Simulating PFAS transport in effluent-irrigated farmland using PRZM5, LEACHM, and HYDRUS-1D models.

Application of wastewater effluent to agricultural lands can serve as a sustainable approach to meet irrigation and nutrient needs for crop production. While nitrogen and phosphorous loadings can be effectively managed, concerns have been raised regarding the fate of emerging contaminants, including per- and polyfluoroalkyl substances (PFAS), which are widely detected in wastewater effluent. The objective of this paper was to evaluate the ability of three unsaturated flow and transport models, Pesticide Root Zone Model 5 (PRZM5), LEACHM, and HYDRUS-1D, to predict the distribution of PFAS in the soil profile at the Pennsylvania State University Living Filter site, which has received daily wastewater effluent applications for several decades. The models were modified to include adsorption at the air-water interface (AWI), which has been shown to be an important factor governing PFAS transport and phase distribution in the vadose zone. Simulations showed that PRZM5 did not accurately reproduce the observed perfluorooctanesulfonic acid (PFOS) behavior, which was attributed to the "tipping bucket" approach used for water flow that results in the disappearance of AWI during water flow. In contrast, both LEACHM and HYDRUS-1D captured the observed retention of PFOS and perfluorooctanoic acid (PFOA) over a 50-year simulation period. Due to differences in the approach used to calculate the AWI area, LEACHM predicted greater accumulation of PFOS and PFOA at the AWI compared to HYDRUS-1D. These findings indicate that mathematical models that directly account for unsaturated water flow and adsorption at the AWI are able to provide reasonable predictions of long-term PFAS leaching resulting from land application of wastewater effluent.

Chlorinated volatile organic compounds (CVOCs) and 1,4-dioxane kinetics and equilibrium adsorption studies on selective macrocyclic adsorbents.

Chlorinated volatile organic compounds (CVOCs) are often found in combination with 1,4-dioxane which has been used as a solvent stabilizer. It would be desirable to separate these compounds since biodegradation of 1,4-dioxane follows an aerobic pathway while anaerobic conditions are needed for biodegrading CVOCs. Conventional adsorbents such as activated carbon (AC) and carbonaceous resins have high adsorption capacities for 1,4-dioxane and CVOCs but lack selectivity, limiting their use for separation (Liu et al., 2019). In the current work, two macrocyclic adsorbents, ß-CD-TFN and Res-TFN, were examined for selective adsorption of chlorinated ethenes in the presence of 1,4-dioxane. Both adsorbents exhibited rapid adsorption of the CVOCs and minimal adsorption of 1,4-dioxane. Res-TFN had a higher adsorption capacity for CVOCs than ß-CD-TFN (measured linear partition coefficient, Kd 2140 -9750 L⋅kg-1 versus 192-918 L⋅kg-1 for 1,1, DCE, cis-1,2-DCE and TCE, respectively) and was highly selective for CVOCs(TCE Kd ~117 Kd for 1,4-dioxane). By comparison, TCE and 1,4-dioxane adsorption on AC was approximately equal at 100 µg⋅L-1 and approximately 1/3 of the adsorption of TCE on the Res-TFN. The greater adsorption and selectivity of Res-TFN suggest that it can be used as a selective adsorbent to separate CVOCs from 1,4-dioxane to allow separate biodegradation.

Modeling 1-D aqueous film forming foam transport through the vadose zone under realistic site and release conditions.

Aqueous film forming foams (AFFFs) have been used to extinguish fires since the 1960s, leading to widespread subsurface contamination by per- and polyfluoroalkyl substances (PFAS), an essential component of AFFF. This study presents 1-D simulations of PFAS migration in the vadose zone resulting from AFFF releases. Simulation scenarios used soil profiles from three US Air Force (USAF) installations, encompassing a range of climatic conditions and hydrogeologic environments. A three-component mixture, representative of major constituents of AFFF, facilitated the exploration of competitive and synergistic effects of co-constituents on PFAS migration. To accurately capture unsaturated transport of PFAS in porous media, the model considers (1) surfactant-induced flow, (2) non-linear sorption to the solid phase, (3) competitive accumulation at the air-water interface, and (4) the moisture-dependence of the air-water interfacial area. Defined PFAS releases were consistent with fire training exercises, emergency responses, and accidental spills of record. Simulation results illustrate the importance of hydrogeologic, climatic, geochemical, and AFFF release conditions on PFAS transport and retention. Comparison of field observations and model simulations for Ellsworth AFB indicate that much of the PFOA and PFOS mass is associated with the air-water interface and the solid phase, which limits their migration potential in the vadose zone. Results also show that rates of migration in the aqueous phase are largely controlled by hydrogeologic properties, including recharge rates and hydraulic conductivity. AFFF spill scenarios varying in volume, concentration, and frequency reveal the importance of release characteristics in determining rates of PFAS migration and concentration peaks. Variability is attributed to non-linear sorption processes, where, contrary to simple linear partitioning formulations, transport is strongly affected by the concentration of PFAS species. Simulations also demonstrate the importance of modeling the AFFF as a mixture since competitive interfacial accumulation effects are shown to enhance the mobility of less surface-active PFAS compounds.

