Conceptualizing future groundwater models through a ternary framework of multisource data, human expertise, and machine intelligence.

Groundwater models are essential for understanding aquifer systems behavior and effective water resources spatio-temporal distributions, yet they are often hindered by challenges related to model assumptions, parametrization, uncertainty, and computational efficiency. Machine intelligence, especially deep learning, promises a paradigm shift in overcoming these challenges. A critical examination of existing machine-driven methods reveals the inherent limitations, particularly in terms of the interpretability and the ability to generalize findings. To overcome these challenges, we develop a ternary framework that synergizes the valuable insights from multisource data, human expertise, and machine intelligence. This framework capitalizes on the distinct strengths of each element: the value and relevance of multisource data, the innovative capacity of human expertise, and the analytical efficiency of machine intelligence. Our goal is to conceptualize sustainable water management practices and enhance our understanding and predictive capabilities of groundwater systems. Unlike approaches that rely solely on abundant data, our framework emphasizes the quality and strategic use of available data, combined with human intellect and advanced computing, to overcome current limitations and pave the way for more realistic groundwater simulations.

Rethinking pump-and-treat remediation as maximizing contaminated groundwater.

For over half a century, the United States has developed water quality regulations (e.g., Safe Drinking Water Act), which has been accompanied by innumerable advances in contaminant transport and fate, site characterization, and remediation. Since the 1980s, "pump-and-treat" techniques have been the most widely used methods for groundwater contamination remediation. By 1982, pump-and-treat was included in 100 % of the U.S. Superfund groundwater remedy decisions, but applications decreased continuously after 1992. This was likely associated with the documented limitations of pump-and-treat for achieving complete remediation with site closure. Several factors can limit the effectiveness of pump-and-treat, a primary one being that contaminant mass residing in NAPL, sorbed, and low-permeability matrices is not removed in an effective or efficient manner. This ineffectiveness leads to extended cleanup times and the generation of enormous volumes of extracted groundwater, in effect creating conditions of maximizing the amount of contaminated groundwater needing treatment. We highlight a means by which to reassess our approach to remediation by recognizing that pump-and-treat, due to its well-documented limitations, often maximizes the generation of contaminated groundwater.

Mechanistic insight into Cr(VI) retention by Si-containing ferrihydrite.

Hexavalent chromium [Cr(VI)] causes serious harm to the environment due to its high toxicity, solubility, and mobility. Ferrihydrites (Fh) are the main adsorbent and trapping agent of Cr(VI) in soils and aquifers, and they usually coexist with silicate (Si), forming Si-containing ferrihydrite (Si-Fh) mixtures. However, the mechanism of Cr(VI) retention by Si-Fh mixtures is poorly understood. In this study, the behaviors and mechanisms of Cr(VI) adsorption onto Si-Fh with different Si/Fe molar ratios was investigated. Transmission electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and other techniques were used to characterize Si-Fh and Cr(VI)-loading of Si-Fh. The results show that specific surface area of Si-Fh increases gradually with increasing Si/Fe ratios, but Cr(VI) adsorption on Si-Fh decreases with increasing Si/Fe ratios. This is because with an increase in Si/Fe molar ratio, the point of zero charge of Si-Fh gradually decreases and electrostatic repulsion between Si-Fh and Cr(VI) increases. However, the complexation of Cr(VI) is enhanced due to the increase in adsorbed hydroxyl (A-OH-) on Si-Fh with increasing Si/Fe molar ratio, which partly counteracts the effect of the electrostatic repulsion. Overall, the increase in the electrostatic repulsion has a greater impact on adsorption than the additional complexation with Si-Fh. Density functional theory calculation further supports this observation, showing the increases in electron variation of bonding atoms and reaction energies of inner spherical complexes with the increase in Si/Fe ratio.

PFOS Mass Flux Reduction/Mass Removal: Impacts of a Lower-Permeability Sand Lens within Otherwise Homogeneous Systems.

