Application of Hydrothermal Alkaline Treatment for Destruction of Per- and Polyfluoroalkyl Substances in Contaminated Groundwater and Soil.

Hydrothermal alkaline treatment (HALT) can effectively degrade per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foam (AFFF). However, information is lacking regarding the treatment of PFASs in actual groundwater and soil from AFFF-impacted sites, especially for complex soil matrices. Given the lack of studies on direct soil treatment for PFAS destruction, we herein applied HALT to two groundwater samples and three soil samples from AFFF-impacted sites and characterized the destruction of PFASs using high-resolution mass spectrometry. Results showed that the 148 PFASs identified in all collected field samples, including 10 cationic, 98 anionic, and 40 zwitterionic PFASs, were mostly degraded to nondetectable levels within 90 min when treated with 5 M NaOH at 350 °C. The near-complete defluorination, as evidenced by fluoride release measurements, confirmed the complete destruction of PFASs. While many structures, including perfluoroalkyl carboxylic acids and polyfluorinated substances, were readily degraded, perfluoroalkyl sulfonates (PFSAs, CnF2n+1-SO3-), most notably with short chain lengths (n = 3-5), were more recalcitrant. Rates of PFSA destruction in groundwater samples were similar to those measured in laboratory water solutions, but reactions in soil were slow, presumably due to base-neutralizing properties of the soil. Further, the degradation of PFASs in groundwaters and soils was found to be a function of reaction temperature, NaOH concentration, and reaction time. These findings have important implications for the remediation of AFFF-impacted sites.

Coupled photocatalytic alkaline media as a destructive technology for per- and polyfluoroalkyl substances in aqueous film-forming foam impacted stormwater.

The release of aqueous film forming foam (AFFF) from fuel fire events, fire training events, and other activities has resulted in the presence of persistent and recalcitrant per- and polyfluoroalkyl substances (PFAS) in soil and water nationwide. This study describes the degradation and defluorination of PFAS in stormwater collected from an AFFF-impacted site. Silica-based granular media (SGM) containing titanium dioxide was packed into a column reactor and placed between ultraviolet (UV) lamps to excite the photocatalyst within the SGM and generate free radicals to degrade PFAS present in water that was passed through the media. The system was amended with nucleophiles (hydroxyls) to facilitate the destruction of PFAS. Results showed rapid degradation of 17 identified PFAS, including perfluoroalkyl acid (PFAA) precursors, perfluorosulfonic acids (PFSAs), and perfluorocarboxylic acids (PFCAs). Significant defluorination was observed, indicating PFAS destruction as a result of the coupled photocatalytic and nucleophilic attack. Column reactor experiment findings indicate SGM in the presence of UV light passively degraded a mixture of PFAS in a concentrated waste stream at ambient conditions.

Hydrothermal Alkaline Treatment for Destruction of Per- and Polyfluoroalkyl Substances in Aqueous Film-Forming Foam.

The widespread use of aqueous film-forming foam (AFFF) for firefighting activities (e.g., fire training to extinguish fuel-based fires at aircraft facilities) has led to extensive groundwater and soil contamination by per- and polyfluoroalkyl substances (PFASs) that are highly recalcitrant to destruction using conventional treatment technologies. This study reports on the hydrothermal alkaline treatment of diverse PFASs present in AFFFs. Quantitative and semiquantitative high-resolution mass spectrometry analyses of PFASs demonstrate a rapid degradation of all 109 PFASs identified in two AFFFs (sulfonate- and fluorotelomer-based formulations) in water amended with an alkali (e.g., 1-5 M NaOH) at near-critical temperature and pressure (350 °C, 16.5 MPa). This includes per- and polyfluoroalkyl acids and a range of acid precursors. Most PFASs were degraded to nondetectable levels within 15 min, and the most recalcitrant perfluoroalkyl sulfonates were degraded within 30 min when treated with 5 M NaOH. 19F NMR spectroscopic analysis and fluoride ion analysis confirm the near-complete defluorination of PFASs in both dilute and concentrated AFFF mixtures, and no stable volatile organofluorine species were detected in reactor headspace gases by the gas chromatography-mass spectrometry analysis. These findings indicate a significant potential for application of hydrothermal treatment technologies to manage PFAS waste streams, including on-site treatment of unused AFFF chemical stockpiles, investigation-derived wastes, and concentrated source zone materials.

Novel treatment technologies for PFAS compounds: A critical review.

Perfluorinated compounds such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have recently drawn great attention due to their wide distribution in aquatic environments. The understanding of the physicochemical properties and fate and transport of PFAs in groundwater is still limited. Preliminary studies indicate that these compounds can readily bioaccumulate and pose human and animal health concerns. Due to their physicochemical properties, PFOS and PFOA are water soluble, nonvolatile and persistent in the environment, which is a cause of concern related to their treatment with conventional remediation technologies. Extraction with inefficient carbon adsorption is one of the most common treatment technologies for remediation of PFOS- or PFOA-impacted groundwater. Several other innovative and promising technologies, including sonochemistry, bioremediation and photolysis, have been tested for their effectiveness in removal of perfluorinated compounds. This paper provides a baseline for understanding research needs to better develop treatment technologies for PFOA and PFOS in groundwater. Frontiers for improving the state of practice for PFOA and PFOS treatment include the development of more cost-effective ex situ treatment methods and the development and demonstration of promising in situ treatment technologies at the pilot and full scale.

