Reversible Exchange Research Articles

Assessment of groundwater quality and suitability for irrigation purpose using irrigation indices, remote sensing and GIS approach

Assessing both the quantitative and qualitative aspects of groundwater is essential for evaluating its suitability for irrigation and drinking purpose. Consequently, this current study showcases its importance by determining groundwater quality in Sundargarh district of, India, where groundwater serves as vital water resources. 360 groundwater samples were collected from various dug wells during pre-monsoon season of 2014–21 and analyzed for major ions, some important irrigation water quality indices along with pH, EC and TDS. Statistical evaluation of groundwater quality parameters was performed by physiochemical analysis with association of ArcGIS 10.4 for developing the spatial mapping. Furthermore, statistical and hydrochemical analysis was executed by exhibiting box plot generation, correlation study and hierarchical cluster analysis followed by categorization of water facies in , 1920; CGWB, 2013; Gad and Hattab, 2019’ has/have not been found in the reference list. Please add the corresponding reference(s) to the reference list.>Xlstat 2023, SPSS 23 and Diagrammes 6.1. Groundwater is mostly characterized as Na+-SO42- and deep meteoric percolation (DMP) type based on Base Exchange Indices with the dominance of Ca2+ and HCO3− as the major cation and anion respectively. Besides that, groundwater from 92%, 96%, 84%, 100%, 99%, 98%, 57%, 64%, 100%, 77%, 98% and 89% dug wells are found to be highly suitable for cultivation of major crops of this district depending on spatial variation of EC, TDS. Cl−, SAR, RSC, KR, PI, %Na, ESP, MAR, SSP and PS respectively. Groundwater facies are mostly categorized as Ca–HCO3 (60.8%) and C2–S1 (65.5%) type based on Piper and Wilcox diagram respectively. The dominant geochemical controlling factors are evaporation, reverse ion exchange and silicate weathering. Therefore, the objectives of this present research may provide necessary information to the regulatory boards and policy makers for efficient monitoring of groundwater quality and contaminated aquifers in Sundargarh district to make fit this crucial water resources for agricultural purpose.

In vivo Metabolic Sensing of Hyperpolarized [1‐13C]Pyruvate in Mice Using a Recyclable Perfluorinated Iridium Signal Amplification by Reversible Exchange Catalyst

AbstractReal‐time visualization of metabolic processes in vivo provides crucial insights into conditions like cancer and metabolic disorders. Metabolic magnetic resonance imaging (MRI), by amplifying the signal of pyruvate molecules through hyperpolarization, enables non‐invasive monitoring of metabolic fluxes, aiding in understanding disease progression and treatment response. Signal Amplification By Reversible Exchange (SABRE) presents a simpler, cost‐effective alternative to dissolution dynamic nuclear polarization, eliminating the need for expensive equipment and complex procedures. We present the first in vivo demonstration of metabolic sensing in a human pancreatic cancer xenograft model compared to healthy mice. A novel perfluorinated Iridium SABRE catalyst in a fluorinated solvent and methanol blend facilitated this breakthrough with a 1.2‐fold increase in [1‐13C]pyruvate SABRE hyperpolarization. The perfluorinated moiety allowed easy separation of the heavy‐metal‐containing catalyst from the hyperpolarized [1‐13C]pyruvate target. The perfluorinated catalyst exhibited recyclability, maintaining SABRE‐SHEATH activity through subsequent hyperpolarization cycles with minimal activity loss after the initial two cycles. Remarkably, the catalyst retained activity for at least 10 cycles, with a 3.3‐fold decrease in hyperpolarization potency. This proof‐of‐concept study encourages wider adoption of SABRE hyperpolarized [1‐13C]pyruvate MR for studying in vivo metabolism, aiding in diagnosing stages and monitoring treatment responses in cancer and other diseases.

In vivo Metabolic Sensing of Hyperpolarized [1-13C]Pyruvate in Mice Using a Recyclable Perfluorinated Iridium Signal Amplification by Reversible Exchange Catalyst.

