[Degradation of Carbamazepine in Water by UV-activated Sulfite Process].

In this study, the degradation efficiency and mechanism of carbamazepine (CBZ), a typical emerging contaminant in water, in the UV/sulfite process were investigated. The effects of different concentrations of dissolved oxygen [ρ(DO)] on the degradation of CBZ by UV-activated sulfite were investigated. Additionally, under a simulated natural water environment-controlled initial ρ(DO) of (8.0 ±0.2) mg·L-1, the effects of different process parameters (sulfite dosages and reaction pH) and water environmental factors (the presence of HCO3-, Cl-, and humic acids) on the degradation of CBZ were comprehensively analyzed. The results showed that the UV/sulfite process efficiently degraded CBZ with a degradation rate of 85.3% during the 30 min reaction time and followed the pseudo-first order kinetic model with the constant of 0.055 7 min-1. Using the electron spin resonance detection, reactive species quenching tests, and the competition kinetics, the sulfate radicals (SO4-·) and hydroxyl radicals (·OH) in the UV/sulfite process were determined to be the main reactive species and were responsible for the degradation of CBZ with contribution rates of 43.9% and 56.1%, respectively. In addition, the degradation efficiency of CBZ decreased with the increasing concentration of HCO3-, and the presence of Cl- had little effect on the degradation of CBZ, whereas the presence of humic acids significantly inhibited the degradation of CBZ. Moreover, the accumulation of sulfate during the reaction was significantly lower than the limit of the Standard for Drinking Water (GB5749-2022). Additionally, the sulfite consumption rate constant was 0.004 4 min-1, which was significantly lower than the degradation rate constant of CBZ, indicating that sulfite could be activated efficiently by UV light to degrade CBZ in water.

Temperature-responsive comprehensive two-dimensional liquid chromatography coupled to high resolution mass spectrometry for the elucidation of the oxidative degradation processes of chemicals of environmental concern.

This study explores the possibilities offered by temperature-responsive liquid chromatography (TRLC) based comprehensive 2-dimensional liquid chromatography in combination with reversed-phase liquid chromatography (RPLC) for the analysis of degradation products formed upon oxidative treatment of persistent organic pollutants, in this case exemplified through carbamazepine (CBZ). The TRLC×RPLC combination offers the possibility to overcome peak overlap and incomplete separation encountered in 1D approaches, while the transfer of the purely aqueous mobile phase leads to refocusing of all analytes on the second dimension column. Consequently, this allows for about method-development free and hence, easier LC×LC. The study focuses on the oxidative degradation of CBZ, a compound of environmental concern due to its persistence in water bodies. The TRLC×RPLC combination effectively separates and identifies CBZ and its degradation products, while offering improved selectivity over the individual TRLC or RPLC separations. This allows gathering more understanding of the degradation cascade and allows real-time monitoring of the appearance and disappearance of various degradation products. The compatibility with high-resolution mass spectrometry is last shown, enabling identification of 21 CBZ-related products, nine of which were not previously reported in CBZ degradation studies. The approach's simplicity, optimization-free aspects, and ease of use make it a promising tool for the analysis of degradation pathways in environmental contaminants.

Predicting environmental risks of pharmaceutical residues by wastewater surveillance: An analysis based on pharmaceutical sales and their excretion data.

Pharmaceutical residues are increasingly becoming a significant source of environmental water pollution and ecological risk. This study, leveraging official national pharmaceutical sales statistics, predicts the environmental concentrations of 33 typical pharmaceuticals in the Tianjin area. The results show that 52 % of the drugs have a PEC/MEC (Predicted Environmental Concentration/Measured Environmental Concentration) ratio within the acceptable range of 0.5-2, including atenolol (1.21), carbamazepine (1.22), and sulfamethoxazole (0.91). Among the selected drugs, tetracycline, ciprofloxacin, and acetaminophen had the highest predicted concentrations. The EPI (Estimation Programs Interface) biodegradation model, a tool from the US Environmental Protection Agency, is used to predict the removal efficiency of compounds in wastewater treatment plants. The results indicate that the EPI predictions are acceptable for macrolide antibiotics and ß-blockers, with removal rates of roxithromycin, spiramycin, acetaminophen, and carbamazepine being 14.1 %, 61.2 %, 75.1 %, and 44.5 %, respectively. However, the model proved to be less effective for fluoroquinolone antibiotics. The ECOSAR (Ecological Structure-Activity Relationships) model was used to supplement the assessment of the potential impacts of drugs on aquatic ecosystems, further refining the analysis of pharmaceutical environmental risks. By combining the concentration and detection frequency of pharmaceutical wastewater, this study identified 9 drugs with significant toxicological risks and marked another 24 drugs as substances of potential concern. Additionally, this study provides data support for addressing pharmaceutical residues of priority concern in subsequent research.