Remediation management of complex sites using an adaptive site management approach.

Complex sites require a disproportionate amount of resources for environmental remediation and long timeframes to achieve remediation objectives, due to their complex geologic conditions, hydrogeologic conditions, geochemical conditions, contaminant-related conditions, large scale of contamination, and/or non-technical challenges. A recent team of state and federal environmental regulators, federal agency representatives, industry experts, community stakeholders, and academia worked together as an Interstate Technology & Regulatory Council (ITRC) team to compile resources and create new guidance on the remediation management of complex sites. This article summarizes the ITRC team's recommended process for addressing complex sites through an adaptive site management approach. The team provided guidance for site managers and other stakeholders to evaluate site complexities and determine site remediation potential, i.e., whether an adaptive site management approach is warranted. Adaptive site management was described as a comprehensive, flexible approach to iteratively evaluate and adjust the remedial strategy in response to remedy performance. Key aspects of adaptive site management were described, including tools for revising and updating the conceptual site model (CSM), the importance of setting interim objectives to define short-term milestones on the journey to achieving site objectives, establishing a performance model and metrics to evaluate progress towards meeting interim objectives, and comparing actual with predicted progress during scheduled periodic evaluations, and establishing decision criteria for when and how to adapt/modify/revise the remedial strategy in response to remedy performance. Key findings will be published in an ITRC Technical and Regulatory guidance document in 2017 and free training webinars will be conducted. More information is available at www.itrc-web.org.

In-situ determination of field-scale NAPL mass transfer coefficients: Performance, simulation and analysis.

Better estimates of non-aqueous phase liquid (NAPL) mass, its persistence into the future, and the potential impact of source reduction are critical needs for determining the optimal path to clean up sites impacted by NAPLs. One impediment to constraining time estimates of source depletion is the uncertainty in the rate of mass transfer between NAPLs and groundwater. In this study, an innovative field test is demonstrated for the purpose of quantifying field-scale NAPL mass transfer coefficients (kl(N)) within a source zone of a fuel-contaminated site. Initial evaluation of the test concept using a numerical model revealed that the aqueous phase concentration response to the injection of clean groundwater within a source zone was a function of NAPL mass transfer. Under rate limited conditions, NAPL dissolution together with the injection flow rate and the radial distance to monitoring points directly controlled time of travel. Concentration responses observed in the field test were consistent with the hypothetical model results allowing field-scale NAPL mass transfer coefficients to be quantified. Site models for groundwater flow and solute transport were systematically calibrated and utilized for data analysis. Results show kl(N) for benzene varied from 0.022 to 0.60d(-1). Variability in results was attributed to a highly heterogeneous horizon consisting of layered media of varying physical properties.

Microbial degradation of steroidal estrogens.

Steroidal estrogens, widespread in the environment, are contaminants of potential concern because exposure to these compounds can cause adverse impacts on aquatic life. Intensive research efforts have been undertaken in order to better understand the environmental occurrence of these compounds. In addition to physical/chemical reactions, biological processes - microbial biodegradation of steroidal estrogens - play a vital role in determining the fate and transport of these compounds in built and natural environments. This review summarizes the current state of knowledge on the microbiology of estrogen biodegradation. Aerobic and anaerobic estrogen-degrading microorganisms are phylogenetically diverse; they are mainly isolated from soils, activated sludge, dental plaque and intestines. Estrogens can be degraded via growth-linked and non-growth-linked reactions, as well as through abiotic degradation in the presence of selective microorganisms. Current knowledge on estrogen biodegradation kinetics and pathways is limited. Molecular methods are useful in deciphering estrogen-degrading microbial community and tracking the quantity of known degraders in bioreactors with different operating conditions. Future research efforts aimed at bridging knowledge gaps on estrogen biodegradation are also proposed.

Quantifying genes and transcripts to assess the in situ physiology of "Dehalococcoides" spp. in a trichloroethene-contaminated groundwater site.