Biotransformation of 6:2 fluorotelomer sulfonate and microbial community dynamics in water-saturated one-dimensional flow-through columns.

Nearly all per- and polyfluoroalkyl substances (PFAS) biotransformation studies reported to date have been limited to laboratory-scale batch reactors. The fate and transport of PFAS in systems that more closely represent field conditions, i.e., in saturated porous media under flowing conditions, remain largely unexplored. This study investigated the biotransformation of 6:2 fluorotelomer sulfonate (6:2 FTS), a representative PFAS of widespread environmental occurrence, in one-dimensional water-saturated flow-through columns packed with soil obtained from a PFAS-contaminated site. The 305-day column experiments demonstrated that 6:2 FTS biotransformation was rate-limited, where a decrease in pore-water velocity from 3.7 to 2.4 cm/day, resulted in a 21.7-26.1 % decrease in effluent concentrations of 6:2 FTS and higher yields (1.0-1.4 mol% vs. 0.3 mol%) of late-stage biotransformation products (C4C7 perfluoroalkyl carboxylates). Flow interruptions (2 and 7 days) were found to enhance 6:2 FTS biotransformation during the 6-7 pore volumes following flow resumption. Model-fitted 6:2 FTS column biotransformation rates (0.039-0.041 cmw3/gs/d) were ∼3.5 times smaller than those observed in microcosms (0.137 cmw3/gs/d). Additionally, during column experiments, planktonic microbial communities remained relatively stable, whereas the composition of the attached microbial communities shifted along the flow path, which may have been attributed to oxygen availability and the toxicity of 6:2 FTS and associated biotransformation products. Genus Pseudomonas dominated in planktonic microbial communities, while in the attached microbial communities, Rhodococcus decreased and Pelotomaculum increased along the flow path, suggesting their potential involvement in early- and late-stage 6:2 FTS biotransformation, respectively. Overall, this study highlights the importance of incorporating realistic environmental conditions into experimental systems to obtain a more representative assessment of in-situ PFAS biotransformation.

Assessment and Management of Mercury Leaching from a Riverbank.

The South River located in the city of Waynesboro, Virginia, contains mercury (Hg) contamination due to historical releases from an industrial facility operating between 1929 and 1950. In 2015, two sampling events were conducted in two of the contaminated bank regions (Constitution Park and North Park) to evaluate non-particulate total mercury (THg) and methylmercury (MeHg) concentrations in bank interstitial waters during river base flows and during bank drainage after flooding events. Porewater THg and MeHg at the bank-water interface were measured using diffusive gradient in thin-film devices (DGTs). The results showed THg mercury concentrations during bank drainage were approximately a factor of 3 higher than during base flow conditions. To have a better understanding of the parameters that control Hg leaching, a series of laboratory experiments were designed using South River sediments. The field and laboratory assessment showed that drainage/inundation cycles can lead to high THg concentration leachate from contaminated sediment due to increased partitioning from solids under oxic bank conditions and mobilization by the drainage waters. The results also demonstrated that methyl mercury concentrations at the bank-water interface are highest under base flow when conditions are more reduced due to the absence of oxic water exchange with the surface water. A remedial approach was implemented involving partial removal of surficial sediments and placement of biochar (to reduce non-particulate THg) and an armoring layer (to reduce erosion). DGT Measurements after bank stabilization showed THg decreased by a factor of ~200 and MeHg concentration by a factor of more than 20.

Long-term monitoring and modeling of PAHs in capped sediments at the Grand Calumet River.