Real-time visualization of metabolic processes in vivo provides crucial insights into conditions like cancer and metabolic disorders. Metabolic magnetic resonance imaging (MRI), by amplifying the signal of pyruvate molecules through hyperpolarization, enables non-invasive monitoring of metabolic fluxes, aiding in understanding disease progression and treatment response. Signal Amplification By Reversible Exchange (SABRE) presents a simpler, cost-effective alternative to dissolution dynamic nuclear polarization, eliminating the need for expensive equipment and complex procedures. We present the first in vivo demonstration of metabolic sensing in a human pancreatic cancer xenograft model compared to healthy mice. A novel perfluorinated Iridium SABRE catalyst in a fluorinated solvent and methanol blend facilitated this breakthrough with a 1.2-fold increase in [1-13C]pyruvate SABRE hyperpolarization. The perfluorinated moiety allowed easy separation of the heavy-metal-containing catalyst from the hyperpolarized [1-13C]pyruvate target. The perfluorinated catalyst exhibited recyclability, maintaining SABRE-SHEATH activity through subsequent hyperpolarization cycles with minimal activity loss after the initial two cycles. Remarkably, the catalyst retained activity for at least 10 cycles, with a 3.3-fold decrease in hyperpolarization potency. This proof-of-concept study encourages wider adoption of SABRE hyperpolarized [1-13C]pyruvate MR for studying in vivo metabolism, aiding in diagnosing stages and monitoring treatment responses in cancer and other diseases.

Modeling Ligand Exchange Kinetics in Iridium Complexes Catalyzing SABRE Nuclear Spin Hyperpolarization.

Large signal enhancements can be obtained for NMR analytes using the process of nuclear spin hyperpolarization. Organometallic complexes that bind parahydrogen can themselves become hyperpolarized. Moreover, if parahydrogen and a to-be-hyperpolarized analyte undergo chemical exchange with the organometallic complex it is possible to catalytically sensitize the detection of the analyte via hyperpolarization transfer through spin-spin coupling in this organometallic complex. This process is called Signal Amplification By Reversible Exchange (SABRE). Signal intensity gains of several orders of magnitude can thus be created for various compounds in seconds. The chemical exchange processes play a defining role in controlling the efficiency of SABRE because the lifetime of the complex must match the spin-spin couplings. Here, we show how analyte dissociation rates in the key model substrates pyridine (the simplest six-membered heterocycle), 4-aminopyridine (a drug), and nicotinamide (an essential vitamin biomolecule) can be examined. This is achieved for the most widely employed SABRE motif that is based on IrIMes-derived catalysts by 1H 1D and 2D exchange NMR spectroscopy techniques. Several kinetic models are evaluated for their accuracy and simplicity. By incorporating variable temperature analysis, the data yields key enthalpies and entropies of activation that are critical for understanding the underlying SABRE catalyst properties and subsequently optimizing behavior through rational chemical design. While several studies of chemical exchange in SABRE have been reported, this work also aims to establish a toolkit on how to quantify chemical exchange in SABRE and ensure that data can be compared reliably.

Reversible electrochemical pH modulation in thin-layer compartments using poly(aniline-co-o-aminophenol)

The analysis of many environmental and clinical samples requires the modification of the original pH, which is conventionally carried out by manual/automatic addition of acid, base, or buffering reagents. In the case of decentralized measurements, often, this approach is not plausible. Instead, reagentless alternatives, such as electrochemically activated in-situ pH adjustments, are suitable. Herein, we present a method for electrochemical, reversible pH modulation of thin-layer samples (<100 µm thickness) using the co-polymer poly(aniline-co-o-aminophenol) (PANOA). The PANOA’s electropolymerization strategy was optimized considering the proton exchange properties in the final material. Thus, limiting the maximum anodic potential to 0.85 V and with the number of cyclic scans being ≤150), the optimal pH modulation capabilities were observed. The reversible proton exchange properties of PANOA were quantified by monitoring the pH inside the thin-layer sample (volume of 0.6 µL), which was defined by a 3D-printed microfluidic cell and a pH-sensor placed in a face planar configuration to the PANOA film. A pH value in the range of 2–4 can repeatably be reached in the samples in 3 min, purely by an electrochemical means and without the addition of external reagents. The concept has been demonstrated to acidify samples at environmental pH (artificial samples and Seawater). The outcomes suggest that the family of polyaniline-co-polymers are interesting to be explored and utilized for electrochemically based pH modulation strategies, if careful considerations are taken regarding their electropolymerization process. Overall, such materials could contribute to the development of continuous, decentralized measuring devices requiring acidification for the formal detection of environmental markers, such as nutrients, carbon species speciation and alkalinity, among others.