Trace analysis of 47 psychotropic medications in environmental samples by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS).

Psychotropic medications are one of the most prescribed pharmaceuticals in the world. Given their frequent detection and ecotoxicity to the no-target organism, the emission of these medications into environments has gradually draw attention. The study developed a sensitive and reliable analytic method to simultaneously investigate 47 psychotropic medications in four matrices: wastewater, surface water, activated sludge, and sediment by ultra-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/MS). These 47 target analytes include 24 antidepressants, 17 antianxiety drugs, 5 anticonvulsants, and 1 relevant hormone. Solid phase extraction (SPE) was employed to extract analytes from water-phase samples. Ultrasonic Solvent Extraction method with Enhanced Matrix Removal clean-up (USE-EMR) was utilized to extract target compounds from solid-phase samples, which requires more straightforward and convenient procedures than previous methods. The extraction recoveries of all analytes ranged from 80 % to 120 % in these four sample matrices. In this study, The limit of quantitation for 47 psychotropic medications were 0.15 ng/L (estazolam) to 2.27 ng/L (lorazepam), 0.08 ng/L (desvenlafaxine) to 2 ng/L (mianserin), 0.22 ng/g (dry weight, dw) (nordiazepam) to 3.65 ng/g (dw) (lorazepam), and 0.07 ng/g (dw) (carbamazepine) to 2.85 ng/g (lorazepam), in wastewater, surface water, sludge, and sediment, respectively. In addition, the developed method was employed to analyse actual samples in two wastewater treatment plants and their receiving rivers. Carbamazepine, escitalopram, clozapine, desvenlafaxine, diazepam, lamotrigine, sertraline, temazepam, and venlafaxine were nearly ubiquitous in all matrices. Moreover, this study indicated that the inadequate removal efficiencies of psychotropic medications in wastewater treatment plants (WWTPs) had resulted in a persistent discharge of these contaminants from human sources into environments.

Combination of advanced biological systems and photocatalysis for the treatment of real hospital wastewater spiked with carbamazepine: A pilot-scale study.

Over the past few decades, the increase in dependency on healthcare facilities has led to the generation of large quantities of hospital wastewater (HWW) rich in chemical oxygen demand (COD), total suspended solids (TSS), ammonia, recalcitrant pharmaceutically active compounds (PhACs), and other disease-causing microorganisms. Conventional treatment methods often cannot effectively remove the PhACs present in wastewater. Hence, hybrid processes comprising of biological treatment and advanced oxidation processes have been used recently to treat complex wastewater. The current study explores the performance of pilot-scale treatment of real HWW (3000 L/d) spiked with carbamazepine (CBZ) using combinations of moving and stationary bed bio-reactor-sedimentation tank (MBSST), aerated horizontal flow constructed wetland (AHFCW), and photocatalysis. The combination of MBSST and AHFCW could remove 85% COD, 93% TSS, 99% ammonia, and 30% CBZ. However, when the effluent of the AHFCW was subjected to photocatalysis, an enhanced CBZ removal of around 85% was observed. Furthermore, the intermediate products (IPs) formed after the photocatalysis was also less toxic than the IPs formed during the biological processes. The results of this study indicated that the developed pilot-scale treatment unit supplemented with photocatalysis could be used effectively to treat HWW.

A critical review on the pathways of carbamazepine transformation products in oxidative wastewater treatment processes.

