Natural Water Research Articles

Silica Functionalized Almond Gum Derivatives for Integrated Flocculation Cycles for Natural and Synthetic Water Systems

Silica Functionalized Almond Gum Derivatives for Integrated Flocculation Cycles for Natural and Synthetic Water Systems

Sex-specific phosphorus acquisition strategies and cycling in dioecious Populus euphratica forests along a natural water availability gradient.

Soil phosphorus (P) availability affects plant growth and distribution. However, it is still unknown how sex-specific variation in functional traits affects plants' P acquisition and soil P transformation. On wet sites, female poplars had a greater specific root length (SRL), and a higher diversity of arbuscular mycorrhizal fungi (AMF) and phosphate-solubilizing bacteria (PSB). Male poplars living on wet sites increased the abundance of AMF and PSB communities and enhanced moderately labile and highly resistant organic P mineralisation via increased phosphatase activity. In contrast, on the dry site, the abundance and diversity of AMF and PSB communities increased in females, enhancing moderately labile and highly resistant organic P mineralisation via elevating phosphatase activities. Males maintained greater SRL and promoted Ca-P mobilisation via the release of root carboxylic acids and rhizosphere acidification on the dry site. The AMF community diversity followed a similar pattern as that of the PSB community when altering the P availability of different-sex plants. Our results indicated that organic P and Ca-P are the major sources of plant-available P in natural P. euphratica forests. Seasonal shifts and geographic locations affected the share of organic and inorganic P pools, and AMF and PSB diversities, ultimately altering sex-specific P acquisition strategies of plants.

Coumarin-Modified Starch Fluorescent Nanoparticles as Sensor of Fe3+ and Zn2+ ions Utilizing Dynamic Quenching and Chelation Mechanisms.

Zinc and iron are two essential trace minerals that play a pivotal role in maintaining optimal health and well-being in the human body. Despite being required in relatively small quantities, their significance can be understated as they participate in a wide array of critical physiological processes such as oxygen transport, DNA synthesis, controlling nutrient availability, etc. Understanding the distribution and behavior of these ions in natural water bodies is essential for assessing water quality, studying ecological processes, and managing environmental impacts. In this study, we have developed a dual fluorescence probe using starch which was functionalized with coumarin derivatives, for efficient detection of Fe3+ and Zn2+ ions. This structure led a self-assembled starch/coumarin (SC) fluorescent nanoparticles with strong fluorescence intensity under ultraviolet light (365nm). The quenching effect of Fe3+ on the SC fluorescent probe enabled efficient specific detection of Fe3+. Furthermore, Zn2+ ions increased fluorescence intensity of coumarin compounds (λemission = 459). This phenomenon occurs when the coumarin compound forms a complex or interacts with the zinc ion, resulting in enhanced fluorescence emission. In summary, the developed fluorescent probe offered a promising approach for sensitive and specific detection of iron and zinc ions in aqueous solutions.

High photoreactivity of chromophoric dissolved organic matter derived from Ulva prolifera and Sargassum

The epipelagic macroalgae of Ulva prolifera and Sargassum are the primary contributors to widespread seaweed tides globally. Both ocean plants release large amounts of chromophoric dissolved organic matter (CDOM) into the surrounding seawater. The photochemical reactivity of this CDOM, however, has not been adequately addressed. In this study, we extracted CDOM from Ulva prolifera and Sargassum, examined their ultraviolet (UV)-visible absorption characteristics, and quantified their broadband apparent quantum yields (AQY) of absorbance photobleaching and photomineralization (in terms of CO2, CO, and CH4 photoproduction). On a per-unit-weight basis, Sargassum leached 3.5 times more CDOM than did Ulva prolifera in terms of the absorption coefficient averaged over 254–500 nm. Both Ulva prolifera and Sargassum CDOM were characterized by quasi-exponential decay absorption spectra, with Sargassum CDOM exhibiting a distinct shoulder over 310–350 nm suggestive of mycosporine amino acids. The Sargassum CDOM had a higher photobleaching AQY but lower photomineralization AQYs compared to Ulva prolifera CDOM. The photobleaching and photomineralization AQYs of both macroalgal CDOM are, however, orders of magnitude higher than those of CDOM in various natural waters. Potential photoproduction rates of CO2 and CO from the Ulva prolifera CDOM and Sargassum CDOM during the bloom periods are several times to orders of magnitude higher than the air-sea fluxes of these gases in the absence of the macroalgae. This study demonstrates that CDOM released by Ulva prolifera and Sargassum is extremely prone to photobleaching and photomineralization, rendering floating mats of these plants in oceans as potential “hotspots” of greenhouse gas emissions to the atmosphere. This photochemical feedback should be considered when assessing ocean afforestation as a CO2 removal approach to mitigate climate warming.