Perfluorooctane sulfonic acid (PFOS) is one of the most common per- and polyfluoroalkyl substances (PFAS) and is a significant risk driver for these emerging contaminants of concern. A series of two-dimensional flow cell experiments was conducted to investigate the impact of flow field heterogeneity on the transport, attenuation, and mass removal of PFOS. A simplified model heterogeneous system was employed consisting of a lower-permeability fine sand lens placed within a higher-permeability coarse sand matrix. Three nonreactive tracers with different aqueous diffusion coefficients, sodium chloride, pentafluorobenzoic acid, and ß-cyclodextrin, were used to characterize the influence of diffusive mass transfer on transport and for comparison to PFOS results. The results confirm that the attenuation and subsequent mass removal of the nonreactive tracers and PFOS were influenced by mass transfer between the hydraulically less accessible zone and the coarser matrix (i.e., back diffusion). A mathematical model was used to simulate flow and transport, with the values for all input parameters determined independently. The model predictions provided good matches to the measured breakthrough curves, as well as to plots of reductions in mass flux as a function of mass removed. These results reveal the importance of molecular diffusion and pore water velocity variability even for systems with relatively minor hydraulic conductivity heterogeneity. The impacts of the diffusive mass transfer limitation were quantified using an empirical function relating reductions in contaminant mass flux (MFR) to mass removal (MR). Multi-step regression was used to quantify the nonlinear, multi-stage MFR/MR behavior observed for the heterogeneous experiments. The MFR/MR function adequately reproduced the measured data, which suggests that the MFR/MR approach can be used to evaluate PFOS removal from heterogeneous media.

Datasets associated with the characterization of produced water and Pecos River water in the Permian Basin, the United States.

The data in this report are associated with "Characterization of Produced Water and Surrounding Surface Water in the Permian Basin, the United States" (Jiang et al. 2022) and include raw data on produced water (PW) quality and Pecos River water quality in the Permian Basin, which is one of the major oil and gas producing areas in the U.S. The data include 46 samples for PW and 10 samples for Pecos River water. The data include wet chemistry, mineral salts, metals, oil and grease, volatile and semi-volatile organic compounds, radionuclides, ammonia, hydraulic fracturing additives, and per- and polyfluoroalkyl substances. The PW samples were collected from five different locations in the Permian Basin. Twenty-four of the PW samples and the ten Pecos River samples were analyzed by the authors. The information for the rest of PW samples (22 samples) was provided by industrial collaborators in the Permian Basin. Statistical analyses were performed on the combined data to obtain Mean, Max, Min, 25th percentile, 50th percentile, and 75th percentile of each analyte.

Global distributions, source-type dependencies, and concentration ranges of per- and polyfluoroalkyl substances in groundwater.

A meta-analysis was conducted of published literature reporting concentrations of per- and polyfluoroalkyl substances (PFAS) in groundwater for sites distributed in 20 countries across the globe. Data for >35 PFAS were aggregated from 96 reports published from 1999 to 2021. The final data set comprises approximately 21,000 data points after removal of time-series and duplicate samples as well as non-detects. The reported concentrations range over many orders of magnitude, from ng/L to mg/L levels. Distinct differences in concentration ranges are observed between sites located within or near sources versus those that are not. Perfluorooctanoic acid (PFOA), ranging from <0.03 ng/L to ~7 mg/L, and perfluorooctanesulfonic acid (PFOS), ranging from 0.01 ng/L to ~5 mg/L, were the two most reported PFAS. The highest PFAS concentration in groundwater is ~15 mg/L reported for the replacement-PFAS 6:2 fluorotelomer sulfonate (6:2 FTS). Maximum reported groundwater concentrations for PFOA and PFOS were compared to concentrations reported for soils, surface waters, marine waters, and precipitation. Soil concentrations are generally significantly higher than those reported for the other media. This accrues to soil being the primary entry point for PFAS release into the environment for many sites, as well as the generally significantly greater retention capacity of soil compared to the other media. The presence of PFAS has been reported for all media in all regions tested, including areas that are far removed from specific PFAS sources. This gives rise to the existence of a "background" concentration of PFAS that must be accounted for in both regional and site-specific risk assessments. The presence of this background is a reflection of the large-scale use of PFAS, their general recalcitrance, and the action of long-range transport processes that distribute PFAS across regional and global scales. This ubiquitous distribution has the potential to significantly impact the quality and availability of water resources in many regions. In addition, the pervasive presence of PFAS in the environment engenders concerns for impacts to ecosystem and human health.

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles.

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO2NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO2NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO2NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO2NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO2NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO2NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.

Characterization of produced water and surrounding surface water in the Permian Basin, the United States.