Carbamazepine (CBZ) is an anticonvulsant drug, released in domestic and hospital wastewater, and one of the drugs most commonly detected in surface water. Conventional secondary processes do a very poor job of removing it (<25 %), but its concentrations are significantly reduced by polishing oxidation processes. However, there are still many unknowns regarding the transformation products generated and their fate. This review first presents the journey of CBZ and its transformation products (TPs) in wastewater, from human consumption to discharge in water bodies. It then goes on to detail the diversity of mechanisms responsible for CBZ degradation and the generation of multiple TPs, laying the emphasis on the different types of advanced oxidation processes (AOP). 135 TPs were reported and a map describing their formation/degradation pathways was drawn up. This work highlights the wide range of physicochemical properties and toxicity effects of TPs on aquatic organisms and provides information about TPs of interest for future research. Finally, this review concludes on the importance of quantifying TPs and of determining kinetic characteristics to produce more accurate reaction schemes and computer-based fate predictions.

Tracking down pharmaceutical pollution in surface waters of the St. Lawrence River and its major tributaries.

A reconnaissance survey was undertaken to evaluate the occurrence and risks of 27 pharmaceuticals and metabolites in the St. Lawrence watershed. Surface water samples were collected over a five-year period (2017-2021) along a 700-km reach of the St. Lawrence River as well as 55 tributary rivers (overall N = 406 samples). Additionally, depth water samples and sediments were collected near a major wastewater effluent. Caffeine, diclofenac, and venlafaxine were the most recurrent substances (detection rates >80 %), and extremely high levels were found near a municipal effluent (e.g., ibuprofen (860 ng/L), hydroxyibuprofen (1800 ng/L) and caffeine (7200 ng/L)). Geographical mapping and statistical analyses indicated that the St. Lawrence River water mass after the Montreal City effluent was significantly more contaminated than the other water masses, and that contamination could extend up to 70 km further downstream. This phenomenon was repeatedly observed over the five years of sampling, confirming that this is not a random trend. A slight increase in contamination was also observed near Quebec City, but concentrations rapidly declined in the estuarine transition zone. Tributaries with the highest pharmaceutical levels (ΣPharmas ∼400-900 ng/L) included the Mascouche, Saint-Régis, and Bertrand rivers, all located in the densely populated Greater Montreal area. When flowrate was factored in, the top five tributaries in terms of mass load (ΣPharmas ∼200-2000 kg/year) were the Des Prairies, Saint-François, Richelieu, Ottawa, and Yamaska rivers. All samples met the Canadian Water Quality Guideline for carbamazepine. Despite the large dilution effect of the St. Lawrence River, a risk quotient approach based on freshwater PNEC values suggested that four compounds (caffeine, carbamazepine, diclofenac, and ibuprofen) could present intermediate to high risks for aquatic organisms in terms of chronic exposure.

On-farm Occurrence of Pharmaceuticals and Their Environmental Hazard: Case Study of a Tropical Dairy farm.

Animal husbandry wastewaters represent an important source of pharmaceuticals into the environment. This work aimed to evaluate the occurrence of pharmaceuticals and their hazard in wastewater from a model dairy farm from Costa Rica. Among the seven pharmaceuticals detected (acetaminophen, caffeine, carbamazepine, ibuprofen, ketoprofen, risperidone, sulfamethazine), caffeine, ibuprofen and acetaminophen showed the highest concentrations, while caffeine, carbamazepine and risperidone were the most frequently detected compounds. High (HQ ≥ 1) or medium (0.1 ≤ HQ < 1) hazard were estimated for three (caffeine, ibuprofen, risperidone) and two (acetaminophen, ketoprofen) pharmaceuticals, respectively; similarly, high overall hazard (∑HQ) and significant ecotoxicity were determined in samples from all sampling points. According to our results, the release of these aqueous matrices is a matter of environmental concern, as the treated wastewater is used for farm irrigation or directly released into nearby water streams. This work contributes to the knowledge on the scarcely described occurrence and risk of pharmaceuticals in Latin American regions.

Exorbitant signatures of pesticides and pharmaceuticals in municipal solid wastes (MSWs): Novel insights through risk analysis, dissolution dynamics, and model-based source identification.