Evaluation of Hepatic Glucose and Palmitic Acid Metabolism in Rodents on High‐Fat Diet Using Deuterium Metabolic Imaging

BackgroundOne of the main features of several metabolic disorders is dysregulation of hepatic glucose and lipid metabolism. Deuterium metabolic imaging (DMI) allows for assessing the uptake and breakdown of 2H‐labeled substrates, giving specific insight into nutrient processing in healthy and diseased organs. Thus, DMI could be a useful approach for analyzing the differences in liver metabolism of healthy and diseased subjects to gain a deeper understanding of the alterations related to metabolic disorders.PurposeEvaluating the feasibility of DMI as a tool for the assessment of metabolic differences in rodents with healthy and fatty livers (FLs).Study TypeAnimal Model.Population18 male Sprague Dawley rats on standard (SD, n = 9, healthy) and high‐fat diet (HFD, n = 9, FL disease).Field Strength/SequencePhase‐encoded 1D pulse‐acquire sequence and anatomy co‐registered phase‐encoded 3D pulse‐acquire chemical shift imaging for 2H at 9.4T.AssessmentLocalized and nonlocalized liver spectroscopy was applied at eight time points over 104 minutes post injection. The obtained spectra were preprocessed and quantified using jMRUI (v7.0) and the resulting amplitudes translated to absolute concentration (mM) according to the 2H natural abundance water peak.Statistical TestsTwo‐way repeated measures ANOVA were employed to assess between‐group differences, with statistical significance at P < 0.05.ResultsDMI measurements demonstrated no significant difference (P = 0.98) in the uptake of [6,6′‐2H2]glucose between healthy and impaired animals (AUCSD = 1966.0 ± 151.5 mM ‐ minutes vs. AUCHFD = 2027.0 ± 167.6 mM·minutes). In the diseased group, the intrahepatic uptake of palmitic acid d‐31 was higher (AUCHFD = 57.4 ± 17.0 mM·minutes, AUCSD = 33.3 ± 10.5 mM·minutes), but without statistical significance owing to substantial in‐group variation (P = 0.73).Data ConclusionDMI revealed higher concentrations of palmitic acid in rats with FL disease and no difference in hepatic glucose concentration between healthy and impaired animals. Thus, DMI appears to be a useful tool for evaluating metabolism in rodents with FL disease.Level of Evidence2Technical EfficacyStage 3.

Zn-CD@Eu Ratiometric Fluorescent Probe for the Detection of Dipicolinic Acid, Uric Acid, and Ex Vivo Uric Acid Imaging.

Development of reliable methods for the detection of potential biomarkers is of the utmost importance for an early diagnosis of critical diseases and disorders. In this study, a novel lanthanide-functionalized carbon dot-based fluorescent probe Zn-CD@Eu is reported for the ratiometric detection of dipicolinic acid (DPA) and uric acid (UA). The Zn-CD@Eu nanoprobe was obtained from a simple room-temperature reaction of zinc-doped carbon dots (Zn-CD) and the EDTA-Eu lanthanide complex. Under optimal conditions, a good linear response was obtained for DPA in two concentration ranges of 0-55 and 55-100 μM with a limit of detection of 0.53 and 2.2 μM respectively, which is significantly below the infectious dosage of anthrax (∼55 μM). Furthermore, the Zn-CD@Eu/DPA system was employed for the detection of UA with a detection limit of 0.36 μM in the linear range of 0-100 μM. The fluorescent probe was successfully implemented for determining DPA and UA in human blood serum, sweat, and natural water bodies with considerable recovery rates. In addition, the potential of the nanoprobe for ex vivo visualization of UA was demonstrated in fruit fly (Drosophila melanogaster) as a model organism.

