Concentration Mechanism of Fluorine, Arsenic, and Uranium in Groundwater of the Hailar Basin, China

Located in semi-arid regions of Hulun Buir League in China Inner Mongolia Autonomous Region, Hailar Basin is a region with less precipitation, where groundwater is the most important source for water supply. It is very important to study groundwater characteristics and hydrogeochemical processes for better management of the groundwater resource.The current status of fluorine (F), arsenic (As), and uranium (U) co-contamination exists in groundwater of the Hailar Basin, China. To understand the concentration mechanism of F, As, and U in groundwater in the study area, groundwater samples were collected for detection and analysis. The results showed that the main hydrochemical types were Cl-Na, HCO3-Na, and HCO3-Ca in the study area. The average values of F, As, and U were 3.94 mg/L, 0.04 mg/L, and 0.07 mg/L, respectively, which all exceeded the World Health Organization(WHO) guidelines. Through the Gibbs diagram and the end member diagram, it can be seen that the groundwater in the study area is mainly affected by the hydrogeochemical effects of evaporative crystallization, rock weathering mechanism, and the dissolution of silicate rock and evaporative salt rock minerals. Mineral dissolution, cation exchange, and weakly alkaline environment are important factors affecting F concentration; Low NO3ˉ and SO42- will cause a reducing environment and the competitive adsorption of HCO3ˉ will promote As pollution; The concentration of Ca2+,Mg2+, SO42-,and NO3ˉ have a great influence on the concentration of U.

Ge/Si Ratio of River Water in the Yarlung Tsangpo: Implications for Hydrothermal Input and Chemical Weathering

Germanium/Silicon (Ge/Si) ratio is a common proxy for primary mineral dissolution and secondary clay formation yet could be affected by hydrothermal and anthropogenic activities. To decipher the main controls of riverine Ge/Si ratios and evaluate the validity of the Ge/Si ratio as a weathering proxy in the Tibetan Plateau, a detailed study was presented on Ge/Si ratios in the Yarlung Tsangpo River, southern Tibetan Plateau. River water and hydrothermal water were collected across different climatic and tectonic zones, with altitudes ranging from 800 m to 5000 m. The correlations between TDS (total dissolved solids) and the Ge/Si ratio and Si and Ge concentrations of river water, combined with the spatial and temporal variations of the Ge/Si ratio, indicate that the contribution of hydrothermal water significantly affects the Ge/Si ratio of the Yarlung Tsangpo River water, especially in the upper and middle reaches. Based on the mass balance calculation, a significant amount of Ge (11–88%) has been lost during its transportation from hydrothermal water to the river system; these could result from the incorporation of Ge on/into clays, iron hydroxide, and sulfate mineral. In comparison, due to the hydrothermal input, the average Ge/Si ratio in the Yarlung Tsangpo River is a magnitude order higher than the majority of rivers over the world. Therefore, evaluation of the contribution of hydrothermal sources should be considered when using the Ge/Si ratio to trace silicate weathering in rivers around the Tibetan Plateau.

Diagenetic Fluid and Its Impact on Sandstone Reservoirs in the Southern Boxing Sag, Dongying Depression, Bohai Bay Basin, China

Diagenesis typically exerts a crucial impact on the formation of high-quality sandstone reservoirs in the Eocene Shahejie Formation, Dongying Depression. To better understand the formation process of petrophysical properties, this research conducts petrographic and geochemical analyses to investigate the nature of diagenetic fluids. Petrographic observations suggest that the dominant cements are carbonate, authigenic quartz, and clay minerals, accompanied with the dissolution of feldspar and calcite. The homogenization temperature of aqueous inclusions in quartz overgrowth usually exceeds 90°C corresponding to the maturity of organic matter. Quartz overgrowths contain higher amounts of CaO and Al2O3 than detrital quartz. This indicates that the siliceous fluid mainly originates from the dissolution of feldspar. Moreover, the conversion of clay minerals also provides trace amounts of silica into pore water during the burial process. Carbonate cements consist of early-stage calcite as well as late-stage Fe-calcite and ankerite. Calcite with relatively higher MnO proportions shows yellow luminescence and dissolution signs. Fe-calcite and ankerite cements have a higher homogenization temperature than that of quartz overgrowth and mainly concentrate in FeO and MgO as well as contain a small amount of Na+, K+, and Sr2+. The rare earth element (REE) pattern of bulk mudstone and carbonate cements as well as C–O isotopic evidences indicate that the diagenetic fluids of carbonate cementation are primarily controlled by the adjacent mudstone, whereas mineral dissolution and altered clay minerals in sandstone provide additional cations for the local reprecipitation of late-stage carbonate. Therefore, diagenetic fluids within sandstone reservoirs are typically subject to alkaline–acid–alkaline conditions and are influenced by internal sources in a closed system. Compaction significantly reduces the pore space of sandstone reservoirs in the Boxing Sag. Carbonate cementation further increases the complexity of pore structure and obeys the principle of mass balance.

