Pharmaceutical Micropollutants Research Articles

Photocatalytic Degradation of Ciprofloxacin: A Combined Experimental and Theoretical Study Using Curcumin and Hydrogen Peroxide

Contamination of soil, water, and wastewater by pharmaceuticals, including antibiotics, is a global health problem. This work evaluated the use of a natural compound, curcumin (CUR), as a homogeneous photocatalyst, together with hydrogen peroxide (H2O2) as a benign oxidant, to promote the photodegradation of ciprofloxacin (CIP). Furthermore, we carried out theoretical calculations using density functional theory (DFT) to assess the chemical reactivity of ciprofloxacin. In addition, the intermolecular interaction patterns of two crystalline polymorphs of the antibiotic drug were analyzed through Hirshfeld surfaces. Finally, calculations using the TD-DFT formalism were carried out to understand the effects on the CIP molecule caused by the simultaneous presence of the CUR molecule and ultraviolet-visible light (UV-Vis). A photooxidative effect was observed in the presence of the CUR photocatalyst (CIP + CUR (1:0.5)), resulting in a degradation of CIP of up to 24.4%. However, increasing the concentration of the CUR photocatalyst (ciprofloxacin + curcumin (1:1)) decreased the photodegradation of CIP, which may be caused by competition between the CIP molecule and CUR for ROS generated in situ. Additionally, the calculation results showed that the electronic excitations caused by the associated CIP + CUR structures affect the CIP molecule, resulting in the effects observed experimentally. The results show that CUR, when applied as a photosensitizing catalyst, presents synergistic potential with H2O2 in the photocatalytic degradation of ciprofloxacin. This photocatalytic process can be applied to the environmental remediation of pharmaceutical micropollutants, a subject of ongoing studies.

Recent advances and future trends in metal oxide photocatalysts for removal of pharmaceutical pollutants from wastewater: a comprehensive review.

The rapid and widespread increase in pharmaceutical micropollutants (PMPs) poses a significant and immediate threat to ecosystems and human health globally. With the demand for clean water becoming increasingly critical, particularly amid escalating global water scarcity challenges, there is an urgent need for innovative approaches. Among the potential solutions, metal oxide photocatalysts such as titanium dioxide-based (TiB) and zinc oxide-based (ZnB) have garnered attention due to their cost-effectiveness, efficient photodegradation capabilities, and inherent stability. This comprehensive review explores recent advancements in the application of TiB and ZnB for the removal of PMPs from wastewater. It examines the multifaceted impacts of PMPs on environmental and public health, evaluates various techniques for their removal, and assesses design strategies aimed at maximizing the photocatalytic efficiency of TiB and ZnB. The mechanisms responsible for the photocatalytic degradation of pharmaceutical micropollutants using TiB and ZnB photocatalysts are comprehensively detailed. Finally, the review outlines the prospects and challenges associated with the use of TiB and ZnB photocatalysts for the removal of PMPs from wastewater. It emphasizes their potential to effectively mitigate PMP contaminants and make substantial contributions to sustainable water management practices in the face of escalating environmental and public health concerns.

Investigating the impact of plasma plume length of atmospheric pressure plasma jet on ampicillin degradation efficiency and toxicity

Emerging pharmaceutical micropollutant: ampicillin-degradation in water using atmospheric pressure plasma jets (APPJs) is examined, and its environmental impact is evaluated. To this end, comprehensive plasma characterization techniques, including electrical and optical analyses, are used, to supplement existing research that primarily focused on degradation outcomes. The results of these techniques provide deeper insights into the degradation process. Additionally, the solution properties are assessed by examining the treated liquids and quantifying the corresponding hydrogen peroxide and nitrite concentrations, clarifying the role of reactive species in the degradation process. High-performance liquid chromatography analysis provides essential insights into degradation kinetics and rate constants. A comprehensive framework is developed for understanding the degradation of ampicillin by APPJs, combining plasma diagnostics, solution characterization, chemical assays, degradation kinetics, and toxicity analysis. Our study, grounded in these multidisciplinary approaches, contributes to both the fundamental understanding of plasma-based degradation and optimization of plasma plume length. Our findings highlight the potential of plasma jet technologies in addressing pharmaceutical pollution and promoting sustainable wastewater management practices. This research can advance efforts to enhance the efficiency of pharmaceutical waste treatment, ultimately safeguarding the health and well-being of aquatic ecosystems and human populations.

