Wastewater reuse and pharmaceutical pollution in agriculture: Uptake, transport, accumulation and metabolism of pharmaceutical pollutants within plants.

The presence of pharmaceutical pollutants in water sources has become a growing concern due to its potential impacts on human health and other organisms. The physicochemical properties of pharmaceuticals based on their intended therapeutical application, which include antibiotics, hormones, analgesics, and antidepressants, is quite diverse. Their presence in wastewater, sewerage water, surface water, ground water and even in drinking water is reported by many researchers throughout the world. Human exposure to these pollutants through drinking water or consumption of aquatic and terrestrial organisms has raised concerns about potential adverse effects, such as endocrine disruption, antibiotic resistance, and developmental abnormalities. Once in the environment, they can persist, undergo transformation, or degrade, leading to a complex mixture of contaminants. Application of treated wastewater, compost, manures or biosolids in agricultural fields introduce pharmaceutical pollutants in the environment. As pharmaceuticals are diverse in nature, significant differences are observed during their uptake and accumulation in plants. While there have been extensive studies on aquatic ecosystems, the effect on agricultural land is more disparate. As of now, there are few reports available on the potential of plant uptake and transportation of pharmaceuticals within and between plant organs. This review summarizes the occurrence of pharmaceuticals in aquatic water bodies at a range of concentrations and their uptake, accumulation, and transport within plant tissues. Research gaps on pharmaceutical pollutants' specific effect on plant growth and future research scopes are highlighted. The factors affecting uptake of pharmaceuticals including hydrophobicity, ionization, physicochemical properties (pKa, logKow, pH, Henry's law constant) are discussed. Finally, metabolism of pharmaceuticals within plant cells through metabolism phase enzymes and plant responses to pharmaceuticals are reviewed.

Bacterial valorization of agricultural-waste into a nano-sized cellulosic matrix for mitigating emerging pharmaceutical pollutants: An eco-benign approach.

For Bacterial Nanocellulose (BNC) production, standard methods are well-established, but there is a pressing need to explore cost-effective alternatives for BNC commercialization. This study investigates the feasibility of using syrup prepared from maize stalk as a valuable nutrient and sustainable carbon source for BNC production. Our study achieved a remarkable BNC production yield of 19.457 g L-1 by utilizing Komagataeibacter saccharivorans NUWB1 in combination with components from the Hestrin-Schramm (HS) medium. Physicochemical properties revealed that the obtained BNC exhibited a crystallinity index of 60.5 %, tensile strength of 43.5 MPa along with enhanced thermostability reaching up to 360 °C. N2 adsorption-desorption isotherm of the BNC displayed characteristics of type IV, indicating the presence of a mesoporous structure. The produced BNC underwent thorough investigation, focusing on its efficacy in addressing environmental concerns, particularly in removing emerging pharmaceutical pollutants like Metformin and Paracetamol. Remarkably, the BNC exhibited strong adsorption capabilities, aligning with the Langmuir isotherm and pseudo-second-order model. Thermodynamic analysis confirmed a spontaneous and endothermic adsorption process. Furthermore, the BNC showed potential for regeneration, enabling up to five recycling cycles. Cytotoxicity and oxidative stress assays validated the biocompatibility of BNC. Lastly, the BNC films displayed an impressive 88.73 % biodegradation within 21 days.

Collaborative adsorption and photocatalytic degradation of high concentration pharmaceutical pollutants in water using a novel dendritic fibrous nano-silica modified with chitosan and UiO-66.

This study presents a novel hybrid mesoporous material for degrading drug pollutants in water. The hybrid materials, derived from UiO-66 metal-organic framework and chitosan, coated on nano-silica, showed excellent drug adsorption through hydrogen-bonding interactions and efficient photodegradation of antibiotics. The hybrid material's enhanced conductivity and reduced band gap significantly improved pollution reduction by minimising electron-hole recombination. This allows for more efficient charge transport and better light absorption, boosting the material's ability to break down pollutants. Structural and morphological analyses were conducted using various techniques, including scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, Brunauer-Emmett-Teller analysis, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Optimising the adsorption-photodegradation process involved investigating pH, catalyst dose, and radiation time. Non-linear optimisation revealed an efficiency exceeding 85 % for 400 mg/L tetracycline and doxycycline, the model antibiotics. The optimal parameters for maximal elimination were determined as pH = 4.3, hybrid mesosphere dose = 4.0 mg/mL, and radiation time = 10 min. Kinetic studies favored pseudo-second-order diffusion models over pseudo-first-order models. The hybrid mesosphere showed sustained efficiency after three cycles and performed well in real aqueous samples, removing over 80 % of each antibiotic. This study demonstrates the potential of the hybrid mesoporous material for removing pharmaceutical pollutants in water systems.