Chemical Compositions in Modified Salinity Waterflooding of Calcium Carbonate Reservoirs: Experiment

Modified or low-salinity waterflooding of carbonate oil reservoirs is of considerable economic interest because of potentially inexpensive incremental oil production. The injected modified brine changes the surface chemistry of the carbonate rock and crude oil interfaces and detaches some of adhered crude oil. Composition design of brine modified to enhance oil recovery is determined by labor-intensive trial-and-error laboratory corefloods. Unfortunately, limestone, which predominantly consists of aqueous-reactive calcium carbonate, alters injected brine composition by mineral dissolution/precipitation. Accordingly, the rock reactivity hinders rational design of brines tailored to improve oil recovery. Previously, we presented a theoretical analysis of 1D, single-phase brine injection into calcium carbonate-rock that accounts for mineral dissolution, ion exchange, and dispersion (Yutkin et al. in SPE J 23(01):084–101, 2018. 10.2118/182829-PA). Here, we present the results of single-phase waterflood-brine experiments that verify the theoretical framework. We show that concentration histories eluted from Indiana limestone cores possess features characteristic of fast calcium carbonate dissolution, 2:1 ion exchange, and high dispersion. The injected brine reaches chemical equilibrium inside the porous rock even at injection rates higher than 3.5 $$\times$$ × 10$$^{-3}$$ - 3 m s$$^{-1}$$ - 1 (1000 ft/day). Ion exchange results in salinity waves observed experimentally, while high dispersion is responsible for long concentration history tails. Using the verified theoretical framework, we briefly explore how these processes modify aqueous-phase composition during the injection of designer brines into a calcium-carbonate reservoir. Because of high salinity of the initial and injected brines, ion exchange affects injected concentrations only in high surface area carbonates/limestones, such as chalks. Calcium-carbonate dissolution only affects aqueous solution pH. The rock surface composition is affected by all processes.

Laboratory-Based Bacterial Weathering of the Merensky Reef and Its Impact on Platinum Group Mineral Migration

Weathering of the Merensky reef was enhanced under laboratory conditions by Fe- and S-oxidizing bacteria: Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, and Leptospirillum ferrooxidans. These bacteria preferentially colonized pyrrhotite and pyrite, versus pentlandite and chalcopyrite (all of which were common within the rock substrate), promoting weathering. Weathering of base metal sulfides resulted in the precipitation of Fe oxides, Fe phosphate, and elemental sulfur as secondary minerals. Fe pyroxene weathered readily under acidic conditions and resulted in mineral dissolution, while other silicates (orthopyroxene and plagio-clase) precipitated Fe phosphate spherules or coatings on their surface. The deterioration of the platinum group metal (PGM) matrix (base metal sulfides and silicates) and the occurrence of a platinum grain associated with platinum nanoparticles observed in the biotic thin sections demonstrate that biogeochemical acid weathering is an important step in the active release of intact PGM grains. A platinum grain embedded in secondary Fe oxides/phosphate that had settled by gravity within the weathering solution demonstrates that secondary minerals that formed during weathering of PGM-hosting minerals also represent targets in PGM exploration by trapping and potentially slowing PGM migration. Dispersion halos surrounding or occurring downstream from PGM occurrences will likely produce two physical target classes—i.e., grains and colloids—under surficial weathering conditions.

Galectin-3 Contributes to the Inhibitory Effect of lα,25-(OH)2D3 on Osteoclastogenesis

The active form of vitamin D, 1α,25-(OH)2D3, not only promotes intestinal calcium absorption, but also regulates the formation of osteoclasts (OCs) and their capacity for bone mineral dissolution. Gal-3 is a newly discovered bone metabolic regulator involved in the proliferation, differentiation, and apoptosis of various cells. However, the role of galectin-3 (gal-3) in OC formation and the regulatory effects of 1α,25-(OH)2D3 have yet to be explored. To confirm whether gal-3 contributes to the regulatory effects of 1α,25-(OH)2D3 on osteoclastogenesis, osteoclast precursors (OCPs) were induced by macrophage colony stimulating factor (M-CSF) and receptor activator of nuclear factor κB ligand (RANKL). TRAP staining and bone resorption analyses were used to verify the formation and activation of OCs. qPCR, Western blotting, co-immunoprecipitation, and immunofluorescence assays were used to detect gene and protein expression. The regulatory effects of gal-3 in OC formation after treatment with 1α,25-(OH)2D3 were evaluated using gal-3 siRNA. The results showed that 1α,25-(OH)2D3 significantly increased gal-3 expression and inhibited OC formation and bone resorption. Expression levels of OC-related genes and proteins, matrix metalloproteinase 9 (MMP-9), nuclear factor of activated T cells 1 (NFATc1), and cathepsin K (Ctsk) were also inhibited by 1α,25-(OH)2D3. Gal-3 knockdown attenuated the inhibitory effects of 1α,25-(OH)2D3 on OC formation, activation, and gene and protein expression. In addition, gal-3 was co-localized with the vitamin D receptor (VDR). These data suggest that gal-3 contributes to the osteoclastogenesis inhibitory effect of lα,25-(OH)2D3, which is involved in bone and calcium homeostasis.

