Search Results (16)

Mediterranean saline wetlands are significant ecological habitats defined by seasonal water availability and various biological communities, forming a unique ecotone that combines traits of both freshwater and marine environments. Moreover, they are regarded as notable natural and economic resources. Since the sustainable management of protected wetlands necessitates a multidisciplinary approach, the purpose of this study is to provide a comprehensive picture of the hydrological, hydrochemical, and ecological dynamics of a man-made groundwater dependent ecosystem (GDE) by combining remote sensing, hydrochemical data, geostatistical tools, and ecological indicators. The study area, called “Le Soglitelle”, is located in the Campania plain (Italy), which is close to the Domitian shoreline, covering a surface of 100 ha. The Normalized Difference Water Index (NDWI), a remote sensing-derived index sensitive to surface water presence, from Sentinel-2 was used to detect changes in the percentage of the wetland inundated area over time. Water samples were collected in four campaigns, and hydrochemical indexes were used to investigate the major hydrochemical seasonal processes occurring in the area. Geostatistical tools, such as principal component analysis (PCA) and independent component analysis (ICA), were used to identify the main hydrochemical processes. Moreover, faunal monitoring using waders was employed as an ecological indicator. Seasonal variation in the inundation area ranged from nearly 0% in summer to over 50% in winter, consistent with the severe climatic oscillations indicated by SPEI values. PCA and ICA explained over 78% of the total hydrochemical variability, confirming that the area’s geochemistry is mainly characterized by the saltwater sourced from the artesian wells that feed the wetland. The concentration of the major ions is regulated by two contrasting processes: evapoconcentration in summer and dilution and water mixing (between canals and ponds water) in winter. Cl⁻/Br⁻ molar ratio results corroborated this double seasonal trend. The base exchange index highlighted a salinization pathway for the wetland. Bird monitoring exhibited consistency with hydrochemical monitoring, as the seasonal distribution clearly reflects the dual behaviour of this area, which in turn augmented the biodiversity in this GDE. The integration of remote sensing data, multivariate geostatistical analysis, geochemical tools, and faunal indicators represents a novel interdisciplinary framework for assessing GDE seasonal dynamics, offering practical insights for wetland monitoring and management. Full article

The different adsorption applications require the development of sorbents with predetermined properties. One of the ways for fine tuning the adsorption properties of the material is using a binary salt system as an active sorbing component. The aim of this work is to conduct a precision investigation of thermodynamic data on the sorption equilibrium of composite sorbents “(CaCl₂ + CaBr₂) confined to the silica gel pores” with water vapour. The isotherms and isosteres (at an uptake of N = 1.5 and 3.6 mole/mole) of water sorption on the composites were measured. It was shown that at a fixed temperature, the composites based on solid solutions of CaCl₂ in CaBr₂ form complexes with water at a pressure that is dependent on the CaCl₂/CaBr₂ molar ratio. The isosteric enthalpy and entropy of water sorption (ΔH = −48 ± 3 kJ/mol ΔS = −108 ± 2 J/(mol·K)) at N = 3.6 mole/mole were midway between the same parameters for composites on the base of the pure salts CaCl₂ and CaBr₂. The novelty of this work is in the design of sorbents optimized for air conditioning in hot climates and air drying cycles. It was shown that the use of the binary CaCl₂ + CaBr₂ system confined to the silica pores can be an effective tool for designing innovative materials with predetermined properties. Full article

Free radicals are highly reactive and unstable particles that are produced in the body during normal metabolic functions or by exposure to toxins in the environment, such as tobacco smoke and ultraviolet light. Free radicals have a lifespan of only a fraction of a second, but during that time can damage DNA, sometimes resulting in mutations that can lead to various diseases, including heart disease and cancer. The antioxidants can neutralize unstable particles, reducing the risk of damage. So the design of new substances as a potent antioxidant is an actual problem in the modern world. For this purpose, it was synthesized coordination compounds of Cu(II) and Ni(II) with 1-(morpholin-4-yl)propane-1,2-dione 4-allylthiosemicarbazone (HL). HL was obtained by the condensation reaction between 1-(morpholin-4-yl)propane-1,2-dione and 4-allylthiosemicarbazide in an ethanol solution. Its structure and purity were proven using ¹H and ¹³C NMR spectroscopy. The coordination compounds were synthesized by the interaction of HL with metal salts in a 1:1 and 1:2 molar ratio. The composition of these compounds was determined using elemental analysis: Cu(L)X (X=Cl⁻, Br⁻, NO₃⁻), Ni(HL)₂(NO₃)_2, Ni(L)Cl. These complexes were studied by molar conductivity, IR spectra, and X-ray diffraction. The study of antioxidant activity by the ABTS^•+ method showed that the most active compound is Ni(HL)₂(NO₃)₂. Its IC₅₀ value toward ABTS^•+ is 19.6 µM, so it is 1.7 times more active than Trolox, a water-soluble antioxidant, which is used in medicine. Full article