Acute exposure to environmentally relevant concentrations of pharmaceutical pollutants induces neurobehavioral toxicity in zebrafish (Danio rerio).

Pharmaceutical waste from point and non-point sources enters, persists, or disseminates in the environment and is known as environmentally persistent pharmaceutical pollutants. Understanding the impacts of pharmaceutical pollutants on the environment and health is essential. This study investigates the behavioral impacts of pharmaceutical pollutants on aquatic organisms and delineates the possible nexus of oxidative stress. The male zebrafish were exposed to four major representative pharmaceutical pollutants, viz., acetaminophen, carbamazepine, metformin, and trimethoprim at environmentally relevant concentrations individually as well as in a mixture for seven days. Substantial alterations in social interaction, aggressive nature, novel tank exploration, and light and dark zone preferences were recorded and the degree varied to different pharmaceutical pollutants. The activity of oxidative stress markers, superoxide dismutase, glutathione-S-transferase, and catalase, was found to be suppressed to 66-20%, 42-25%, and 59-20% respectively with the elevated malondialdehyde generation (180-260%) compared to control. The activity level of acetylcholine esterase was found to be increased to 200-500% across all treatment groups. Despite the synergistic impacts of pharmaceutical pollutants on the whole system that could not be ascertained, this comprehensive study highlights their toxicity nature to induce neurobehavioral toxicity in zebrafish through oxidative stress mechanisms and altered cholinergic systems.

Degradation of pharmaceuticals and other emerging pollutants employing bi-metal catalysts/magnesium and/or (green) hydrogen in aqueous solution.

Contaminations by pharmaceuticals, personal care products, and other emerging pollutants in water resources have become a seriously burgeoning issue of global concern in the first third of the twenty-first century. As societal reliance on pharmaceuticals continues to escalate, the inadvertent introduction of these substances into water reservoirs poses a consequential environmental threat. Therefore, the aim of this study was to investigate reductive degradation, particularly, catalytic hydrogenation regarding model pollutants such as diclofenac (DCF), ibuprofen (IBP), 17α-ethinylestradiol (EE2), or bisphenol-A (BPA), respectively,  in aqueous solutions at lab scale. Iron bimetals (zero valent iron, ZVI, and copper, Cu, or nickel, Ni) as well as zero valent magnesium (Mg, ZVM) in combination with  rhodium, Rh, or palladium, Pd, as hydrogenation catalysts (HK), were investigated. Studies were executed through various short-term batch experiments, with multiple sample collections, over a total range of 120 min. The results indicated that DCF was attenuated at over 90 % when exposed to Fe-Cu or a Fe-Ni bimetal (applied as a single model pollutant). However, when DCF was part of a mixture alongside with IBP, EE2, and BPA, the attenuation efficacy decreased to 79 % with Fe-Cu and 23 % with Fe-Ni. Conversely, both IBP and BPA exhibit notably low attenuation levels with both bimetals, less than 50 %, both deployed as single substances or in mixtures. No reaction (degradation) products could be identified employing LC-MS, but sometimes a release of the parent pollutant when applying an acetic acid buffer could be noted to a certain extent, suggesting adsorption processes on corrosion products such as iron hydroxide and/or oxides. Surprisingly, Mg in combination with Rh (Rh-HK) or Pd (Pd-HK) showed a significantly rapid decrease in the concentrations of DCF, EE2, and BPA, in part up to approximately 100 %, that is, within a few minutes only in part due to hydrogenation degradation reactions (related reaction products could actually be identified by LC-MS; adsorption processes were not observed here). Moreover, kinetic modeling of the DCF degradation with Mg-Rh-HK was conducted at different temperatures (15 °C, 20 °C, 25 °C, 35 °C) and varied initial concentrations (2.5 mg/L, 5.0 mg/L, 7.5 mg/L, 10.0 mg/L). The outcomes prove that the degradation of DCF at the Rh-HK's surface followed a modified first-order kinetics, most probably by catalytic hydrodehalogenation and subsequent hydrogenation of the aromatic moieties (molecular hydrogen was provided by the corrosion of Mg). From the determined reaction rate constants at four different temperatures, the activation energy was estimated to be 59.6 kJ/mol by means of the Arrhenius equation what is in good agreement with similar results reported in the literature. This coupled hydrodehalogenation and hydrogenation approach may be upscaled into a new promising technical process for comprehensively removing such pharmaceuticals and similar pollutants in sewage plants in a single step, furthermore, even in combination with adsorption by activated carbon and/or ozonation which have already been established at some sewage plants in Switzerland and Germany recently.