Ocean Alkalinity Enhancement – Avoiding runaway CaCO₃ precipitation during quick and hydrated lime dissolution

Ocean Alkalinity Enhancement (OAE) has been proposed as a method to remove carbon dioxide (CO2) from the atmosphere and to counteract ocean acidification. It involves the dissolution of alkaline minerals such as quick lime, CaO, and hydrated lime, Ca(OH)2. However, a critical knowledge gap exists regarding their dissolution in natural seawater. Particularly, how much can be dissolved before secondary precipitation of calcium carbonate (CaCO3) occurs is yet to be established. Secondary precipitation should be avoided as it reduces the atmospheric CO2 uptake potential of OAE. Here we show that both CaO and Ca(OH)2 powders (> 63 µm of diameter) dissolved in seawater within a few hours. However, CaCO3 precipitation, in the form of aragonite, occurred at a saturation (ΩAr) threshold of about 5. This limit is much lower than what would be expected for typical pseudo-homogeneous precipitation in the presence of colloids and organic materials. Secondary precipitation at unexpectedly low ΩAr was the result of so-called heterogeneous precipitation onto mineral phases, most likely onto CaO and Ca(OH)2 prior to full dissolution. Most importantly, this led to runaway CaCO3 precipitation by which significantly more alkalinity (TA) was removed than initially added, until ΩAr reached levels below 2. Such runaway precipitation would reduce the CO2 uptake efficiency from about 0.8 moles of CO2 per mole of TA down to only 0.1 mole of CO2 per mole of TA. Runaway precipitation appears to be avoidable by dilution below the critical ΩAr threshold of 5, ideally within hours of the addition to minimise initial CaCO3 precipitation. Finally, model considerations suggest that for the same ΩAr threshold, the amount of TA that can be added to seawater would be more than three times higher at 5 °C than at 30 °C, and that equilibration to atmospheric CO2 levels during mineral dissolution would further increase it by a factor of ~6 and ~3 respectively.

Integrating water quality index, GIS and multivariate statistical techniques towards a better understanding of drinking water quality

Groundwater is considered as an imperative component of the accessible water assets across the world. Due to urbanization, industrialization and intensive farming practices, the groundwater resources have been exposed to large-scale depletion and quality degradation. The prime objective of this study was to evaluate the groundwater quality for drinking purposes in Mewat district of Haryana, India. For this purpose, twenty-five groundwater samples were collected from hand pumps and tube wells spread over the entire district. Samples were analyzed for pH, electrical conductivity (EC), total dissolved solids (TDS), total hardness (TH), turbidity, total alkalinity (TA), cations and anions in the laboratory using the standard methods. Two different water quality indices (weighted arithmetic water quality index and entropy weighted water quality index) were computed to characterize the groundwater quality of the study area. Ordinary Kriging technique was applied to generate spatial distribution map of the WQIs. Four semivariogram models, i.e. circular, spherical, exponential and Gaussian were used and found to be the best fit for analyzing the spatial variability in terms of weighted arithmetic index (GWQI) and entropy weighted water quality index (EWQI). Hierarchical cluster analysis (HCA), principal component analysis (PCA) and discriminant analysis (DA) were applied to provide additional scientific insights into the information content of the groundwater quality data available for this study. The interpretation of WQI analysis based on GWQI and EWQI reveals that 64% of the samples belong to the “poor” to “very poor” bracket. The result for the semivariogram modeling also shows that Gaussian model obtains the best fit for both EWQI and GWQI dataset. HCA classified 25 sampling locations into three main clusters of similar groundwater characteristics. DA validated these clusters and identified a total of three significant variables (pH, EC and Cl) by adopting stepwise method. The application of PCA resulted in three factors explaining 69.81% of the total variance. These factors reveal how processes like rock water interaction, urban waste discharge and mineral dissolution affect the groundwater quality.