Bifunctional titanium boron-phosphate glass containing Ag nanoparticles for the detection and photocatalysis of organic compounds

This study delves into the structural characterization of a composition comprising Ag-NPs/phosphate plasmonic glass. Additionally, it explores two applications aimed at addressing one of the numerous challenges facing the modern world. The continuous technological progress of society has led to the proliferation of chemicals in natural water sources, posing a significant threat to ecosystems due to their low concentrations, making them difficult to detect and remove. The findings presented herein showcase the potential of Ag-NPs/sodium/titanium-phosphate glasses as a promising solution for detecting and degrading organic pollutants in freshwater. To achieve this, Ag nanoparticles were integrated into the glass surface via the ion exchange method, followed by thermal treatment. Subsequently, the detection of crystal violet solutions, applied dropwise onto the sample surface, was successfully carried out using surface-enhanced Raman spectroscopy, reaching a detection limit as low as 10−6 M. Furthermore, the glass composition demonstrated heterogeneous photocatalytic properties for UV degradation of methylene blue, with enhanced photoactivity attributed to the presence of silver nanoparticles, resulting in a 111 % increase in the kinetic constant compared to unmodified glass. Thus, these newly developed Ag-NPs sodium titanium-phosphate glasses exhibit remarkable bifunctional capabilities, offering improved optical detection and efficient photodegradation of organic molecules.

Exploring the Impact of Campus Landscape Visual Elements Combination on Short-Term Stress Relief among College Students: A Case from China

Although the effect of campus landscape space on stress relief among college students has been confirmed, few existing studies have considered the impact on stress recovery from the perspective of factor combination, and the key visual elements and the most effective combination of visual elements to relieve stress are still unclear. This study attempts to conduct a natural experiment within Chinese campuses, measuring physiological indicators of stress such as heart rate (HR), frequency domain index of heart rate variability (LF/HF), skin conductance level (SCL), skin temperature (SKT), and respiratory rate (RESP) using physiological instruments. It explored the effects of visual elements and their combinations in campus landscape spaces on short-term stress relief among college students through semantic segmentation, multifactorial analysis of variance, and post hoc multiple comparison methods. Research results demonstrate that the presence of water elements in the field of vision can effectively improve the stress relief effects of landscape spaces. Reasonable combinations of natural landscape elements and artificial landscape elements in the design can also effectively promote stress relief among students. Building facade area and sky area, water area and sky area, and plant species and pavement area are three combinations of factors with the strongest interactive effects. “Natural water scenery” and “exquisite artificial” are two campus landscape design patterns most conducive to short-term stress relief.

Largely enhanced Piezoelectric-Fenton capability in rationally designed PVDF/Fe2O3 flexible porous film

The burgeoning piezocatalysts have attracted huge attentions due to their ability to convert natural mechanical energy to degrade water pollutants. However, traditional powder-based piezocatalysts still face an inevitable bottleneck of the secondary pollution because of the diffusion of nanoparticles during the piezocatalysis process. In this work, novel porous polymer-based composite films combining Fenton fillers (α-Fe2O3) and ferroelectric polymer (polyvinylidene fluoride, PVDF) are prepared by rationally designed solution-casted method with a sacrificial “hard template” of table salt. The as-prepared porous PVDF/Fe2O3 film exhibits superior decomposition efficiency of organic pollutants under ultrasonication. Particularly, the easily recyclable porous film with optimized composition and spatial structure offers an ultrahigh rate constant of 0.0498 min−1, which means it can degrade 94.8% rhodamine B (RhB) in 60 min, exceeding that of most reported polymer-based piezocatalysts. Additionally, it has a comprehensive decomposition effect on dyes, antibiotics and natural water with a good cycle performance. The outstanding degradation performance is attributed to the massive hydroxyl radical generated from the enhanced Piezoelectric-Fenton effect, which is ascribed to the synergistic effect of improved piezoelectricity in PVDF, enhanced hydrophilicity and optimized spatial structures in the porous composite films.

