Aqueous Film-Forming Foams Exhibit Greater Interfacial Activity than PFOA, PFOS, or FOSA.

Perfluoroalkyl acids spontaneously concentrate at air-water and non-aqueous phase liquid (NAPL)-water interfaces, which can influence their retention during subsurface transport. This work presents measurements of air- and NAPL-water interfacial tension for synthetic groundwater containing perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorooctanesulfonamide (FOSA), or aqueous film-forming foam (AFFF) formulations at concentrations ranging from 0.1 to greater than 1000 mg/L. The NAPLs tested included dodecane, tetrachloroethylene, and jet fuel. AFFF formulations were less efficient at lowering interfacial tension than PFOA, FPOS, or FOSA substances below 100 mg/L, while above 100 mg/L, these formulations were more effective, achieving tensions of less than 3 mN/m. Infiltration of solutions with such low tension could lead to mobilization of residual NAPL. Equations based on interfacial tension measurements show that concentrations of PFOA, PFOS, and FOSA at the air-water interface were from 2 to 16 times greater than at the NAPL-water interface below 100 mg/L and were 10-50 times greater for AFFF below 20 mg/L. Calculations for unsaturated soil estimate that up to 87% of PFOS mass was at the air-water interface and less than 4% at the dodecane-water interface for bulk-water concentrations below 1 mg/L.

Accumulation of six PFAS compounds by woody and herbaceous plants: potential for phytoextraction.

Per and polyfluoroalkyl substances (PFAS) consist of a large group of compounds used to make products more resistant to stains, grease, and water and for fire suppression. They have been widely detected in the environment and exposure has been linked to adverse human health effects. Phytoremediation could be used to remediate PFAS-impacted sites, but there is little information on herbaceous and woody plant species uptake of PFAS compounds from soil. A greenhouse study evaluated the potential for eight herbaceous and seven woody plant species to absorb PFAS compounds. Six PFAS compounds: PFPeA, PFHxA, PFOA, PFBS, PFHxS, and PFOS were added weekly to irrigation water, and the plants grown for up to 14 weeks after an initial establishment period. Significant accumulation of all PFAS compounds occurred in at least one plant species. Mass recovery in above-ground tissue by the best performing plant ranged from a low of 3.8% for PFOS by Festuca rubra to a high of 42% for PFPeA by Schedonorus arundinaceus. Hyperaccumulation, defined as tissue/soil concentrations >10/1, was observed for all six PFAS compounds in at least one plant species. These results demonstrate the potential use of phytoremediation as a tool for remediating PFAS-contaminated sites.

Enhanced mobility of fullerene (C60) nanoparticles in the presence of stabilizing agents.

Experimental and mathematical modeling studies were performed to examine the effects of stabilizing agents on the transport and retention of fullerene nanoparticles (nC(60)) in water-saturated quartz sand. Three stabilizing systems were considered: naturally occurring compounds known to stabilize nanoparticles (Suwannee river humic acid (SRHA) and fulvic acid (SRFA)), synthetic additives used to enhance nanoparticle stability (Tween 80, a nonionic surfactant), and residual contaminants resulting from the manufacturing process (tetrahydrofuran (THF)). The results of column experiments demonstrated that the presence of THF, at concentrations up to 44.5 mg/L, did not alter nC(60) transport and retention behavior, whereas addition of SRHA (20 mg C/L), SRFA (20 mg C/L), or Tween 80 (1000 mg/L) to the influent nC(60) suspensions dramatically increased the mobility of nC(60), as demonstrated by coincidental nanoparticle and nonreactive tracer effluent breakthrough curves (BTCs) and minimal nC(60) retention. When columns were preflushed with surfactant, nC(60) transport was significantly enhanced compared to that in the absence of a stabilizing agent. The presence of adsorbed Tween 80 resulted in nC(60) BTCs characterized by a declining plateau and retention profiles that exhibited hyperexponential decay. The observed nC(60) transport and retention behavior was accurately captured by a mathematical model that accounted for coupled surfactant adsorption-desorption dynamics, surfactant-nanoparticle interactions, and particle attachment kinetics.

Effects of elevated temperature on Dehalococcoides dechlorination performance and DNA and RNA biomarker abundance.

