Enhancing groundwater management using aggregated-data analysis and segmented robust regression: A case study on spatiotemporal changes in water quality.

Groundwater quality management, crucial for ensuring sustainable water resources and public health, is the scope of this study. Our objective is to demonstrate the significance of secondary data analysis for the spatiotemporal characterization of groundwater quality. To this end, we develop and employ a robust trend analysis method, in tandem with a spatiotemporal data aggregation method, to accurately identify shifts in groundwater quality over time, even in the face of inflection points or breakpoints. The methods and results reveal diverse trends and characteristics in water quality over space and time across the entire dataset from selected regions in South Korea, emphasizing the importance of analyzing aggregated data beyond individual business locations. The conclusions indicate that this study contributes to the development of more reliable and effective groundwater quality management strategies by addressing gaps in traditional monitoring methods and the challenges of limited monitoring resources and uneven data quality. Future research directions include the application of the developed methods to other regions and data sources, opening avenues for further advances in groundwater quality management.

The geochemistry and isotopic compositions of the Nakdong River, Korea: weathering and anthropogenic effects.

The Nakdong River is the longest river in South Korea, and flows through various geological terrains with different land use characteristics; therefore, the geochemistry of its water is expected to be influenced by many factors. In this work, the geochemical characteristics of the Nakdong River were examined, and its chemical compositions, δD, δ18O, and δ13CDIC values, and 87Sr/86Sr ratios were determined to investigate the geological and anthropogenic effects on the geochemistry of the Nakdong River water. The obtained concentrations of major ions were strongly affected by both the anthropogenic activity and weathering of the rocks. With increasing the flow distance, the ion concentrations slightly increased; and after the inflow of the Kumho River, which was the largest tributary running through Daegu (the fourth largest city in South Korea), the concentrations of Na and SO4 ions abruptly increased and decreased again, suggesting the existence of strong anthropogenic effects caused by sewage treatment plants and dyeing industrial complex. Other activities such as agricultural ones also increased the NO3 concentration. In July, the high precipitation level from tropical cyclones and downpours decreased the ion concentrations as well as the δD and δ18O values. The δ13CDIC magnitudes showed that the dissolved inorganic carbon mainly originated from mineral weathering upstream, while the oxidation of soil organic materials influenced by agricultural activity became more important downstream. The 87Sr/86Sr ratios revealed that in the upstream regions, the weathering of granite and gneiss complex was dominant, while in the downstream regions, the weathering of sedimentary rocks became more important. The weathering and anthropogenic effects on the river water chemistry were also demonstrated using statistical analysis, which revealed that the water geochemistry was mostly influenced by the anthropogenic sources, including industrial complex, represented by Na, Cl, and SO4. The obtained results show that, as compared to the geochemistry of the Han River (which is also a major river in Korea), the geochemistry of the Nakdong River is more influenced by anthropogenic activities (including agriculture and the industrial complex) due to the different land use.

Super-hydration and reduction of manganese oxide minerals at shallow terrestrial depths.

Manganese oxides are ubiquitous marine minerals which are redox sensitive. As major components of manganese nodules found on the ocean floor, birnessite and buserite have been known to be two distinct water-containing minerals with manganese octahedral interlayer separations of ~7 Å and ~10 Å, respectively. We show here that buserite is a super-hydrated birnessite formed near 5 km depth conditions. As one of the most hydrous minerals containing ca. 34.5 wt. % water, super-hydrated birnessite, i.e., buserite, remains stable up to ca. 70 km depth conditions, where it transforms into manganite by releasing ca. 24.3 wt. % water. Subsequent transformations to hausmannite and pyrochroite occur near 100 km and 120 km depths, respectively, concomitant with a progressive reduction of Mn4+ to Mn2+. Our work forwards an abiotic geochemical cycle of manganese minerals in subduction and/or other aqueous terrestrial environments, with implications for water storage and cycling, and the redox capacity of the region.

Mineral transformation and dissolution of jarosite coprecipitated with hazardous oxyanions and their mobility changes.