A thorough understanding of produced water (PW) quality is critical to advance the knowledge and tools for effective PW management, treatment, risk assessment, and feasibility for beneficial reuse outside the oil and gas industry. This study provides the first step to better understand PW quality to develop beneficial reuse programs that are protective of human health and the environment. In total, 46 PW samples from unconventional operations in the Permian Basin and ten surface water samples from the Pecos River in New Mexico were collected for quantitative target analyses of more than 300 constituents. Water quality analyses of Pecos River samples could provide context and baseline information for the potential discharge and reuse of treated PW in this area. Temporal PW and river water quality changes were monitored for eight months in 2020. PW samples had total dissolved solids (TDS) concentrations ranging from 100,800-201,500 mg/L. Various mineral salts, metals, oil and grease, volatile and semi-volatile organic compounds, radionuclides, ammonia, hydraulic fracturing additives, and per- and polyfluoroalkyl substances were detected at different concentrations. Chemical characterization of organic compounds found in Pecos River water showed no evidence of PW origin. Isometric log-ratio Na-Cl-Br analysis showed the salinity in the Pecos River samples appeared to be linked to an increase in natural shallow brine inputs. This study outlines baseline analytical information to advance PW research by describing PW and surrounding surface water quality in the Permian Basin that will assist in determining management strategies, treatment methods, potential beneficial reuse applications, and potential environmental impacts specific to intended beneficial use of treated PW.

Toxicological characterization of produced water from the Permian Basin.

Produced water (PW) is a hypersaline waste stream generated from the shale oil and gas industry, consisting of numerous anthropogenic and geogenic compounds. Despite prior geochemical characterization, the comprehensive toxicity assessment is lacking for evaluating treatment technologies and the beneficial use of PW. In this study, a suite of in vitro toxicity assays using various aquatic organisms (luminescent bacterium Vibrio fischeri, fish gill cell line RTgill-W1, and microalgae Scenedesmus obliquus) were developed to investigate the toxicological characterizations of PW from the Permian Basin. The exposure to PW, PW inorganic fraction (PW-IF), and PW salt control (PW-SC) at 30-50% dilutions caused significant toxicological effects in all model species, revealing the high salinity was the foremost toxicological driver in PW. In addition, the toxicity level of PW was usually higher than that of PW-IF, suggesting that organic contaminants might also play a critical role in PW toxicity. When comparing the observed toxicity with associated chemical characterizations in different PW samples, strong correlations were found between them since higher concentrations of contaminants could generally result in higher toxicity towards exposed organisms. Furthermore, the toxicity results from the pretreated PW indicated that those in vitro toxicity assays had different sensitives to the chemical components present in PW. As expected, the combination of multiple pretreatments could lead to a more significant decrease in toxicity compared to the single pretreatment since the mixture of contaminants in PW might exhibit synergistic toxicity. Overall, the current work is expected to enhance our understanding of the potential toxicological impacts of PW to aquatic ecosystems and the relationships between the chemical profiles and observed toxicity in PW, which might be conducive to the establishment of monitoring, remediation, treatment, and reuse protocols for PW.

The Co-Transport of PFAS and Cr(VI) in porous media.

PFAS and Cr are present at some sites as co-contaminants. The objective of this research was to investigate the co-transport behavior of per- and polyfluoroalkyl substances (PFAS) and hexavalent chromium (Cr(VI)) in porous media. Miscible-displacement experiments were conducted using two soils and an aquifer sediment with different geochemical properties. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were employed as model PFAS. The retardation of PFOS was decreased in the presence of Cr(VI). Conversely, the transport and retardation of PFOA was not affected by the presence of Cr(VI). The reduction of PFOS retardation caused by Cr(VI) is likely due to sorption competition for both organic-carbon and inorganic (metal-oxides and clay minerals) domains. The relative contributions of the three soil constituents to PFOS sorption and the potential for competition between PFOS and Cr(VI) is a function of the geochemical composition of the porous media (i.e., organic carbon, metal-oxides and clay minerals). The PFAS had minimal impact on the retention and transport of Cr(VI). To our knowledge, the results presented herein represent the first reported data for PFOS and Cr(VI) co-transport in porous media. The results of this study indicate that the presence of Cr(VI) has the potential to increase the migration potential of PFOS in soil and groundwater, which should be considered when characterizing electroplating facilities, leather tanning facilities, and other co-contaminated sites.

Analysis and prediction of produced water quantity and quality in the Permian Basin using machine learning techniques.