Hydrochemical characterization and health risk assessment of different types of water bodies in Fenghuang Mountain Area, Northeast China.

Groundwater, as an essential resource, holds significant importance for human production and livelihoods. With the deterioration of the water environment, the issue of groundwater quality has become an urgent international concern. This study focused on the Fenghuang Mountain Area (FMA) and collected a total of 41 sets of samples including pore groundwater (PGW), fissure groundwater (FGW), karst groundwater(KGW), and river water(RW). Hydrochemical analysis methods were employed to identify the hydrochemical characteristics and controlling factors. The entropy-weighted water quality index (EWQI) and health risk assessment model were utilized to assess the groundwater quality and nitrate health risk, respectively. The results indicated that the dominant anion and cation in both groundwater and surface water in the FMA were HCO3- and Ca2+, respectively, with the main hydrochemical type being HCO3-Ca. Groundwater and surface water in the FMA were primarily controlled by rock weathering process, with ion concentrations influenced mainly by the dissolution of halite, sylvite, carbonates (calcite and dolomite), silicates, and gypsum, as well as by reverse anion exchange process. PGW was significantly affected by agricultural activities, with NO3- concentration closely related to human activities. The water quality of FGW was relatively good, with Class I and Class II water accounting for the highest proportion, reaching 84.62%. The high-value area of EWQI in PGW was influenced by human activities. The impact of nitrate health risk on children was significantly greater than on adults, with FGW having the lowest health risk and PGW having the highest health risk. The research results can provide important guarantees for the rational development and utilization of water resources in the FMA and the sustainable development of the economy in Northeast China.

Groundwater hydro-geochemical inferences and eXplainable Artificial Intelligence augmented groundwater quality prediction in arid and semi-arid segment of Rajasthan, India

Groundwater quality is a crucial aspect especially in the arid and semi-arid segments of the world due to its restricted availability. With increasing consumptions over time period, it is essential to ensure its quality by appraising complex hydro-geochemistry. In the present study, an attempt has been made to evaluate the groundwater hydro-geochemistry in the arid and semi-arid segment of Rajasthan, India and to fill the gap in understanding of groundwater quality by incorporating eXplainable Artificial Intelligence (XAI). 120 groundwater samples were collected during post monsoon season of 2022 and sixteen physico-chemical parameters were analyzed and corresponding inferences were drawn. The hydro-chemical facies indicated Na–Cl composition of groundwater with the dominance of evaporation. Majority of the samples showed reverse ion exchange process along with positive Saturation Index value of Calcite (CaCO3) and tendency towards leaching F− in the groundwater. Water Quality Index for drinking as well as irrigation purpose showed relatively better quality in the central segment than the marginal region. The SHAP values derived from the XGBoost model depicted fluoride (F-) as the primary feature influencing overall groundwater quality for drinking purposes, whereas the Sodium Absorption Ratio (SAR) emerged as the key predictor influencing overall groundwater quality for irrigation. The implication of proposed method signifies the importance of incorporating hydro-geochemical inferences with machine learning technique to understand the complex character of groundwater. Further, due to its robustness as well as cost-effectiveness, the application of the method would be helpful in policymaking to safeguard the groundwater resource in arid and semi-arid regions at global scale.

Exploring spatial and temporal symptoms of the freshwater salinization syndrome in a rural to urban watershed

The freshwater salinization syndrome (FSS), a concomitant watershed-scale increase in salinity, alkalinity, and major-cation and trace-metal concentrations, over recent decades, has been described for major rivers draining extensive urban areas, yet few studies have evaluated temporal and spatial FSS variations, or causal factors, at the subwatershed scale in mixed-use landscapes. This study examines the potential influence of land-use practices and wastewater treatment plant (WWTP) effluent on the export of major ions and trace metals from the mixed-use East Branch Brandywine Creek watershed in southeastern Pennsylvania, during the 2019 water year. Separate analysis of baseflow and stormflow subsets revealed similar correlations among land-use characteristics and streamwater chemistry. Positive associations between percent impervious surface cover, which ranged from 1.26 % to 21.9 % for the 13 sites sampled, and concentrations of Ca2+, Mg2+, Na+, and Cl− are consistent with road-salt driven reverse cation exchange and weathering of the built environment. The relative volume of upstream WWTP was correlated with Cu and Zn, which may be derived in part from corroded water-conveyance infrastructure; chloride to sulfate mass ratios (CSMR) ranged from ~6.3 to ~7.7× the 0.5 threshold indicating serious corrosivity potential. Observed exceedances of U.S. Environmental Protection Agency Na+ and Cl− drinking water and aquatic life criteria occurred in winter months. Finally, correlations between percent cultivated cropland and As and Pb concentrations may be explained by the persistence of agricultural pesticides that had been used historically. Study results contribute to the understanding of FSS solute origin, fate, and transport in mixed-use watersheds, particularly those in road salt-affected regions. Study results also emphasize the complexity of trace-metal source attribution and explore the potential for FSS solutes to affect human health, aquatic life, and infrastructure.

