Field Treatment of MTBE‐Contaminated Groundwater Using Ozone/UV Oxidation

Methyl‐tertiary butyl ether (MTBE) is often found in groundwater as a result of gasoline spills and leaking underground storage tanks. An extrapolation of occurrence data in 2008 estimated at least one detection of MTBE in approximately 165 small and large public water systems serving 896,000 people nationally (United States Environmental Protection Agency [U.S. EPA] 2008). The objective of this collaborative field study was to evaluate a small groundwater treatment system to determine the effectiveness of ultraviolet (UV)/ozone treatment in removing MTBE from contaminated drinking water wells. A pilot‐scale advanced oxidation process (AOP) system was tested to evaluate the oxidation efficiency of MTBE and intermediates under field conditions. This system used ozone as an oxidizer in the presence of UV light at hydraulic retention times varying from 1 to 3 min. MTBE removal efficiencies approaching 97% were possible with this system, even with low retention times. The intermediate t‐butyl alcohol (TBA) was removed to a lesser extent (71%) under the same test conditions. The main intermediate formed in the oxidation process of the contaminated groundwater in these studies was acetone. The concentrations of the other anticipated intermediates t‐butyl formate (TBF), isopropyl alcohol (IPA), methyl acetate (MAc), and possible co‐occurring aromatics (BTEX) in the effluent were negligible.     

Electrical Resistivity Imaging of a Permanganate Injection During In Situ Treatment of RDX‐Contaminated Groundwater

Groundwater beneath the former Nebraska Ordnance Plant (NOP) is contaminated with the explosive hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and trichloroethene (TCE). Previous treatability experiments confirmed that permanganate could mineralize RDX in NOP aquifer material. The objective of this study was to determine the efficacy of permanganate to transform RDX in the field by monitoring a pilot‐scale in situ chemical oxidation (ISCO) demonstration. In this demonstration, electrical resistivity imaging (ERI) was used to create two‐dimensional (2‐D) images of the test site prior to, during, and after injecting sodium permanganate. The ISCO was performed by using an extraction‐injection well configuration to create a curtain of permanganate. Monitoring wells were positioned downgradient of the injection zone with the intent of capturing the permanganate‐RDX plume. Differencing between ERI taken preinjection and postinjection determined the initial distribution of the injected permanganate. ERI also quantitatively corroborated the hydraulic conductivity distribution across the site. Groundwater samples from 12 downgradient wells and 8 direct‐push profiles did not provide enough data to quantify the distribution and flow of the injected permanganate. ERI, however, showed that the permanganate injection flowed against the regional groundwater gradient and migrated below monitoring well screens. ERI combined with monitoring well samples helped explain the permanganate dynamics in downgradient wells and support the use of ERI as a means of monitoring ISCO injections.     

Reinterpreting the Importance of Oxygen‐Based Biodegradation in Chloroethene‐Contaminated Groundwater

Chlororespiration is common in shallow aquifer systems under conditions nominally identified as anoxic. Consequently, chlororespiration is a key component of remediation at many chloroethene‐contaminated sites. In some instances, limited accumulation of reductive dechlorination daughter products is interpreted as evidence that natural attenuation is not adequate for site remediation. This conclusion is justified when evidence for parent compound (tetrachloroethene, PCE, or trichloroethene, TCE) degradation is lacking. For many chloroethene‐contaminated shallow aquifer systems, however, nonconservative losses of the parent compounds are clear but the mass balance between parent compound attenuation and accumulation of reductive dechlorination daughter products is incomplete. Incomplete mass balance indicates a failure to account for important contaminant attenuation mechanisms and is consistent with contaminant degradation to nondiagnostic mineralization products like CO₂. While anoxic mineralization of chloroethene compounds has been proposed previously, recent results suggest that oxygen‐based mineralization of chloroethenes also can be significant at dissolved oxygen concentrations below the currently accepted field standard for nominally anoxic conditions. Thus, reassessment of the role and potential importance of low concentrations of oxygen in chloroethene biodegradation are needed, because mischaracterization of operant biodegradation processes can lead to expensive and ineffective remedial actions. A modified interpretive framework is provided for assessing the potential for chloroethene biodegradation under different redox conditions and the probable role of oxygen in chloroethene biodegradation.     

