Passive flux meters (PFMs) directly measure groundwater chemistry mass flux and Darcy flux, providing insight into contaminant source-zone architecture and transport properties. This study uses PFMs to characterize PFAS flux in groundwater at a semiarid site with a thick (greater than 90-m) unsaturated zone where groundwater has been contaminated with per- and polyfluoroalkyl substances (PFAS) related to the use of aqueous film-forming foam (AFFF) for fire training and fire suppression. PFAS mass discharge (PFAS mass flux integrated over a control plane) in groundwater downgradient from several PFAS release areas is calculated using PFM results. In groundwater downgradient from fire-training areas, total PFAS mass discharge (summed across 14 compounds) was estimated to be between 6.0 and 31 g per day in 2020 and between 5.9 and 23 g per day in 2021. Site-specific documentation, generic information on AFFF properties, and literature values of PFAS concentration in AFFF are used to estimate site-specific PFAS-application rates at fire-training areas. These PFAS-application rates are compared to groundwater PFAS-discharge rates. Results suggest that transformation processes (exact pathways unknown) have led to increased discharge of measured PFAS in groundwater relative to initial AFFF formulations. The mass balance approach has broad applicability as a high-level approach that can provide insight into PFAS transport at AFFF sites.

Per- and polyfluoroalkyl substances (PFAS) are persistent in the environment due to their chemical stability and can spread quickly in a lake system due to mixing. Passive samplers allow for time-weighted average concentration monitoring and the ability to detect low concentrations, which are difficult to measure with conventional grab sampling. This study demonstrates the feasibility of deploying both ceramic dosimeters and Sediment Bed Passive Flux Meters (SBPFMs) to assess time integrated PFAS concentrations and fluxes, respectively, at a historically contaminated PFAS lake near Baden-Baden, Germany. Long-term surface water grab samples resulted in the detection of PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFBS, PFHxS, and PFOS at a total concentration of approximately 1 mu g/L. Dosimeters were deployed for 66 and 126 d, resulting in detected concentrations ranging from approximately 250 to 380 ng/L and 120 to 460 ng/L, respectively. The 66 d deployment resulted in the detection of PFPeA, PFHxA, PFHpA, and PFOA, whereas the 126 d deployment additionally detected PFBA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFPeS, PFOS, PFNS, and PFDS. SBPFMs resulted in the detection of PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFUnA, PFTrDA, and PFBS and the determination of a total mass discharge of 5.6 g/d into the lake. Overall, dosimeters and SBPFMs are more sensitive than grab samples at detecting PFAS at low concentrations and can be used to better understand spatial distribution of PFAS in a lake system.

This study presents the use of organic gel-forming material for the construction of hydraulic barriers in aquifer, which can be easily removed after use. Experiments on the performance of the temporary hydraulic barrier during NAPL removal (aquifer flushing) were also conducted. An aqueous solution of sodium alginate was injected into the horizontally oriented, 2-dimensional flow chamber packed with sand, followed by gelation using a calcium solution. The alginate gel formed in the porous media produced a circular shape barrier (24 cm diameter, 1.3 cm thickness) that was successfully removed using sodium bicarbonate solution (1.0 M) in 72 h, whereas the gel was stable for 7 days during simulated groundwater flushing at the same flow rate as the sodium bicarbonate solution. When circular hydraulic barriers (12 cm diameter each, 14 cm apart) were set on either side of the NAPL (n-hexane and PCE mixture)-contaminated zone, the increased water flux during water flushing resulted in significantly increased PCE removal by almost 108%. When a surfactant solution (sodium dodecyl sulfate, 0.037%) was applied, the influenced groundwater flow controlled by hydraulic barriers on the NAPL removal was amplified by 196% removal.