CHIRAL SWITCHING CONTROL OF PHARMACEUTICAL SUBSTANCES

Objective: The aim of this study was to demonstrate that chiral switching should be recognized as a widespread phenomenon that extends beyond the production of pure enantiomeric drugs. Methods: To investigate the optical activity of substances from various chemical classes, enantiomers of chiral compounds (Sigma-Aldrich, USA) were chosen: valine and its racemic form (D-valine, L-valine, and racemic valine with optical purity ≥ 99%), L-ascorbic acid (content ≥ 99%), carbohydrates (D-glucose, D-galactose, L-galactose, contents ≥ 99.5%). Solutions were prepared using deuterium-depleted water (DDW–"light" water, D/H=4 ppm), natural deionized high-ohmic water (BD, D/H=140 ppm), and heavy water (99.9% D2O; Sigma-Aldrich). Optical activity was measured using the Atago POL-1/2 polarimeter. Results: One of the components in the racemic medication mixture can act as an inert agent, exhibit toxicity, or undergo undesirable biotransformation mechanisms, resulting in the formation of products with unknown properties. It has been established that a change in the deuterium/protium (D/H) ratio in water leads to a change in the equilibrium and kinetic characteristics of optically active compounds across various chemical classes, such as amino acids, carboxylic acids, and carbohydrates. An inequality was observed in the absolute values of the optical rotation of the L-and D-isomers of valine and galactose, depending on the D/H isotope ratio. The impact of chiral water clusters on optical rotation accounts for the sudden shift in the specific rotation of dilute solutions (less than 0.5%) of L-ascorbic acid in water, based on the D/H ratio. The influence of the isotopic composition of water was confirmed by studying the temperature-dependent mutarotation kinetics of D-glucose and L-and D-galactose in Arrhenius coordinates. The mutarotation process in natural high-resistivity water is characterized by an activation energy (Ea) of 40.8±1.4 kJ mol-1, while in deuterium-depleted water, Ea = 63.6±3.5 kJ mol-1. This results in a kinetic isotope effect for deuterium (KIED) of 1.6. Conclusion: Methodological approaches have been developed to control chiral switching based on the isotopic composition of water in vivo and in vitro. The study of changes in the optical activity of hierarchical structures in the human body, the influence of solvent properties on the mechanisms of optical rotation, as well as the use of KIED values, can be utilized to monitor various chiral transitions in vitro and living organisms.

Developing a Drought Resilience Matrix to Evaluate Water Supply Alternatives

Cities around the world are facing increased sensitivity to drought effects. Climate-change-induced drought affects not only the natural hydrology of the broad macroclimate but also those in the urban microclimates. The increasing frequency and duration of droughts are creating challenges for urban water utilities to convey water through distribution systems to customers reliably and consistently. This has led many urban areas like San Francisco, California, to search for unique alternative water supply projects to help bolster the drought resilience of the coupled human and natural water system. This paper focuses on applying the features of resilience (i.e., plan, adapt, absorb, and recover) through a drought resilience matrix to water supply alternatives to analyze how the addition of these projects would increase the overall water system’s drought resilience. San Francisco, California, was used as the case study to test the use of this matrix. Three portfolios (modifying existing supply, recycling, and desalination, as well as local approaches) were created and tested in the matrix. Each portfolio is composed of various alternative water supply projects that the San Francisco Public Utilities Commission (SFPUC) is considering for implementation. Results concluded that the local approaches portfolio provided the most drought resilience, with the recycling and desalination portfolio providing the least resilience. The study approach and the presented findings will provide guidance to water utility professionals in supply planning to enhance drought resilience.

Tailoring electrospun nanocomposite fibers of polylactic acid for seamless methylene blue dye adsorption applications.