GROUNDWATER QUALITY ASSESSMENT FOR RESIDENTIAL AND IRRIGATION PURPOSES: A CASE STUDY OF FUTUK AND ITS ENVIRONS, NORTHERN BENUE TROUGH, NORTHEAST NIGERIA

This research assesses the suitability of groundwater quality in the region for residential and agricultural use. To evaluate the water quality for domestic purposes, 15 samples of groundwater were taken and tested for various physicochemical parameters including pH, electrical conductivity (EC), total dissolved solids (TDS), calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), sulfate (SO4), chloride (Cl), bicarbonate (HCO3), carbonate (CO3), and nitrate (NO3). The quality of irrigation water was evaluated using several parameters: permeability index (PI), sodium absorption ratio (SAR), total hardness (TH), residual sodium carbonate (RSC), and water quality index (WQI). Piper diagrams, Gibbs diagrams, and the chloro-alkaline index were used to determine groundwater facie classification and ion exchange mechanisms. When compared to the WHO 2011 standard, the physiochemical parameters are within the appropriate limits, with the exception of EC and NO3, which revealed excessive values in some samples. All of the measured parameters are suitable for irrigation activities. According to the Kelly index, there is just one sample that is inappropriate for irrigation. The predominant groundwater type in the area is calcium chloride, with sodium chloride constituting the second most common groundwater facies. The hydrochemical mechanism that regulates the local groundwater chemistry is reverse ion exchange. This indicates a positive index, resulting from the exchange of sodium (Na) and potassium (K) in the groundwater with calcium (Ca) and magnesium (Mg) in the aquifer components.

Deciphering hydrogeochemical evolution in the multilayered Ilhas-São Sebastião aquifer system, Brazil: Implications for groundwater resources management

This study examines the hydrogeochemical processes shaping groundwater quality in the Ilhas-São Sebastião aquifer system, situated at the interface of the Central and Southern Recôncavo basins in the densely populated area near the Brazilian metropolis Salvador. Analysis of 71 groundwater samples reveals distinctive hydrogeochemical compositions in aquifers. In the São Sebastião aquifer, alkalis (Na+ + K+) and strong acids (Cl− and SO42−) prevail. Furthermore, a moderate correlation of Na+–Cl-marks an evolution from Mg–Ca–HCO3 to Mg–Ca–Cl and Na–Cl facies. In contrast, the Ilhas aquifer displays a Na+>Ca2+>Mg2+>K+ relationship for cations and HCO3− > Cl− > SO42− > CO32− for anions and a recharge-discharge trajectory from the Mg–Ca–HCO3 to the Ca–Na–HCO3 facies. Additionally, it presents greater mineralization and dispersion of physicochemical parameters, especially around sub-basin depocenters. Its hydrogeochemical signature is characterized by robust correlations between TDS and EC, and between these parameters and SO42−, HCO3−, Ca2+, and Mg2+, complemented by moderate correlations of EC with Na+ and Cl−. Bivariate Gibbs diagrams and ionic ratios indicate silicate weathering and ion exchange as the primary geochemical processes controlling solute concentrations in both aquifers. However, in the Ilhas aquifer, a subordinate contribution from reverse ion exchange is indicated by weak (TDS–Na+, TDS–K+, Na+–Ca2+, K+–Ca2+) and positive TDS–Ca2+ and TDS–Mg2+ correlations. Conversely, negative chloroalkaline indices and the moderate Na+–Cl- correlation indicate that reverse ion exchange processes are mostly absent in the São Sebastião aquifer. Instead, both chloroalkaline imbalance reactions and silicate weathering contribute equally to the observed geochemical patterns. Groundwater geochemical signatures indicate recharge on flexural margins, active water-rock interaction in large depocenters, and mixing of hydrogeochemical facies between aquifer units. These insights contribute to a comprehensive understanding of groundwater evolution, crucial for effective water resource management in the region.

