Pharmaceutical Pollutants Research Articles

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.

Hymenaea courbaril resin-mediated gold nanoparticles as catalysts in organic dyes degradation and sensors in pharmaceutical pollutants

In this study, green synthesis of gold nanoparticles (AuNPs) using aqueous extract from Hymenaea courbaril resin (HCR) is reported. The successful formation, functional group involvement, size, and morphology of the subject H. courbaril resin mediated gold nanoparticles (HCRAuNPs) were confirmed by Ultra Violet-Visible (UV–vis) spectroscopy, Fourier-Transform Infrared spectroscopy (FTIR), and Transmission Electron Microscopy (TEM) techniques. Stable and high yield of HCRAuNPs was formed in 1:15 (aqueous solution: salt solution) reacted in sunlight as indicated by the visual colour change and appearance of surface Plasmon resonance (SPR) at 560 nm. From the FT-IR results, the phenolic hydroxyl (–OH) functional group was found to be involved in synthesis and stabilization of nanoparticles. The TEM analysis showed that the particles are highly dispersed and spherical in shape with average size of 17.5 nm. The synthesized HCRAuNPs showed significant degradation potential against organic dyes, including methylene blue (MB, 85 %), methyl orange (MO, 90 %), congo red (CR, 83 %), and para nitrophenol (PNP, 76 %) up to 180 min. The nanoparticles also demonstrated the effective detection of pharmaceutical pollutants, including amoxicillin, levofloxacin, and azithromycin in aqueous environment as observable changes in color and UV–Vis spectral graph.

Temperature-dependent toxicity of fluoxetine alters the thermal plasticity of marine diatoms

Anthropogenic activities have led to the emergence of pharmaceutical pollution in marine ecosystems, posing a significant threat to biodiversity in conjunction with global climate change. While the ecotoxicity of human drugs on aquatic organisms is increasingly recognized, their interactions with environmental factors, such as temperature, remain understudied. This research investigates the physiological effects of the selective serotonin reuptake inhibitor (SSRI), fluoxetine, on two diatom species, Phaeodactylum tricornutum and Thalassiosira weissflogii. Results demonstrate that fluoxetine significantly reduces growth rate and biomass production, concurrently affecting pigment contents and the thermal performance curve (TPC) of the diatoms. Fluoxetine reduces the synthesis of chlorophyll a (Chl a) and carotenoid (Car), indicating inhibition of photosynthesis and photoprotection. Furthermore, fluoxetine decreases the maximum growth rate (μmax) while increasing the optimum temperature (Topt) in both species, suggesting an altered thermal plasticity. This shift is attributed to the observed decrease in the inhibition rate of fluoxetine with rising temperatures. These findings emphasize the physiological impacts and ecological implications of fluoxetine on phytoplankton and underscore the significance of considering interactions between multiple environmental drivers when accessing the ecotoxicity of potential pollutants. The present study provides insights into crucial considerations for evaluating the impacts of pharmaceutical pollution on marine primary producers.

Occurrence of Pharmaceutical Micropollutants in Lake Nahuel Huapi, Argentine Patagonia.

Tourism is one of the most important activities for the economy of Nor Patagonia Argentina. In Bariloche City, located on the shores of Lake Nahuel Huapi, both the permanent and the temporary populations have increased significantly in recent decades, and this has not necessarily been accompanied by an improvement in sewage networks. Emerging micropollutants such as pharmaceutical compounds reach aquatic systems directly, in the absence of a domestic sewage network, or through effluents from wastewater treatment plants (WWTP), which do not efficiently remove these substances and represent a major threat to the environment. Therefore, the objective of our study was to monitor the presence of pharmaceutical compounds discharged both through wastewater effluents and diffusely from housing developments into Lake Nahuel Huapi. The results obtained demonstrate the presence of pharmaceuticals in Lake Nahuel Huapi with concentrations ranging from not detectable (ND) to 110.6 ng L-1 (caffeine). The highest pharmaceutical concentration recorded in WWTP influent corresponded to caffeine (41728 ng L-1), and the lowest concentration was paracetamol (18.8 ng L-1). The removal efficiency of pharmaceuticals in the WWTP was calculated, and ranged from 0% for carbamazepine to 66% for ciprofloxacin. This antibiotic showed the lowest % of attenuation (73%) in Lake Nahuel Huapi. These results on the occurrence of a wide variety of pharmaceuticals are the first generated in Patagonia, representing a regional baseline for this type of micropollutant and valuable information for the subsequent design of removal strategies for emerging pharmaceutical pollutants in surface water. Environ Toxicol Chem 2024;43:1274-1284. © 2024 SETAC.