Influence of Surfactants on Degradation of 1‐(2‐Chlorobenzoyl)‐3‐(4‐chlorophenyl) Urea by Nanoscale Zerovalent Iron

Nanoscale zerovalent iron (NZVI) has been proved to be effective in the degradation of environmental pollutants and exhibits advantages in the removal of 1‐(2‐chlorobenzoyl)‐3‐(4‐chlorophenyl) urea (CCU), an analog of diflubenzuron. This present study focused on the influence of surfactants in the degradation procedure with NZVI in order to provide a simple and rapid removal method for CCU. Triton X‐100, Tween 20, Tween 80, sodium dodecyl sulfonate (SDS), and cetyltrimethylammonium bromide (CTAB) were investigated under anaerobic conditions. The experimental results demonstrated that the degradation rate increased sharply with the presence of SD during the first 15 min, up to 99.97% with addition of 0.01 g L^?1 SDS, whereas the presence of Triton X‐100, Tween 80, and Tween 20 resulted in a slight enhancement of the degradation of CCU. The enhancement strength of them was in the order Tween 20, Triton X‐100, and Tween 80. However, addition of the cationic surfactant CTAB resulted in a significant inhibitive effect. In contrast, the mixed surfactants did not result in the expected performance, and the performance was lower than that using some certain single surfactant among the mixed surfactants.     

Field Investigation of Vapor‐Phase‐Based Groundwater Monitoring

The use of in‐field analysis of vapor‐phase samples to provide real‐time volatile organic compound (VOC) concentrations in groundwater has the potential to streamline monitoring by simplifying the sample collection and analysis process. A field validation program was completed to (1) evaluate methods for collection of vapor samples from monitoring wells and (2) evaluate the accuracy and precision of field‐portable instruments for the analysis of vapor‐phase samples. The field program evaluated three vapor‐phase sample collection methods: (1) headspace samples from two locations within the well, (2) passive vapor diffusion (PVD) samplers placed at the screened interval of the well, and (3) field vapor headspace analysis of groundwater samples. Two types of instruments were tested: a field‐portable gas chromatograph (GC) and a photoionization detector (PID). Field GC analysis of PVD samples showed no bias and good correlation to laboratory analysis of groundwater collected by low‐flow sampling (slope = 0.96, R² = 0.85) and laboratory analysis of passive water diffusion bag samples from the well screen (slope = 1.03; R² = 0.96). Field GC analysis of well headspace samples, either from the upper portion of the well or at the water‐vapor interface, resulted in higher variability and much poorer correlation (consistently biased low) relative to laboratory analysis of groundwater samples collected by low‐flow sample or passive diffusion bags (PDBs) (slope = 0.69 to 0.76; R² = 0.60 to 0.64). These results indicate that field analysis of vapor‐phase samples can be used to obtain accurate measurements of VOC concentrations in groundwater. However, vapor samples collected from the well headspace were not in equilibrium with water collected from the well screen. Instead, PVD samplers placed in the screened interval represent the most promising approach for field‐based measurement of groundwater concentrations using vapor monitoring techniques and will be the focus of further field testing.     

Evaluation of an Ultrafiltration Method for Surfactant Recovery and Reuse During In Situ Washing of Contaminated Sites: Laboratory and Field Studies

Feasibility studies were conducted on the use of ultrafillration to recover surfactant from aqueous waste streams generated from the in situ surfactant washing of a site contaminated with poly-chlorinated biphenyls (PCBs) and oils. A Romicon Model HF-Lab-5 ultrafiltration unit and three types of ultrafillration membranes (PM500, XM50, and CM50) were evaluated for their permeability to a nonionic surfactant previously selected for the in situ washing. Results from laboratory studies using the XM50 membrane cartridge showed that 78 percent of the surfactant passed through the membrane surface (permeate) and was recovered.
Two field-pilot tests of the ultrafiltralion system were conducted using leachate containing a mixture of water, oils, PCBs, and surfactant that was collected from an in situ surfactant-washing demonstration test. Forty-six percent of the surfactant (mass) was recovered during the first field test using the XM50 membrane. The membrane retained 94 percent of the PCBs and 89 percent of the oils. The second field test showed that the PM500 membrane recovered 67 percent of the surfactant in the permeate and retained more than 90 percent and 83 percent of the PCBs and oils, respectively. This study indicates that a significant volume of a nonionic surfactant can be recovered from leachatc mixture containing PCBs and oils by ultrafillration. The recovered surfactant could be reused to improve the economic viability of in situ surfactant washing of contaminated sites.     