Trace cisplatin adsorption by thiol-functionalized sponge (TFS) and Sn/SnO2-coated TFS: Adsorption study and mechanism investigation.

To remove trace cisplatin from aqueous solution, commercial sponges were functionalized by esterification with 3-mercaptopropionic acid, followed by reduction with Na2S·9H2O or SnCl2·2H2O. The resulting thiol-functionalized sponges (TFSs), TFS_1 and TFS_2, were tested for the removal of cisplatin (235 µg L-1) achieving maximum removal of 95.5 ± 0.8% and 99.5 ± 0.1% respectively, which were significantly higher than the non-functionalized counterpart. The successful grafting of thiol groups, verified through FTIR, elemental analysis, SEM-EDS, and XPS characterization, facilitated Pt-S complexation during adsorption. The aqua-derivatives of cisplatin, formed through hydration, complexed with thiol sites through ligand displacement. Additionally, the presence of Sn/SnO2 coating on TFS_2 further enhanced the adsorption process. The rapid adsorption process conformed to pseudo-second-order kinetic model, involving both diffusion and chemisorption. While the Langmuir isotherm model generally described the monolayer adsorption behavior of cisplatin, the aggregation of Sn/SnO2 onto TFS_2 at 343 K introduced surface heterogeneity, rendering the Freundlich model a better fit for the adsorption isotherm. Differential pH dependence and the evaluation of mean free energy, derived from the Dubinin-Radushkevich isotherm model, indicated that cisplatin adsorption onto TFS_1 involved physisorption, including electrostatic attraction, while chemisorption predominated for TFS_2. Increasing the temperature notably promoted adsorption by facilitating the thermal-favored formation of Pt-S bonds.

Attuning doped ZnO-based composites for an effective light-driven mineralization of pharmaceuticals via PMS activation.

Water treatment technologies need to go beyond the current control of organic contaminants and ensure access to potable water. However, existing methods are still costly and often inadequate. In this context, novel catalysts that improve the mineralization degree of a wider range of pharmaceuticals through more benign and less consuming methodologies are highly sought after. ZnO, especially when doped, is a well-known semiconductor that also excels in the photocatalytic removal of persistent organic pollutants. In this study, we investigated the effect of doping ZnO nanoparticles with either copper, gallium or indium on the structure, morphology, photophysical properties and photocatalytic mineralization of pharmaceuticals. Their architecture was further improved through the fabrication of composites, pairing the best performing doped ZnO with either BaFe12O19 or nickel nanoparticles. Their suitability was tested on a complex 60-ppm multi-pollutant solution (tetracycline, levofloxacin and lansoprazole). The activation strategy combined photocatalysis with peroxymonosulfate (PMS) as an environmentally friendly source of highly oxidative sulfate radicals. The alliance of doped ZnO and BaFe12O19 was particularly successful, resulting in magnetic microcroquette-shaped composites with excellent inter-component synergy. In fact, indium outperformed the other proposed metal dopants, exceeding 97% mineralization after 1 h and achieving complete elimination after 3 h. All composites excelled in terms of reusability, with no catalytic loss after 10 consecutive cycles and minimal leakage of metal ions, highlighting their applicability in water remediation.

Ecological impact of pharmaceutical pollutants and options of river health improvements - A risk analysis-based approach.