A critical determinant of the effective denitrification potential in karst aquifers is the relative contribution of matrix and non-matrix (e.g., conduits) to the total groundwater flow. This work tests the hypothesis that observed karst aquifer-scale denitrification rates represent the superposition of the effects from matrix zones, which have low denitrification rates and long residence times, and non-matrix zones, which have higher denitrification rates and short residence times. To better evaluate karst whole-aquifer denitrification capacity, this study examined groundwater chemical data from 69 individual wells across the springshed of Silver Springs, FL, and conducted five push-pull tracer tests (PPTTs) in matrix and non-matrix aquifer sections. Mean residence times and mean zero-order denitrification rates (K0) were determined using reduced-complexity analytical models for matrix and non-matrix zones. Significant nitrate degradation at the local scale was observed in wells that sampled matrix portions of the aquifer (K0 & AP;5 to 7 x 103 & mu;mol N/L/d), indicating denitrification hotspots comparable to previous results employing the same PPTT method. However, PPTTs in matrix portions of the aquifer found no evidence of aquifer denitrification, likely due to the short residence times experienced during PPTTs. The analytical models coupled with the measured nitrate concentrations and excess N2 data in groundwater discharged at the spring vents showed whole-aquifer estimates of residence times tavg = 4.2 years and aquifer denitrification rate K0,avg = 0.01 & PLUSMN; 0.01 & mu;mol N/L/d that were consistent with previous studies. However, the average denitrification rate for non-matrix zones K0,nm = 1.29 & PLUSMN; 0.92 & mu;mol N/L/d was two orders of magnitude higher than that for matrix zones K0,m = 0.002 & PLUSMN; 0.001 & mu;mol N/L/d. Whole-aquifer denitrification measures thus reflect the weighted contributions of low denitrification in non-matrix zones, which constitute the majority of the groundwater flow, and high-denitrification but low-flow matrix zones. The modeling approach with non-matrix networks from this study can provide insight into the catchment-scale N budget and transport in karst aquifers.

The dynamic behavior of the freshwater-saltwater interface (FSI) in coastal aquifers can introduce unexpected lags between recharge and stream discharge, especially when recharge is forced by long-term cyclical precipitation patterns. This work seeks to assess these FSI impacts at the watershed scale. Recharge-discharge time lags were evaluated in 68 watersheds overlying the Floridan Aquifer System in the coastal region of the southeastern United States (Florida, Georgia, and South Carolina). Utilizing the strength of the Atlantic multidecadal oscillation (AMO) signal in this region, 10–20 year averaged recharge and discharge time series were used for the selected watersheds. Lags of 10–25 years between recharge and discharge were found in 16% of the basins considered, possibly induced by a dynamic FSI which responded slowly to the AMO-scale recharge signal. Freshwater storage coefficients (S) were estimated from time series of change-in-storage and groundwater level, with 11 basins showing S>1.5 indicating water storage well above that expected for unconfined aquifers. These 11 basins with both multidecadal recharge-discharge time lags and high S values showed a positive linear relationship between time lag and FSI depth with slope 0.016 yr/m (R-squared = 0.30). These large time lags may be directly impacting the management of these basins as they obscure water and solute mass balances in the southeastern US.

The effect of lowered groundwater surface tension using alcohols and surfactants, and increased viscosity using a thickener on the performance of the air sparging (AS) process was investigated, and the mechanism of facilitated air intrusion into the saturated zone during surfactant-enhanced air sparging (SEAS) was proposed.When aqueous solutions of alcohols (e.g., ethyl alcohol) displaced the resident water in a sand-packed column, the air saturation slightly decreased during AS, whereas the addition of surfactants increased air saturation. During the AS process, a significant difference in the air pressure measurements was observed, depending on the chemicals (alcohols and surfactants). Significantly higher air pressure was measured during SEAS than AS process with alcohol solutions. In this study, it is proposed that the foam formation and displacement through the soil interstices during the SEAS process increases air pressure. And this additional air pressure is responsible for the additional air intrusion into the smaller pores at lowered surface tension. Increased hydraulic pressure or water viscosity showed no significant effect on the air saturation during alcohol-applied AS. However, during SEAS, the increased viscosity using a thickener increased the viscosity of the foam inducing high air pressure, resulting in further enhanced air saturation.