Colorimetric detection of clotrimazole environmental pollutant using a newly developed chemosensor; an experimental and theoretical study

ABSTRACT Clotrimazole (CTZ), as an antifungal medication, is used to treat dermatological infections in humans, and to remove fungal infections from plants in agriculture, but its widespread usage has led to pharmaceutical pollution and environmental concerns. In this study, a new bromopyrogallol red (BPR) and N i 2 + based colorimetric sensor was developed for the selective and sensitive detection of CTZ. The BPR-Ni complex showed a clear colour change from purple to violet in the presence of CTZ, and a significant change was observed in the UV-Vis spectrum. The stoichiometric ratio of 1:1 between BPR and N i 2 + was determined using the Benesi-Hildebrand method. DFT and time-dependent DFT (TD-DFT) were applied to identify the molecular and electronic structures of the BPR, BPR-Ni, and BPR-Ni-CTZ in ground and excited states. The nature of electronic excitations and charge transfers was evaluated using the natural transition orbitals (NTO). The NTO analysis reveals that the Ni atom facilitates the charge transfer process between BPR and CTZ and improves the sensitivity of the chemosensor. The quantum theory of atoms in molecules (QTAIM) was employed to determine the nature of interactions between BPR, N i 2 + , and CTZ. This study paves the way for the detection of environmentally harmful pharmaceutical pollution using simple but effective colorimetric sensors.

Highly sensitive plasmonic paper substrate fabricated via amphiphilic polymer self-assembly in microdroplet for detection of emerging pharmaceutical pollutants

We report an innovative and facile approach to fabricating an ultrasensitive plasmonic paper substrate for surface-enhanced Raman spectroscopy (SERS). The approach exploits the self-assembling capability of poly(styrene-b-2-vinyl pyridine) block copolymers to form a thin film at the air-liquid interface within the single microdroplet scale for the first time and the subsequent in situ growth of silver nanoparticles (AgNPs). The concentration of the block copolymer was found to play an essential role in stabilizing the droplets during the mass transfer phase and formation of silver nanoparticles, thus influencing the SERS signals. SEM analysis of the morphology of the plasmonic paper substrates revealed the formation of spherical AgNPs evenly distributed across the surface of the formed copolymer film with a size distribution of 47.5 nm. The resultant enhancement factor was calculated to be 1.2 × 107, and the detection limit of rhodamine 6G was as low as 48.9 pM. The nanohybridized plasmonic paper was successfully applied to detect two emerging pollutants—sildenafil and flibanserin—with LODs as low as 1.48 nM and 3.45 nM, respectively. Thus, this study offers new prospects for designing an affordable and readily available, yet highly sensitive, paper-based SERS substrate with the potential for development as a lab-on-a-chip device.

Preparation of antimicrobial composite from Arabic gum-grafted-poly(p-phenylene diamine)/MOF(Fe) decorated with Cu nanoparticles as a unique nanobiosorbent for removal of cloxacillin antibiotic

The growth of the world population has led to an increase in the demand for fresh water. Water pollution is often caused by hasty urbanization without proper management of hazardous waste. Therefore, it is vital to implement new methods to remove pollutants from water. In the current study, an antimicrobial nanocomposite adsorbent composed of Arabic gum-grafted-poly(para phenylene diamine) (AG-g-PpPA) decorated with metal-organic framework and copper nanoparticles (AG-g-PpPA@MOF(Fe)/Cu) was synthesized via in-situ copolymerization. The nanocomposite was utilized for eliminating the antibiotic cloxacillin from water solutions. The effects of different factors were analyzed, including pH, the quantity of adsorbent, contact time, and preliminary cloxacillin concentrations. Ideal parameters were pH 7, 5 mg adsorbent dosage, 10 min contact time, and an initial 500 mg/L cloxacillin concentration. The adsorption process followed the Freundlich isotherm equation, with a maximum adsorption ability of 400 mg/g. The kinetics information appropriately fits a pseudo-second-order model. Thermodynamic calculation showed the adsorption occurred spontaneously. The nanocomposite also displayed antibacterial action in contradiction to Escherichia coli and Staphylococcus aureus. Additionally, the adsorbent could be recovered and reused effectively. The excellent adsorption ability highlights the potential of AG-g-PpPA@MOF(Fe)/Cu adsorbent for eliminating pharmaceutical pollutants from wastewater.