Pharmaceuticals are one of the emerging pollutants (EPs) in river waters across the world. Due to their toxic effects on aquatic organisms, they have drawn the global attention of the scientific community concerned with river ecosystems. This paper reviews the existing occurrence data for various pharmaceutical pollutants (PPs) reported in river waters in some part of the world and their ecological impacts. Using algae, macroinvertebrates (MI), and fish as biotic indicator groups in water to reflect river health conditions, an attempt has been made to assess the ecological risk due to the presence of PPs in the water environment. After ascertaining the predicted no-effect concentration (PNEC) of PPs for selected groups of aquatic organisms, the risk quotient (RQ) is estimated based on their measured environmental concentration (MEC). When MEC > PNEC and RQ > 1 for any of the biotic indicator, ecologically it is 'high risk' condition. The determination of PNEC uses a minimum assessment factor (AF) of 10 due to uncertainty in data over the no observed effect level (NOEL) or lowest observed effect level (LOEL). Accordingly, MEC 10 times higher than PNEC, (RQ = 10) represents a threshold risk concentration (RCT) beyond which adverse effects may start showing observable manifestations. In the present study, a new classification system of 'high risk' conditions for RQ = 1-10 has been proposed, starting from 'moderately high' to 'severely high'. For RQ > 10, the ecological condition of the river is considered 'impaired'. For river health assessment, in the present study, the whole range of physico-chemical characteristics of river water quality has been divided into three groups based on their ease of measurement and frequency of monitoring. Dissolved oxygen related parameters (DORPs), nutrients (NTs), and EPs. PPs represent EPs in this study. A framework for calculating separate indicator group score (IGS) and the overall river health index (RHI) has been developed to predict indicator group condition (IGC) and river health condition (RHC), respectively. Color-coded hexagonal pictorial forms representing IGC and RHC provide a direct visible perception of the existing aquatic environment and a scientific basis for prioritization of corrective measures in terms of treatment technology selection for river health improvements. The analyses indicate that many rivers across the world are under 'high risk' conditions due to PPs having MEC > PNEC and RQ > 1. Up to RCT, (where RQ = 10), the 'high risk' condition varies from 'moderately high' to 'severely high'. In many instances, RQ is found much more higher than 10, indicating that the ecological condition of river may be considered as 'impaired'. Algae is the most frequently affected group of biotic indicators, followed by MI and fish. A review of treatment methods for selection of appropriate technology to reduce the pollution load, especially PPs from the wastewater streams has been summarized. It appears that constructed wetlands (CWs) are at present the most suitable nature-based solutions, particularly for the developing economies of the world, to reduce the concentrations of PPs within limits to minimize the ecological impacts of pharmaceutical compounds on biotic indicators and restore the river health condition. Some suggestive design guidelines for the CWs have also been presented to initiate the process.

Evaluation of Antibiotic Biodegradation by a Versatile and Highly Active Recombinant Laccase from the Thermoalkaliphilic Bacterium Bacillus sp. FNT.

Laccases are industrially relevant enzymes that have gained great biotechnological importance. To date, most are of fungal and mesophilic origin; however, enzymes from extremophiles possess an even greater potential to withstand industrial conditions. In this study, we evaluate the potential of a recombinant spore-coat laccase from the thermoalkaliphilic bacterium Bacillus sp. FNT (FNTL) to biodegrade antibiotics from the tetracycline, ß-lactams, and fluoroquinolone families. This extremozyme was previously characterized as being thermostable and highly active in a wide range of temperatures (20-90 °C) and very versatile towards several structurally different substrates, including recalcitrant environmental pollutants such as PAHs and synthetic dyes. First, molecular docking analyses were employed for initial ligand affinity screening in the modeled active site of FNTL. Then, the in silico findings were experimentally tested with four highly consumed antibiotics, representatives of each family: tetracycline, oxytetracycline, amoxicillin, and ciprofloxacin. HPLC results indicate that FNTL with help of the natural redox mediator acetosyringone, can efficiently biodegrade 91, 90, and 82% of tetracycline (0.5 mg mL-1) in 24 h at 40, 30, and 20 °C, respectively, with no apparent ecotoxicity of the products on E. coli and B. subtilis. These results complement our previous studies, highlighting the potential of this extremozyme for application in wastewater bioremediation.

Enzymatic crosslinking of lignin nanoparticles and nanocellulose in cryogels improves adsorption of pharmaceutical pollutants.

Pharmaceuticals, designed for treating diseases, ironically endanger humans and aquatic ecosystems as pollutants. Adsorption-based wastewater treatment could address this problem, however, creating efficient adsorbents remains a challenge. Recent efforts have shifted towards sustainable bio-based adsorbents. Here, cryogels from lignin-containing cellulose nanofibrils (LCNF) and lignin nanoparticles (LNPs) were explored as pharmaceuticals adsorbents. An enzyme-based approach using laccase was used for crosslinking instead of fossil-based chemical modification. The impact of laccase treatment on LNPs alone produced surface-crosslinked water-insoluble LNPs with preserved morphology and a hemicellulose-rich, water-soluble LNP fraction. The water-insoluble LNPs displayed a significant increase in adsorption capacity, up to 140 % and 400 % for neutral and cationic drugs, respectively. The crosslinked cryogel prepared by one-pot incubation of LNPs, LCNF and laccase showed significantly higher adsorption capacities for various pharmaceuticals in a multi-component system than pure LCNF or unmodified cryogels. The crosslinking minimized the leaching of LNPs in water, signifying enhanced binding between LNPs and LCNF. In real wastewater, the laccase-modified cryogel displayed 8-44 % removal for cationic pharmaceuticals. Overall, laccase treatment facilitated the production of bio-based adsorbents by improving the deposition of LNPs to LCNF. Finally, this work introduces a sustainable approach for engineering adsorbents, while aligning with global sustainability goals.