The surfactant-enhanced gas sparging process designed to specifically target the source zone of an organic contaminant in an aquifer with minimal usage of injected additives was investigated using a physical model. Aqueous solutions of the anionic surfactant Sodium dodecylbenzne sulfonate (SDBS) and/or the thickener Sodium carboxymethylcellulose (SCMC) were applied in a contaminated horizontal layer in the simulated laboratory aquifer model followed by gas sparging. Fluorescein sodium salt (FSS) was added to the SDBS/SCMC solutions and represented the organic contaminant. Air and ozone were injected to generate gas sparging. A modified surfactant-enhanced ozone sparging method was also tested by applying additional air venting ports installed in the aquifer above the gas injection zone. Both non-aqueous phase liquid (NAPL) and water-dissolved TCA were applied to the SDBS-applied region to evaluate the removal of contaminants during gas sparging. A significant expansion of the de-saturated zone for the SDBS-applied region was observed during air sparging. During ozone sparging, the fluorescence by FSS in the SDBS-applied layer disappeared over a much wider range than that of the control experiment. SCMC application enhanced the performance of the SDBS-applied gas sparging process. The TCA mass removed by volatilization during air sparging from the SDBS-applied layer was 2.3 times the application in the absence of SDBS. Among five regions of injected NAPL contamination located above the single gas injection port, and during 2 h of ozone sparging, with SDBS applied, more than 50% of fluorescence in the NAPL was removed, whereas under the same conditions with no SDBS applied, less than 30% was removed. Diverted gas flow through the venting ports installed in the aquifer model induced a horizontally expanded oxidative reaction zone during ozone sparging. This study demonstrates enhanced gas sparging performance for the removal of contaminants from the aquifer with limited usage of additives applied specifically to the source zone.

Large volumes of per- and polyfluoroalkyl substances (PFAS)-contaminated wastewaters, such as municipal solid waste landfill leachates, pose a challenge for PFAS treatment technologies in practice today. In this study, the surfactant properties of PFAS were exploited to concentrate the compounds in foam produced via the bubble aeration of landfill leachate. The effectiveness of the foaming technique for concentrating PFAS varied by compound, with a mean removal percentage (the percent difference between PFAS in leachate before and after foam removal) of 69% and a median removal percentage of 92% among the 10 replicate foaming experiments. This technique appears to be similarly effective at sequestering sulfonates and carboxylate PFAS compounds and is less effective at concentrating the smallest and largest PFAS molecules. The results of this study suggest that for the pretreatment or preconcentration of landfill leachates, foaming to sequester PFAS may provide a practical approach that could be strategically coupled to high-energy PFAS-destructive treatment technologies. The process described herein is simple and could feasibly be applied at a relatively low cost at most landfills, where leachate aeration is already commonplace.

Evaluating how nitrogen (N) sources are attenuated throughout the landscape is critical to further our understanding of catchment-scale N budgets. We developed a catchment-scale N budget for a mixed land use karst springshed using in situ measurements (nitrate leaching fluxes and attenuation) and long-term records (surface N inputs and spring exports) to estimate 20-year average landscape-scale N loading, attenuation, and export. We introduce a conceptual model framework to compute N export that can be applied consistently for point or nonpoint sources. The model is based on the product of only four components for each N source: population density or proportion of land cover, P; specific load, ; anthropogenic attenuation, ; and natural attenuation,. The product of these components is computed for each N source and then integrated at the basin scale. The concise PLAN model framework predicted attenuation of 90% 3% of N inputs, in close agreement with the estimate based on measured spring mass discharge (87% 3%). Further, when this attenuation is disaggregated along the hydrological flow path, we estimate that 64% of inputs are lost in the surface soil, 20% in the vadose zone, and 6% in the aquifer. Livestock and human wastes were estimated to be the dominant contributors to spring N export, which was independently supported by isotopic data. The PLAN model is a simple, transferable framework that supports systematically computing N export based on proportioning of load and attenuation. Identifying the main sources of N ultimately contributing to discharged N loads is a critical step toward source-related water-quality management. Key Points Our concise model framework predicted attenuation of 90% of N inputs We found that 64% of surface N inputs were attenuated in the surface soil Manure and septic-treated wastewater were the largest contributors to spring N export

Coastal aquifers are an important freshwater resource for significant portions of the global population. Understanding the dynamic relationship between aquifer recharge, storage and discharge is fundamental for sustainable groundwater management. Here we present an expanded freshwater balance equation that considers the dynamic interaction between fresh groundwater and underlying saltwater through a respective storage term, which may explain significant time lags in long-term trends between recharge, storage and discharge. We demonstrate the presence of such a time lag and its effect on freshwater budget calculations with data from a major karst spring in Florida. We develop and validate a parsimonious aquifer model and show that our expanded water balance is consistent with an observed time lag on the order of 15 years between multi-decadal averages of rainfall and spring discharge. Long-term trends in precipitation are known to occur in many regions of the world, and we expect our findings to have direct relevance for coastal aquifers at a global scale.