The chemical characterization of the Ghis-Nekor groundwater has become a concern of many researchers in Morocco. It is a crucial indicator for the environment situation and the socioeconomic development of this Moroccan region. Indeed, it helps decisionmakers carry out conscious and sustainable management. For this reason, 20 samples of the Ghis-Nekor aquifer were examined in terms of physicochemical parameters such as pH, temperature, electrical conductivity (EC), and total alkalinity (Alk), major cations–anions (Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃⁻, Cl⁻, ${\mathrm{SO}}_4^{2-}$, ${\mathrm{NO}}_3^{-}$, and TDS), isotopic elements (δ¹⁸O, δ²H, and δ¹³C), and concentrations of Br and Sr anions in 2020. Furthermore, spatial data analysis with a geographic information system (GIS) using the ArcGis software (Redlands, California, USA). Indeed, static maps show significant water quality information that helps characterize the groundwater of the study area. The spatial analysis by the GIS indicates that except the EC (from 2630 to 6950 mS/cm), all the physical parameters showed standard concentration values in most of the samples. A significant concentration above the Moroccan norm of groundwater quality for sodium (Na⁺) from 264.3 to 1500 mg/L, chlorides (Cl⁻) concentrations from 408.3 to 1510 mg/L, ${\mathrm{SO}}_4^{2-}$ from 313.1 to 999.2 mg/L, and bicarbonate (HCO₃⁻) from 283.7 to 679.8 mg/L was observed, while all the points exceeded the recommended standards norm for ${\mathrm{SO}}_4^{2-}$. Most of the points met the potability standards for potassium (K⁺). In terms of the isotopic elements, the concentration values of δ¹⁸O were from −3.92‰ to –5.60‰, while the δ²H concentration values varied between −28.67‰ and −39.99‰. The analysis revealed values of carbon isotope δ¹³C ranging between −3.15‰ and −8.61‰, thus suggesting that the origin of the carbon is mineral, mainly deriving from calcite dissolution. The analysis of the bromide and strontium contents made it possible to discriminate the origin of the salinity anomalies. The Cl/Br, Br/Cl, and Sr/Ca molar ratios distinguished the areas of influence of geological setting (saliferous facies outcrops) or anthropogenic effect (wastewater). The results of the analysis shed light on factors of contamination, which are as follows: urban zones (Imzourene, Ait Youssef, and Souani) and agricultural activities. Therefore, the use of these waters could pose a risk to the health of humans and animals. Similarly, the GIS is a practical and effective tool for the Ghis-Nekor groundwater quality diagnostics and could help decisionmakers establish solutions. Full article

The resolution of halogenated mandelic acids using levetiracetam (LEV) as a resolving agent via forming enantiospecific co-crystal was presented. Five halogenated mandelic acids, 2-chloromandelic acid (2-ClMA), 3-chloromandelic acid (3-ClMA), 4-chloromandelic acid (4-ClMA), 4-bromomandelic acid (4-BrMA), and 4-fluoromandelic acid (4-FMA), were selected as racemic compounds. The effects of the equilibrium time, molar ratio of the resolving agent to racemate, amount of solvent, and crystallization temperature on resolution performance were investigated. Under the optimal conditions, the resolution efficiency reached up to 94% and the enantiomeric excess (%e.e.) of (R)-3-chloromandelic acid was 63%e.e. All five halogenated mandelic acids of interest in this study can be successfully separated by LEV via forming enantiospecific co-crystal, but the resolution performance is significantly different. The results showed that LEV selectively co-crystallized with S enantiomers of 2-ClMA, 3-ClMA, 4-ClMA, and 4-BrMA, while it co-crystallized with R enantiomers of 4-FMA. This indicates that the position and type of substituents of racemic compounds not only affect the co-crystal configuration, but also greatly affect the efficiency of co-crystal resolution. Full article