Fabrication of the flower-like Z-scheme heterojunction photocatalyst Bi-BiOI/UiO 66 for enhanced photodegradation of acetaminophen in simulated wastewater.

Acetaminophen is a representative contaminant of emerging persistent organic pollutants that can cause environmental problems when it enters municipal wastewater. An innovative flower-like Z-scheme photocatalyst Bi-BiOI/UiO 66 heterojunction composite was designed and constructed via a one-step solvothermal method. Investigations demonstrated that the Z-scheme structure strongly contributes to increasing the degradation efficiency of micropollutants. The results indicate that the bandgap energy (Eg) of the Bi-BiOI/UiO 66 composite decreases significantly from 3.22 eV to 2.43 eV, in comparison with that of pure copper-based UiO 66. Under suitable conditions (5 mg/L Ace, pH 3, 0.05 g/L), the organic pollutants in the water can be removed completely. A k value of 5.67 × 10-2 min-1 for the Bi-BiOI/UiO 66 heterojunction composite was found to effectively represent the acetaminophen photodegradation process. The reaction mechanism of acetamide in aqueous solution is also discussed. The Bi in Bi-BiOI can use surface plasmon resonance to form an electric field and accelerate the separation of photogenerated electrons and holes. This study highlights the potential of a novel photocatalyst for practical application.

Synergistic effects of layered Ti3C2TX MXene/MIL-101(Cr) heterostructure as a sonocatalyst for efficient degradation of sulfadiazine and acetaminophen in water.

In this work, different mass loadings of MXene-coupled MIL-101(Cr) (MXe/MIL-101(Cr)) nanocomposites were generated through a hydrothermal process in order to investigate the potential of this nanocomposite as a novel sonocatalyst for the elimination of sulfadiazine (SD) and acetaminophen (AAP) in aqueous media. The sonocatalytic activity of different MXe/MIL-101(Cr) compositions and surface functionalities was investigated. In addition, the sonocatalytic activities at various pH values, temperatures, pollutant concentrations, catalyst dosages, initial H2O2 concentrations, and organic matter contents were investigated. The experiments on the sonocatalytic elimination of SD and AAP revealed that MXe/MIL-101(Cr) exhibited a catalytic efficiency of âˆ¼ 98% in 80 min when the MXene loading was 30 wt% in the nanocomposite. Under optimized reaction conditions, the degradation efficiency of MXe/MIL-101(Cr) reached 91.5% for SD and 90.6% for AAP in 60 min; these values were 1.2 and 1.8 times greater than those of MXene and MIL-101(Cr), respectively. The high surface area of the MXe/MIL-101(Cr) nanocomposite increased from 4.68 m2/g to 294.21 m2/g, and the band gap of the tagged MIL-101(Cr) on the MXene surface was minimized. The superior sonocatalytic activity of MXe/MIL-101(Cr) was attributed to the effective contact interface, the effective separation rate of e- - h+ pairs through the type II heterostructure interface, and the favorable high free •OH radical production rates that promoted the degradation of SD and AAP. The solid heterointerface between MIL-101(Cr) and MXene was confirmed through Raman and FTIR analysis and was found to promote accessible •OH radical production under sonication, thus maximizing the catalytic activity of nanocomposites. The present results present an effective strategy for the design of a highly efficient, low-cost, reliable sonocatalyst that can eradicate pharmaceutical pollutants in our environment.

Lignin nanoparticles as co-stabilizers and modifiers of nanocellulose-based Pickering emulsions and foams.