This paper introduces and tests the Sediment Bed Borehole Advection Method (SBBAM), a low cost, point-measurement technique which utilizes a push-point probe to quantify the vertical direction and magnitude of Darcy flux at the surface water—groundwater sediment interface. The Darcy flux measurements are derived from the residence-time analysis of tracer arrival calculated from measured tracer concentration time-series data. The technique was evaluated in the laboratory using a sediment bed simulator tank at eight flow rates (1–90 cm/day). Triplicate test runs for each flow rate returned average errors between 4–20 percent; r2 = 0.9977.

Aqueous solutions of micro-nano bubbles (MNBs) containing ozone gas were injected through a NAPL-contaminated glass bead column. The glass column (15 cm x 2.5 cm) was packed with glass beads: the first 12 cm was packed with coarse glass beads while much finer glass beads were used to pack the remaining 3.0 cm of the column. Decane was used as the representative NAPL, to which an oil-soluble fluorescence tracer was added. The fluorescence tracer was considered as a constituent of the NAPL that readily reacts with ozone. Air and ozone-containing oxygen were used to generate MNB solutions, and injected through the column. In addition, H2O2 was introduced to the O-3-containing MNB (O-3-MNB) solution to investigate the effect of hydroxyl free radicals on the NAPL removal. An ozone gas sparging experiment was also conducted for comparison. After 72 h of O-3-MNB application, a significant mass of n-decane (27.6% of the initial mass applied) was removed from the column. H2O2 injection into the column during O-3-MNB application was effective in increasing the n-decane mass removal by 22%, compared to the O-3-MNB experiment. The rate of NAPL removal during O-3-MNB flushing was significant, although slower than ozone sparging. During O-3-MNB application, fast decay of fluorescence was observed; whereas, during co-injection of H2O2 and O-3-MNB solutions, only a slight change in the fluorescence was observed. This indicates that oxidative degradation of NAPL during H2O2 and O-3-MNB injection takes place only at the NAPL-water interface due to the reactivity of hydroxyl free radical, whereas ozone diffusion into NAPL induced the decay of the fluorescence tracer in the bulk NAPL. The removal characteristics during MNB application and ozone gas sparging were investigated based on the analysis of NAPL using mass spectrophotometer. When O-3-MNB and H2O2 were co-injected, only n-decane was detected in the NAPL; while when O-3-MNB was used for flushing, oxidative products were found in the NAPL. More hydrophilic compounds were found in the NAPL after ozone sparging. This implies different removal mechanisms depending on the kind of oxidation agent, and the state of oxidizing fluid. Based on the findings in this study, the application of O-3-MNB could be a feasible option for cleaning up NAPL-contaminated aquifers.

