On‐Site Vapor‐Phase Analysis as a Novel Approach for Monitoring Groundwater Wells

The results of comprehensive field testing of on‐site vapor‐phase‐based groundwater monitoring methods are presented to demonstrate their utility as a robust and cost‐effective approach for rapidly obtaining volatile organic compounds (VOCs) concentration data from a monitoring well. These methods—which rely on sensitive, commercially available field equipment to analyze vapor in equilibrium with groundwater—proved easy to implement and can be tailored to site‐specific needs, including multilevel sampling. During field testing, low‐flow groundwater concentrations could be reasonably estimated using submerged passive vapor diffusion samplers or field equilibration of collected groundwater (R² = 0.85 to 0.96). These two methods are not as reliant on in‐well mixing to overcome vertical stratification within wells as simpler headspace methods. The importance of well and aquifer‐specific factors on concentration data (and therefore method selection) is highlighted, including the effect of changing in‐well patterns due to seasonal temperature gradients. Results indicated that vertical stratification was relatively limited within the set of wells included in these studies, resulting in similar performance for short depth‐discrete passive vapor diffusion samplers (constructed from 40‐mL vials) and longer samplers (2.5 to 5 feet in length) designed to cover a larger portion of the screened interval. A year‐long, multi‐event evaluation demonstrated that vapor‐phase‐based monitoring methods are no more variable than conventional groundwater monitoring methods, with both types subject to similar spatial and temporal variability that can be difficult to reduce. Vapor sampling methods represent a promising approach for estimation of groundwater concentrations by reducing the cost liabilities associated with monitoring while providing a more sustainable approach.     

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.     

A Stream‐Based Methane Monitoring Approach for Evaluating Groundwater Impacts Associated with Unconventional Gas Development

Gaining streams can provide an integrated signal of relatively large groundwater capture areas. In contrast to the point‐specific nature of monitoring wells, gaining streams coalesce multiple flow paths. Impacts on groundwater quality from unconventional gas development may be evaluated at the watershed scale by the sampling of dissolved methane (CH₄) along such streams. This paper describes a method for using stream CH₄ concentrations, along with measurements of groundwater inflow and gas transfer velocity interpreted by 1‐D stream transport modeling, to determine groundwater methane fluxes. While dissolved ionic tracers remain in the stream for long distances, the persistence of methane is not well documented. To test this method and evaluate CH₄ persistence in a stream, a combined bromide (Br) and CH₄ tracer injection was conducted on Nine‐Mile Creek, a gaining stream in a gas development area in central Utah. A 35% gain in streamflow was determined from dilution of the Br tracer. The injected CH₄ resulted in a fivefold increase in stream CH₄ immediately below the injection site. CH₄ and δ¹³C_CH4 sampling showed it was not immediately lost to the atmosphere, but remained in the stream for more than 2000 m. A 1‐D stream transport model simulating the decline in CH₄ yielded an apparent gas transfer velocity of 4.5 m/d, describing the rate of loss to the atmosphere (possibly including some microbial consumption). The transport model was then calibrated to background stream CH₄ in Nine‐Mile Creek (prior to CH₄ injection) in order to evaluate groundwater CH₄ contributions. The total estimated CH₄ load discharging to the stream along the study reach was 190 g/d, although using geochemical fingerprinting to determine its source was beyond the scope of the current study. This demonstrates the utility of stream‐gas sampling as a reconnaissance tool for evaluating both natural and anthropogenic CH₄ leakage from gas reservoirs into groundwater and surface water.     

Accelerating Groundwater Flow Simulation in MODFLOW Using JASMIN‐Based Parallel Computing