Using DNA‐Stable Isotope Probing to Identify MTBE‐ and TBA‐Degrading Microorganisms in Contaminated Groundwater

Although the anaerobic biodegradation of methyl tert‐butyl ether (MTBE) and tert‐butyl alcohol (TBA) has been documented in the laboratory and the field, knowledge of the microorganisms and mechanisms involved is still lacking. In this study, DNA‐stable isotope probing (SIP) was used to identify microorganisms involved in anaerobic fuel oxygenate biodegradation in a sulfate‐reducing MTBE and TBA plume. Microorganisms were collected in the field using Bio‐Sep® beads amended with ¹³C₅‐MTBE, ¹³C₁‐MTBE (only methoxy carbon labeled), or ¹³C₄‐TBA. ¹³C‐DNA and ¹²C‐DNA extracted from the Bio‐Sep beads were cloned and 16S rRNA gene sequences were used to identify the indigenous microorganisms involved in degrading the methoxy group of MTBE and the tert‐butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading ¹³C‐labeled MTBE and TBA in situ and the ¹³C was incorporated into their DNA. Several sequences related to known MTBE‐ and TBA‐degraders in the Burkholderiales and the Sphingomonadales orders were detected in all three ¹³C clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate‐reducing bacteria and iron‐reducers, such as Geobacter and Geothrix, were only detected in the clone libraries where MTBE and TBA were fully labeled with ¹³C, suggesting that they were involved in processing carbon from the tert‐butyl group. Sequences similar to the Pseudomonas genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with ¹³C. It is likely that members of this genus were secondary degraders cross‐feeding on ¹³C‐labeled metabolites such as acetate.     

Laboratory Evaluation of Zero Valent Iron and Sulfur‐Modified Iron for Agricultural Drainage Water Treatment

Agricultural subsurface drainage waters containing nutrients (nitrate/phosphate) and pesticides are discharged into neighboring streams and lakes, frequently producing adverse environmental impacts on local, regional, and national scales. On‐site drainage water filter treatment systems can potentially prevent the release of agricultural contaminants into adjacent waterways. Zero valent iron (ZVI) and sulfur‐modified iron (SMI) are two types of promising filter materials that could be used within these treatment systems. Therefore, water treatment capabilities of three ZVI and three SMI filter materials were evaluated in the laboratory. Laboratory evaluation included saturated falling‐head hydraulic conductivity tests, contaminant removal batch tests, and saturated solute transport column experiments. The three ZVI and the three SMI filter materials, on average, all had a sufficient hydraulic conductivity greater than 1 × 10^–3 cm/s. Batch test results showed a phosphate decrease of at least 94% for all tests conducted with the ZVI and SMI. Furthermore, the three SMI filter materials removed at least 86% of the batch test nitrate originally present, while batch tests for one of the ZVI filter materials exhibited an 88% decrease in the pesticide, atrazine. Saturated solute transport column experiments were carried on the best ZVI filter material, or the best SMI filter material, or both together, in order to better evaluate drainage water treatment effectiveness and efficiency. Results from these column tests additionally document the drainage water treatment ability of both ZVI and SMI to remove the phosphate, the ability of SMI to remove nitrate, and the ability of a select ZVI material to remove atrazine. Consequently, these findings support further investigation of ZVI and SMI subsurface drainage water treatment capabilities, particularly in regard to small‐ and large‐scale field tests.     

Reuse of Drinking Water Treatment Waste for Remediation of Heavy Metal Contaminated Groundwater

Lime softening produces an estimated 10,000 metric tons of dry drinking water treatment wastes (DWTW) per year, costing an estimated one billion dollars annually for disposal worldwide. Lime softening wastes have been investigated for reuse as internal curing agents or supplementary cementitious materials in concrete as well as a high-capacity sorbent for heavy metal removal. Lead, cadmium, and zinc are common heavy metals in groundwater contaminated by mine tailings. Cement-based filter media (CBFM) are a novel material-class for heavy metal remediation in groundwater. This study investigated the incorporation of DWTW as a recycled, low-cost additive to CBFM for the removal of lead, cadmium, and zinc. Jar testing at three different metal concentrations and breakthrough column testing using synthetic groundwater were performed to measure removal capacity and reaction kinetics. Jar testing results show as DWTW content increases at low concentrations, removal approaches 100% but at high metal concentrations removal decreases due to saturation or exhaustion of the removal mechanisms. Removal occurs through the formation of metal carbonate precipitates, surface sorption, and ion exchange with calcium according to the preferential series Pb⁺² > Zn⁺² > Cd²⁺. Removal kinetics were also measured through column testing and exceeded estimated calculations derived from batch jar testing isotherms due to the large formation of oolitic metal carbonates. Lead, cadmium, and zinc was concentrated in the column precipitates from 0.29, 0.23, and 20.0 μg/g in the influent solution to approximately 200, 130, 14,000 μg/g in the reacted DWTW-CBFM. The control and DWTW-CBFM columns had statically similar removal for zinc and lead. In the DWTW-CBFM, cadmium had decreased removal of approximately 25% due to proportionately decreased hydroxide content from cement replacement with 25% DWTW. This study shows the potential for DWTW as an enhancement to CBFM, thereby valorizing an otherwise waste material. Furthermore, the concentrative abilities of CBFM through precipitate and oolitic mineral formation could provide a minable waste product and close the waste-product cycle for DWTW.     