An experimental and a theoretical study on the so far less investigated Cu(I) salt-catalyzed Hirao reaction of iodobenzene and diarylphosphine oxides (DAPOs) revealed that Cu(I)Br or Cu(I)Cl is the most efficient catalyst under microwave irradiation. The optimum conditions included 165 °C and a 1:2 molar ratio for DAPOs and triethylamine. The possible ligations of Cu(I) were studied in detail. Bisligated P---Cu(I)---P (A), P---Cu(I)---N (B) and N---Cu(I)---N (C) complexes were considered as the catalysts. Calculations on the mechanism suggested that complexes A and B may catalyze the P–C coupling, but the latter one is more advantageous both according to experiments and calculations pointing out the Cu(I) → Cu(III) conversion in the oxidative addition step. The P–C coupling cannot take place with PhBr, as in this case, the catalyst complex cannot be regenerated. Full article

In this study, the ion concentrations (K⁺, Na⁺, Ca²⁺, Mg²⁺, Cl⁻, SO₄²⁻, Br⁻, NO₃⁻, and B³⁺) and boron isotope compositions (δ¹¹B) of 34 halite and brines samples from the Neoproterozoic Salt Range Formation, Punjab, Pakistan were studied. Relation among B³⁺ vs. Mg²⁺, B³⁺ vs. SO₄²⁻, δ¹¹B vs. B³⁺, and δ¹¹B vs K⁺ were observed, they indicated that these elements originate from multiple sources and the end members were identified as seawater, B desorption from clays, and meteoric precipitation. Halite samples of the area under study displayed a Na-HCO₃-type to Ca-Cl type sedimentary basin of deposition, on δ¹¹B vs. 1/B plot. Molar ratios of B/Cl vs. δ¹¹B revealed the addition of B in some of the studied samples from desorption of clay minerals. This type of diagenetic desorption of B from clays is the consequence of a stress driven mechanism, generated in the proximity of a decollement zone. Results confirm that the number of B stable isotopes that fractionate between the brine and the halite is low. The halite δ¹¹B from the Salt Range Formation vary from +2.1 to +24.4‰, compared to +17.3 to +26.1‰ in the salt pool brines, and suggest that boron isotope compositions are controlled by the δ¹¹B of the B sources. The positive relationship between the boron content and the corresponding δ¹¹B indicates a higher salinity and drier paleoclimate conditions during the formation process, associated with a high evaporation rate in the Late Neoproterozoic time. Presence of elevated δ¹¹B in the present study, demonstrate compatibility with other marine basins of the world, arising the need for further investigations to better characterize the ¹¹B-enriching processes. Full article

Saltwater contamination seriously affects water quality and land productivity of reclaimed farmlands along the Venice Lagoon, Italy. To characterize the hydrogeochemical dynamics involved in this phenomenon, a three-year study was carried out in an experimental field located at the southern margin of the Venice Lagoon. Soil matric potential, quality of soil pore water and groundwater, and soil physical and chemical properties were monitored at five monitoring stations. Relationships between Cl⁻, Na⁺, Mg^2+, Ca²⁺, K⁺, SO₄²⁻, Br⁻ ionic concentrations, and electrical conductivity of the water samples with the soil characteristics (e.g., texture, exchangeable cations) were investigated. Soil water flux direction was calculated and related to ion concentrations. Moreover, specific molar ratios (Mg/Ca, Na/Cl, Cl/Br, and SO₄/Cl) were calculated to identify the main drivers affecting salinity in the field. The study confirmed that the experimental site was strongly affected by soil and water salinity, and two major contamination dynamics were identified. The first one was mainly driven by seawater intrusion from the near lagoon and salty watercourses, while the second was derived by the interactions between the peaty soil and salts that were originally in place, since the area was only reclaimed a few decades ago. The latter highlighted the potentiality of the experimental field to become an acidic sulfate environment. Ionic ratios were implemented and proved to be an important tool for the identification of salinity origin. Full article