Transport of reactive contaminant in a wetland flow with the effects of reversible and irreversible reactions on the bed surface

Wetlands are crucial for maintaining biodiversity in ecosystems. The reversible chemical reactions can significantly affect the pollutant reduction capacity in wetland flow. The spatial transport of contaminants in wetlands is further complicated by phase exchange kinetics due to reversible reactions in the wetland bed. This paper provides an analytical solution for studying the multi-dimensional concentration distribution of solutes in wetland flow, considering both reversible and irreversible boundary reactions. Unlike previous one-dimensional studies (Jiang et al. (2022), Zhan et al. (2024)), our approach offers a comprehensive view of wetland contaminant transport, accounting for complex interactions between different phases and environmental factors. The solute may undergo reversible sorptive phase exchange between the immobile (wetland bed phase) and the mobile phase (fluid phase). Multi-scale homogenization methods are used to determine the dispersion coefficient, mean concentration, longitudinal and vertical real concentration distributions, rate of variation of vertical concentration distribution under the influence of vegetation force, and reversible and irreversible reactions at a stationary wetland bed. The effects of retention parameter (θ), Damkohler number (Da), vegetation effect (α), dispersion time (τ), and first-order irreversible boundary reaction (β′) on solute mixing are thoroughly analyzed. The study's analytical results are validated by numerical results obtained using the finite difference method with a Shishkin mesh, and other comparisons are made with the limiting case of Taylor dispersivity. Results show that an increase in Damkohler number and vegetation force weakens contaminant transport in wetland flow, but an increase in Da enhances contaminant concentration in the mobile phase. The presence of reversible phase exchange kinetics causes non-uniform vertical concentration variation across the wetland cross-section. Critical values where the multi-scale homogenization technique may fail are suggested as θ≤0.5 and Da≥1. The study's findings have potential applications to pollution control in wetlands.

Solvent Effects in Hyperpolarization of 15N Nuclei in [15N3]Metronidazole and [15N3]Nimorazole Antibiotics via SABRE‐SHEATH**

Metronidazole and nimorazole are antibiotics of a nitroimidazole group which also may be potentially utilized as hypoxia radiosensitizers for the treatment of cancerous tumors. Hyperpolarization of 15N nuclei in these compounds using SABRE‐SHEATH (Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei) approach provides dramatic enhancement of detection sensitivity of these analytes using magnetic resonance spectroscopy and imaging. Methanol‐d4 is conventionally employed as a solvent in SABRE hyperpolarization process. Herein, we investigate SABRE‐SHEATH hyperpolarization of isotopically labeled [15N3]metronidazole and [15N3]nimorazole in nondeuterated methanol and ethanol solvents. Optimization of such hyperpolarization parameters as polarization transfer magnetic field, temperature, parahydrogen flow rate and pressure allowed us to obtain an average 15N polarization of up to 7.2–7.4% for both substrates. The highest 15N polarizations were observed in methanol‐d4 for [15N3]metronidazole and in ethanol for [15N3]nimorazole. At a clinically relevant magnetic field of 1.4 T the 15N nuclei of these substrates possess long characteristic hyperpolarization lifetimes (T1) of ca. 1 to ca. 7 min. This study represents a major step toward SABRE in more biocompatible solvents, such as ethanol, and also paves the way for future utilization of these hyperpolarized nitroimidazoles as molecular contrast agents for MRI visualization of tumors.

Delineating the mechanisms controlling groundwater salinization using chemo-isotopic data and meta-heuristic clustering algorithms (case study: Saguenay-Lac-Saint-Jean region in the Canadian Shield, Quebec, Canada).

