Identifying the origin and fate of dissolved U in the Boeun aquifer based on microbial signatures and C, O, Fe, S, and U isotopes.

The uranium inventory in the Boeun aquifer is situated near an artificial reservoir (40-70 m apart) intended to supply water to nearby cities. However, toxic radionuclides can enter the reservoir. To determine the U mobility in the system, we analyzed groundwater and fracture-filling materials (FFMs) for environmental tracers, including microbial signatures, redox-sensitive elements and isotopes. In the site, U mass flux ranged from only 9.59 × 10-7 µg/L/y to 1.70 × 10-4 µg/L/y. The δ18O-H2O and 14C signatures showed that groundwater originated mainly from upland recharges and was not influenced by oxic surface water. We observed U accumulations (∼157 mg/kg) in shallow FFMs and Fe enrichments (∼226798 mg/kg) and anomalies in the 230Th/238U activity ratio (AR), 230Th/234U AR, δ56Fe and δ57Fe isotopes, suggesting that low U mobility in shallow depths is associated with a Fe-rich environment. At shallow depths, anaerobic Fe-oxidizers, Gallionella was prevalent in the groundwater, while Acidovorax was abundant near the U ore deposit depth. The Fe-rich environment at shallow depths was formed by sulfide dissolution, as demonstrated by δ34S-SO4 and δ18O-SO4 distribution. Overall, the Fe-rich aquifer including abundant sulfide minerals immobilizes dissolved U through biotic and abiotic processes, without significant leaching into nearby reservoirs.

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.

Evaluating the sources and fate of nitrate in riparian aquifers under agricultural land using in situ-measured noble gases, stable isotopes, and metabolic genes.

Riparian zones with their buffering ability and abundant water supply are often subjected to intensive agricultural activities. We investigated a riparian aquifer located near a stream in South Korea that recently experienced sharply decreasing groundwater levels and elevated nitrate (NO3-) concentrations, which were attributed to local agricultural activities. Our goal was to identify the predominant nitrogen sources and NO3- removal processes. Multiple approaches including geochemical and isotopic tracers, land-use analysis, metabolic gene quantification, and inert gas tracers were used to elucidate groundwater and nutrient dynamics in stream-side granitic aquifers. The dual isotopic composition of NO3- identified manure and sewage as the major sources of NO3- contamination. Denitrification was the dominant NO3- removal process in the aquifer, as demonstrated by the negative relationship between δ15N and δ18O values in NO3-and NO3-/Cl-. Denitrification and anammox genes were also observed in microbial communities of the aquifer throughout the study site, suggesting that these processes support effective natural NO3- attenuation in groundwater. A mixing model constructed using a catchment-scale dataset including SiO2 concentrations and δ18O-H2O suggested that mixing with paddy soil water was the major driver of denitrification in the aquifer at the study site, where impervious layers provided anaerobic conditions for natural NO3- attenuation. Denitrification reduced the NO3- flux into the nearby stream by up to 114.4 NO3- kg/ha/y (26 kg N/ha/y). The N2 generated by denitrification did not accumulate in the groundwater, but mostly escaped from groundwater to the atmosphere, as demonstrated by the degassed signature of dissolved inert gases below the air saturated water level. This study identified the predominant NO3- sources and conceptualized N cycling in the heavily developed agricultural riparian aquifer using multiple tracers, demonstrating that NO3- is partially removed through denitrification and possibly anammox while N2 mostly escapes into the atmosphere.

Estimation of nutrient sources and fate in groundwater near a large weir-regulated river using multiple isotopes and microbial signatures.

The excessive input of nutrients into groundwater can accelerate eutrophication in associated surface water systems. This study combined hydrogeochemistry, multi isotope tracers, and microbiological data to estimate nutrient sources and the effects of groundwater-surface water interactions on the spatiotemporal variation of nutrients in groundwater connected to a large weir-regulated river in South Korea. δ11B and δ15N-NO3- values, in combination with a Bayesian mixing model, revealed that manure and sewage contributed 40 % and 25 % respectively to groundwater nitrate, and 42 % and 27 % to nitrate in surface water during the wet season. In the dry season, the source apportionment was similar for groundwater while the sewage contribution increased to 52 % of nitrate in river water. River water displayed a high correlation between NO3- concentration and cyanobacteria (Microcystis and Prochlorococcus) in the wet season. The mixing model using multiple isotopes indicated that manure-derived nutrients delivered with increased contributions of groundwater to the river during the wet season governed the occurrence of cyanobacterial blooms in the river. We postulate that the integrated approach using multi-isotopic and microbiological data is highly effective for evaluating nutrient sources and for delineating hydrological interactions between groundwater and surface water, as well as for investigating surface water quality including eutrophication in riverine and other surface water systems.

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.

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.

Complexity of groundwater age mixing near a seawater intrusion zone based on multiple tracers and Bayesian inference.

Aquifer flow systems near seawater interfaces can be complicated by density-driven flows and the formation of stagnation zones, which inevitably introduces uncertainty into groundwater age-dating. While age-dating has proved effective to understand the seawater intrusion and aquifer salinization process in coastal aquifers, further efforts are needed to propagate model and data uncertainty to the uncertainty associated with the inferred age distributions. This study was performed in a coastal aquifer located close to the Yellow Sea, South Korea, where there is a decreasing trend of groundwater levels due to recent heavy exploitation, raising a warning of induced seawater intrusion. We inferred the groundwater age distributions in wells around the intrusion zone and estimated the uncertainty associated with the inference based on multiple age tracers including 3H, tritiogenic 3He, radiogenic 4He, CFC-11, CFC-12 and CFC-113 using Bayesian inference. We examined various models representing the age distributions including traditional parametric Lumped Parameter Models (LPMs) and two non-parametric "shape-free" models. The results showed that the mean ages at the study site ranged from 10.9 to 522.5 y. Complex, multimodal distributions of ages occurred near a seawater intrusion area and upland recharge zones, implying converging paths of a wide range of different ages in those regions. In particular, the age distributions estimated near the seawater intrusion interface were characterized by heavy-tailed mixing structures with elevated concentrations of 4He. This likely indicates density-driven upward flow at the seawater intrusion interface, forcing old groundwater rich in 4He into the shallow aquifer. The Bayesian inference estimated large uncertainties particularly for the old age distributions, which was attributed partly to the gradual accumulation of 4He in groundwater. The Bayesian inference improved understanding of flow dynamics at a complex seawater interface and identified opportunities to further reduce uncertainty of old water age estimates that characterize upwelling groundwater near the interface.

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.