Antimony-doped cerium ferrite: a robust photocatalyst for the mitigation of diclofenac potassium, an emerging contaminant

The present work reports an improvement in the photocatalytic performance of cerium ferrite (CeFeO3) via doping of antimony (Sb) towards the photodegradation of toxic pharmaceutical pollutant i.e. diclofenac potassium. The variable concentrations of Ce1-xSbxFeO3 (x = 0.00, 0.01, 0.03, 0.05, 0.06, 0.07, 0.09) were prepared using facile co-precipitation route and subsequently characterized for their optical, structural, morphological, and dielectric properties using various analytical techniques. It was established that an increase in Sb concentration as dopant (up to x = 0.07) reduced the optical band gap from 2.74 eV to 2.42 eV making it suitable candidate for photodegradation. The X-ray diffraction (XRD) pattern revealed orthorhombic phase of synthesized materials with small crystallite sizes in the range of 15.28 to 2.42 nm. The high value of dielectric constant (3.5841 × 106) for Ce0.93Sb0.07FeO3 with small loss tan (3.1208) compared with the CeFeO3 indicated its ability as photocatalyst to effectively store charges to make them utilize for photocatalytic activity. The degradation efficiency of Ce0.93Sb0.07FeO3 reached 86.7% in 120 min of light irradiation under optimized conditions (pH = 4, catalyst dosage = 15 mg, primary drug concentration = 5 mg/L). Ce0.93Sb0.07FeO3 was also found to be stable over its multiple catalytic runs as only 6.5% decline in degradation efficiency was observed in recyclability test. The remarkable performance of antimony doped cerium ferrite against the removal of persistent pharmaceutical pollutant indicated its strong potential to be used in wastewater treatment in future works.

Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments.

Pharmaceutical residues in sediments are concerning as ubiquitous emerging contaminants. Pyrite is the most abundant sulfide minerals in the estuarine and coastal sediments, making it a major sink for pharmaceutical pollutants such as sulfamethoxazole (SMX). However, research on the adsorption and redox behaviors of SMX on the pyrite surface is limited. Here, we investigated the impact of the nonphotochemical process of pyrite on the fate of coexisting SMX. Remarkably, sulfur vacancies (SVs) on pyrite promoted the generation of nonradical species (hydrogen peroxide, H2O2 and singlet oxygen, 1O2), thereby exhibiting prominent SMX degradation performance under darkness. Nonradical 1O2 contributed approximately 73.1% of the total SMX degradation. The SVs with high surrounding electron density showed an advanced affinity for adsorbing O2 and then initiated redox reactions in the sediment electron-storing geobattery pyrite, resulting in the extensive generation of H2O2 through a two-electron oxygen reduction pathway. Surface Fe(III) (hydro)oxides on pyrite facilitated the decomposition of H2O2 to 1O2 generation. Distinct nonradical products were observed in all investigated estuarine and coastal samples with the concentrations of H2O2 ranging from 1.96 to 2.94 μM, while the concentrations of 1O2 ranged from 4.63 × 10-15 to 8.93 × 10-15 M. This dark-redox pathway outperformed traditional photochemical routes for pollutant degradation, broadening the possibilities for nonradical species use in estuarine and coastal sediments. Our study highlighted the SV-triggered process as a ubiquitous yet previously overlooked source of nonradical species, which offered fresh insights into geochemical processes and the dynamics of pollutants in regions of frequent redox oscillations and sulfur-rich sediments.

Fabrication of MXene-derived TiO2/Ti3C2 integrated with a ZnS heterostructure and their synergistic effect on the enhanced photocatalytic degradation of tetracycline