This study employed meta-heuristic clustering algorithms to determine the source and mechanism of groundwater salinization in Quebec's Saguenay-Lac-Saint-Jean (SLSJ) region, utilizing hydrogeochemical (38 inorganic constituents, including minor, major, and trace elements) and isotopic data (δ18O and δ2H). A total of 382 groundwater and precipitation samples were examined. Among the meta-heuristic algorithms, Artificial Bee Colony K-Means (ABCKM), Differential Evolution K-Means (DEKM), Harmony Search K-Means (HSKM), Particle Swarm Optimization K-Means (PSOKM), and Genetic K-Means (GKM) were used and investigated, and finally, PSOKM displayed superior performance and was chosen for further investigation. Analysis of diverse plots and hydrogeochemical modeling unveiled the impact of the Laflamme Sea invasion on groundwater chemistry. PSOKM1, PSOKM4, and PSOKM5 exhibited notable carbonate and silicate dissolution, with PSOKM4 demonstrating predominant carbonate dissolution. Cation exchange was identified through binary plots and Chloro Alkaline Index (CAI), with reverse cation exchange predominantly observed in most PSOKM4 samples, while positive values suggested direct cation exchange in other clusters. Spatial dynamics analysis using HFE-D indicated that salinization occurs as groundwater flows through crystalline bedrock aquifers, resulting in a transition from HCO3- dominance in PSOKM4 to Cl- dominance in the remaining clusters. Interaction between groundwater and rock along this path facilitated a transformation towards a Na-Cl end-member. The closely aligned stable isotopes with the Global Meteoric Water Line (GMWL) indicated a blend of meteoric water and seawater as the groundwater source.

Toward Next-Generation Molecular Imaging with a Clinical Low-Field (0.064 T) Point-of-Care MRI Scanner.

Low-field (LF) MRI promises soft-tissue imaging without the expensive, immobile magnets of clinical scanners but generally suffers from limited detection sensitivity and contrast. The sensitivity boost provided by hyperpolarization can thus be highly synergistic with LF MRI. Initial efforts to integrate a continuous-bubbling SABRE (signal amplification by reversible exchange) hyperpolarization setup with a portable, point-of-care 64 mT clinical MRI scanner are reported. Results from 1H SABRE MRI of pyrazine and nicotinamide are compared with those of benchtop NMR spectroscopy. Comparison with MRI signals from samples with known H2O/D2O ratios allowed quantification of the SABRE enhancements of imaged samples with various substrate concentrations (down to 3 mM). Respective limits of detection and quantification of 3.3 and 10.1 mM were determined with pyrazine 1H polarization (PH) enhancements of ∼1900 (PH ∼0.04%), supporting ongoing and envisioned efforts to realize SABRE-enabled MRI-based molecular imaging.

Synergic Origin and Evolution of TDS, Mg and Fluoride in Groundwater as Relative to Chronic Kidney Disease of Unknown Etiology (CKDu) in Sri Lanka

The rural population in the Dry Zone of Sri Lanka is largely affected by Chronic Kidney Disease of Unknown etiology (CKDu). According to the multidisciplinary research carried out so far, quality of groundwater is considered one of the possible causative factors for CKDu. Therefore, assessment of the quality of groundwater being used for drinking and its evolution mechanism is the key to identifying the linkage between CKDu and drinking water. This study aimed to perform a detailed investigation on groundwater sources using isotopic, chemical, and hydrogeological methods in the CKDu-endemic (site A) and the control area (sedimentary formation—site B) in the Malwathu Oya basin and the control areas in the Malala Oya basin (site C) selected for a systematic comparison. Our investigation shows that elevated levels of TDS, magnesium, and fluoride in the shallow groundwater affected by climatic, geochemical, and hydrogeological processes may contribute to the CKDu in the Dry Zone of Sri Lanka. All the groundwater samples analysed have exceeded the hardness threshold. Prominent Mg hardness proportion together with excess F− in the CKDu endemic area may produce nephrotoxic MgF2 complexes that may trigger renal damage. In contrast, NaF complexes in the CKDu control area leads to reduction of F− toxicity in the human body. Elevated F− and Mg2+ are found in site A, low F− and high Mg2+ in site B, and either combinations of low F− and low Mg2+, high F− and low Mg2+, or low F− with high Mg2+ in site C. TDS, hardness, Mg2+, Na+, and F− are formed with different mechanisms in the three selected areas. The primary process that regulates the evolution of groundwater types and contents in sites A and C is the weathering of silicates. Similarly, in site A, carbonate dissolution and reverse ion exchange are quite strong. Cation exchange and evaporite dissolution are more pronounced in site C. Shallow groundwaters are evapo-concentrated, hence their quality deteriorates more significantly than the deep groundwater in the CKDu endemic area. Dilution decreases the ion content in site A while evaporite dissolution increases it in site C after the rainy season. Evaporation and seawater mixing affect the quality of groundwater in site B. It is also found that a statistically significant difference exists in the F−/Na+, F−/Mg2+, and F−/Ca2+ between the endemic and control areas. Intensive rock weathering combined with desorption has added excess F− to the groundwater in site A, while cation exchange and fluorite dissolution are contributing factors in site C.