Nanocellulose is very hydrophilic, preventing interactions with the oil phase in Pickering emulsions. This limitation is herein addressed by incorporating lignin nanoparticles (LNPs) as co-stabilizers of nanocellulose-based Pickering emulsions. LNP addition decreases the oil droplet size and slows creaming at pH 5 and 8 and with increasing LNP content. Emulsification at pH 3 and LNP cationization lead to droplet flocculation and rapid creaming. LNP application for emulsification, prior or simultaneously with nanocellulose, favors stability given the improved interactions with the oil phase. The Pickering emulsions can be freeze-dried, enabling the recovery of a solid macroporous foam that can act as adsorbent for pharmaceutical pollutants. Overall, the properties of nanocellulose-based Pickering emulsions and foams can be tailored by LNP addition. This strategy offers a unique, green approach to stabilize biphasic systems using bio-based nanomaterials without tedious and costly modification procedures. Supplementary Information: The online version contains supplementary material available at 10.1007/s10570-023-05399-y.

Starch-Based Polymer Materials as Advanced Adsorbents for Sustainable Water Treatment: Current Status, Challenges, and Future Perspectives.

Over the past three decades, chemical and biological water contamination has become a major concern, particularly in the industrialized world. Heavy metals, aromatic compounds, and dyes are among the harmful substances that contribute to water pollution, which jeopardies the human health. For this reason, it is of the utmost importance to locate methods for the cleanup of wastewater that are not genuinely effective. Owing to its non-toxicity, biodegradability, and biocompatibility, starch is a naturally occurring polysaccharide that scientists are looking into as a possible environmentally friendly material for sustainable water remediation. Starch could exhibit significant adsorption capabilities towards pollutants with the substitution of amide, amino, carboxyl, and other functional groups for hydroxyl groups. Starch derivatives may effectively remove contaminants such as oil, organic solvents, pesticides, heavy metals, dyes, and pharmaceutical pollutants by employing adsorption techniques at a rate greater than 90%. The maximal adsorption capacities of starch-based adsorbents for oil and organic solvents, pesticides, heavy metal ions, dyes, and pharmaceuticals are 13,000, 66, 2000, 25,000, and 782 mg/g, respectively. Although starch-based adsorbents have demonstrated a promising future for environmental wastewater treatment, additional research is required to optimize the technique before the starch-based adsorbent can be used in large-scale in situ wastewater treatment.

Electrochemical oxidation technique to pharmaceutical pollutants removal.

Human progress in medical science and drug production has improved the growth process and increased human lifespan. Most of the drugs used are to control or prevent common human diseases. These drugs can be produced in different ways such as synthetic, chemical, biological, etc. On the other hand, pharmaceutical companies have a large volume of pharmaceutical effluents and wastewater that enters the environment and harms nature and human life. The main problems of entering the pharmaceutical effluent into the environmental cycle are the creation of drug resistance against the active substance of the drugs and the occurrence of abnormalities in the next generations. Therefore, the process of pharmaceutical wastewater treatment is used to reduce the level of pharmaceutical pollutants in order to enter the pharmaceutical wastewater into the environmental cycle. Until recently, filtration, passing through reverse osmosis and ion exchange resins, cleaning facilities, etc., have been various methods to remove pharmaceutical pollutants. Due to the low efficiency of the usual and old systems, the use of new methods has attracted more attention. In this article, the aim is to investigate the electrochemical oxidation method in order to remove the active ingredient of some commonly used drugs (aspirin, atorvastatin, metformin, metronidazole and ibuprofen) from the wastewater of pharmaceuticals. Therefore, in order to observe the initial conditions of the samples, a cyclic voltammetry diagram with a scanning rate of 100 mV/s has been performed. Next, by using the chronoamperometry process and applying a constant potential, the desired drugs were subjected to the electrochemical process of oxidation. As a result, the re-examined samples were subjected to cyclic voltammetry test to determine the conditions of sample oxidation peaks as well as the removal efficiency of the samples by examining the surface under the initial and final voltammetry graph. The results indicate that this method for removing selected drugs has a high removal efficiency of about 70% and 100% for atorvastatin samples. Therefore, this method is accurate, reproducible (RSD 2%), efficient, easy and economical and can be used in drug manufacturing industries. This method is used in a wide range of drug concentration. This means that by increasing the concentration of the drug, without the need to change the equipment used and the applied potential, by spending more time in the oxidation process, it is possible to remove very high amounts of the drug (more than 1000 ppm).

A Thorough Examination of the Solution Conditions and the Use of Carbon Nanoparticles Made from Commercial Mesquite Charcoal as a Successful Sorbent for Water Remediation.