Coupling thermal treatment with microbial reductive dechlorination is a promising remedy for tetrachloroethene (PCE) and trichloroethene (TCE) contaminated source zones. Laboratory experiments evaluated Dehalococcoides (Dhc) dechlorination performance, viability, and biomarker gene (DNA) and transcript (mRNA) abundances during exposure to elevated temperatures. The PCE-dechlorinating consortia BDI and OW produced ethene when incubated at temperatures of 30 °C, but vinyl chloride (VC) accumulated when cultures were incubated at 35 or 40 °C. Cultures incubated at 40 °C for less than 49 days resumed VC dechlorination following cooling; however, incubation at 45 °C resulted in complete loss of dechlorination activity. Dhc 16S rRNA, bvcA, and vcrA gene abundances in cultures showing complete dechlorination to ethene at 30 °C exceeded those measured in cultures incubated at higher temperatures, consistent with observed dechlorination activities. Conversely, biomarker gene transcript abundances per cell in cultures incubated at 35 and 40 °C were generally at least one order-of-magnitude greater than those measured in ethene-producing cultures incubated at 30 °C. Even in cultures accumulating VC, transcription of the vcrA gene, which is implicated in VC-to-ethene dechlorination, was up-regulated. Temperature stress caused the up-regulation of Dhc reductive dehalogenase gene expression indicating that Dhc gene expression measurements should be interpreted cautiously as Dhc biomarker gene transcript abundances may not correlate with dechlorination activity.

PCE oxidation by sodium persulfate in the presence of solids.

Batch reactor experiments were performed to determine the effects of solids on the oxidation of tetracholoroethylene (PCE) by sodium persulfate in aqueous solution. Based on the rates of PCE degradation and chloride formation, PCE oxidation by heat-activated sodium persulfate at 50 °C in the presence of solids ranged from no detectable oxidation of PCE to the levels observed in water-only reactors. Repeated doses of sodium persulfate, undertaken to overcome the inherent solids oxidant demand, improved the rate and extent of PCE oxidation in reactors containing reference solids; however, no improvement was observed in reactors containing field soils. Additionally, no improvements in PCE oxidation were observed after pretreating Great Lakes and Appling soils with ca. 15 g/kg of sodium persulfate or 30% hydrogen peroxide to remove oxidizable fractions, or acetic acid to remove the carbonate fraction. Based on these results, in situ treatment of Great Lakes and Appling soils with heat-activated sodium persulfate is not anticipated to result in substantial PCE oxidation, while in situ treatment of Fort Lewis soils is anticipated to result in PCE oxidation. This work demonstrates the need to perform soil-specific contaminant treatability tests rather than soil oxidant demand tests when determining oxidant dosage requirements.

Comparison of PCE and TCE disappearance in heated volatile organic analysis vials and flame-sealed ampules.

The rates of hydrolysis reported for tetrachloroethylene (PCE) and trichloroethylene (TCE) at elevated temperatures range over two orders-of-magnitude, where some of the variability may be due to the presence of a gas phase. Recent studies suggest that volatile organic analysis (VOA) vials provide a low-cost and readily available zero headspace system for measuring aqueous-phase hydrolysis rates. This work involved measuring rates of PCE and TCE disappearance and the corresponding appearance of dechlorination products in water-filled VOA vials and flame-sealed ampules incubated at 21 and 55 degrees C for up to 95.5 days. While PCE and TCE concentrations readily decreased in the VOA vials to yield first-order half lives of 11.2 days for PCE and 21.1 days for TCE at 55 degrees C, concentrations of anticipated dechlorination products, including chloride, remained constant or were not detected. The rate of PCE disappearance was 34 times faster in VOA vials at 55 degrees C compared to values obtained with flame-sealed ampules containing PCE-contaminated water. In addition, the concentration of TCE increased slightly in flame-sealed ampules incubated at 55 degrees C, while a decrease in TCE levels was observed in the VOA vials. The observed losses of PCE and TCE in the VOA vials were attributed to diffusion and sorption in the septa, rather than to dechlorination. These findings demonstrate that VOA vials are not suitable for measuring rates of volatile organic compound hydrolysis at elevated temperatures.

Use of the bioaccumulation factor to screen chemicals for bioaccumulation potential.