Quantitative PCR (qPCR) was coupled with reverse transcription (RT) to analyze both gene copy numbers and transcripts of the 16S rRNA gene and three reductive dehalogenase (RDase) genes (tceA, vcrA, and bvcA) as biomarkers of "Dehalococcoides" spp. in the groundwater of a trichloroethene-dense nonaqueous-phase liquid site at Fort Lewis, WA, that was sequentially subjected to biostimulation and bioaugmentation. Dehalococcoides cells carrying the tceA, vcrA, and bvcA genes were indigenous to the site. The sum of the three identified RDase gene copy numbers closely correlated to 16S rRNA gene copy numbers throughout the biostimulation and bioaugmentation activity, suggesting that these RDase genes represented the major Dehalococcoides metabolic functions at this site. Biomarker quantification revealed an overall increase of more than 3 orders of magnitude in the total Dehalococcoides population through the 1-year monitoring period (spanning biostimulation and bioaugmentation), and measurement of the respective RDase gene concentrations indicated different growth dynamics among Dehalococcoides cells. The Dehalococcoides cells containing the tceA gene consistently lagged behind other Dehalococcoides cells in population numbers and made up less than 5% of the total Dehalococcoides population, whereas the vcrA- and bvcA-containing cells represented the dominant fractions. Quantification of transcripts in groundwater samples verified that the 16S rRNA gene and the bvcA and vcrA genes were consistently highly expressed in all samples examined, while the tceA transcripts were detected inconsistently, suggesting a less active physiological state of the cells with this gene. The production of vinyl chloride and ethene toward the end of treatment supported the physiological activity of the bvcA- and vcrA-carrying cells. A clone library of the expressed RDase genes in field samples produced with degenerate primers revealed the expression of two putative RDase genes that were not previously monitored with RT-qPCR. The level of abundance of one of the putative RDase genes (FtL-RDase-1638) identified in the cDNA clone library tracked closely in field samples with abundance of the bvcA gene, suggesting that the FtL-RDase-1638 gene was likely colocated in genomes containing the bvcA gene. Overall, results from this study demonstrate that quantification of biomarker dynamics at field sites can provide useful information about the in situ physiology of Dehalococcoides strains and their associated activity.

Formation of nitrosodimethylamine (NDMA) during chlorine disinfection of wastewater effluents prior to use in irrigation systems.

The probable human carcinogen nitrosodimethylamine (NDMA) is produced when wastewater effluent is disinfected with chlorine. In systems where wastewater effluent is used for landscape or crop irrigation, relatively high chlorine doses (i.e., up to 2,000,mg-min/L) are often used to ensure adequate disinfection and to minimize biofouling in the irrigation system. To assess the formation of NDMA in such systems, samples were collected from several locations in full-scale wastewater treatment systems and their associated irrigation systems. Up to 460 ng/L of NDMA was produced in full-scale systems in which chloramines were formed when wastewater effluent was disinfected with chlorine in the presence of ammonia. Less than 20 ng/L of NDMA was produced in systems that used free chlorine (i.e., HOCl/OCl(-)) for disinfection in the absence of ammonia. The production of NDMA in ammonia-containing systems was correlated with the concentration of NDMA precursors in the wastewater effluent and the overall dose of chlorine applied. Much of the NDMA formation occurred in chlorine contact basins or in storage basins where water that contained chloramines was held after disinfection. When landscape or crop irrigation is practiced with ammonia-containing wastewater effluent, NDMA production can be controlled by use of lower chlorine doses or by application of alternative disinfectants.

Sources and fate of nitrosodimethylamine and its precursors in municipal wastewater treatment plants.

To assess the occurrence and fate of nitrosodimethylamine (NDMA) and its precursors in wastewater treatment plants, samples from wastewater treatment plants and industrial sources were analyzed for NDMA, total NDMA precursors, and dimethylamine (DMA). The median concentration of NDMA in untreated wastewater was approximately 80 ng/L, with maximum concentrations up to 790 ng/L presumably occuring because of sources unrelated to domestic wastewater. Concentrations of DMA in untreated wastewater ranged from approximately 50 to 120 microg/L and accounted for a majority of the NDMA precursors. The removal of NDMA during secondary biological treatment exhibited considerable variability, with overall removal ranging from 0 to 75%. In contrast, removal of NDMA precursors and DMA generally exceeded 70%. The median concentration of NDMA in secondary effluent before disinfection was 46 ng/L. Although DMA was removed during secondary treatment, other NDMA precursors in wastewater effluent will result in formation of additional NDMA upon disinfection with chloramines.

The occurrence of cyanide formation in six full-scale publicly owned treatment works.

This paper presents results from an intensive monitoring program implemented at six full-scale publicly owned treatment works (POTWs) to investigate the fate and formation of cyanide in wastewater treatment processes, with a focus on chlorination and dechlorination processes. A review of historical monitoring data for cyanide species in these POTWs was also conducted. This POTW monitoring program provided a database for the investigation of cyanide formation in wastewater secondary treatment. Data from participating POTWs showed evidence of cyanide formation in this 1-year monitoring effort, although the cyanide formation pattern varied significantly from one plant to another and among seasons. Generally, the chlorination of thiocyanate (SCN-) seems to be the most important mechanism for the formation of cyanide in wastewater treatment processes, especially in chlorination and dechlorination. This hypothesis is supported by the findings of a related laboratory study of mechanisms of cyanide formation in POTWs. It is recommended that POTWs monitor SCN in influent and secondary effluent to identify its presence and adjust chlorine dose appropriately.