Appropriate produced water (PW) management is critical for oil and gas industry. Understanding PW quantity and quality trends for one well or all similar wells in one region would significantly assist operators, regulators, and water treatment/disposal companies in optimizing PW management. In this research, historical PW quantity and quality data in the New Mexico portion (NM) of the Permian Basin from 1995 to 2019 was collected, pre-processed, and analyzed to understand the distribution, trend and characteristics of PW production for potential beneficial use. Various machine learning algorithms were applied to predict PW quantity for different types of oil and gas wells. Both linear and non-linear regression approaches were used to conduct the analysis. The prediction results from five-fold cross-validation showed that the Random Forest Regression model reported high prediction accuracy. The AutoRegressive Integrated Moving Average model showed good results for predicting PW volume in time series. The water quality analysis results showed that the PW samples from the Delaware and Artesia Formations (mostly from conventional wells) had the highest and the lowest average total dissolved solids concentrations of 194,535 mg/L and 100,036 mg/L, respectively. This study is the first research that comprehensively analyzed and predicted PW quantity and quality in the NM-Permian Basin. The results can be used to develop a geospatial metrics analysis or facilitate system modeling to identify the potential opportunities and challenges of PW management alternatives within and outside oil and gas industry. The machine learning techniques developed in this study are generic and can be applied to other basins to predict PW quantity and quality.

Transport of PFOS in aquifer sediment: Transport behavior and a distributed-sorption model.

The objectives of this research were to examine the transport of perfluorooctane sulfonic acid (PFOS) in aquifer sediment comprising different geochemical properties, and to compare the behavior to that observed for PFOS transport in soil and sand. PFOS retardation was relatively low for transport in all aquifer media. The PFOS breakthrough curves were asymmetrical and exhibited extensive concentration tailing, indicating that sorption/desorption was significantly nonideal. The results of model simulations indicated that rate-limited sorption/desorption was the primary cause of the nonideal PFOS transport. Comparison of PFOS transport in aquifer media to data reported for PFOS transport in two soils and a quartz sand showed that PFOS exhibited more extensive elution tailing for the soils, likely reflecting differences in the relative contributions of various media constituents to sorption. A three-component distributed-sorption model was developed that accounted for contributions from soil organic carbon, metal oxides, and silt + clay fraction. The model produced very good predictions of Kd for the five media with lower soil organic­carbon contents (≤0.1%). Soil organic carbon was estimated to contribute 19-42% of the total sorption for all media except the sand, to which it contributed ~100%. The contribution of silt + clay ranged from 51 to 80% for all media except the sand. The only medium for which the contribution of metal-oxides was significant is Hanford, with an estimated contribution of 15%. Overall, the results of the study indicate that sorption of PFOS by these aquifer media comprised contributions from multiple soil constituents.

Column versus batch methods for measuring PFOS and PFOA sorption to geomedia.

The objective of this study is to compare the consistency between column and batch experiment methods for measuring solid-phase sorption coefficients and isotherms for per and polyfluoroalkyl substances (PFAS). Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are used as representative PFAS, and experiments are conducted with three natural porous media with differing geochemical properties. Column-derived sorption isotherms are generated by conducting multiple experiments with different input concentrations (multi-C0 method) or employing elution-front integration wherein the entire isotherm is determined from a single breakthrough curve (BTC) elution front. The isotherms generated with the multi-C0 column method compared remarkably well to the batch isotherms over an aqueous concentration range of 3-4 orders of magnitude. Specifically, the 95% confidence intervals for the individual isotherm variables overlapped, producing statistically identical regressions. The elution-front integration isotherms generally agreed with the batch isotherms, but exhibited noise and systematic deviation at lower concentrations in some cases. All data sets were well described by the Freundlich isotherm model. Freundlich N values ranged from 0.75 to 0.81 for PFOS and was 0.87 for PFOA and are consistent with values reported in the literature for different geomedia. The results of this study indicate that column and batch experiments can measure consistent sorption isotherms and sorption coefficients for PFOS and PFOA when robust experimental setup and data analysis are implemented.

Natural attenuation method for contaminant remediation reagent delivery assessment for in situ chemical oxidation using aqueous ozone.