Water pollution has invaded seas, rivers, and tap water worldwide. This work employed commercial Mesquite charcoal as a low-cost precursor for fabricating Mesquite carbon nanoparticles (MUCNPs) using a ball-milling process. The scanning electron energy-dispersive microscopy results for MUCNPs revealed a particle size range of 52.4-75.0 nm. The particles were composed mainly of carbon with trace amounts of aluminum, potassium, calcium, titanium, and zinc. The X-ray diffraction peaks at 26.76 and 43.28 2θ° ascribed to the (002) and (100) planes indicated a crystalized graphite phase. Furthermore, the lack of FT-IR vibrations above 3000 cm-1 showed that the MUCNPs were not functionalized. The MUCNPs' pore diameter, volume, and surface area were 114.5 Ǻ, 0.363 cm3 g-1, and 113.45 m2 g-1. The batch technique was utilized to investigate MUCNPs' effectiveness in removing chlorohexidine gluconate (CHDNG) from water, which took 90 min to achieve equilibrium and had an adsorption capacity of 65.8 mg g-1. The adsorption of CHDNG followed pseudo-second-order kinetics, with the rate-limiting step being diffusion in the liquid film. The Langmuir isotherm dominated the CHDNG adsorption on the MUCNPs with a correlation coefficient of 0.99. The thermodynamic studies revealed that CHDNG adsorption onto the MUCNPs was exothermic and favorable, and its spontaneity increased inversely with CHDNG concentration. The ball-milling-made MUCNPs demonstrated consistent efficiency through regeneration-reuse cycles.

Lignin nanoparticle-decorated nanocellulose cryogels as adsorbents for pharmaceutical pollutants.

Adsorption is a relatively simple wastewater treatment method that has the potential to mitigate the impacts of pharmaceutical pollution. This requires the development of reusable adsorbents that can simultaneously remove pharmaceuticals of varying chemical structure and properties. Here, the adsorption potential of nanostructured wood-based adsorbents towards different pharmaceuticals in a multi-component system was investigated. The adsorbents in the form of macroporous cryogels were prepared by anchoring lignin nanoparticles (LNPs) to the nanocellulose network via electrostatic attraction. The naturally anionic LNPs were anchored to cationic cellulose nanofibrils (cCNF) and the cationic LNPs (cLNPs) were combined with anionic TEMPO-oxidized CNF (TCNF), producing two sets of nanocellulose-based cryogels that also differed in their overall surface charge density. The cryogels, prepared by freeze-drying, showed layered cellulosic sheets randomly decorated with spherical lignin on the surface. They exhibited varying selectivity and efficiency in removing pharmaceuticals with differing aromaticity, polarity and ionic characters. Their adsorption potential was also affected by the type (unmodified or cationic), amount and morphology of the lignin nanomaterials, as well as the pH of the pharmaceutical solution. Overall, the findings revealed that LNPs or cLNPs can act as functionalizing and crosslinking agents to nanocellulose-based cryogels. Despite the decrease in the overall positive surface charge, the addition of LNPs to the cCNF-based cryogels showed enhanced adsorption, not only towards the anionic aromatic pharmaceutical diclofenac but also towards the aromatic cationic metoprolol (MPL) and tramadol (TRA) and neutral aromatic carbamazepine. The addition of cLNPs to TCNF-based cryogels improved the adsorption of MPL and TRA despite the decrease in the net negative surface charge. The improved adsorption was attributed to modes of removal other than electrostatic attraction, and they could be π-π aromatic ring or hydrophobic interactions brought by the addition of LNPs or cLNPs. However, significant improvement was only found if the ratio of LNPs or cLNPs to nanocellulose was 0.6:1 or higher and with spherical lignin nanomaterials. As crosslinking agents, the LNPs or cLNPs affected the rheological behavior of the gels, and increased the firmness and decreased the water holding capacity of the corresponding cryogels. The resistance of the cryogels towards disintegration with exposure to water also improved with crosslinking, which eventually enabled the cryogels, especially the TCNF-based one, to be regenerated and reused for five cycles of adsorption-desorption experiment for the model pharmaceutical MPL. Thus, this study opened new opportunities to utilize LNPs in providing nanocellulose-based adsorbents with additional functional groups, which were otherwise often achieved by rigorous chemical modifications, at the same time, crosslinking the nanocellulose network.

Iron (II) phthalocyanine loaded tourmaline efficiently activates PMS to degrade pharmaceutical contaminants under solar light.