Jarosite coprecipitation with hazardous oxyanions can attenuate the concentrations of these elements in acid mine drainage. However, jarosite can be easily transformed to goethite with changes in geochemical conditions. Consequently, the released oxyanions can greatly affect environments. The changes in the mineralogy and mobility of five oxyanions, namely AsO4, SeO3, SeO4, MoO4, and CrO4, which were coprecipitated with jarosite, are investigated herein during the mineral transformation. Our results show that the oxyanion species and the pH values greatly affect the mineral transformation and dissolution rates of jarosite-containing oxyanions. The transformation and dissolution rates of the jarosite samples at pH 8 are noticeably higher than those at pH 4. The X-ray diffraction results show that the CrO4 and SeO4 jarosites are as effectively transformed to goethite as the jarosite without oxyanions, while the SeO3 and AsO4 jarosites are least transformed, resulting in different sulfate and oxyanion concentrations in the solution. The oxyanions in jarosite are the main controlling factor in the mineral transformation and dissolution rates. In acid mine drainage, although CrO4 is easily attenuated by the jarosite precipitation, it has the highest mobility during the goethite transformation. On the contrary, AsO4 shows the opposite case.

Schwertmannite transformation to goethite and the related mobility of trace metals in acid mine drainage.

In acid mine drainage (AMD), precipitated schwertmannite can reduce the trace metal concentration by adsorption and co-precipitation. With the geochemical changes in the water, the precipitated minerals are transformed into more stable goethite. However, no detailed systematic studies have been performed on the mobility changes of trace metals during iron-mineral transformation. The behaviors of trace metals during the transformation of schwertmannite to goethite are investigated for core samples from an AMD treatment. Schwertmannite had gradually transformed to goethite from the top to the bottom of the core samples. Among trace metals, Pb was highly retained in schwertmannite during precipitation, probably by co-precipitation with schwertmannite. Arsenate and chromate were also relatively well retained in schwertmannite, probably because of the substitution of sulfate during precipitation. Sequential extraction results showed that during the transformation of schwertmannite to goethite, most trace metals decreased their mobility by decreasing their exchangeable fraction. However, only Pb increased its mobility during transformation. Some elements, such as Cd and Co, had higher contents of exchangeable fractions compared to other metals and can be relatively easily released into water with slight geochemical changes, greatly affecting the environments of ecological systems.

Mineral phases and mobility of trace metals in white aluminum precipitates found in acid mine drainage.

The white aluminum precipitates (S1,S2,S4-1,S4-2) collected at three different locations affected by acid mine and rock drainage were studied to characterize the mineral phases and mobility of trace metals. Chemical analysis, XRD, SEM, NMR, and sequential extraction method were mainly used. XRD data showed that most white aluminum precipitates are amorphous with small amount of gypsum, which was also confirmed by SEM. The (27)Al MAS NMR spectra provide more detailed information on the local environments of aluminum in those samples. The samples collected at two locations (S3, and S4-1 and S4-2) contain 4-coordinated aluminum, suggesting that the samples contain a significant amount of amorphous phase from Al13-tridecamer. Chemical data of calcium and sulfur with (27)Al MAS NMR spectra suggest that the relative amounts of amorphous phase from Al13-tridecamer, hydrobasaluminite, aluminum hydroxide, and gypsum are different for each sample. Different amount of amorphous phase from Al13-tridecamer in those samples are probably caused by the different geochemical conditions and hydrolysis by aging in water. Sequential extraction results show that water soluble fraction and sorbed and exchangeable fraction of trace metals in sample collected as suspended particles (S1) are higher than other samples, and can affect the ecological system in waters by releasing aluminum and trace metals. These results suggest that careful characterization of white aluminum precipitates is needed to estimate the environmental effects of those precipitates in acid mine drainage.

Chromium isotope fractionation during reduction of Cr(VI) under saturated flow conditions.

Chromium isotopes are potentially useful indicators of Cr(VI) reduction reactions in groundwater flow systems; however, the influence of transport on Cr isotope fractionation has not been fully examined. Laboratory batch and column experiments were conducted to evaluate isotopic fractionation of Cr during Cr(VI) reduction under both static and controlled flow conditions. Organic carbon was used to reduce Cr(VI) in simulated groundwater containing 20 mg L(-1) Cr(VI) in both batch and column experiments. Isotope measurements were performed on dissolved Cr on samples from the batch experiments, and on effluent and profile samples from the column experiment. Analysis of the residual solid-phase materials by scanning electron microscopy (SEM) and by X-ray absorption near edge structure (XANES) spectroscopy confirmed association of Cr(III) with organic carbon in the column solids. Decreases in dissolved Cr(VI) concentrations were coupled with increases in δ(53)Cr, indicating that Cr isotope enrichment occurred during reduction of Cr(VI). The δ(53)Cr data from the column experiment was fit by linear regression yielding a fractionation factor (α) of 0.9979, whereas the batch experiments exhibited Rayleigh-type isotope fractionation (α = 0.9965). The linear characteristic of the column δ(53)Cr data may reflect the contribution of transport on Cr isotope fractionation.