A Monitored Natural Attenuation (MNA) assessment approach typically used for contaminant remediation feasibility assessment was developed here for remediation-reagent delivery assessment. Subsurface delivery of oxidants, such as aqueous ozone (O3) for in situ chemical oxidation (ISCO) of groundwater contaminants, is naturally attenuated by oxidant demand and reactivity. We compared mixed reactor kinetic experiments, sand column tracer transport experiments, and reactive transport modeling and assessment methods to quantify natural attenuation kinetics, aqueous O3 solute transport, oxidant demand kinetics, and ISCO reagent delivery limitations. Sorption of aqueous O3 to quartz sand was observed during transport of O3 through water-saturated porous media. Pseudo 1st order decomposition rate constants of O3 bulk attenuation with transport were comparable to mixed reactor experiments without transport, and reactive transport modeling of miscible-displacement column experiments was used to quantify each attenuation process. Aqueous ionic strength was correlated with O3 decomposition rate constants, which was the dominant reagent delivery attenuation process. These results suggest that aqueous O3 decomposition and oxidant delivery attenuation can be predictable upon characterization of the sediment oxidant demand and dispersion, and increasing groundwater velocity during aqueous O3 injection can maximize transport distance for reagent delivery.

Nonideal Transport and Extended Elution Tailing of PFOS in Soil.

The objective of this research was to examine the influence of nonideal sorption/desorption on the transport of polyfluorinated alkyl substances (PFASs) in soil, with a specific focus on characterizing and quantifying potential extended, mass-transfer-limited elution behavior. Perfluorooctane sulfonic acid (PFOS) was used as a representative PFAS, and miscible-displacement experiments were conducted with two soils comprising contrasting geochemical properties. The influence of nonlinear, rate-limited, hysteretic, and irreversible sorption/desorption on transport was investigated through experiments and model simulations. The breakthrough curves measured for PFOS transport in the two soils were asymmetrical and exhibited extensive elution tailing, indicating that sorption/desorption was significantly nonideal. The widely used two-domain sorption kinetics model could not fully simulate the observed transport behavior, whereas a multirate model employing a continuous distribution of sorption domains was successful. The overall results indicated that sorption/desorption was significantly rate-limited and that nonlinear, hysteretic, and irreversible sorption/desorption had minimal impact on PFOS transport. Comparison of PFOS transport data to data reported for two hydrophobic organic contaminants (HOCs) showed that the HOCs exhibited much more extensive elution tailing, likely reflecting differences in sorption/desorption mechanisms. The projected influence of rate-limited sorption/desorption on PFOS transport at the field scale was investigated through simulation. The results of the study suggest that rate-limited sorption/desorption may affect the field-scale transport of PFOS and other PFAS for systems influenced by transient or short-residence-time conditions and in some cases could possibly increase the amount of flushing required to reduce PFOS concentrations to levels below those associated with human-health concerns.

1,4-Dioxane cosolvency impacts on trichloroethene dissolution and sorption.

Solvent stabilizer 1,4-dioxane, an emerging recalcitrant groundwater contaminant, was commonly added to chlorinated solvents such as trichloroethene (TCE), and the impact of co-disposal on contaminant transport processes remains uncertain. A series of batch equilibrium experiments was conducted with variations of 1,4-dioxane and TCE composition to evaluate aqueous dissolution of the two components and their sorption to aquifer sediments. The solubility of TCE increased with increasing amounts of 1,4-dioxane, indicating that 1,4-dioxane acts as a cosolvent causing solubility enhancement of co-contaminants. The solubilization results compared favorably with predictions using the log-linear cosolvency model. Equilibrium sorption coefficients (Kd and Kf) were also measured for different 1,4-dioxane and TCE compositions, and the findings indicate that both contaminants adsorb to aquifer sediments and TCE Kd values increased with increasing organic matter content. However, the Kd for TCE decreased with increases in 1,4-dioxane concentration, which was attributed to cosolvency impacts on TCE solubility. These findings further advance our understanding of the mass-transfer processes controlling groundwater plumes containing 1,4-dioxane, and also have implications for the remediation of 1,4-dioxane contamination.

Comprehensive retention model for PFAS transport in subsurface systems.