Developing innovative photocatalysts for the efficient degradation of pharmaceutical pollutants is crucial in environmental remediation. In this study, we investigate the synthesis of TiO2 nanosheets derived from MXene, specifically integrated onto highly conductive Ti3C2 MXene, and subsequently combined with zinc sulfide (ZnS) to form a heterojunction. This integration process is accomplished using a hydrothermal approach followed by a self-assembly method. We aim to assess the effectiveness of this integrated system in enhancing the photocatalytic degradation of tetracycline (TC). TiO2/Ti3C2 (TT) synthesized in situ exhibits high-energy lattice facets (001) of TiO2 nanosheets, thereby contributing to an exclusive heterojunction within the TiO2/Ti3C2/ZnS (ZTT) heterostructure. The loading of ZnS nanoparticles significantly increases the surface area with a narrow band gap, enhancing the potential for light emission within the visible region. Consequently, ZnS synergistically affects the ZTTx (where x = wt% of ZnS on TT) heterostructure matrix, notably promoting the separation and transfer abilities of the photogenerated carriers. The ZTT5 heterostructure exhibits remarkable adsorption and photoreduction efficiencies, achieving a 97.1 % TC removal in 60 min under UV light. Moreover, under simulated solar light, the ZTT5 heterostructure exhibits an impressive TC removal rate of ∼93.8 % in 90 min. These results highlight the effective performance of the ZTT5 heterojunction catalyst in facilitating photogenerated charge carriers, leading to improved photocatalytic capabilities. Furthermore, the band structure and density of states of TiO2 (101), Ti3C2 (002), and ZnS (111) were investigated using density functional theory. In addition, a photoreduction mechanism was proposed for TC, involving the transfer of electrons from TiO2 to the MXene surface. After the transfer, the electrons react with O2 to generate •O2−, attributed to the high electron mobility of MXene. The results of this study emphasize the significant potential of the ZTT5 heterostructure for efficiently degrading pharmaceutical pollutants from wastewater.

The Environmental Oxidation of Acetaminophen in Aqueous Media as an Emerging Pharmaceutical Pollutant Using a Chitosan Waste-Based Magnetite Nanocomposite

Clean water is a precious and limited resource that plays a crucial role in supporting life on our planet. However, the industrial sector, especially the pharmaceutical industry, significantly contributes to water consumption, and this can lead to water body pollution. Fenton’s reagent was introduced in the current investigation to oxidize acetaminophen as an emerging pollutant in such effluents. Therefore, we employed a straightforward co-precipitation method to fabricate chitosan-coated magnetic iron oxide, which is referred to in this study as Chit@Fe3O4. X-ray diffraction spectroscopy (XRD), Fourier transform infrared (FTIR), diffuse reflectance spectra (DRS), scanning electron microscopy (TEM), and transmission electron microscopy (TEM) were utilized to characterize the sample. It is crucial to treat such effluents due to the rapid increase in emerging pollutants. In this study, a photo-Fenton system was introduced as a combination of a Chit@Fe3O4 catalyst augmented with hydrogen peroxide under ultraviolet (UV) illumination conditions. The results reveal that only 1 h of irradiance time is efficient in oxidizing acetaminophen molecules. Doses of 20 and 200 mg/L of Chit@Fe3O4 and H2O2, respectively, and a pH of 2.0 were recorded as the optimal operational conditions that correspondingly oxidize 20 mg/L of acetaminophen to a 95% removal rate. An increase in the reaction temperature results in a decline in the reaction rate, and this, in turn, confirms that the reaction system is exothermic in nature. The sustainability of the catalyst was verified and deemed adequate in treating and oxidizing acetaminophen, even up to the fourth cycle, achieving a 69% removal rate. A kinetic modeling approach is applied to the experimental results, and the kinetic data reveal that the oxidation system conforms to second-order kinetics, with rate constants ranging from 0.0157 to 0.0036 L/mg·min. Furthermore, an analysis of the thermodynamic parameters reveals that the reaction is exothermic and non-spontaneous, predicting an activation energy of 36.35 kJ/mol. Therefore, the proposed system can address the limitations associated with the homogeneous Fenton system.

Interface engineering of 1D/2D FeVO4/MoS2 hetero-structured nanocomposite with effective interfacial charge transfer: Facile synthesis and antibiotic drug degradation

The rapid accumulation of organic contaminants in wastewater is a considerable environmental concern. We are investigating nanoscale FeVO4 and MoS2 structures for enhanced removal of organic pollutants to overcome this challenge. The FeVO4/MoS2 nanocomposite was synthesized via a hydrothermal technique. This study looks at how the FeVO4/MoS2 nanocomposite could be explored as a good catalyst for the degradation of ciprofloxacin drug through Photo-Fenton process. The synergy between FeVO4 and MoS2 and hydroxyl radicals leads to accelerated degradation. Our findings imply that FeVO4/MoS2 nanocomposites could remove pharmaceutical pollutants from wastewater sources, contributing to water treatment technology.