The assessment of a cap for remediation of sediments requires long-term monitoring because of the slow migration of contaminants in porous media. In this study, coring and passive sampling tools were used to assess the transport and degradation of polycyclic aromatic hydrocarbons (PAHs) in an amended cap (sand + Organoclay® PM-199) in the Grand Calumet River (Indiana, USA) during four sampling events from 2012 to 2019. Measurements of three PAHs (phenanthrene (Phe), pyrene (Pyr) and benzo[a]pyrene (BaP), representing low, medium, and high molecular weight compounds, respectively) showed a difference of at least two orders of magnitude between bulk concentrations in the native sediments and the remediation cap. Averages of pore water measurements also showed lower levels in the cap respective to the native sediments by a factor of at least 7 for Phe and 3 for Pyr. In addition, between the baseline (BL), which corresponds to observations from 2012 to 2014, and the measurements in 2019, there was a decrease in depth-averaged pore water concentrations of Phe (C2019/CBL=0.20-0.07+0.12 in sediments and 0.27-0.10+0.15 in cap) and Pyr (C2019/CBL=0.47-0.12+0.16 in sediments and 0.71-0.20+0.28 in the cap). In the case of BaP in pore water, no change was observed in native sediments (C2019/CBL=1.0-0.24+0.32) and there was an increase in the cap (C2019/CBL=2.0-0.54+0.72). Inorganic anions and estimates of pore water velocity along with measurements of PAHs were used to model the fate and transport of contaminants. The modeling suggested that degradation of Phe (t1/2=1.12-0.11+0.16 years) and Pyr (t1/2=5.34-1.8+5.3 years) in the cap is faster than migration, thus the cap is expected to be protective of the sediment-water interface indefinitely for these constituents. No degradation was noted in BaP and the contaminant is expected to reach equilibrium in the capping layer over approximately 100 years if there exists sufficient mass of BaP in the sediments and there is no deposition of clean sediment at the surface.

Improved assessment and performance monitoring of a biowall at a chlorinated solvent site using high-resolution passive sampling.

This study contrasts the use of high-resolution passive sampling and traditional groundwater monitoring wells (GWMW) to characterize a chlorinated solvent site and assess the effectiveness of a biowall (mulch, compost and sand) that was installed to remediate trichloroethene (TCE), the primary contaminant of concern. High-resolution passive profilers (HRPPs) were direct driven hydraulically upgradient, within, and hydraulically downgradient of the biowall and in close proximity to existing GWMWs. Compared with hydraulically upgradient locations, the biowall was highly reducing, there were higher densities of bacteria/genes capable of reductive dechlorination, and TCE was being reductively transformed, but not completely, as cis-1,2-dichloroethene (cis-DCE) was detected within and hydraulically downgradient of the biowall. However, based on the high-resolution data, there were a number of important findings which were not discoverable using data from GWMWs alone. Data from the HRPPs indicate that the biowall was completely transforming TCE to ethene (C2H4) except within a high velocity interval, where the concentrations were reduced, but breakthrough of cis-DCE was apparent. Hydraulically upgradient of the biowall, concentrations of TCE increased with depth where a very low permeability zone exists that will likely remain as a long-term source. In addition, although low concentrations of cis-DCE were present downgradient of the biowall, surfacing into a downgradient stream was not detected. This study demonstrates the advantages of high-resolution passive sampling of aquifers to assess the performance of remediation techniques compared to traditional methods such as GWMWs.

In Situ Passive Sampling to Monitor Long Term Cap Effectiveness at a Tidally Influenced Shoreline.

Polydimethylsiloxane solid-phase microextraction passive samplers were used to evaluate long-term performance of a sand/gravel cap placed in 2005 in a tidally influenced shoreline in Puget Sound to reduce polycyclic aromatic hydrocarbon (PAH) transport into overlying surface water. Sampling in both 2010 and 2018 measured porewater concentrations of <1 ng/L total PAHs in the cap layer. d-PAH performance reference compounds were used to evaluate the extent of equilibration of the contaminants onto the samplers and to estimate net upwelling velocities through a mass-transfer model. The upwelling velocities were used to predict long-term migration of selected PAHs through the cap, showing that the cap is expected to continue being effective at limiting exposure of contaminants at the cap−water interface.

Estimation of Interstitial Velocity Using a Direct Drive High-Resolution Passive Profiler.

The fate and transport of groundwater contaminants depends partially on groundwater velocity, which can vary appreciably in highly stratified aquifers. A high-resolution passive profiler (HRPP) was developed to evaluate groundwater velocity, contaminant concentrations, and microbial community structure at ∼20 cm vertical depth resolution in shallow heterogeneous aquifers. The objective of this study was to use mass transfer of bromide (Br- ), a conservative tracer released from cells in the HRPP, to estimate interstitial velocity. Laboratory experiments were conducted to empirically relate velocity and the mass transfer coefficient of Br- based on the relative loss of Br- from HRPP cells. Laboratory-scale HRPPs were deployed in flow boxes containing saturated soils with differing porosities, and the mass transfer coefficient of Br- was measured at multiple interstitial velocities (0 to 100 cm/day). A two-dimensional (2D) quasi-steady-state model was used to relate velocity to mass transfer of Br- for a range of soil porosities (0.2-0.5). The laboratory data indicate that the mass transfer coefficient of Br- , which was directly-but non-linearly-related to velocity, can be determined with a single 3-week deployment of the HRPP. The mass transfer coefficient was relatively unaffected by sampler orientation, length of deployment time, or porosity. The model closely simulated the experimental results. The data suggest that the HRPP will be applicable for estimating groundwater velocity ranging from 1 to 100 cm/day in the field at a minimum depth resolution of 10 cm, depending on sampler design.