The introduction of biopolymers, which are sustainable and green materials, desegregated nature's water purification proficiency with science and technology, opens a new sustainable methodology in water reclamation. In order to introduce an efficacious adsorbent system for MB dye-toxic pollutant, adsorption, providing robust mechanical properties and facile processability, a facile system was introduced via electrospinning utilizing polylactic acid (PLA) and Ti3C2Tx, viz., PMX. The addition of 3 wt.% Ti3C2Tx led to a 3-fold substantial augmentation in the uptake capacity of the membrane from 197.28 to 307 mg/g when the adsorbate concentration was 100 ppm. The adsorption followed a PSO behavior, proposing that the rate-limiting stage is chemisorption and data best fitted to Freundlich isotherm, indicating heterogeneous adsorption sites and multi-layer adsorption. Further, biodegradability was studied by simulating natural environmental conditions where the nanofibers exhibited 42-64% degradation after 270 days. Based on the result with PLA, it is anticipated that the prepared fibrous system will introduce a new perspective as a potential candidate for MB removal from wastewater, opening new directions toward the research and development in wastewater treatment with electrospun biopolymer fibers using waste PLA.

Enhanced mitigation of membrane fouling and degradation of perfluorooctanoic acid in the treatment of natural surface water through the application of dielectric barrier discharge/sulfite

The present study employed a dielectric barrier discharge (DBD)/sulfite system to mitigate membrane fouling and enhance the degradation of perfluorooctanoic acid (PFOA) in surface water. Results showed that the membrane flux was remarkably enhanced by 93.6%, and the degradation of PFOA showed an impressive increase of 87.9%. The synergistic redox effect of free radicals, including hydroxyl radical (•OH), sulfate radical (SO4∙-), electron (e-/eaq-), su-peroxide anion radicals (∙O2-), and other radical, played a crucial role in mitigating membrane fouling, accounting for 36.26%, 30.10%, 18.69%, 6.75%, and 8.20%, respectively. The correlation analysis revealed that effective removal of UV254 and TOC emerged as the most crucial factors positively contributing to mitigating membrane fouling. Additionally, SO4∙-, •OH, and eaq- were identified as the primary active substances responsible for attacking PFOA, accounting for 41.30%, 25.20%, and 23.70%, respectively. The degradation pathway of PFOA was proposed through analysis using density functional theory and mass spectrometry, reducing the biotoxicity of its degradation products. This study presents a suitable strategy for simultaneous mitigation of membrane fouling and enhancement of PFOA degradation, which holds great potential for advancing the field of water treatment towards practical applications.

Biodiversity of mosquitoes (Diptera: Culicidae) in phytotelmata from Car Nicobar Island, India.

The Culicidae mosquito family breeds in various natural and artificial water bodies. Phytotelmata are plant structures that hold water and are used by many mosquito species during their life cycle. Mosquitoes are disease vectors, and phytotelmata play an important role in harbouring them. Investigating these phytotelmata will facilitate to develop appropriate site specific vector control strategy. Approximately 750 phytotelmata in 16 locations on Car Nicobar Island was examined. Mosquito larvae were collected from different habitats such as tree holes, root holes, leaf axils, and bamboo stumps. On average, the number of larvae per 10 ml of water ranged from 0.003 to 3.833. Among the 16 mosquito species identified, there were vectors of malaria (Anopheles sundaicus), dengue (Aedes aegypti and Aedes albopictus) and filariasis (Culex quinquefasciatus), belonging to seven genera. The most common phytotelmata were coconut trees (17.5%) followed by Java apple trees (10.3%) and bamboo stumps (7.1%). The most widespread mosquito species was Aedes edwardsi, followed by Aedes malayensis and Ae. albopictus, and the per cent of phytotelmata that contained these species were 42.6, 22.0, and 16.8% respectively. Anopheles mosquitoes had the highest container index (6.1%) in root holes, while Aedes and Culex mosquitoes were more frequently found in bamboo stumps. The alpha biodiversity indices indicated that the mosquito population in Car Nicobar Island was highly diverse (S = 16; DMg = 36.9). Tree holes showed the highest diversity, as all 16 species were collected from them. Assessment of phytotelmata, there is a significant relationship observed between mosquito genus, village, habitat, and tree families, on the remote island of Car Nicobar. Considering the presence of disease-transmitting mosquito vectors in the phytotelmata, these habitats should be considered when implementing control measures to eliminate mosquito-borne infections.