A comprehensive compartment model is presented for PFAS retention that incorporates all potential processes relevant for transport in source zones. Miscible-displacement experiments were conducted to investigate separately the impact of adsorption at the air-water and decane-water interfaces on PFAS retention and transport. Two porous media were used, a quartz sand and a soil, and perfluorooctanesulfonic acid (PFOS) was used as the model PFAS. The breakthrough curves for transport under water-unsaturated conditions were shifted noticeably rightward (delayed arrival) compared to the breakthrough curves for saturated conditions, indicating greater retardation due to adsorption at the air-water or decane-water interface. The retardation factor was 7 for PFOS transport in the sand for the air-water system, compared to 1.8 for saturated conditions. PFOS retardation factors for transport in the soil were 7.3 and 3.6 for unsaturated (air-water) vs saturated conditions. Air-water interfacial adsorption is a significant source of retention for PFOS in these two systems, contributing more than 80% of total retention for the sand and 32% for the soil. For the experiments conducted with decane residual emplaced within the sand, adsorption at the decane-water interface contributed more than 70% to total retention for PFOS transport. Methods to determine or estimate key distribution variables are presented for parameterization of the model. Predicted retardation factors were similar to the measured values, indicating that the conceptual model provided adequate representation of the relevant retention processes and that the parameter estimation methods produced reasonable values. The results of this work indicate that adsorption by fluid-fluid interfaces in variably saturated porous media can be a significant retention process for PFAS that should be considered when characterizing their transport and fate behavior in source zones.

Cyclodextrin-enhanced 1,4-dioxane treatment kinetics with TCE and 1,1,1-TCA using aqueous ozone.

Enhanced reactivity of aqueous ozone (O3) with hydroxypropyl-ß-cyclodextrin (HPßCD) and its impact on relative reactivity of O3 with contaminants were evaluated herein. Oxidation kinetics of 1,4-dioxane, trichloroethylene (TCE), and 1,1,1-trichloroethane (TCA) using O3 in single and multiple contaminant systems, with and without HPßCD, were quantified. 1,4-Dioxane decay rate constants for O3 in the presence of HPßCD increased compared to those without HPßCD. Density functional theory molecular modeling confirmed that formation of ternary complexes with HPßCD, O3, and contaminant increased reactivity by increasing reactant proximity and through additional reactivity within the HPßCD cavity. In the presence of chlorinated co-contaminants, the oxidation rate constant of 1,4-dioxane was enhanced. Use of HPßCD enabled O3 reactivity within the HPßCD cavity and enhanced 1,4-dioxane treatment rates without inhibition in the presence of TCE, TCA, and radical scavengers including NaCl and bicarbonate. Micro-environmental chemistry within HPßCD inclusion cavities mediated contaminant oxidation reactions with increased reaction specificity.

Spectroscopic methods for aqueous cyclodextrin inclusion complex binding measurement for 1,4-dioxane, chlorinated co-contaminants, and ozone.

Recalcitrant organic contaminants, such as 1,4-dioxane, typically require advanced oxidation process (AOP) oxidants, such as ozone (O3), for their complete mineralization during water treatment. Unfortunately, the use of AOPs can be limited by these oxidants' relatively high reactivities and short half-lives. These drawbacks can be minimized by partial encapsulation of the oxidants within a cyclodextrin cavity to form inclusion complexes. We determined the inclusion complexes of O3 and three common co-contaminants (trichloroethene, 1,1,1-trichloroethane, and 1,4-dioxane) as guest compounds within hydroxypropyl-ß-cyclodextrin. Both direct (ultraviolet or UV) and competitive (fluorescence changes with 6-p-toluidine-2-naphthalenesulfonic acid as the probe) methods were used, which gave comparable results for the inclusion constants of these species. Impacts of changing pH and NaCl concentrations were also assessed. Binding constants increased with pH and with ionic strength, which was attributed to variations in guest compound solubility. The results illustrate the versatility of cyclodextrins for inclusion complexation with various types of compounds, binding measurement methods are applicable to a wide range of applications, and have implications for both extraction of contaminants and delivery of reagents for treatment of contaminants in wastewater or contaminated groundwater.

Borehole Diffusive Flux Apparatus for Characterizing Diffusive Mass-transfer in Subsurface Systems.

The concept of the Borehole Diffusive Flux Apparatus (BDFA) is presented herein. The BDFA is an innovative apparatus designed to provide continuous direct access to an undisturbed column of sediment that can be monitored at multiple discrete vertical intervals to provide high-resolution characterization of local-scale mass transfer and attenuation. The conceptual basis and technical design of the device are presented, along with an example of borehole design and installation at a field site. Mathematical simulations are used to illustrate its application for two scenarios. The results of these simulations indicate that test periods of several weeks to a few months should be sufficient to obtain robust results. The device has the potential to improve our ability to characterize critical mass-transfer and attenuation processes and to quantify the associated rates. This information is key to the evaluation of remediation alternatives, for enhancing the accuracy of mathematical models, and to support more effective long-term management of large groundwater contaminant plumes present at many sites.