The fish bioconcentration factor (BCF), as calculated from controlled laboratory tests, is commonly used in chemical management programs to screen chemicals for bioaccumulation potential. The bioaccumulation factor (BAF), as calculated from field-caught fish, is more ecologically relevant because it accounts for dietary, respiratory, and dermal exposures. The BCFBAF™ program in the U.S. Environmental Protection Agency's Estimation Programs Interface Suite (EPI Suite™ Ver 4.10) screening-level tool includes the Arnot-Gobas quantitative structure-activity relationship model to estimate BAFs for organic chemicals in fish. Bioaccumulation factors can be greater than BCFs, suggesting that using the BAF rather than the BCF for screening bioaccumulation potential could have regulatory and resource implications for chemical assessment programs. To evaluate these potential implications, BCFBAF was used to calculate BAFs and BCFs for 6,034 U.S. high- and medium-production volume chemicals. The results indicate no change in the bioaccumulation rating for 86% of these chemicals, with 3% receiving lower and 11% receiving higher bioaccumulation ratings when using the BAF rather than the BCF. All chemicals that received higher bioaccumulation ratings had log K(OW ) values greater than 4.02, in which a chemical's BAF was more representative of field-based bioaccumulation than its BCF. Similar results were obtained for 374 new chemicals. Screening based on BAFs provides ecologically relevant results without a substantial increase in resources needed for assessments or the number of chemicals screened as being of concern for bioaccumulation potential.

Electron donor availability for microbial reductive processes following thermal treatment.

Thermal treatment is capable of removing significant free-phase chlorinated solvent mass while potentially enhancing bioremediation effectiveness by establishing temperature gradients in the perimeter of the source zone and by increasing electron donor availability. The objectives of this study were to determine the potential for enhanced reductive dechlorination activity at the intermediate temperatures that establish in the perimeter of the heated source zone, and to evaluate the effect of electron donor competition on the performance of the microbial reductive dechlorination process. Microcosms, constructed with tetrachloroethene- (PCE-) and trichloroethene- (TCE-) impacted soils from the Great Lakes, IL, and Ft. Lewis, WA, sites were incubated at temperatures of 24, 35, 50, 70, and 95 °C for 4 months. Reductive dechlorination did not occur in microcosms incubated at temperatures above 24 °C even though mesophilic PCE-to-cis-1,2-dichloroethene dechlorinators were present in Ft. Lewis soil suggesting electron donor limitations. Five days after cooling the microcosms to 24 °C and bioaugmentation with the methanogenic, PCE-to-ethene-dechlorinating consortium OW, at least 85% of the initial PCE and TCE were dechlorinated, but dechlorination ceased prior to complete conversion to ethene. Subsequent biostimulation with hydrogen gas mitigated the dechlorination stall, and conversion to ethene resumed. The results of this study demonstrated that temperatures >35 °C inhibit reductive dechlorination activity at the Great Lakes and Ft. Lewis sites, and that the majority of reducing equivalents released from the soil matrix during heat treatment are consumed in methanogenesis rather than reductive dechlorination. These observations suggest that bioaugmenting thermal treatment sites with cultures that do not contain methanogens may allow practitioners to realize enhanced dechlorination activity, a potential benefit of coupling thermal treatment with bioremediation.

Effectiveness of nanoscale zero-valent iron for treatment of a PCE-DNAPL source zone.

Nanoscale zero-valent iron (nZVI) has received considerable attention as a potential in situ remediation technology for treating chlorinated solvent source zones. Experimental and mathematical modeling studies were conducted to investigate the performance of nZVI in the transformation of tetrachloroethene (PCE) entrapped as a dense nonaqueous phase liquid (DNAPL). Injection of a 60 g/L suspension of nZVI into a column containing 20-30 mesh Ottawa sand and PCE-DNAPL at a residual saturation of 5.5% resulted in a uniform distribution of nZVI and minimal displacement of PCE. Subsequent flushing with 267 pore volumes of water containing 3mM CaCl(2) at a Darcy velocity of 0.75 m/day resulted in steady-state effluent concentrations of PCE near the solubility limit (ca. 200mg/L) and production of dissolved-phase ethene (10-30 mg/L). Over the duration of the experiment, approximately 30% of the initial PCE-DNAPL mass reacted to form ethene, 50% was eluted as dissolved-phase PCE, and 20% remained in the column as PCE-DNAPL. To further explore the implications of the nZVI column results, a multiphase transport model was developed that incorporated rate-limited PCE-DNAPL dissolution and reactions with nZVI. Using a fitted pseudo first-order transformation rate coefficient of 1.421/h, the model accurately captured observed trends in effluent concentrations of PCE and ethene and overall mass balance. A model sensitivity study reveals a strong dependence of treatment effectiveness on system characteristics. The sensitivity analysis suggests that an increase in the extent of PCE transformation is facilitated by decreasing flow rate, emplacement of nZVI down-gradient of the DNAPL source zone, and decreasing length of the DNAPL source zone. These findings indicate that, although emplacement of high concentrations of nZVI within a PCE-DNAPL source zone can result in substantial transformation of the parent compound, careful attention to design parameters (e.g. flow rate, location and amount nZVI delivered) will be required to achieve complete conversion to benign reaction products.