Hydrogeochemical analyses were carried out to identify geochemical processes occurring in the low-lying coastal aquifer of Ravenna, North Adriatic Sea (Italy). The area is characterized by a complex coexistence of several environments: coastal dunes, paleodunes, pine forests, freshwater wetlands, rivers, brackish lagoons, gravel pit lakes, reclaimed lands, agricultural fields and industrial areas. Water quality is of primary importance for the sustainability of these, areas and a full understanding of geochemical processing is fundamental for their management. A total of 104 water samples was collected from groundwater wells and surface water bodies, and analyzed for the major and trace elements (TEs). Field measurements of chemical-physical parameters were carried out by a multiparameter device XS PCD650; major elements were analyzed following the Italian National Environmental Agency standards (APAT-IRSA 2003), while TEs were analyzed by ICP-AES/ICP-MS. The major findings include: organic matter degradation in salinized and anoxic conditions; TEs concentrations related to water–sediment interactions, i.e., adsorption, ion exchange, redox reactions, mineral dissolution and precipitation; anthropogenic contamination from pesticides and fertilizers use; pollution from industrial district; TEs enrichments and depletion due to groundwater salinization and water management practices; comparison of TEs concentrations with respect to national and international thresholds. The findings can provide water managers and local authorities with a comprehensive framework of the coastal water hydrochemistry, allowing a better understanding of the effects of current management practices and the design of mitigation measures to reduce water resource deterioration in the studied coastal area. Full article

The CsPbX₃ nanocrystals (NCs) with X = I, Br, Cl, or the mixture of Br:I and Br:Cl in a 1:1 ratio were synthesized and characterized by TEM, DLS, and XRD. Recrystallization of the small luminescent NCs in the metastable cubic phase into bigger orthorhombic nanocrystals was monitored by XRD and identified as the main cause of the nanocolloid coagulation. The recrystallization also leads to a decrease in the photoluminescence quantum yield (QY) of the colloidal solution and shortening of the emission lifetime. The two-photon absorption cross-section σ₂ values calculated from femtosecond Z-scan measurements were compared with those obtained based on the two-photon excited emission technique. These two techniques were shown to be equivalent with the cross-section values calculated per molar mass of CsPbX₃ perovskite being in the range of 10–200 GM depending on the halide anions X⁻. The σ₂ values recalculated for the mole of the NCs were in the range of 10⁴–10⁵ GM, which is in good agreement with values previously reported elsewhere and the σ₂/M parameter was in the range of 0.01 to 0.33. This study shows the perovskite NCs to be a good nonlinear material with the third-order nonlinear optical susceptibility χ⁽³⁾ of the NCs on the order of 10⁻¹¹ esu. Full article

The effect of seawater on the groundwater in archipelago of South Korea where it has rarely been investigated was analyzed by examining the hydrogeochemical characteristics. A total of 74 groundwater samples were classified by water quality type and Cl⁻/HCO₃⁻ molar ratio. First, 36 samples of the Ca–Cl type and 32 samples of the Na–Cl type (accounting for 91.9% of the total) were considered to have been influenced by seawater. When the samples had been classified based on the Cl⁻/HCO₃⁻ molar ratio, the samples with a Cl⁻/HCO₃⁻ molar ratio of 2.8 or higher (indicating that seawater had highly influenced the groundwater) accounted for 40 out of 74 samples. This confirms that the groundwater in the study area had been affected by seawater. When quantitatively determining the influence of seawater on the groundwater, the seawater mixing ratios using either Cl or Br ion were found to be almost the same. In the case of Cl ion, the mixing ratio was in the range of 0–10.4% (average of 1.0%), while when using Br ion, the mixing ratio was in the range of 0–7.6% (average of 0.6%). From a principal component analysis, it can be seen that the influence of seawater occupied the first component of 54.1% and it is evident that the samples with a large mixing ratio of seawater were from regions where seawater has a large influence. The ion-exchange reaction was proceeded by calculating the ionic delta value to indicate the seawater intrusion and cation exchange, and specific trends of the ions participating in the geochemical reaction related to the seawater mixing ratio are reported herein. It was found that the ionic delta value of each ion had a mixing ratio and specific tendency according to the change in mixing ratio before the constant value of the seawater mixing ratio saturated with Na²⁺. Our results show that it can be possible to grasp the contribution of the geochemical reactions of each ion to the seawater mixing ratio. Full article