Attenuation processes of chlorinated ethenes in complex near-stream systems result in site-specific outcomes of great importance for risk assessment of contaminated sites. Additional interdisciplinary and comprehensive field research is required to enhance process understanding in these systems. In this study, several methods were combined in a multi-scale interdisciplinary in-situ approach to assess and quantify the near-stream attenuation of a chlorinated ethene plume, mainly consisting of cisdichloroethene (cis-DCE) and vinyl chloride (VC), discharging to a lowland stream (Grindsted stream, Den mark) over a monitoring period of seven years. The approach included: hydrogeological characterisation, reach scale contaminant mass balance analysis, quantification of contaminant mass discharge, streambed fluxes of chlorinated ethenes quantified using Sediment Bed Passive Flux Meters (SBPFMs), assessment of redox conditions, temporal assessment of contaminant concentrations, microbial analysis, and compoundspecific isotope analysis (CSIA). This study site exhibits a special attenuation behaviour not commonly encountered in field studies: the conversion from an initially limited degradation case (2012-16), despite seemingly optimal conditions, to one presenting notable levels of degradation (2019). Hence, this study site provides a new piece to the puzzle, as sites with different attenuation behaviours are required in order to acquire the full picture of the role groundwater-surface water interfaces have in risk mitigation. In spite of the increased degradation in the near-stream plume core, the contaminant attenuation was still incomplete in the discharging plume. A conceptualization of flow, transport and processes clarified that hydrogeology was the main control on the natural attenuation, as short residence times of 0.5-37 days restricted the time in which dechlorination could occur. This study reveals the importance of: taking an integrated approach to understand the influence of all attenuation processes in groundwater - surface water interactions; considering the scale and domain of interest when determining the main processes; and monitoring sufficiently both spatially and temporally to cover the transient conditions. (c) 2020 Elsevier Ltd. All rights reserved.

Groundwater flow discharging to springs from carbonate aquifers is governed by the interaction of slow matrix flow and fast fracture/conduit flow, which creates highly complex flow and transport conditions. An important unknown is the relative contribution of matrix and conduit flow to the total discharge. This study experimentally investigated groundwater fluxes in the Floridan aquifer within the springshed of Silver Springs, FL, one of the largest freshwater springs in the world with mean discharge of approximately 20 m(3)/s. Using in situ passive flux meters (PFMs, n = 48 at 16 wells) and a new karstic borehole dilution (KBHD, n = 21 at 7 wells) technique we measured groundwater fluxes in rock matrix and non-matrix (conduit and fracture) zones of 0.06 +/- 0.003 m/day and 3.05 +/- 1.8 m/day (mean +/- standard error). These data, combined with previously conducted tracer tests (n = 12 at 3 sites), were coupled with simple analytical and numerical solutions to identify the proportion of the aquifer that contributes most significantly to water flow to the spring with three different modeling scenarios: single domain, dual domain including matrix and non-matrix zones, and triple domain including matrix, fracture, and conduit zones. The analytical and numerical models coupled with the in situ measured fluxes for the dual and triple domain scenarios showed good agreement with measured head profiles (Nash-Sutcliffe E > 0.90), when compared to the homogeneous porous domain scenario (E = -1.84). Conduit and fracture zones were estimated to represent between 2% and 22% of the aquifer cross-sectional area (at radial distance of 3 km from the spring outlet), yet these zones contributed between 75 and 96% of the total groundwater flow. The results of this study offer field-measured hydrogeologic data that can be used for active resource management in springsheds, and the simple modeling approach presented here may be applicable to other springsheds with fairly simple geometry to estimate the relative contributions of fast and slow water flow and solute transport pathways to the spring outlet.

Two important factors that affect groundwater contaminant persistence are the temporal pattern of contaminant source depletion and solute diffusion into and out of aquitards. This study provides a framework to evaluate the relative importance of these effects on contaminant persistence, with emphasis on the importance of thin aquitards. We developed one-dimensional (1D) analytical solutions for forward and back diffusion in a finite domain with a no flux boundary using the method of images and demonstrated their applicability to measured data from three well-controlled laboratory diffusion experiments with exponentially depleting sources. We used both in situ aquitard solute concentrations and aquifer breakthrough curves for sorbing and non-sorbing solutes. The finite-domain no flux boundary solutions showed better agreement with measured data than was available with semi-infinite approaches, with increasing discrepancy for dimensionless relative diffusion length scale beyond a critical threshold value (Z(d) > 0.7). We also used a mass balance to demonstrate that the temporal pattern of contaminant source depletion controls the duration of solute mass accumulation in the aquitard, as well as the total solute mass release back into the aquifer. Lower rates of source depletion result in a longer period of mass accumulation in the aquitard and later back diffusion initiation time. The amount of solute mass stored in the aquitard increases with longer loading duration, thereby contributing to overall longer contaminant persistence in aquifers. This study entails widespread implications for anthropogenic waste and contamination sites, which are all dependent on efficient and cost-effective contaminant management strategies.