To accelerate the groundwater flow simulation process, this paper reports our work on developing an efficient parallel simulator through rebuilding the well‐known software MODFLOW on JASMIN (J Adaptive Structured Meshes applications Infrastructure). The rebuilding process is achieved by designing patch‐based data structure and parallel algorithms as well as adding slight modifications to the compute flow and subroutines in MODFLOW. Both the memory requirements and computing efforts are distributed among all processors; and to reduce communication cost, data transfers are batched and conveniently handled by adding ghost nodes to each patch. To further improve performance, constant‐head/inactive cells are tagged and neglected during the linear solving process and an efficient load balancing strategy is presented. The accuracy and efficiency are demonstrated through modeling three scenarios: The first application is a field flow problem located at Yanming Lake in China to help design reasonable quantity of groundwater exploitation. Desirable numerical accuracy and significant performance enhancement are obtained. Typically, the tagged program with load balancing strategy running on 40 cores is six times faster than the fastest MICCG‐based MODFLOW program. The second test is simulating flow in a highly heterogeneous aquifer. The AMG‐based JASMIN program running on 40 cores is nine times faster than the GMG‐based MODFLOW program. The third test is a simplified transient flow problem with the order of tens of millions of cells to examine the scalability. Compared to 32 cores, parallel efficiency of 77 and 68% are obtained on 512 and 1024 cores, respectively, which indicates impressive scalability.     

Building a Low-Cost,Internet-of-Things,Real-Time Groundwater Level Monitoring Network

A community-based, real-time, groundwater level monitoring network consisting of 11 sites was built in Nova Scotia, Canada, using privately owned domestic wells and low-cost, custom-made water level meters. The real-time meters use an ultrasonic sensor to measure water levels and an Internet-of-Things device to transmit the data to the Internet by WiFi or cellular connection. The water level data are plotted in real-time on a time-series graph and are available immediately for online viewing and downloading. Based on observations at three sites, the real-time water level meter data compare well to pressure transducer measurements, with mean absolute errors of less than 0.02 m. The meters are simple to build, and components are readily available from online suppliers at low cost.     

Quantification of TCE Co‐Oxidation in Groundwater Using a 14C–Assay

Bacteria that degrade natural organic matter in groundwater contain oxygenase enzymes that can co‐oxidize trichloroethene (TCE). This degradation pathway is promising for large dilute plumes, but its evaluation is limited because the density of the bacteria with oxygenase enzymes has not been correlated to field scale rates of degradation. A ¹⁴C–TCE assay was developed to determine pseudo first‐order rate constants for the aerobic co‐oxidation of TCE in groundwater. The assay involved incubating ¹⁴C–TCE in samples of groundwater contained in 160 mL serum bottles, and monitoring the accumulation of radiolabel in degradation products. A first‐order rate constant for co‐oxidation was extracted from the rate of accumulation of ¹⁴C in products, accounting for volumetric changes in the serum bottles due to sampling and subsequent changes to the distribution of TCE between the aqueous and gaseous phases. Of the groundwater samples evaluated from 19 wells at five sites, eight samples at three sites had ¹⁴C product accumulation rates that exceeded the accumulation rate in filter‐sterilized groundwater controls. First‐order rate constants ranged from 2.65 to 0.0066 year^?1, which is equivalent to half‐lives of 0.26 to 105 years. Groundwater samples from a few of the wells in which co‐oxidation occurred had volatile organic contaminants in addition to TCE; their presence may have induced the oxygenase enzymes that are needed for TCE co‐oxidation. ¹⁴CO₂ represented ~37% to 97% of the ¹⁴C products that accumulated; the balance of the products was soluble and non‐volatile.     

Pump‐and‐Treat Groundwater Remediation Using Chlorine/Ultraviolet Advanced Oxidation Processes

Comparative studies of the use of chlorine/ultraviolet (Cl₂/UV) and hydrogen peroxide/ultraviolet (H₂O₂/UV) Advanced oxidation processes (AOPs) to remove trichloroethylene (TCE) from groundwater in a pump‐and‐treat application were conducted for the first time at the full‐scale operational level at two water treatment facilities in Northern California. In these studies, aqueous chlorine replaced hydrogen peroxide in the AOP treatment step, where the oxidant is exposed to UV light to produce highly reactive radical species that degrade groundwater contaminants. TCE removal rates as a function of initial chlorine dose and pH were then determined. At the site where the natural pH of the water was 7.1, TCE was removed (to a concentration of less than 0.5 µg/L) for nearly every chlorine dose point tested, and pH adjustment slightly enhanced the treatment process at this facility. The second site had a high natural pH of 7.7, and here, TCE was not completely removed for any chlorine dose up to 5.7 mg/L, although TCE removal did increase when the chlorine dose increased between 0.9 and 3.6 mg/L. Residual TCE remaining in the water post‐Cl₂/UV was readily removed using active carbon filtration, which is part of the overall treatment train at this facility. These studies also verified that Cl₂/UV AOP did not interfere with the photolysis of N‐nitrosodimethylamine or result in an effluent acutely toxic toward Ceriodaphnia dubia. Comparative economic analysis revealed that the chemical costs associated with Cl₂/UV AOP were 25 to 50% of the costs associated with in place H₂O₂/UV AOP treatment.     