Water Banking as a Strategy for the Management and Conservation of a Critical Resource: A Case Study from Tunisia’s Medjerda River Basin (MRB)

The increasingly adverse impacts of climate change (e.g., rainfall patterns, droughts, and floods), coupled with the ever-increasing water demands, are often translated into a contingent liability for water users’ communities. Additional complexities arise due to competing priorities, water rights, and transboundary water sources. Therefore, conventional water management practices should shift toward more comprehensive and responsive integrative approaches, even for systems with limited data. Furthermore, water managers must prioritize dynamic and interactive management techniques for existing systems. One such management technique is water banking, which is the focus of this study. Herein, a dynamic interactive water allocation model, which encompasses the water managers and heterogeneous parties with competing demands, is developed. The voluntary sales of water shares between parties are illustrated through the specific case of the Medjerda River in Tunisia, an excellent example of a transboundary basin with limited hydrologic data and conflicting water use requirements between its upstream and downstream sectors. A set of scenarios is developed for the first analysis with this model: two management scenarios that include the no-water trade and the water banking option; three demand scenarios that include a combination of steady-, low-, and high-water demand conditions; and two hydrologic scenarios that include dry and wet conditions. Based on an economic model, the economic impacts of water banking are calculated using estimates of the costs of water shortages brought to users that illustrate the magnitude. The results show that the water banking technique can improve water resource availability by optimizing the management, operation, and conservation of natural and artificial water storage systems and water distribution infrastructure. Specifically, water banking can offset users’ profit losses during severe conditions (i.e., drought), even with limited hydrologic data. This water management technique would allow the Tunisian government to minimize the economic impacts on farmers from drought and to plan for future uncertainties by optimizing the water storage potential in years of abundant rainfall.

Nanoplastics in Water: Artificial Intelligence-Assisted 4D Physicochemical Characterization and Rapid In Situ Detection.

For the first time, we present a much-needed technology for the in situ and real-time detection of nanoplastics in aquatic systems. We show an artificial intelligence-assisted nanodigital in-line holographic microscopy (AI-assisted nano-DIHM) that automatically classifies nano- and microplastics simultaneously from nonplastic particles within milliseconds in stationary and dynamic natural waters, without sample preparation. AI-assisted nano-DIHM identifies 2 and 1% of waterborne particles as nano/microplastics in Lake Ontario and the Saint Lawrence River, respectively. Nano-DIHM provides physicochemical properties of single particles or clusters of nano/microplastics, including size, shape, optical phase, perimeter, surface area, roughness, and edge gradient. It distinguishes nano/microplastics from mixtures of organics, inorganics, biological particles, and coated heterogeneous clusters. This technology allows 4D tracking and 3D structural and spatial study of waterborne nano/microplastics. Independent transmission electron microscopy, mass spectrometry, and nanoparticle tracking analysis validates nano-DIHM data. Complementary modeling demonstrates nano- and microplastics have significantly distinct distribution patterns in water, which affect their transport and fate, rendering nano-DIHM a powerful tool for accurate nano/microplastic life-cycle analysis and hotspot remediation.

Design of ESIPT-Based Fluorescent Probes for Dual-Mode Sensing of Cyanide: Application to Rapid On-Location Detection and Screening of Natural Water Samples

Design of ESIPT-Based Fluorescent Probes for Dual-Mode Sensing of Cyanide: Application to Rapid On-Location Detection and Screening of Natural Water Samples

Construction of functionalized In-based metal organic framework/BiOCl1−xIx Z-scheme heterojunction for efficient photocatalytic degradation of tetracycline: Performance and mechanism