Iron (II) phthalocyanine (FePc) is loaded on the surface of the tourmaline (TM) by the reflow method to obtain FePc/TM. This research effectively prevents the π-π stacking of FePc, increased the effective utilization rate of PMS activation under solar light, and further improved the catalytic performance of the catalytic system. The catalytic oxidation efficiency of FePc/TM on carbamazepine (CBZ) and sulfadiazine (SD) can reach 99% under solar light for 15 and 5 min, the total organic carbon (TOC) removal rate can reach 58% and 69% under solar light for 120 min. After 6 cycles, the CBZ removal rate remained above 95%. In addition, the FePc/TM catalytic system has an excellent removal rate for other pharmaceuticals. The results of spin-trapped electron paramagnetic resonance and classical quenching experiments show that FePc/TM can effectively activate PMS to generate active species under solar light, including superoxide radical (•O2-), singlet oxygen (1O2), hydroxyl radicals(•OH), and sulphate radicals (SO4•-). The intermediates of CBZ were identified by Ultra-high performance liquid chromatography and high resolution mass spectrometry, and the degradation pathway was proposed. As the reaction progresses, all CBZ and intermediates are reduced and converted into small acids, or mineralized to H2O, CO2. This work provides an alternative method for the design of efficient activation of PMS activation catalysts under solar light to eliminate residual pharmaceuticals in actual water bodies.

Pharmaceuticals in water as emerging pollutants for river health: A critical review under Indian conditions.

The wastewaters from pharmaceutical manufacturing units, hospitals, and domestic sewage contaminated with excretal matters of medicine users are the prime sources of pharmaceutical pollutants (PPs) in natural water bodies. In the present study, PPs have been considered one of the emerging pollutants (EPs) and a cause of concern in river health assessment. Beyond the reported increase in antibiotic-resistant bacteria (ABRB), PPs have been found adversely affecting the biotic diversity in such water environments. Considering Algae, Macroinvertebrates, and Fishes as three distinct trophic level indicators, the present study puts forward a framework for showing River Health Condition (RHC) based on the calculation of a River Health Index (RHI). The RHI is calculated using six Indicator Group Scores (IGS) which individually reflect river health in a defined category of water quality characteristics. While Dissolved Oxygen Related Parameters (DORP), Nutrients (NT), and PPs are taken as causative agents affecting RHCs, scores of Algal-Bacterial (AB) symbiosis, Macroinvertebrates (MI), and Fishes (F) are considered as an effect of such environmental conditions. Current wastewater treatment technologies are also not very effective in the removal of PPs. The objective of the present study is to review the harmful effects of PPs on the aquatic environment, particularly on the chemical and biotic indicators of river health. Based on predicted no-effect concentrations (PNEC) for algae, macroinvertebrates, and fishes in the aquatic environment and measured environmental concentration (MEC) in the river, the estimated risk quotient (RQ) for norfloxacin in the Isakavagu-Nakkavagu stream of river Godavari, Hyderabad is found 293 for algae, 39 for MI, and 335 for fish. Among PPs, in Indian rivers, the presence of caffeine is the most frequent, with algae at the highest level of risk (RQmax= 24.5). Broadly six PPs, including azithromycin, caffeine, diclofenac, naproxen, norfloxacin, and sulfamethoxazole are found above PNEC values in Indian rivers. The application of IGS and RHI in understanding and presenting the river health condition (RHC) through colored hexagons has been demonstrated for the river Ganga near Varanasi (India) as an example. Identification of critical indicator groups, based on IGS provides a scientific basis for planned intervention for river health restoration to achieve an acceptable category.

MXene-Based Photocatalysts in Degradation of Organic and Pharmaceutical Pollutants.

These days, explorations have focused on designing two-dimensional (2D) nanomaterials with useful (photo)catalytic and environmental applications. Among them, MXene-based composites have garnered great attention owing to their unique optical, mechanical, thermal, chemical, and electronic properties. Various MXene-based photocatalysts have been inventively constructed for a variety of photocatalytic applications ranging from pollutant degradation to hydrogen evolution. They can be applied as co-catalysts in combination with assorted common photocatalysts such as metal sulfide, metal oxides, metal-organic frameworks, graphene, and graphitic carbon nitride to enhance the function of photocatalytic removal of organic/pharmaceutical pollutants, nitrogen fixation, photocatalytic hydrogen evolution, and carbon dioxide conversion, among others. High electrical conductivity, robust photothermal effects, large surface area, hydrophilicity, and abundant surface functional groups of MXenes render them as attractive candidates for photocatalytic removal of pollutants as well as improvement of photocatalytic performance of semiconductor catalysts. Herein, the most recent developments in photocatalytic degradation of organic and pharmaceutical pollutants using MXene-based composites are deliberated, with a focus on important challenges and future perspectives; techniques for fabrication of these photocatalysts are also covered.