Monitoring of Impact of Ferti‐irrigation by Post‐methanated Distillery Effluent on Groundwater Quality

The impact assessment of molasses‐based distillery‐effluent irrigation on groundwater quality around village Gajraula in the district of Jyotiba Phule Nagar, Uttar Pradesh, India was studied by sampling groundwater on monthly intervals consecutively for summer, winter and monsoon seasons during 2006–2007 and water quality parameters, viz. pH, electrical conductivity (EC), chloride (Cl^?), sulphate (SO), nitrate (NO), chemical oxygen demand (COD), total solids (TS), total dissolved solids (TDS), sodium (Na⁺), potassium (K⁺), calcium (Ca²⁺), magnesium (Mg²⁺), zinc (Zn²⁺), iron (Fe³⁺), and total coliforms (TC) were monitored. Results depicted that the values of all parameters decreased with increasing depth of water table. Sulphate, nitrate and potassium contents were maximal in agricultural site during monsoon while EC, Cl^?, TS, TDS, Na⁺, Ca²⁺, Mg²⁺, Zn, and Fe were maximal in industrial sites during summer. Groundwater samples of residential site harboured maximum coliforms especially during monsoon, highlighting threat to groundwater. Significant positive correlation matrix between coliforms with nitrate, sulphate and potassium ions explained their survival on these nutrients. To overcome this, important measures emphasizing improvement in effluent treatment technology matching site‐specific characteristics are recommended for eco‐friendly ferti‐irrigation.     

A review of the National Groundwater Monitoring Network in Korea

The drastic expansion of cities and the rapid economic growth in Korea have caused dramatic increases to demand from groundwater supplies for drinking, domestic, agricultural and industrial water usage. The Ministry of Construction and Transportation and the Korea Water Resources Corporation have constructed and operated the National Groundwater Monitoring Network (NGMN) throughout the country since 1995. The NGMN, an official project establishing a total of 320 groundwater monitoring stations, was completed in 2005. Each national groundwater monitoring station serves as a baseline and primary station to monitor long‐term general trends in water‐level fluctuations and in groundwater quality. The present NGMN and its monitoring capabilities were evaluated to enhance the efficiency of groundwater monitoring and to meet the new societal conditions. Based on reviews and evaluations, some suggestions and recommendations are made with regard to improvements of the national network, including the installation of rainfall gauges in groundwater monitoring stations, gathering groundwater data every hour instead of every 6 h as at present, involving major cations and anions in the regular and periodic chemical analyses, regular periodic analyses of collected groundwater data, and construction of 199 additional groundwater monitoring stations to supplement the existing groundwater monitoring network. Copyright © 2006 John Wiley & Sons, Ltd.     

The Trend of Groundwater Level Using Threshold-Based Wavelet De-Noising Approach

Water Resources - The aims of this study was to identify the groundwater level (GWL) trend and dominant periodic component of Ardabil plain (North-west of Iran) using three variations of the...     

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.     

Homotopy Perturbation Method‐Based Analytical Solution for Tide‐Induced Groundwater Fluctuations

The groundwater variations in unconfined aquifers are governed by the nonlinear Boussinesq's equation. Analytical solution for groundwater fluctuations in coastal aquifers under tidal forcing can be solved using perturbation methods. However, the perturbation parameters should be properly selected and predefined for traditional perturbation methods. In this study, a new dimensional, higher‐order analytical solution for groundwater fluctuations is proposed by using the homotopy perturbation method with a virtual perturbation parameter. Parameter‐expansion method is used to remove the secular terms generated during the solution process. The solution does not require any predefined perturbation parameter and valid for higher values of amplitude parameter A/D, where A is the amplitude of the tide and D is the aquifer thickness.     