Facile synthesis of CoFeAl-layered double hydroxides activated by peroxymonosulfate for enhanced ciprofloxacin degradation

Advanced oxidation processes (AOPs) have consistently attracted interest in the treatment of pharmaceutical pollutants. However, certain AOPs such as peroxymonosulfate (PMS) activation require effective catalysts for enhanced pollutant degradation. Herein, we have engineered a CoFeAl-layered double hydroxide (LDH) catalyst that is reliable and efficient. The objective of this project was to initiate the use of PMS to break down ciprofloxacin (CIP), thus addressing the problem of pharmaceutical contamination. CoFeAl-LDH catalysts were prepared using different high-temperature sintering times, and their catalytic performance and efficiency were observed. In a duration of 60 min, the CIP decomposition rate was found to be 91.4%, accompanied by a removal rate constant (Kobs) of 0.036 min−1; this indicates the high activity and efficiency of the CoFeAl-LDH catalyst. The catalyst additionally showcased a substantial specific surface area and exceptional recyclability, thereby offering valuable understanding into the mechanisms of activation and degradation, and positioning it as a potential contender for applications in pollutant treatment.

Novel CuBi2O4-BiOCl/rGO heterostructure nanocomposite as high-performance visible light photocatalyst for the disintegration of persistent antimicrobials in aquatic environment

The article highlights the fabrication of a novel CuBi2O4-BiOCl/rGO heterojunction nanocomposite as a renewable visible light photocatalyst for the quick disintegration of a persistent fluoroquinolone-based antimicrobial drug, i.e., enrofloxacin (ENF) in aquatics. CuBi2O4-BiOCl (CBO-BOC) nanocomposites (NCs) of varying BOC stoichiometric ratios were synthesized, of which CBO-(30%) BOC NC (CB-30) revealed top photocatalytic traits, which was analogously dispersed onto reduced graphene oxide (rGO) nanosheets, to serve as the visible light photon responsive materials. The electron microscopic and spectroscopic techniques were deployed to understand the CB-30/rGO heterostructure's surface topography and structural morphology. The FE-SEM, HR-TEM and XPS analysis confirmed the dispersion of CBO nanospheres onto the BOC nanoflakes and further confirmed the successful imbuement of CB-30 NCs onto the rGO nanosheets. The CB-30/rGO photocatalyst revealed excellent porosity and surface area for the fast dissipation of pharmaceutical pollutants. The impact of various operating parameters, such as solution pH, drug concentration, CBO-BOC stoichiometry, CB-30/rGO dosage, photosensitizers/electron acceptors, light intensity and matrix tolerance limits, were augmented to enhance the photocatalytic efficiency of the proposed new-age photocatalyst. Under optimized conditions, complete drug mineralization was achieved in ≤0.33 h for complete mineralization of 30 ppm of ENF, using 0.075 g of photocatalyst. The time-dependent profiling of photoproducts/intermediates derived from the photocatalytic degradation of ENF was monitored by HR-MS analysis. The acute and chronic toxicity effects of ENF and its organic intermediate were predicted using the ECOSAR model for selected aquatic life forms. The photocatalyst exhibited reusability up to seven cycles, with excellent thermal/chemical stability, for pollutant decontamination from industrial effluents and environmental samples.

Photocatalytic degradation of tetracycline using a novel WO3–ZnO/AC under visible light irradiation: Optimization of effective factors by RSM-CCD

Mitigating pharmaceutical pollution in the global environment is imperative, and tetracycline (TC) is a commonly utilized antibiotic in human and veterinary medicine. The persistent existence of TC highlights the necessity of establishing efficient measures to protect water systems and the environment from detrimental contaminants. Herein, a novel rhubarb seed waste-derived activated carbon-supported photocatalyst (WO3–ZnO/RUAC) was synthesized by combining wet impregnation and ultrasonic methods. The activated carbon (AC) was obtained from rhubarb seed waste for the first time via chemical activation. The function of AC as an electron acceptor and in separating electron-hole pairs was illuminated by characterization analyses that included XRD, FTIR, XPS, SEM, TEM, PL, EIS, TPC, and UV-DRS. Using the response surface methodology-central composite design (RSM-CCD) technique, the synthesis parameters of the composite were systematically optimized. Under ideal conditions, with a TC concentration of 33 mg. L−1, pH of 4.57, irradiation time of 108 min, and catalyst dose of 0.85 g. L−1, the highest degradation efficiency of TC by this composite, achieved 96.5%, and it was reusable for five cycles. Subsequently, trapping tests and electron spin resonance (ESR) analysis were conducted, elucidating that •OH and •O2− radicals played pivotal roles in the photocatalytic degradation of TC. This research offers valuable insights into utilizing the AC-based photocatalyst to degrade pharmaceutical micropollutants effectively.