Dynamic covalent bonds of hemiacetals and acetals enables reprocessability and raw material recyclability of high performance cellulosic thermosetting resins

Despite covalent adaptable networks (CANs) imparting the reprocessing performance of crosslinked polymers, due to reversible bond exchange of the dynamic covalent bonds; it is still a huge challenge to design catalyst-free, fast reprocessing, controlled degradation and raw material recycling biomass base CANs. Here, for the first time, we prepared cellulose CANs base on hemiacetal and acetal bonds (ACCs) via aldehyde and hydroxyl reaction of the dialdehyde crosslinker with hydroxypropyl cellulose (HPC). By regulating the crosslink density and chemical structure of the crosslinked network, ACCs exhibit tunable thermal and mechanical properties. The crosslinked network structure of the ACCs benefits from the rapid bond exchange of the hemiacetal and acetal bonds at elevated temperatures, which allows for rapid stress relaxation and thus, superior reprocessing properties. In addition, it was found that the dynamic exchange of acetals in the ACCs is influenced by the chain length and flexibility of the crosslinker. Moreover, ACCs possess good degradation and cellulose feedstock recycling properties due to the acid sensitivity of the acetal bonds. This work provides an effective solution to the problems of resource waste caused by petroleum-based thermoset plastics.

Hydrogeochemical characteristics of shallow groundwater and salinization evaluation in the coastal aquifers of Cangzhou, China

To investigate the hydrogeochemical characteristics of shallow groundwater and evaluate groundwater salinization state in Cangzhou, China, two sampling campaigns have been conducted. In summer, 33 groundwater samples, 3 seawater samples and 5 river water samples were collected. In winter, 22 groundwater samples were collected. The hydrochemical type was determined by the Piper diagram. Evolution mechanisms of groundwater were analyzed by the Gibbs diagram. The trend of de-salinization or salinization of groundwater was determined by the hydrochemical facies evolution diagram. The groundwater salinization grade was evaluated by both the seawater intrusion groundwater quality index (GQISWI) and the attribute recognition model based on entropy weight (ARMEW). The Piper diagram shows that Na+ is the dominant cation and Cl- is the dominant anion in shallow groundwater, and the groundwater in this area is mainly of Cl-Na type followed by Cl-Ca·Mg type. The evaporation-crystallization process has significant influence on the evolution of saline groundwater. In summer, most brackish groundwater exhibit compositions of the freshening stage with direct cation exchange, and most saline groundwater is mainly at the seawater intrusion stage with reverse cation exchange. In winter, compared to the summer season, more groundwater samples in the middle of study area exhibit intrusion trend, and without obvious Na-HCO3 facies. In summer, values of GQISWI range from 20.47 to 75.38 with an average of 59.31. The GQISWI gradually increases from east to west, denoting the degree of groundwater salinization is alleviated from coast to inland. In winter, values of GQISWI range from 54.47 to 79.09 with an average of 66.00, slightly higher than that in summer. The proportion of no salinization (Grade I), minor salinization (Grade II) and serious salinization (Grade III) of groundwater samples in Cangzhou identified by ARMEW is 3.0%, 21.2% and 75.8% in summer, respectively. In winter, the proportion is 9.1% for Grade II and 90.9% for Grade III. The GQISWI index shows the largest area of Grade II, and ARMEW presents the largest area of Grade III in both seasons. Compared with GQISWI index, ARMEW model gives more conservative evaluation results of groundwater salinization. The results provide useful information on the groundwater salinization status for the local area, and help for the management of groundwater resources in Cangzhou.