Co-contamination of arsenic and fluoride in the groundwater of unconsolidated aquifers under reducing environments.

The co-contamination of arsenic (As) and fluoride (F(-)) in shallow aquifers is frequently observed worldwide, and the correlations between those contaminants are different according to the redox conditions. This study geochemically explores the reasons for the co-contamination and for the redox-dependent correlations by investigating the groundwater of an alluvial aquifer in Korea. Geochemical signatures of the groundwater in the study area show that the As concentrations are enriched by the reductive dissolution of Fe-(hydr)oxides, and the correlations between As and F(-) concentrations are poor comparatively to those observed in the oxidizing aquifers. However, F(-) concentrations are strongly dependent on pH. Desorption/adsorption experiments using raw soils and citrate-bicarbonate-dithionite treated soils indicated that Fe-(hydr)oxides are the important As and F(-) hosts causing the co-contamination phenomenon. The weaker correlation between F(-) and As in reducing aquifers is likely to be associated with sulfate reduction, which removes As from groundwater without changing the F(-) concentration.

Arsenic concentration in porewater of an alkaline coal ash disposal site: Roles of siderite precipitation/dissolution and soil cover.

The geochemical behavior of As in porewaters of an alkaline coal ash disposal site was investigated using multilevel samplers. The disposal site was in operation from 1983 until 1994 and was covered with 0.3-0.5m thick soils in 2001 when this study was initiated. Sequential extraction analyses and batch leaching experiments were also performed using the coal ash samples collected from the disposal site. The results suggest the important roles of siderite (FeCO(3)) precipitation/dissolution and soil cover, which have been ignored previously. Arsenic levels in the porewater were very low (average of 10microgL(-1)) when the site was covered with soil due to coprecipitation with siderite. The soil cover enabled the creation of anoxic conditions, which raised the Fe concentration by the reductive dissolution of Fe-(hydr)oxides. Because of the high alkalinity generated from the alkaline coal ash, even a small increase in the Fe concentration (0.66mgL(-1) on average) could cause siderite precipitation. When the soil cover was removed, however, an oxidizing condition was created and triggered the precipitation of dissolved Fe as (hydr)oxides. As a result, the dissolution of previously precipitated As-rich siderite caused higher As concentration in the porewater (average of 345microgL(-1)).

The accumulation of radiocesium in coarse marine sediment: effects of mineralogy and organic matter.

The controlling factors affecting the accumulation of (137)Cs in marine sediment have not been investigated in detail, especially in coarse grained sediment. Eighty eight coarse marine sediment samples near Wuljin, Korea, were characterized by quantitative X-ray-diffraction (XRD), gamma-ray, and total organic carbon (TOC) analysis. Those factors were then compared. The grain size was in the range of -0.48 to 3.6Mdphi corresponding to sand grains. TOC content was in the range of 0.06-1.75%, and the concentration of (137)Cs was

Radiocesium reaction with illite and organic matter in marine sediment.

The mineralogical effect on the (137)Cs reaction with marine sediment has not been systematically studied yet, even though illite has been known to adsorb Cs preferentially on its frayed edge sites in a low Cs concentration. Ninety-three marine sediment samples were collected near Yangnam, Korea for quantitative X-ray-diffraction (XRD), gamma-ray, and total organic carbon (TOC) analysis. Illite content was in the range of 0-23 wt.% and those of (137)Cs and TOC were minimum detectable activity (MDA) approximately 7.19 Bq/kg-dry and approximately 3.32%, respectively. The illite content in the marine sediment showed a good relationship with the (137)Cs content (R(2)=0.69), but with an increase in the illite content, the relationship became less linear. This trend can be clearly shown in two groups of samples with different size fractions (< and >5Mdvarphi). For the samples of larger particle sizes (low contents of illite), the relationship is linear, but for the samples of the smaller particle sizes (high illite content) it is less linear with a decreased slope, indicating that increase in illite content does not significantly contribute to the fixation of (137)Cs in marine sediment. Rather, the TOC has a more linear relationship with (137)Cs content with no slope change in all particle size ranges. This may indicate that humic materials in marine sediment block the access of (137)Cs to the frayed edge site and reduces the adsorption of (137)Cs on illite and that the organic materials in marine sediment play more important roles in adsorbing Cs than illite.