Valorization of agricultural olive waste as an activated carbon adsorbent for the remediation of water sources contaminated with pharmaceuticals

The present study investigates the performance of activated carbon from olive pomace (ACOP) in the removal of hydrophilic organic pharmaceutical micropollutants such as the antibiotic sulfamethoxazole (SMX) from water. The adsorption behavior of two chemically modified ACOP was investigated considering their interesting textural properties, relevant surface functions and charges. The performances in terms of adsorption capacity were investigated and optimized with respect to the main operating conditions. Comparison of SMX adsorption capacities on ACOP with commercial powdered activated carbon and nanoporous carbonaceous materials prepared from argan shells revealed that ACOP enabled the highest adsorption capacities (39.68 mg g−1). The adsorption behavior was attributed not only to the textural properties, such as the large surface area (1857 m2 g−1) and porosity, but also to the charge and functional groups of the surface.

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.

Evaluation of Phenobarbital Adsorption Efficiency on Biosorbents or Activated Carbon Obtained from Adansonia Digitata Shells.

The removal of pharmaceutically active compounds present in relatively low concentration in wastewater is critical. This is because they have a severe, negative impact on life and the environment. To address this issue, adsorption was used, which is an effective wastewater treatment method for removing substances found in low concentrations in water. This study compared the adsorption performance of active carbon to three biosorbents derived from Adansonia digitata shells. The adsorbents were prepared and characterized using TGA, SEM, EDX, and FTIR analyses and pHPZC. To better understand the adsorption process, equilibrium and reaction kinetics studies were conducted. The effect of contact time, initial phenobarbital concentration, adsorbent mass, and pH was investigated in static conditions. The adsorption results revealed that the biosorbent B3 has a higher affinity for the eliminated compound, with an equilibrium time of 60 min and an adsorption capacity of 47.08 mg/g at an initial concentration of 50 mg/L. The experimental data are consistent with Langmuir and Sips adsorption isotherm models, and with the pseudo-second order and Elovich models for kinetics description. This indicates strong interactions between the adsorbent materials and the pharmaceutical micropollutant. Based on these findings, it appears that, among the tested materials, B3 biosorbent is the most efficient for removing phenobarbital present in low concentrations in water.

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.

Silver (Ag) doped graphitic carbon nitride (g-C3N4) photocatalyst for enhanced degradation of Ciprofloxacin (CIP) under visible light irradiation

Pharmaceutical industry wastewater is causing an increased risk of resistant pharmaceutical micropollutants (PMP) e.g. antibiotic resistant bacteria (super bug) in the ecosystem. Amongst variety of wastewater treatment approaches, Advanced oxidation processes (AOPs) employing photocatalysis provides a cost-effective and sustainable approach for fixation of PMP in an economical and efficient manner to counter the potential risks. Until today, tremendous efforts have been made to trig the performance of photocatalytic wastewater treatment, with the key focus on development of cost-effective, efficient and a moderately stable photocatalyst. Such attempts succeeded with different types of photocatalysts using different synthesis techniques. In recent years, graphitic carbon nitride (GCN) has emerged as one of the cost effective, moderately stable, nontoxic and efficient photocatalyst, and has been scarcely studied specifically for pharmaceutical micropollutants (PMPs) degradation. Hence, considering these factors alongside the facile synthesis and moderate optical absorption of GCN, an effort was made in the present work with effective customization of GCN i.e. silver (Ag) doping to extend light absorption in visible light range which may enhance the photocatalytic performance for Ciprofloxacin (CIP) degradation. The optimization of photocatalytic performance was executed with varied Ag dopant content to obtain an optimum sample with supreme photocatalytic activity for the maximum degradation of CIP, a common antibiotic. The best Ag-doped GCN sample (0.1 AGCN) exhibits a photocatalytic degradation efficiency of 84%, which is 2.15 times greater than pure GCN (39%). The obtained results showed that the strategy of Ag doping substantially enhances the photocatalytic performance, thus offering an efficient mean for developing visible light active photocatalyst for PMP removal and encouraging further research. The photocatalytic performance of the prepared samples was evaluated by degradation of CIP under visible light irradiation. Several characterization techniques were used to characterize and analyze the prepared samples, such as X-ray diffraction (XRD), Scanning electron microscopy (SEM), Raman spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, UV Visible absorption, and Photoluminescence (PL) spectroscopy.

