A modified and rapid method for the single-well push-pull (SWPP) test using SF6, Kr, and uranine tracers.

In the present study, a single-well push-pull (SWPP) test was conducted with multi-component tracers, including inert gas (SF6 and Kr) and uranine (conservative), to understand the volatile/semi-volatile component transport characteristics in the groundwater system. In an SWPP test, it is essential to obtain an initial breakthrough curve (BTC) of the inert gas concentration at the beginning of the pulling stage to analyze the hydraulic properties of the groundwater system. As a result of the SWPP test using a proposed method in this study, physicochemical parameters of the groundwater and BTC of gas tracers and uranine were acquired simultaneously and successfully. In addition, on-site measurements of uranine, pCO2, and water quality data, such as electrical conductivity (EC), temperature, pH, and dissolved oxygen, were undertaken. Modification of an existing pCO2 measuring system allowed the gas samples to be collected, transported, and analyzed for inert gas components within a few hours. As a result, reliable and interpretable data with a recovery ratio of 26%, 85%, and 95% for SF6, Kr, and uranine, respectively, were obtained. The differences in the recovery ratio were utilized to identify the environmental system, whether it contains gas inside the isolated system (closed) or not (open), and to understand plume behavior characteristics in the experimental zone. By applying a two-dimensional advection-dispersion model to the acquired tracer test data and comparing the observed and computed tracer concentrations, helpful information was obtained on the hydraulic and transport characteristics of the targeted zone. This method can be extended to the design of dissolved CO2 transport monitoring of an aquifer above a CCS site.

Constraining the effectiveness of inherent tracers of captured CO2 for tracing CO2 leakage: Demonstration in a controlled release site.

Geological storage of carbon dioxide (CO2) is an integral component of cost-effective greenhouse gas emissions reduction scenarios. However, a robust monitoring regime is necessary for public and regulatory assurance that any leakage from a storage site can be detected. Here, we present the results from a controlled CO2 release experiment undertaken at the K-COSEM test site (South Korea) with the aim of demonstrating the effectiveness of the inherent tracer fingerprints (noble gases, δ13C) in monitoring CO2 leakage. Following injection of 396 kg CO2(g) into a shallow aquifer, gas release was monitored for 2 months in gas/water phases in and above the injection zone. The injection event resulted in negative concentration changes of the dissolved gases, attributed to the stripping action of the depleted CO2. Measured fingerprints from inherent noble gases successfully identified solubility-trapping of the injected CO2 within the shallow aquifer. The δ13C within the shallow aquifer could not resolve the level of gas trapping, due to the interaction with heterogeneous carbonate sources in the shallow aquifer. The time-series monitoring of δ13CDIC and dissolved gases detected the stripping action of injected CO2(g), which can provide an early warning of CO2 arrival. This study highlights that inherent noble gases can effectively trace the upwardly migrating and fate of CO2 within a shallow aquifer.

Evaluating backward probability model under various hydrogeologic and hydrologic conditions.

Contaminant source identification improves the understanding of contaminant source characteristics including location and release time, which can lead to more effective remediation and water resources management plans. The backward probability model can provide probabilities of source locations and release times under various contaminant properties and hydrogeologic conditions. The backward probability model has been applied to numerous synthetic and real contamination sites for locating possible contaminant sources, but it is also important to evaluate the reliability of the backward probability model through rigorous verification analyses. Here, we present a model verification framework for the backward probability model using a stepwise approach from simple to complex model settings: comparison with previous studies, transient saturated flow under various hydrogeologic conditions, and transient variably-saturated flow conditions. As a simple condition, one-dimensional homogeneous problems under steady-state and transient flow conditions were verified by comparing with previous studies. Model verifications with complex conditions were conducted by comparing forward and backward probability simulation results. The verification results demonstrate that the backward probability model performs well for homogeneous problems. For heterogeneous problems, the backward probability model results in slightly different backward travel times due to differences in solute decay and boundary conditions assigned for both forward and backward probability simulations, but the backward travel time at the maximum probability can be reproduced well.

Differentiation of natural and anthropogenic contaminant sources using isotopic and microbial signatures in a heavily cultivated coastal area.

Hydrogeochemical and multiple isotope data for groundwater samples were obtained and interpreted to discriminate anthropogenic and natural contaminant sources in a coastal aquifer underlying a heavily cultivated watershed in Hwaseong, South Korea. The local aquifers are vulnerable to contamination, due to high anthropogenic N inputs and the location close to the ocean facilitating seawater intrusion. Thus, to effectively control the groundwater quality in the study area, it is necessary to differentiate between anthropogenic and natural contaminant sources. The concentrations of NO3-N in the groundwater ranged between 0.14 and 45.6 mg/L in August 2015 and 0.2-39.6 mg/L in March 2016. High concentrations of Cl- (388-1107 mg/L) and a high electrical conductivity (1027-2715 µS/cm) were observed in the study area, suggesting that the groundwater was affected by seawater intrusion. Furthermore, δ15N-NO3-, δ34S-SO42- values and 87Sr/86Sr of groundwater were determined to reveal the origins of the natural and anthropogenic contaminants and the groundwater mean residence times (MRT) and 87Sr/86Sr ratios were used to assess the hydrogeochemical processes along the flow path in the study area. Young groundwater was affected by an anthropogenic contamination source with contributions of 26-46% adding nitrate to the aquifer, whereas old groundwater was impacted by mixing with seawater with contributions of 10-20% with low concentrations of NO3-N, but elevated concentrations of chloride and sulfate. Recently recharged uncontaminated groundwater showed oxic conditions with a diverse microbial community structure, whereas young groundwater contaminated by anthropogenic sources showed a less diverse microbial community structure. The results of this study suggest that multiple isotopes combined with groundwater MRT and microbial data can be applied to distinguish natural and anthropogenic contaminant sources in a groundwater system.