Fate of TCE in heated Fort Lewis soil.

This study explores the transformation of trichloroethene (TCE) caused by heating contaminated soil and groundwater samples obtained from the East Gate Disposal Yard (EGDY) located in Fort Lewis, WA. After field samples transferring into glass ampules and introducing 1.5 micromol of TCE, the sealed ampules were incubated at temperatures of 25, 50, and 95 degrees C for periods of up to 95.5 days. Although TCE was completely transformed into cis-1,2-dichloroethene (cis-DCE) after 42 days at 25 degrees C by microbial activity, this transformation was not observed at 50 or 95 degrees C. Chloride levels increased after 42 days at 25 degrees C corresponding to the mass of TCE transformed to cis-DCE, were constant at 50 degrees C, and increased at 95 degrees C yielding a TCE degradation half-life of 1.6-1.9 years. These findings indicate that indigenous microbes contribute to the partial dechlorination of TCE to cis-DCE at temperatures of less than 50 degrees C, whereas interphase mass transfer and physical recovery of TCE will predominate over in situ degradation processes at temperatures of greater than 50 degrees C during thermal treatment at the EGDY site.

Distribution and abiotic degradation of chlorinated solvents in heated field samples.

The objective of this study was to evaluate the abiotic degradation of tetrachloroethylene (PCE) in contaminated soil and groundwater samples obtained from the Camelot Cleaners Superfund site, West Fargo, ND. The field samples were incubated at temperatures of 25, 55, 75, and 95 degrees C in sealed ampules containing aqueous, gas, and solid phases for periods of up to 75 days to simulate thermal treatment temperatures. Aqueous PCE concentrations increased with incubation temperature but remained constant over time. The degradation of dolomite to form CO2 facilitated the transfer of sorbed-phase PCE from the solid to the aqueous phase in heated ampules. While compounds associated with PCE degradation were detected in the heated ampules, these compounds were also detected in ampules with PCE-free Camelot soil and were attributed to soil diagenesis rather than PCE degradation. Trichloroethylene underwent hydrogenolysis to form cis-DCE at 95 degrees C, and TCE levels decreased with first-order half-lives of 157 days at 55 degrees C and 26 days at 95 degrees C. The relatively small decrease in total PCE levels after 75 days of heating at 95 degrees C suggests that abiotic degradation of PCE will not result in significant mass reduction during thermal treatment of the Camelot Cleaners Superfund site.

Abiotic degradation of trichloroethylene under thermal remediation conditions.

The degradation of trichloroethylene (TCE) to carbon dioxide (CO2) and chloride (Cl-) has been reported to occur during thermal remediation of subsurface environments. The effects of solid-phase composition and oxygen content on the chemical reactivity of TCE were evaluated in sealed ampules that were incubated at 22 and 120 degrees C for periods ranging from 4 to 40 days. For all treatments, no more than 15% of the initial amount of TCE was degraded, resulting in the formation of several non-chlorinated products including Cl-, CO2, carbon monoxide, glycolate, and formate. First-order rate coefficients for TCE disappearance ranged from 1.2 to 6.2 x 10(-3) day(-1) at 120 degrees C and were not dependent upon oxygen content orthe presence of Ottawa sand. However, the rate of TCE disappearance at 120 degrees C increased by more than 1 order-of-magnitude (1.6 to 5.3 x 10(-2) day(-1)), corresponding to a half-life of 13-44 days in ampules containing 1% (wt) goethite and Ottawa sand. These results indicate that the rate of TCE degradation in heated, three-phase systems is relatively insensitive to oxygen content, but may increase substantially in the presence of iron bearing minerals.