Isolation, and characterization of Cladosporium alboflavescens for Acetaminophen biodegradation

One of the pharmaceutical micropollutants with a detrimental effect on the environment is paracetamol. Mycoremediation of the pollutants is a widely accepted concept based on cost and eco-friendly nature. Fungi isolated from pharmaceutical industry effluent have been used to target the biodegradation of paracetamol. The fungus’s internal transcribed spacer (ITS 1) sequencing matched that of Cladosporium alboflavescens (GenBank accession number OQ977005) by 99.81%. The strain demonstrated 89% biodegradation of paracetamol (1000 ppm) after 96 hours of incubation with 4-aminophenol as the predominant biodegradative metabolite, according to the spectrophotometric and high-performance liquid chromatographic analysis. The half-life of 1.44 days and simple first order kinetics were proposed by the Computer Assisted Kinetic Evaluation (CAKE) tool used to examinethe biodegradation kinetics.
 Key words: Acetaminophen, 4-aminophenol, Cladosporium, Mycoremediation

Lab-scale tubular LED UV reactor for continuous photocatalysis

Photocatalytic water treatment is considered a promising technique to prevent micropollutants from entering the environment. However, no off-the-shelf UV reactors on lab scale are available to study new processes and photocatalysts. In this study, we present a tubular UV reactor equipped with 30 UV-LEDs, emitting UV light at 367 nm and a total radiant flux of 42W. The UV reactor has an irradiated length of 300 mm and can host any transparent chemical reactor on the inside with a maximum diameter of 28 mm. The device is optimized for lab experiments with total dimensions of just 334 mm x 193 mm x 172 mm. Besides water treatment, a broad range of other photochemical and photocatalytic experiments can be performed with the reactor. Two identical UV reactors have been built and are successfully used for photocatalytic water treatment experiments. The degradation of methylene blue with TiO2 as photocatalyst was studied to validate the UV reactor. Furthermore, photocatalytic and hybrid processes were conducted in the UV reactor to degrade a broad range of pharmaceutical micropollutants.

Treatment of Wastewater Containing Pharmaceutical Micropollutants by Adsorption under Flow in Highly Porous Carbon Monoliths

Treatment of Wastewater Containing Pharmaceutical Micropollutants by Adsorption under Flow in Highly Porous Carbon Monoliths

Removal of low concentration ibuprofen using green diluent and novel formulated supported ionic liquid membrane

Removal of pharmaceutical micropollutants is critical to reduce detrimental contaminants found in the environment. The current study focuses on developing a new formulation of supported ionic liquid membrane (SILM) for removing low concentration of ibuprofen (IBP) using green diluent and ionic liquid. Parameters such as solid support properties, variation of diluents, type of carrier and carrier concentration are investigated. The results demonstrate that liquid carrier consisted of sunflower oil (SFO) and Aliquat 336 successfully impregnated on the PVDF support via FTIR and SEM analysis. Liquid carrier loss from the PVDF support is less than 1% by impregnating green diluents consisting of SFO. 18PVDF-DMAC/300 is selected owing to its asymmetric finger-like and spongy structure with porosity, mean pore diameter, contact angle and thickness of (82.2 ± 0.7) %, (0.19 ± 0.01) μm, (89.4 ± 0.2)° and (90.3 ± 0.8) μm, respectively. Under 72-hour operation, a maximum extraction and stripping efficiency are obtained at 93% and 87% respectively, indicating a stable SILM process. Results obtained suggest that the newly formulated SILM is advantageous and may be used to extract low concentrations of IBP from the feed phase.