Studies on the occurrence and fates of emerging organic micropollutants (EOMPs) like pharmaceuticals and pesticides in MSWs are scarce in the literature. Therefore, MSWs were sampled from 20 Indian landfills and characterized for five widely consumed EOMPs (chlorpyrifos, cypermethrin, carbofuran, carbamazepine, and sodium diclofenac), physicochemical, and biological properties. The pesticide (median: 0.17-0.44 mg kg-1) and pharmaceutical (median: 0.20-0.26 mg kg-1) concentrations significantly fluctuated based on landfill localities. Eventually, principal component and multi-factor (MFA) models demonstrated close interactions of EOMPs with biological (microbial biomass and humification rates) and chemical (N, P, K, Ca, S, etc.) properties of MSWs. At the same time, the MFA resolved that EOMPs' fates in MSWs significantly differ from bigger cosmopolitan cities to smaller rural townships. Correspondingly, the concentration-driven ecological risks were high in 15 MSWs with EOMP-toxicity ranks of diclofenac > carbofuran = chlorpyrifos > cypermethrin > carbamazepine. The EOMPs' dissolution dynamics and source apportionments were evaluated using the positive matrix factorization (PMF) model for the first time on experimental data, extracting four anthropogenic sources (households, heterogeneous business centers, agricultural, and open drains). The most significant contribution of EOMPs to MSWs was due to heterogeneous business activity. Notably, the aging of soluble chemical fractions seems to influence the source characteristics of EOMPs strongly.

Removal efficiency and energy consumption optimization for carbamazepine degradation in wastewater by electrohydraulic discharge.

OBJECTIVE: The treatment of recalcitrant emerging pollutants is a major concern in wastewater treatment. The purpose of this study was the optimization of emerging recalcitrant pollutant degradation using carbamazepine as a representative pollutant. Investigations of the carbamazepine degradation in wastewater was carried out by manipulating discharge current, air flow rate, and initial concentration to maximize removal efficiency and minimize energy consumption. METHOD: The study utilized a three-factor at two levels factorial design with randomized central runs. Discharge current, air flow rate, and initial concentration were the independent variables while to maximize removal efficiency and minimize energy consumption were the response variables. Analysis of variance (ANOVA) was performed on the data. RESULTS: Discharge current, air flow rate, and initial concentration significantly impacted the removal efficiency to different degrees. However, for energy consumption, only current and air flow rate were the significant variables. The highest removal efficiency obtained was 93% ± 4% for 10 and 40 mg/L initial carbamazepine concentration after 10 min of plasma treatment at a current of 0.45 A and no air flow rate. CONCLUSION: The plasma reactor demonstrated the capability to treat high cyclic organic chemical contaminant concentration in wastewater with possible applications in preconcentrated wastewater remediation. However, there is still room for reactor design optimization. One key area of focus is reducing treatment cost, which may be achieved theoretically, pending further experimental investigation, by introducing an alternating current power supply, which can reduce energy consumption by 50%-60%. PRACTITIONER POINTS: Discharge current, air flow rate, and initial concentration all influenced the removal efficiency of carbamazepine. For energy consumption, only current and air flow rate were significant variables. Higher currents result in an improved highly reactive species and UV generation. Treatment cost per m3 for the plasma reactor is higher than established technologies. The plasma reactor in the study still requires significant optimization.

Reusable passive sampler with carbon nanotubes for monitoring contaminants in wastewater: Application, regeneration and reuse.

Progress in excogitation suitable strategies for monitoring chemical compounds in wastewater is an essential step for further research into the occurrence, impact, and fate of the pollutants in the aquatic environment. At present, it is desirable to advance and use economical, environmentally friendly and non-labour intensive methods of environmental analysis. In this study, carbon nanotubes (CNTs) were successfully applied, regenerated, and reused as a sorbent in passive samplers for monitoring contaminants in treated and untreated wastewater at three wastewater treatment plants (WWTPs) located in different urbanization areas in northern Poland. Three cycles of chemical and thermal regeneration of used sorbents were performed. It was shown that it is possible to regenerate CNTs a minimum of three times and reuse them in passive samplers while maintaining the desired sorption properties. The obtained results confirm that the CNTs are perfectly in line with the main principles of green chemistry and sustainability. Carbamazepine, ketoprofen, naproxen, diclofenac, p-nitrophenol, atenolol, acebutolol, metoprolol, sulfapyridine and sulfamethoxazole were detected in each of the WWTPs, both in treated and untreated wastewater. The obtained data drastically show the inefficiency of the removal of contaminants by conventional WWTPs. More importantly, the results even indicate negative contaminant removal in most cases, i.e. higher concentrations (up to 863%) of these substances in the effluent compared to the influent.

Detection of Carbamazepine and Its Metabolites in Blood Samples by LC-MS/MS.