A Systematic Approach to Designing a Multiphase Unsaturated Zone Monitoring Network

A systematic approach is presented for the design of a multiphase vadose zone monitoring system recognizing that, as in ground water monitoring system design, complete subsurface coverage is not practical. The approach includes identification and prioritization of vulnerable areas: select ion of cost-effective indirect monitoring methods that will provide early warning of contaminant migration: selection of direct monitoring methods for diagnostic confirmation; identification of background monitoring locations; and identification of an appropriate temporal monitoring plan. An example of a monitoring system designed for a solid waste landfill is presented and utilized to illustrate the approach and provide details of system implementation. The example design described incorporates the use of neutron moisture probes deployed in both vertical and horizontal access tubes beneath the lcachate recovery collection system of the landfill. Early warning of gaseous phase contaminant migration is monitored utilizing whole-air active soil gas sampling points deployed in gravel- filled trenches beneath the subgrade. Diagnostic confirmation of contaminant migration is provided utilizing pore- liquid samplers. Conservative tracers can be used to distinguish between chemical species released by a landfill from those attributable to other (e.g. off-site) sources or present naturally in the subsurface. A discussion of background monitoring point location is also presented.     

Data‐Driven Approach for Analyzing Hydrogeology and Groundwater Quality Across Multiple Scales

Recent trends of assimilating water well records into statewide databases provide a new opportunity for evaluating spatial dynamics of groundwater quality and quantity. However, these datasets are scarcely rigorously analyzed to address larger scientific problems because they are of lower quality and massive. We develop an approach for utilizing well databases to analyze physical and geochemical aspects of groundwater systems, and apply it to a multiscale investigation of the sources and dynamics of chloride (Cl^?) in the near‐surface groundwater of the Lower Peninsula of Michigan. Nearly 500,000 static water levels (SWLs) were critically evaluated, extracted, and analyzed to delineate long‐term, average groundwater flow patterns using a nonstationary kriging technique at the basin‐scale (i.e., across the entire peninsula). Two regions identified as major basin‐scale discharge zones—the Michigan and Saginaw Lowlands—were further analyzed with regional‐ and local‐scale SWL models. Groundwater valleys (“discharge” zones) and mounds (“recharge” zones) were identified for all models, and the proportions of wells with elevated Cl^? concentrations in each zone were calculated, visualized, and compared. Concentrations in discharge zones, where groundwater is expected to flow primarily upwards, are consistently and significantly higher than those in recharge zones. A synoptic sampling campaign in the Michigan Lowlands revealed concentrations generally increase with depth, a trend noted in previous studies of the Saginaw Lowlands. These strong, consistent SWL and Cl^? distribution patterns across multiple scales suggest that a deep source (i.e., Michigan brines) is the primary cause for the elevated chloride concentrations observed in discharge areas across the peninsula.     

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.     

Evaluation of Hydraulic Properties of Aquitards Using Earthquake‐Triggered Groundwater Variation

The hydraulic properties of aquitards are not easily obtained because monitoring wells are usually installed in aquifers for groundwater resources management. Earthquake‐induced crust stress (strain) triggers groundwater level variations over a short period of time in a large area. These groundwater anomalies can be used to investigate aquifer systems. This study uses a poroelastic model to fit the postseismic variations of groundwater level triggered by the Chi‐Chi earthquake to evaluate the hydraulic properties of aquitards in the Jhoushuei River alluvial fan (JRAF), Taiwan. Six of the adopted eight wells with depths of 70 to 130 m showed good agreement with the recovery theory. The mean hydraulic conductivities (K) of the aquifers for the eight wells are 1.62 × 10^?4 to 9.06 × 10^?4 m/s, and the thicknesses are 18.8 to 46.1 m. The thicknesses of the aquitards are 11.3 to 42.0 m. Under the isotropic assumption for K, the estimated values of K for the aquitards are 3.0 × 10^?8 to 2.1 × 10^?6 m/s, corresponding to a silty medium. The results match the values obtained for the geological material of the drilling core and those reported in previous studies. The estimated values were combined with those given in previous studies to determine the distribution of K in the first two aquitards in the JRAF. The distribution patterns of the aquitards reflect the sedimentary environments and fit the geological material. The proposed technique can be used to evaluate the K value of aquitards using inverse methods. The inversion results can be used in hydrogeological analyses, contaminant modeling, and subsidence evaluation.     

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.