Characterization of a NAPL-contaminated site using the partitioning behavior of noble gases.

Noble gases have been used for oil field exploration due to their partitioning behavior in oil-water systems. However, their application to study sites contaminated with non-aqueous phase liquids (NAPL) has been limited, except for 222Rn, which has been traditionally used as a partitioning tracer for contaminated sites. This study applied natural noble gas components such as 222Rn, He, Ne, Ar, Kr, and Xe to the characterization of a field site contaminated with trichloroethylene (TCE) located in Wonju, Korea. Groundwater at the site showed a maximum level of TCE that exceeded 1000 µg/L, with an approximate average of 400 µg/L, indicating the presence of residual TCE in the subsurface system even after remediation. The traditional tracer (i.e., 222Rn) was first used to characterize residual TCE. However, its heterogeneous distribution throughout the fractured bedrock aquifer negated its usefulness as a TCE indicator. The use of radiogenic 4He was also limited by the wide distribution of radiogenic sources on the site. By contrast, changes in the TCE level had clear effects on the conditions of other noble gases, such as Ne, Ar, and Xe, making them useful for characterization of the TCE-contaminated site. Furthermore, calculation of the TCE/water ratio including residual TCE was achieved, but identification of the TCE originating from the vadose zone was relatively hard. The results of this study indicate that based on their partitioning behavior, naturally-occurring noble gases can be used to delineate and quantify residual TCE.

Ultrahigh areal number density solid-state on-chip microsupercapacitors via electrohydrodynamic jet printing.

Microsupercapacitors (MSCs) have garnered considerable attention as a promising power source for microelectronics and miniaturized portable/wearable devices. However, their practical application has been hindered by the manufacturing complexity and dimensional limits. Here, we develop a new class of ultrahigh areal number density solid-state MSCs (UHD SS-MSCs) on a chip via electrohydrodynamic (EHD) jet printing. This is, to the best of our knowledge, the first study to exploit EHD jet printing in the MSCs. The activated carbon-based electrode inks are EHD jet-printed, creating interdigitated electrodes with fine feature sizes. Subsequently, a drying-free, ultraviolet-cured solid-state gel electrolyte is introduced to ensure electrochemical isolation between the SS-MSCs, enabling dense SS-MSC integration with on-demand (in-series/in-parallel) cell connection on a chip. The resulting on-chip UHD SS-MSCs exhibit exceptional areal number density [36 unit cells integrated on a chip (area = 8.0 mm × 8.2 mm), 54.9 cells cm-2] and areal operating voltage (65.9 V cm-2).

Evaluation of the fate and transport of chlorinated ethenes in a complex groundwater system discharging to a stream in Wonju, Korea.

Chlorinated ethenes such as trichloroethylene (TCE) are common and persistent groundwater contaminants. If contaminated groundwater discharges to a stream, then stream water pollution near the contamination site also becomes a problem. In this respect, the fate and transport of chlorinated ethenes around a stream in an industrial complex were evaluated using the concentration of each component, and hydrogeochemical, microbial, and compound-specific carbon isotope data. Temporal and spatial monitoring reveal that a TCE plume originating from main and local source zones continues to be discharged to a stream. Groundwater geochemical data indicate that aerobic conditions prevail in the upgradient area of the studied aquifer, whereas conditions become anaerobic in the downgradient. The TCE molar fraction is high at the main and local source zones, ranging from 87.4 to 99.2% of the total volatile organic compounds (VOCs). An increasing trend in the molar fraction of cis-1, 2-Dichloroethene (cis-DCE) and vinyl chloride (VC) was observed in the downgradient zone of the study area. The enriched δ(13)C values of TCE and depleted values of cis-DCE in the stream zone, compared to those of the source zone, also suggest biodegradation of VOCs. Microbial community structures in monitoring wells adjacent to the stream zone in the downgradient area were analyzed using 16S rRNA gene-based pyrosequencing to identify the microorganisms responsible for biodegradation. This was attributed to the high relative abundance of dechlorinating bacteria in monitoring wells under anaerobic conditions farthest from the stream in the downgradient area. The multilateral approaches adopted in this study, combining hydrogeochemical and biomolecular methods with compound-specific analyses, indicate that contaminants around the stream were naturally attenuated by active anaerobic biotransformation processes.