This study assessed the long-term effectiveness of bioremediation as a remedial strategy for a chlorinated, ethene dense, non-aqueous phase liquid (DNAPL) source area, consisting of a higher- and a lower-permeability zone at Alameda Point, California. The evaluation was performed over 3.7 years after cessation of active source area bioremediation using passive flux meters (PFMs), push-pull tracer tests, and soil cores. PFMs showed that total chlorinated ethene molar discharge emanating from the source area remained relatively unchanged pre-and post-bioremediation, but molar discharge compositions shifted from trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE) to vinyl chloride (VC) and ethene dominated during post-remedial monitoring. First-order rate constants, derived from PFM data at the edge of the source area and describing the complete dechlorination of TCE at 3.7 years following active bioremediation, were approximately 1.05 yr-1, which was over three times lower than the rate 3.6 yr-1 determined using compound stable isotope analysis (CSIA). Soil cores and push-pull tracer test data showed that DNAPL volume estimates were relatively unchanged pre- and post-bioremediation due to the remaining presence of DNAPL in the lower-permeability zone. These data suggest biotransformation processes are continuing in the higher-permeability zone, whereas DNAPL in the lower-permeability zone continues to serve as a significant source of groundwater contamination. The results suggest that it will take many years under current conditions to attain the United States Environmental Protection Agency (EPA) Maximum Contaminant Levels (MCLs) cleanup objectives.

The effects of surface-tension and/or viscosity changes in groundwater on the remedial performance of air sparging for heterogeneous aquifers were investigated. The study used a one-dimensional (1-D) column and a two-dimensional (2-D) flow-chamber aquifer model. To introduce a heterogeneous setting, the middle part of the model was packed with a finer soil [LKZ, low hydraulic conductivity ( K ) zone]. Fluorescein sodium salt was used at 200 mg/L for all experiments as a surrogate contaminant. For the 1-D column experiments, the rate of fluorescence decay in the LKZ during surfactant-enhanced air sparging (SEAS) was significantly higher than during the standard air sparing (AS) process without additives; the area of fluorescence loss, measured after 17 h of air sparging (including ozone), was double and triple that of the conventional AS process, for SEAS without thickener (SEAS1) and SEAS with thickener (SEAS2), respectively. Experimental results using the 2-D chamber also confirmed the enhanced air intrusion into the LKZ during the SEAS process. The air fluxes through the LKZ increased by 47 and 103% for the SEAS1 and SEAS2 compared to AS, respectively; and 79 and 90% of fluorescence disappeared in the LKZ during ozone injection for SEAS1 and SEAS2, respectively, whereas only 10% disappeared for AS during the 3-h experimental period. The findings of this study indicate that the AS process, at low surface tension and increased groundwater viscosity may be a viable alternative to the conventional AS process for aquifers of heterogeneous hydrogeological formations.

This work enhances our understanding of catchment-scale N budgets by demonstrating the modification and application of a simple method for direct in situ measurements of vadose zone nitrate leaching and attenuation. We developed a soil passive flux meter (SPFM) to measure solute leaching based on a modified design of ion-exchange resin columns, and we tested the design in numerical simulations, laboratory experiments, plot-scale field experiments, and a catchment-scale field deployment. Our design minimized flow divergence around the resin column to attain nearly 100% capture of surface applied tracers in plot- and catchment-scale deployments. We found that mixing resin with native soil and extending the column height 10 cm above the resin layer minimized divergence of soil water around the column, resulting in a field-measured convergence factor (χ) of 1.3 that was consistent with numerical simulations. For catchment-scale testing, SPFMs were used at nine sites in three dominant land uses (crop, pasture, and turf) with known N inputs in two deployments, one during the 4-mo wet season and an additional set during the 8-mo dry season, to obtain integral annual measures of soil nitrate fluxes. In situ measured nitrate leaching determined from the SPFMs was positively correlated with known N inputs ( = 0.55, < 0.05) and attenuation averaged 67% (± 24% SD) of inputs across all sites. Although N inputs explain a large portion of the variability, our results emphasize the importance of both inter- and intra-land use variability in landscape-scale N budgets.