Reactions of [VCl₃(thf)₃] or VBr₃ with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) in a 1:1 molar ratio in air under solventothermal conditions has afforded polymeric oxidovanadium(IV) four complexes 1–4 of a general formula [VO(L)X₂]_n (L = bpy, phen and X = Cl, Br). Monomeric complex [VO(DMF)(phen)Br₂] (4a) has been obtained by the treatment of compound 4 with DMF. The complexes were characterized by IR spectroscopy and elemental analysis. The crystal structures of 3 and 4a were determined by an X-ray diffraction (XRD) analysis. The {VOBr₂(bpy)} fragments in 3 form infinite chains due to the V = O…V interactions. The vanadium atom has a distorted octahedral coordination environment. Complexes 1–4 have been tested as catalysts in the homogeneous oxidation of alkanes (to produce corresponding alkyl hydroperoxides which can be easily reduced to alcohols by PPh₃) and alcohols (to corresponding ketones) with H₂O₂ or tert-butyl hydroperoxide in MeCN. Compound 1 exhibited the highest activity. The mechanism of alkane oxidation was established using experimental selectivity and kinetic data and theoretical DFT calculations. The mechanism is of the Fenton type involving the generation of HO^• radicals. Full article

High aspect ratio silver nanowires (AgNWs) with ultra-long length and thin diameter were synthesized through bromine ion (Br⁻)-assisted one-step synthesis method. The bromine ions were used as pivotal passivating agent. When the molar ratio of Br⁻/Cl⁻ was 1:4, the average diameter of AgNWs was as low as ~40 nm, the average length was as high as ~120 μm, and the aspect ratio reached 2500. Networks of AgNWs were fabricated using as-prepared high-quality AgNWs as conducting material and hydroxyethyl cellulose (HEC) as the adhesive polymer. As a result, a low sheet resistance down to ~3.5 Ω sq⁻¹ was achieved with a concomitant transmittance of 88.20% and a haze of 4.12%. The ultra-low sheet resistance of conductive film was attributed to the long and thin AgNWs being able to form a more effective network. The adhesion of the AgNWs to the substrate was 0/5B (ISO/ASTM). The insights given in this paper provide the key guidelines for bromine ion-assisted synthesis of long and thin AgNWs, and further designing low-resistance AgNW-based conductive film for optoelectronic devices. Full article

CH₃NH₃PbI_3-xCl_x species were fabricated as light-absorbing layers for perovskite solar cells (PSCs), by employing NH₄I, NH₄Br, and NH₄Cl as additives via annealing at 100 °C for different times. Solutions containing CH₃NH₃I, PbI₂, and PbCl₂ (4:1:1 molar ratio) in N,N-dimethylformamide were used to prepare perovskites with NH₄I, NH₄Br, and NH₄Cl as additives, at concentrations of 0.1 M and 0.3 M. The additives helped increase the grain size and reduce pinholes in the perovskite films, as confirmed by field-emission scanning electron microscopy. The X-ray diffraction profiles of CH₃NH₃PbI_3-xCl_x clearly showed peaks at 14° and 28° for the samples with additives, indicative of crystallinity. The best PSC performance with a power conversion efficiency of 9.13%, was achieved using 0.1 M NH₄I by annealing for 5 min, whereas the power conversion efficiency of the perovskite solar cells without additives was 5.40%. Full article

Fabrication and characterization of CH₃NH₃PbI_3−x−yBr_xCl_y perovskite solar cells using mesoporous TiO₂ as electron transporting layer and 2,2′,7,7′-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9′-spirobifluorene as a hole-transporting layer (HTL) were performed. The purpose of the present study is to investigate role of halogen doping using iodine (I), bromine (Br) and chlorine (Cl) compounds as dopant on the photovoltaic performance and microstructures of CH₃NH₃PbI_3−x−yBr_xCl_y perovskite solar cells. The X-ray diffraction identified a slight decrease of crystal spacing in the perovskite crystal structure doped with a small amount of I, Br, and Cl in the perovskite compounds. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) showed the perovskite crystal behavior depended on molar ratio of halogen of Pb, I, Br and Cl. Incorporation of the halogen doping into the perovskite crystal structure improved photo generation, carrier diffusion without carrier recombination in the perovskite layer and optimization of electronic structure related with the photovoltaic parameters of open-circuit voltage, short-circuit current density and conversion efficiency. The energy diagram and photovoltaic mechanisms of the perovskite solar cells were discussed in the context of the experimental results. Full article