The environmental implications of antibiotics have drawn widespread attention. Numerous monomer-based bismuth oxide halide catalysts have been extensively studied to remove tetracycline (TC) from aquatic environments. Integrating bismuth oxide halide composites with In-based metal organic framework (NH2-MIL-68(In)) might potentially serve as a novel strategy. By meticulously adjusting Cl and I within the composite bismuth halide oxide (B-x), a suite of purpose built heterojunctions (NMB-x) were synthesized, which were engineered to facilitate the efficient photodegradation of TC in simulated and actual aquatic environments. The incorporation of Z-scheme heterojunctions yielded a significant enhancement in photocatalytic responsiveness and charge carrier separation. Notably, NMB-0.3 demonstrated remarkable TC removal efficiency of 88.52 ± 3.05%, which is 3.74 times of B-0.3 within 90 min. The apparent quantum yield was also increased from 8.97% (B-0.3) to 19.68% (NMB-0.3). The removal of TC from natural water bodies was also assessed. Moreover, the photocatalyst concentration, assessed using response surface method, was found to show influential factors on TC removal. In addition, density functional theory (DFT) simulations were employed to identify vulnerable sites within TC. Intermediates and pathways in the photodegradation of TC have also been inferred. Furthermore, a comprehensive environmental toxicity assessment of representative intermediates demonstrated that these intermediates exhibited significantly reduced environmental toxicity compared to TC. This study provides a new approach to the design strategy of efficient and environmentally friendly MOF-based photocatalysts.

Tailoring supramolecular solvents with phosphoryl groups for highly efficient extraction of chlorophenols in natural waters

BackgroundChlorophenols are routinely determined in aquatic systems to check compliance with the restrictive international legislations set for protection of human and aquatic life. Their control requires affordable analytical methods, particularly in labs at low- and medium-income countries. Liquid chromatography-UV detection is a convenient technique for this purpose, but the availability of suitable sample processing remains pending. Organic solvents are inefficient for extracting the whole range of chlorophenols whereas solid-phase extractions are expensive and labour-intensive. So, an efficient, fast and cheap extraction of chlorophenols, amenable to any lab, would help to cope with their worldwide analytical control in natural waters. ResultsA supramolecular solvent (SUPRAS) was tailored for providing mixed interaction mechanisms aimed at the efficient extraction of chlorophenols prior to LC-UV. The SUPRAS was synthesized from the self-assembly of hexylphosphonic acid under acidic conditions and consisted of sponge-like nanostructures made up of amphiphile and water. The phosphoryl (PO) group was selected as the major driver of the extraction because of its ability to act as halogen and hydrogen bond acceptor for chlorophenols. Additional interactions were hydrogen bonds from O–H amphiphilic groups and the surrounding water, and dispersion and CH-π interactions in the hydrocarbon chains. The number of binding sites in the SUPRAS could be modulated by addition of salt. The SUPRAS formed in situ in the sample, the extraction took 5 min, the concentration factor was around 220, quantification limits (0.1–0.3 μg L−1) were below the EU standards, and the method worked for natural waters. SignificanceA fast, low-cost, and organic solvent-free sample processing only requiring conventional lab equipment (stirrers and centrifuges) provided SUPRAS extracts that could be directly analyzed by LC-UV. SUPRAS synthesis occurred spontaneously in the water sample under addition of hexylphosphonic acid and the whole process required low skills. The method meets the analytical and operational performances for the analytical control of chlorophenols in natural waters and it is within the reach of any lab.

Natural mineral raw materials as granular filtering materials in industrial and waste water treatment

Analysis of currently existing methods of natural and waste water treatment from heavy metals has shown that one of the most promising is the sorption method using natural inorganic materials as sorbents: zeolite, diatomite, and vermiculite. The relevance of the topic is dictated by the need to develop an original technology of wastewater treatment and water treatment, which allows constant monitoring of the level of pollution of natural waters by industrial wastewater from metallurgical enterprises. The proposed methods of sorbent modification create a basis for studying the structure, porosity, and sorption capabilities of the mentioned natural materials. All three minerals: zeolite, diatomite, and vermiculite belong to highly porous, structured materials, promising for use as stable sorption systems in water treatment and water purification. The influence of physical and chemical characteristics of natural sorbents and the application of new promising environmentally safe materials and reagents for water treatment are considered. The sorption of copper ions on natural zeolite material before and after its modification by hydrothermal method was investigated. The activity of sorbents was estimated by the value of sorption capacity, i.e. the amount of heavy metal ions absorbed by a unit mass of sorbent based on zeolite and its modified form.