Pharmaceuticals in the Water: Emerging Concerns and Innovative Remediation Solutions

Abstract: Pharmaceutical contamination, resulting from the discharge of active pharmaceutical ingredients (APIs) and other related compounds into the water, has become a growing concern due to its potential adverse effects on ecosystems and human health. This review article aims to examine the many facets of pharmaceutical contamination and highlight the most recent developments in its remediation. The effects of pharmaceuticals, sources, and pathways of pharmaceutical contamination, as well as the difficulties in detecting and evaluating its toxicities, have been included in the present manuscript. Nowadays various remediation strategies are employed to mitigate pharmaceutical contamination in water. Conventional wastewater treatment techniques, including activated sludge processes and membrane filtration, are effective in removing a portion of the pharmaceutical compounds. However, advanced oxidation processes such as ozonation and photocatalysis have shown promising results in enhancing the degradation of recalcitrant APIs. Nanotechnology-based approaches, such as the use of nanoparticles for adsorption and degradation, and bioremediation methods utilizing microbial degradation, enzymatic processes, and phytoremediation, offer potential future directions for efficient and sustainable remediation. This review describes the most recent developments, current status, and potential research directions with the future prospects of pharmaceutical pollutants.

A Comprehensive Strategy for Stepwise Design of a Lab PROTOTYPE for the Removal of Emerging Contaminants in Water Using Cyclodextrin Polymers as Adsorbent Material.

The significant environmental issue of water pollution caused by emerging contaminants underscores the imperative for developing novel cleanup methods that are efficient, economically viable, and that are intended to operate at high capacity and under continuous flows at the industrial scale. This study shows the results of the operational design to build a prototype for the retention at lab scale of pollutant residues in water by using as adsorbent material, insoluble polymers prepared by β-cyclodextrin and epichlorohydrin as a cross-linking agent. Laboratory in-batch tests were run to find out the adsorbent performances against furosemide and hydrochlorothiazide as pollutant models. The initial evaluation concerning the dosage of adsorbent, pH levels, agitation, and concentration of pharmaceutical pollutants enabled us to identify the optimal conditions for conducting the subsequent experiments. The adsorption kinetic and the mechanisms involved were evaluated revealing that the experimental data perfectly fit the pseudo second-order model, with the adsorption process being mainly governed by chemisorption. With KF constant values of 0.044 (L/g) and 0.029 (L/g) for furosemide and hydrochlorothiazide, respectively, and the determination coefficient (R2) being higher than 0.9 for both compounds, Freundlich yielded the most favorable outcomes, suggesting that the adsorption process occurs on heterogeneous surfaces involving both chemisorption and physisorption processes. The maximum monolayer adsorption capacity (qmax) obtained by the Langmuir isotherm revealed a saturation of the β-CDs-EPI polymer surface 1.45 times higher for furosemide (qmax = 1.282 mg/g) than hydrochlorothiazide (qmax = 0.844 mg/g). Based on these results, the sizing design and building of a lab-scale model were carried out, which in turn will be used later to evaluate its performance working in continuous flow in a real scenario.

Occurrence, Source Apportionment, and Ecological Risk of Typical Pharmaceuticals in Surface Waters of Beijing, China.

Various studies have shown that the heavy use of pharmaceuticals poses serious ecological risks, especially in metropolitan areas with intensive human activities. In this study, the spatial distribution, sources, and ecological risks of 29 pharmaceuticals in 82 surface waters collected from the North Canal Basin in Beijing were studied. The results showed that the pharmaceutical concentrations ranged from not detected to 193 ng/L, with ampicillin being undetected while ofloxacin had a 100% detection frequency, which indicates the widespread occurrence of pharmaceutical pollution in the North Canal Basin. In comparison with other freshwater study areas, concentrations of pharmaceuticals in the North Canal Basin were generally at moderate levels. It was found that pharmaceutical concentrations were always higher in rivers that directly received wastewater effluents. Source analysis was conducted using the positive matrix factorization model. Combining the spatial pollution patterns of pharmaceuticals, it has been found that wastewater effluents contributed the most to the loads of pharmaceuticals in the studied basin, while in suburban areas, a possible contribution of untreated wastewater was demonstrated. Risk assessment indicated that approximately 55% of the pharmaceuticals posed low-to-high ecological risks, and combining the results of risk analyses, it is advised that controlling WWTP effluent is probably the most cost-effective measure in treating pharmaceutical pollution.