Adsorption of naproxen pharmaceutical micropollutant from aqueous solutions on superior activated carbon synthesized from sheep manure: Kinetics, thermodynamics, and mechanism

The performance of a new method for synthesizing super activated carbon derived from sheep manure in the adsorption of naproxen micropollutant from an aqueous solution was investigated in this research. Chemical activation employing ZnCl2 as an activator was used to produce activated carbon. The effects of several parameters such as the rate of impregnation, temperature of activation, and duration of activation on the synthesis of activated carbon were examined. FTIR, SEM, and BET measurements were used to characterize the produced activated carbons. The surface area of the manufactured activated carbon was determined to be 2170 m2 g−1. On naproxen adsorption, the effects of solution initial pH, solution initial concentration, and amount of activated carbon were examined. When the pH of the solution was 4, the adsorption capacity was found to be greater. The pseudo-second order kinetic model was found to fit the adsorption kinetics. The data on adsorption equilibrium was found to be consistent with the Langmuir and Freundlich isotherm. According to Langmuir isotherm adsorbent capacity qm was found 7790 mg g−1. ΔG0, ΔS0, and ΔH0, among other thermodynamic parameters, were estimated. The thermodynamics of the naproxen–Activated Carbon combination show that the reaction is endothermic and favourable. This high surface area and adsorption capacity showed that the material is innovatively important.

Extraction of diclofenac sodium from water using N-benzylethanolamine based ionic liquids: Computational and experimental approach

Despite the existence of numerous conventional wastewater treatment techniques, an efficient method for removing micropollutants remains elusive. Micropollutants (MPs)are chemicals that occur in trace amounts in the aquatic environment, which include pharmaceuticals, food additives, cosmetics, and dyes. The need to develop sustainable and cost-effective alternatives to eliminate these toxins has become a pressing issue. Recently, ionic liquids (ILs) have emerged as a potential candidate for wastewater treatment because of the ease in structure tunability and other unique chemical properties. This study aims to develop four N-benzylethanolamine based ionic liquids to eliminate diclofenac sodium, one of the top priority pharmaceutical micropollutants, from the aquatic environment. The ILs chosen were optimised with B3LYP theory and 6-311++G(d, p) basis set in Gaussian 16. Using integral equation formalism polar continuum model (IEFPCM) solvation as an aid, the interactions between the ILs and diclofenac medium were investigated. For the experimental studies, the liquid-liquid extraction (LLE) method was used, and parameters affecting extraction efficiencies (EE) such as IL concentration, rotation time, rotation speed, temperature, and equilibration time were optimised. The reusability of the best-performed IL was explored. Hydrophobicity, hydrogen bonding and π-π interactions were found to have a significant impact on the extraction efficiency of ILs.

Fungi Laccases: Structure, Functions, and Potential Application in the Biodegradation of Pharmaceutical Micropollutants

Fungi Laccases: Structure, Functions, and Potential Application in the Biodegradation of Pharmaceutical Micropollutants

Investigations Regarding The Contamination with Emerging Pharmaceutical Pollutants in Representative Rivers and Lakes in Romania

The presence of emerging pharmaceutical pollutants in the aquatic environment is generally related to anthropogenic activities such as domestic, industrial and hospital wastewater discharges and landfills. Special attention should be paid to the contamination of surface waters, as they are partly used for drinking water supply, since they directly collect partly untreated wastewater from wastewater treatment plant. Within this paper, the identification, quantification and distribution of pharmaceutical micropollutants, from different complex environmental matrices, respectively: surface water, sediment and biota in the river basins of Arges-Vedea, Buzau-Ialomita and Dobrogea-Litoral and of the Danube River, were achieved. Also, preliminary investigations were carried out regarding the contamination of lakes with active pharmaceutical ingredients (APIs) the metropolitan area of the municipality of Bucharest. Among the pharmaceutical micropollutants identified in the Arges-Vedea river basin, the most frequently detected was paracetamol with a frequency of 69% and antibiotics with a frequency of 65.52%, in the Dobrogea-Litoral basin paracetamol was detected with a frequency of 74.2% and antibiotics with a frequency of 54.84%, while antibiotics were identified in all surface water samples and paracetamol with a frequency of 80% in the Buzau-Ialomita river basin. Considering the contamination of sediments with pharmaceutical residues, these were identified in all studied areas and in biota samples (fish) up to 18.21 ng/g were detected. The preliminary identification of active pharmaceutical ingredients (APIs) from Lakes Plumbuita, Carol, Morii, Alexandru Ioan Cuza (IOR), Herastrau and Tei indicated the frequent presence of several items, such as paracetamol, tinidazole, carbamazepine, moxifloxacin, clarithromycin, and caffeine.