OBJECTIVES: To establish a method for the detection of carbamazepine and its metabolites 10,11-dihydro-10,11-epoxycarbamazepine and 10,11-dihydro-10-hydroxycarbamazepine in blood samples by liquid chromatography-tandem mass spectrometry (LC-MS/MS). METHODS: The blood samples were treated with 1-butyl-3-methylimidazolium hexafluorophosphate as an extraction solvent. The samples were extracted by ultrasound-assisted extraction and separated by ZORBAX Eclipse Plus C18, 95Å column. The mobile phase A aqueous solution containing 0.1% formic acid and 10 mmol/L ammonium acetate, and mobile phase B mixed organic solvent containing acetonitrile/methanol (Vacetonitrile∶Vmethanol=2∶3) were used for gradient elution at the flow rate of 1.00 mL/min. An electrospray ion source in positive mode was used for detection in the multiple reaction monitoring. RESULTS: The linearities of carbamazepine and its metabolites 10,11-dihydro-10,11-epoxycarbamazepine and 10,11-dihydro-10-hydroxycarbamazepine in blood samples were good within the corresponding range, with correlation coefficients (r) greater than 0.995 6. The limits of detection were 3.00, 0.40 and 1.30 ng/mL, respectively. The limit of quantitation were 8.00, 1.00 and 5.00 ng/mL, respectively. The extraction recoveries ranged from 76.00% to 106.44%. The relative standard deviations of the intra-day and inter-day precisions were less than 16%. Carbamazepine and its main metabolite 10,11-dihydro-10,11-epoxycarbamazepine were detected in blood samples of death cases with a mass concentration of 2.71 µg/mL and 252.14 ng/mL, respectively. CONCLUSIONS: This method has high sensitivity and good selectivity, which is suitable for the detection of carbamazepine and its metabolites in blood samples, and can be used for carbamazepine-related forensic identifications.

Hydrogen Peroxide/Phosphoric Acid Modification of Hydrochars for Sulfamethoxazole and Carbamazepine Adsorption: The Role of Oxygen-Containing Functional Groups.

Emerging pollutants, such as sulfonamide antibiotics and pharmaceuticals, have been widely detected in water and soils, posing serious environmental and human health concerns. Thus, it is urgent and necessary to develop a technology for removing them. In this work, a hydrothermal carbonization method was used to prepare the hydrochars (HCs) by pine sawdust with different temperatures. To improve the physicochemical properties of HCs, phosphoric acid (H3PO4) and hydrogen peroxide (H2O2) were used to modify these HCs, and they were referred to as PHCs and HHCs, respectively. The adsorption of sulfamethoxazole (SMX) and carbamazepine (CBZ) by pristine and modified HCs was investigated systematically. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results indicated that the H2O2/H3PO4 modification led to the formation of a disordered carbon structure and abundant pores. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy results suggested that carboxyl (-COOH) and hydroxyl (-OH) functional groups of HCs increased after modification, which is the main reason for the higher sorption of SMX and CBZ on H3PO4/H2O2-modified HCs when compared with pristine HCs. In addition, the positive correlation between -COOH/C=O and logKd of these two chemicals also suggested that oxygen-containing functional groups played a crucial role in the sorption of SMX and CBZ. The strong hydrophobic interaction and π-π interaction between CBZ and pristine/modified HCs resulted in its higher adsorption when compared with SMX. The results of this study provide a novel perspective on the investigation of adsorption mechanisms and environmental behaviors for organic contaminants by pristine and modified HCs.

Wastewater surveillance of 105 pharmaceutical drugs and metabolites by means of ultra-high-performance liquid-chromatography-tandem high resolution mass spectrometry.