A New Pumping Strategy for Petroleum Product Recovery from Contaminated Hydrogeologic Systems: Laboratory and Field Evaluations

More than 200,000 gallons of automatic transmission fluid (ATF) leaked from an underground storage tank system and contaminated an area of about 64,000 ft² of a soil and ground water system. A pumping strategy for improved drainage and recovery of free oil was developed, tested in a laboratory model aquifer, and implemented and evaluated at the field site. This pumping strategy differs from conventional approaches in two important ways: (1) The oil recovery rate is carefully controlled to maximize the pumping rate while maintaining continuity between the oil layer in the soil and the recovery well, to avoid isolation of the oil in the subsurface; and (2) The rate of ground water pumping is controlled to maintain the depressed oil/water interface at its prepumped position. This approach prevents further spread of oil into the ground water, prevents reduction in the volume of recoverable oil due to residual retention, and maintains a gradient for oil flow toward the recovery well. In a model aquifer study, nearly 100 percent of the recoverable volume of ATF was pumped from the system, and about 56,000 gallons of the ATF has been recovered from the field site.     

Synthesis,Mechanism, and Performance Assessment of Zero‐Valent Iron for Metal‐Contaminated Water Remediation: A Review

Recently, increased industrial and agriculture activities have resulted in toxic metal ions, which has increased public concern about the quality of surface and groundwater. Various types of physical, biological, and chemical approaches have been developed to remove surface and groundwater metal ions contaminants. Among these practices, zero‐valent iron (ZVI) is the most studied reactive material for environmental clean‐up over the last two decade and so. Although ZVI can remove the contaminants even more efficiently than any other reactive materials. However, low reactivity due to its intrinsic passive layer, narrow working pH, and the loss of hydraulic conductivity due to the precipitation of metal hydroxides and metal carbonates limits its wide‐scale application. The aim of this work is to document properties, synthesis, and reaction mechanism of ZVI for the treatment of metal ions from the surface and groundwater in recent 10 years (2008–2018). So far, different modified techniques such as conjugation with support, bimetal alloying, weak magnetic field, and ZVI/oxidant coupling system have been developed to facilitate the use of ZVI in various environmental remediation scenarios. However, some challenges still remain to be addressed. Therefore, development and research in this field are needed to overcome or mitigate these limitations.     

A Comparison of Data‐Driven Groundwater Vulnerability Assessment Methods

Increasing availability of geo‐environmental data has promoted the use of statistical methods to assess groundwater vulnerability. Nitrate is a widespread anthropogenic contaminant in groundwater and its occurrence can be used to identify aquifer settings vulnerable to contamination. In this study, multivariate Weights of Evidence (WofE) and Logistic Regression (LR) methods, where the response variable is binary, were used to evaluate the role and importance of a number of explanatory variables associated with nitrate sources and occurrence in groundwater in the Milan District (central part of the Po Plain, Italy). The results of these models have been used to map the spatial variation of groundwater vulnerability to nitrate in the region, and we compare the similarities and differences of their spatial patterns and associated explanatory variables. We modify the standard WofE method used in previous groundwater vulnerability studies to a form analogous to that used in LR; this provides a framework to compare the results of both models and reduces the effect of sampling bias on the results of the standard WofE model. In addition, a nonlinear Generalized Additive Model has been used to extend the LR analysis. Both approaches improved discrimination of the standard WofE and LR models, as measured by the c‐statistic. Groundwater vulnerability probability outputs, based on rank‐order classification of the respective model results, were similar in spatial patterns and identified similar strong explanatory variables associated with nitrate source (population density as a proxy for sewage systems and septic sources) and nitrate occurrence (groundwater depth).     

