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.

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.

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.

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.

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.

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.

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.

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, β-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.

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.

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.
UNASSIGNED: The online version contains supplementary material available at 10.1007/s10570-023-05399-y.