Toward Decontamination in Coastal Regions: Groundwater Quality, Fluoride, Nitrate, and Human Health Risk Assessments within Multi-Aquifer Al-Hassa, Saudi Arabia

Contamination in coastal regions attributed to fluoride and nitrate cannot be disregarded, given the substantial environmental and public health issues they present worldwide. For effective decontamination, it is pivotal to identify regional pollution hotspots. This comprehensive study was performed to assess the spatial as well as indexical water quality, identify contamination sources, hotspots, and evaluate associated health risks pertaining to nitrate and fluoride in the Al-Hassa region, KSA. The physicochemical results revealed a pervasive pollution of the overall groundwater. The dominant water type was Na-Cl, indicating saltwater intrusion and reverse ion exchange impact. Spatiotemporal variations in physicochemical properties suggest diverse hydrochemical mechanisms, with geogenic factors primarily influencing groundwater chemistry. The groundwater pollution index varied between 0.8426 and 4.7172, classifying samples as moderately to very highly polluted. Similarly, the synthetic pollution index (in the range of 0.5021–4.0715) revealed that none of the samples had excellent water quality, with various degrees of pollution categories. Nitrate health quotient (HQ) values indicated chronic human health risks ranging from low to severe, with infants being the most vulnerable. Household use of nitrate-rich groundwater for showering and cleaning did not pose significant health risks. Fluoride HQ decreased with age, and children faced the highest risk of fluorosis. The hazard index (HI) yielded moderate- to high-risk values. Nitrate risks were 1.21 times higher than fluoride risks, as per average HI assessment. All samples fell into the vulnerable category based on the total hazard index (THI), with 88.89% classified as very high risk. This research provides valuable insights into groundwater quality, guiding water authorities, inhabitants, and researchers in identifying safe water sources, vulnerable regions, and human populations. The results highlight the need for appropriate treatment techniques and long-term coastal groundwater management plans.

15N Hyperpolarization of Metronidazole Antibiotic in Aqueous Media Using Phase-Separated Signal Amplification by Reversible Exchange with Parahydrogen.

Metronidazole is a prospective hyperpolarized MRI contrast agent with potential hypoxia sensing utility for applications in cancer, stroke, neurodegenerative diseases, etc. We demonstrate a pilot procedure for production of ∼30 mM hyperpolarized [15N3]metronidazole in aqueous media by using a phase-separated SABRE-SHEATH hyperpolarization method, with nitrogen-15 polarization exceeding 2.2% on all three 15N sites achieved in less than 2 min. The 15N polarization T1 of ∼12 min is reported for the 15NO2 group at the clinically relevant field of 1.4 T in the aqueous phase, demonstrating a remarkably long lifetime of the hyperpolarized state. The produced aqueous solution of [15N3]metronidazole that contained only ∼100 μM of residual Ir was deemed biocompatible via validation through the MTT colorimetric test for assessing cell metabolic activity using human embryotic kidney HEK293T cells. This low-cost and ultrafast hyperpolarization procedure represents a major advance for the production of a biocompatible HP [15N3]metronidazole (and potentially other hyperpolarized drugs) formulation for MRI sensing applications.

Molecular Simulation of Covalent Adaptable Networks and Vitrimers: A Review.

Covalent adaptable networks and vitrimers are novel polymers with dynamic reversible bond exchange reactions for crosslinks, enabling them to modulate their properties between those of thermoplastics and thermosets. They have been gathering interest as materials for their recycling and self-healing properties. In this review, we discuss different molecular simulation efforts that have been used over the last decade to investigate and understand the nanoscale and molecular behaviors of covalent adaptable networks and vitrimers. In particular, molecular dynamics, Monte Carlo, and a hybrid of molecular dynamics and Monte Carlo approaches have been used to model the dynamic bond exchange reaction, which is the main mechanism of interest since it controls both the mechanical and rheological behaviors. The molecular simulation techniques presented yield sufficient results to investigate the structure and dynamics as well as the mechanical and rheological responses of such dynamic networks. The benefits of each method have been highlighted. The use of other tools such as theoretical models and machine learning has been included. We noticed, amongst the most prominent results, that stress relaxes as the bond exchange reaction happens, and that at temperatures higher than the glass transition temperature, the self-healing properties are better since more bond BERs are observed. The lifetime of dynamic covalent crosslinks follows, at moderate to high temperatures, an Arrhenius-like temperature dependence. We note the modeling of certain properties like the melt viscosity with glass transition temperature and the topology freezing transition temperature according to a behavior ruled by either the Williams-Landel-Ferry equation or the Arrhenius equation. Discrepancies between the behavior in dissociative and associative covalent adaptable networks are discussed. We conclude by stating which material parameters and atomistic factors, at the nanoscale, have not yet been taken into account and are lacking in the current literature.