Trends in 1,4-Dioxane Analyses: Implications for Identification and Characterization of Contaminated Groundwater Sites

1,4-Dioxane is a contaminant of emerging concern, and there is significant uncertainty about how its environmental occurrence in groundwater is being assessed given the various analytical methods available. This study compiled public sampling records from 2000 to 2019 that included >106,000 analyses of 1,4-dioxane from 822 different U.S. sites. The 1,4-dioxane detection frequency in the entire dataset (including all methods) was 45%, and the median detected concentration was 10 μg/L, highlighting the dilute nature of 1,4-dioxane in environmental media and the importance of selecting methods with adequate sensitivity. The annual distribution of samples analyzed by each method type confirmed a shift towards methods designed for semi-volatile compounds (Method 8270 and Method 8270 SIM) that exhibited consistently lower reporting limits (median reporting limit for each year typically ≤1 μg/L). In contrast, the method designed for volatile compounds (Method 8260) exhibited less sensitivity for 1,4-dioxane (median reporting limit per year between 40 and 100 μg/L) and its use declined significantly over time with increasing use of the moderately sensitive Method 8260 SIM in later years. This shift contributed to an increase in the 1,4-dioxane detection frequency over time, with a strong correlation between the annual detection frequency and the median reporting limit. Sites where 1,4-dioxane was analyzed but not detected overwhelmingly used less-sensitive methods that may not have been adequate for the expected concentration levels. Given the sub-μg/L groundwater criteria issued for 1,4-dioxane by some regulatory agencies, more sensitive and accurate methods will be increasingly needed to assess compliance.     

DNAPL Flow Behavior in a Contaminated Aquifer: Evaluation of Field Data

A pool of dense nonaqueous phase liquid (DNAPI.) containing TCE and other chlorinated solvents has been removed from the subsurface at Hill Air Force Base, Uthah. as part of an interim remedial action. The removal of the DNAPI. pool means that future off-site migration of dissolved contaminants in the ground water is minimized, and costs for final remedial actions are reduced. A pump-and-treat system recovered more than 23.000) gallons of DNAPI. and one million gallons of contaminated ground water from the aquifer. The efficiency of this remedial action was evaluated on the basis of extensive field and laboratory data. The behavior of DNAPI. flow in the aquifer sands was characterized by collecting core samples from two borings in the DNAPL pool and measuring relative permeabilities and DMAPI. saturation. Core Hooding results show that approximately one-third of the DNAPI. originally in the pool is not recovered by water displacement, but remains as a residual saturation held in place by capillary pressure. However, subsequent Hooding with two pore volumes of surfactant solution reduced the residual DNAPI. saturation in the sand by one order of magnitude. Analytical and numerical models for the DNAPI flow behavior at the site were developed. This is the first time that such models have been developed and applied to an actual DNAPI. pumping lest conducted in the field. Because measured permeabilities and residual saturations were used lo calibrate the models. the model predictions could be used lo provide valuable insights into the controlling mechanisms for DNAPL recovery. The data collection and modeling procedures outlined in this paper can be used lo enhance the efficiency and minimize the cost 10 clean up this and other DNAPI.-contaminated sites.     

Adsorbed and Bound Residues in Fulvic Acid Fractions of a Contaminated Groundwater – Isolation:, Chromatographic and Spectroscopic Characterization

Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.     

Concurrent Treatment of 1,4‐Dioxane and Chlorinated Aliphatics in a Groundwater Recirculation System Via Aerobic Cometabolism

This research demonstrates that groundwater contaminated by a relatively dilute but persistent concentration of 1,4‐dioxane (1,4‐D), approximately 60 μg/L, and chlorinated aliphatic co‐contaminants (1.4 to 10 μg/L) can be efficiently and reliably treated by in situ aerobic cometabolic biodegradation (ACB). A field trial lasting 265 days was conducted at Operable Unit D at the former McClellan Air Force Base and involved establishing an in situ ACB reactor through amending recirculated groundwater with propane and oxygen. The stimulated indigenous microbial population was able to consistently degrade 1,4‐D to below 3 μg/L while the co‐contaminants trichloroethene (TCE) and 1,2‐dichloroethane (1,2‐DCA) were decreased to below 1 μg/L and 0.18 μg/L, respectively. A stable treatment efficiency of more than 95% removal for 1,4‐D and 1,2‐DCA and of more than 90% removal for TCE was achieved. High treatment efficiencies for 1,4‐D and all co‐contaminants were sustained even without propane and oxygen addition for a 2‐week period.