Carbon-based composites for removal of pharmaceutical components from water

Carbon-based materials. including carbon nanotubes, graphene, and activated carbon, are among the most effective materials for pharmaceutical components removal from water. Despite the severe effect of pharmaceutical micropollutants in the aquatic environments and the effectiveness of carbon-based composites for water treatment, only a few studies has reviewed carbon-based materials for the removal of pharmaceutical components. Carbon-based materials with special properties like tunable surface functions, abundant pore structure, and high specific surface are used in different water treatment mechanisms such as adsorption and advanced oxidation processes. Graphene, activated carbon, and carbon nanotubes have been widely studied for pharmaceutical components removal. Herein, we have introduced carbon-based materials and reviewed recent studies on their properties, application in water treatment, and possible mechanism for removal of pharmaceutical components from aquatic environments.

Life Cycle Assessment and Cost-Benefit Analysis of Technologies in Water Resource Recovery Facilities: The Case of Sludge Pyrolysis.

In Europe, sewage sludge is mostly used in agriculture (49%) or incinerated (25%). Technologies for sludge management that can support the transformation of wastewater treatment plants (WWTPs) to water resource recovery facilities (WRRFs) are emerging. Sludge pyrolysis is one of them. It can generate two main high-value co-products: heat and biochar. Moreover, biochar can be transformed into activated carbon. The economic and environmental impacts of sludge pyrolysis and its comparison to the direct application of sludge in agriculture and incineration are unknown. Therefore, we applied a life cycle assessment (LCA) and a cost-benefit analysis (CBA) of sludge pyrolysis. We quantified environmental externalities in an LCA and then applied the benefit transfer method to monetize these externalities, which were included in an economic CBA. Pyrolysis reduced impacts in five to nine LCA categories and had a positive economic net present value (NPV) compared to using sludge in agriculture. Pyrolysis with biochar production was not better than incineration, showing increased impacts in nine categories and negative NPVs (-19 to -22 €/t sludge). The factor driving differences between the alternatives was the assumed CO2 externality price (164 €/ton CO2-eq) and the removal rate of pharmaceutical micropollutants of the sludge-based activated carbon. High uncertainty in environmental prices is one of the limitations of our study.

Microbial Cell Factories For the Management of Pharmaceutical Micropollutants

Extensive use of pharmaceutical drugs and its disposal in soil and water reservoirs leads to serious environmental pollution. These pharmaceutical micropollutants are highly water soluble, low biodegradable and easily accumulated in the food chain. Thus, these micropollutants persist in the environment and may cause a serious threat to ecosystem. This review highlights the sources of pharmaceutical micropollutants and adverse effects on ecosystem. The pharmaceutical drugs like such as anti-convulsive drugs, antidepressants and cytostatic drugs are more ecotoxic, hence need to remove them from contaminated environments. Further, review also insights the importance of microbial degradation in management of pharmaceutical pollutions

Strategic insight into enhanced photocatalytic remediation of pharmaceutical contaminants using spherical CdO nanoparticles in visible light region

The sustainable control of pharmaceutical micropollutants in water and wastewater environments is a great challenge in the 21st century. To address these issues, unique CdO nanoparticles (NPs) were synthesized using a facile hydrothermal approach and investigated for photocatalytic control of the antibiotic tetracycline, multidrug-resistant bacteria (MDRB), and total coliform in the wastewater effluent. The NPs were characterized using a range of techniques and it exhibited a spherical-like crystal structure with a mean size of 40 nm. The vibrational stretching mode of 1419 cm−1 confirmed the formation of Cd–O (M − O). The synthesis protocol formed smoother surfaces and 1.88 eV band gap energy of CdO NPs, inducing excellent photocatalytic activity under visible LED light (blue and white) irradiation. The optimal catalyst dose and pH were 100 mg/L and 8–9, respectively. Blue light proved more effective than white light, resulting in 28% higher efficiency (93 ± 0.47%) in tetracycline degradation than white light under an identical intensity (20 mW/cm2). White light required a four-fold higher light intensity (80 mW/cm2) than blue light to induce comparable photocatalytic MDRB inactivation. Bacterial cell lysis by the photocatalytic treatment was confirmed by transmission electron microscopy (TEM). The used catalyst was easily recovered by 5 min of centrifugation and re-used without any noticeable change in the photocatalytic decomposition. The trapping experiment revealed that the CdO-based NPs contributed primarily to the generation of •O2− and •OH radicals (Type I), but the •O2− radicals were the dominant reactive oxygen species (ROS) in the photocatalytic process.