A Sustainable Banana Peel Activated Carbon for Removing Pharmaceutical Pollutants from Different Waters: Production, Characterization, and Application.

Due to the growing concerns about pharmaceutical contamination and its devastating impact on the economy and the health of humans and the environment, developing efficient approaches for removing such contaminants has become essential. Adsorption is a cost-effective technique for removing pollutants. Thus, in this work, banana peels as agro-industrial waste were utilized for synthesizing activated carbon for removing pharmaceuticals, namely amoxicillin and carbamazepine from different water matrices. The chemically activated carbon by phosphoric acid (H3PO4) was carbonized at temperatures 350 °C, 450 °C and 550 °C. The material was characterized by several techniques such as scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), Boehm titration, point of zero charge (pHPZC), BET surface area (SBET), the proximate and ultimate analyses, X-ray powder diffraction (XRD), and thermos-gravimetric analysis (TGA). The SEM of banana peel activated carbon (BPAC) depicted a semi-regular and heterogeneous morphology, characterized by an abundance of pores with diverse forms and sizes. Boehm titration revealed an increase in the amounts of acidic groups by 0.711 mmol/g due to activation by H3PO4. FTIR recorded different peaks suggesting significant modifications in the spectroscopic characteristics of the BPAC surface due to the successful activation and adsorption of the pollutant molecules. The pHpzc of BPAC was calculated to be 5.005. The SBET surface area dramatically increased to 911.59 m2/g after the activation. The optimum conditions were 25 °C, a materials dosage of 1.2 g/L, a saturation time of 120 min, a pollutants mixture of 25 mg/L, and a pH of 5. Langmuir exhibits a slightly better fit than Freundlich with a low value of the residual sum of squares (SSE) and the data were better fitted to the pseudo-second-order kinetic. Furthermore, the efficacy of BPAC in eliminating pharmaceuticals from Milli Q water, lake water, and wastewater was successfully investigated over the seven cycles. The results of the present work highlighted a potential usage of agro-industrial waste in eliminating organic micropollutants while exhibiting sustainable management of this waste.

Enhanced photocatalytic removal of tetracycline and methyl orange using Ta3N5@ZnIn2S4 nanocomposites

The presence of toxic substances in wastewater poses a severe threat to human survival and development. In recent years, photocatalytic technology has emerged as a promising solution for the efficient removal of harmful pharmaceutical pollutants and organic dyes. This study focuses on the synthesis and characterization of a novel Ta3N5@ZnIn2S4 (TN@ZIS) nanocomposite, which exhibits remarkable photocatalytic performance in degrading tetracycline hydrochloride (TC) and methyl orange (MO) under LED irradiation. The TN@ZIS nanocomposite was synthesized using a simple route involving flux-assisted nitridation and in-situ hydrothermal treatment processes. The resulting structure consists of layered ZnIn2S4 nanosheets firmly anchored onto the surface of Ta3N5 nanorods, as confirmed by SEM and TEM analysis. XPS tests revealed a strong interfacial interaction within the nanocomposite, which is advantageous for the separation of photogenerated charge carriers. Notably, the TN@ZIS hybrids demonstrated a significant improvement in photocatalytic activity compared to bare Ta3N5 nanorods. During the entire photocatalytic degradation process (60 min and 100 min), TC and MO achieved degradation efficiencies of approximately 72.3 % and 81.2 %, respectively. These results highlight the competitive nature of TN@ZIS among Ta3N5-based materials. The enhanced photocatalytic performance can be primarily attributed to the synergistic effect of improved separation of photogenerated charge carriers and the increased active sites provided by the TN@ZIS nanocomposite. This study contributes to the development of efficient and stable photocatalysts for the removal of pharmaceutical pollutants and organic dyes from wastewater, thereby addressing the urgent need for effective water treatment technologies.