelling system (MUS), which is an alternative on-site waste water treatment system for coastal areas. Field tracer studies were performed to investigate the fresh waste water plume movement within the saline ground water. Pore velocities were calculated using first detection times and ranged from 0.68 to 10.7 x 10(-4) cm/sec for the loamy sandy soil matrix present at the site. Use of RWT in the field also allowed determination of main and preferential flowpaths. One- and two-dimensional laboratory experiments were performed using silica sand to investigate the interactions of the organically rich waste water with RWT within the zone surrounding the point of injection (one-dimensional) and the impact of background salinity on plume movement (two-dimensional). The results from these studies were used to help explain the field data. One-dimensional breakthrough curves revealed retardation factors for the RWT in the waste water mixture of 1.73 to 1.90. These results were similar to other researchers, indicating little interaction between the waste water and RWT. Variations in pore water salinity (5, 15, 25, and 35 ppt) were found to have a significant effect on pore water velocities of the fresh water plume (two-dimensional), indicating the need to incorporate background salinities into the design process for MUS.

Desorption and bioavailability of polycyclic aromatic hydrocarbons in contaminated soil subjected to long-term in situ biostimulation.

The distribution and potential bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soil from a former manufactured-gas plant (MGP) site were examined before and after long-term biostimulation under simulated in situ conditions. Treated soil was collected from the oxygenated zones of two continuous-flow columns, one subjected to biostimulation and the other serving as a control, and separated into low- and high-density fractions. In the original soil, over 50% of the total PAH mass was associated with lower density particles, which made up <2% of the total soil mass. However, desorbable fractions of PAHs were much lower in the low-density material than in the high-density material. After more than 500 d of biostimulation, significant removal of total PAHs occurred in both the high- and low-density materials (77 and 53%, respectively), with three- and four-ring PAHs accounting for the majority of the observed mass loss. Total PAHs that desorbed over a 28-d period were substantially lower in treated soil from the biostimulated column than in the original soil for both the high-density material (23 vs. 63%) and the low-density material (5 vs. 20%). The fast-desorbing fractions quantified by a two-site desorption model ranged from 0.1 to 0.5 for most PAHs in the original soil but were essentially zero in the biostimulated soil. The fast-desorbing fractions in the original soil underestimated the extent of PAH biodegradation observed in the biostimulated column and thus was not a good predictor of PAH bioavailability after long-term, simulated in situ biostimulation.

Effects of enrichment with phthalate on polycyclic aromatic hydrocarbon biodegradation in contaminated soil.

The effect of enrichment with phthalate on the biodegradation of polycyclic aromatic hydrocarbons (PAH) was tested with bioreactor-treated and untreated contaminated soil from a former manufactured gas plant (MGP) site. Soil samples that had been treated in a bioreactor and enriched with phthalate mineralized (14)C-labeled phenanthrene and pyrene to a greater extent than unenriched samples over a 22.5-h incubation, but did not stimulate benzo[a]pyrene mineralization. In contrast to the positive effects on (14)C-labeled phenanthrene and pyrene, no significant differences were found in the extent of biodegradation of native PAH when untreated contaminated soil was incubated with and without phthalate amendment. Denaturing-gradient gel electrophoresis (DGGE) profiles of bacterial 16S rRNA genes from unenriched and phthalate-enriched soil samples were substantially different, and clonal sequences matched to prominent DGGE bands revealed that beta-Proteobacteria related to Ralstonia were most highly enriched by phthalate addition. Quantitative real-time PCR analyses confirmed that, of previously determined PAH-degraders in the bioreactor, only Ralstonia-type organisms increased in response to enrichment, accounting for 89% of the additional bacterial 16S rRNA genes resulting from phthalate enrichment. These findings indicate that phthalate amendment of this particular PAH-contaminated soil did not significantly enrich for organisms associated with high molecular weight PAH degradation or have any significant effect on overall degradation of native PAH in the soil.