Water pollution from pharmaceutical drugs is becoming an environmental issue of increasing concern, making water quality monitoring a crucial priority to safeguard public health. In particular, the presence of antidepressants, benzodiazepines, antiepileptics, and antipsychotics require specific attention as they are known to be harmful to aquatic biota. In this study, a multi-class comprehensive method for the detection of 105 pharmaceutical residues in small (30 mL) water samples was developed according to fit-for-purpose criteria and then applied to provide wide screening of samples obtained from four Wastewater Treatment Plants (WWTPs) in northern Italy. The filtered samples (0.22 µm filters) were extracted by SPE, and then eluted. 5 µL of the concentrated samples were analyzed by a UHPLC-QTOF-HRMS method validated for screening purposes. Adequate sensitivity was recorded for all target analytes, with limits of detection below 5 ng/L for 76 out of 105 analytes. A total of 23 out of the 105 targeted pharmaceutical drugs was detected in all samples. Several further compounds were detected over wide concentration intervals, ranging from ng/L to µg/L. In addition, the retrospective analysis of full-scan QTOF-HRMS data was exploited to carry out an untargeted screening of some drugs' metabolites. As a proof of concept, it was investigated the presence of the carbamazepine metabolites, which is among the most frequently detected contaminants of emerging concern in wastewater. Thanks to this approach, 10,11-dihydro-10-hydroxycarbamazepine, 10,11-dihydro-10,11-dihydroxycarbamazepine and carbamazepine-10,11-epoxide were identified, the latter requiring particular attention, since it exhibits antiepileptic properties similar to carbamazepine and potential neurotoxic effects in living organism.

Electrochemical degradation of 10,11-dihydro-10-hydroxy carbamazepine as the main metabolite of carbamazepine.

10,11-Dihydro-10-hydroxy carbamazepine has been degraded in deionized water and wastewater samples using an electrochemical process. The anode used in the treatment process was graphite-PVC. Different factors such as initial concentration, NaCl amount, type of matrix, applied voltage, role of H2O2, and pH solution were investigated in the treatment of 10,11-dihydro-10-hydroxy carbamazepine. From the outcome of the results, it was noticed that the chemical oxidation of the compound followed a pseudo-first-order reaction. The rate constants were ranged between 22 × 10-4 and 483 × 10-4 min-1. After electrochemical degradation of the compound, several by-products were raised, and they were analyzed using an accurate instrument, liquid chromatography-time of flight-mass spectrometry (LC-TOF/MS). In the present study, the treatment of the compound was followed by high energy consumption under 10 V and 0.5 g NaCl, reaching up to 0.65 Wh mg-1 after 50 min. The inhibition of E. coli bacteria after incubation of the treated 10,11-dihydro-10-hydroxy carbamazepine sample was investigated in terms of toxicity.

Pharmaceutical active compounds in a heavily industrialized and urbanized bay, Eastern China.

Bays are transition zones connecting freshwater ecosystems and marine ecosystems, and they are strongly influenced by intensive human activities. Pharmaceuticals are of concern in bay aquatic environments because of their potential threat to marine food web. We studied the occurrence, spatial distribution, and ecological risks of 34 pharmaceutical active compounds (PhACs) in Xiangshan Bay, a heavily industrialized and urbanized area in Zhejiang Province, Eastern China. PhACs were ubiquitously detected in the coastal waters of the study area. A total of twenty-nine compounds were detected in at least one sample. Carbamazepine, lincomycin, diltiazem, propranolol, venlafaxine, anhydro erythromycin, and ofloxacin had the highest detection rate (≥ 93%). These compounds were detected with maximum concentrations of 31, 127, 0.52, 1.96, 2.98, 75, and 98 ng/L, respectively. Human pollution activities included marine aquacultural discharge and effluents from the local sewage treatment plants. These activities were the most influential sources in this study area based on principal component analysis. Lincomycin was an indicator of veterinary pollution of coastal aquatic environment, and the concentrations of lincomycin were positively related to the total phosphorus in this area (r = 0.28, p < 0.05). Typical PhACs such as venlafaxine, ofloxacin, norfloxacin, roxithromycin, and clarithromycin were significantly and positively correlated with nitrate and total nitrogen (r > 0.26, p < 0.05) based on Pearson's correlation analysis. Carbamazepine was negatively correlated with salinity (r < - 0.30, p < 0.01). Land use pattern was also correlated with the occurrence and distribution of PhACs in the Xiangshan Bay. Some PhACs, i.e., ofloxacin, ciprofloxacin, carbamazepine, and amitriptyline posed medium to high ecological risks to this coastal environment. The results of this study could be helpful to understand the levels of pharmaceuticals, potential sources, and ecological risks in marine aquacultural environment.

Selective enrichment, identification, and isolation of diclofenac, ibuprofen, and carbamazepine degrading bacteria from a groundwater biofilm.

Diclofenac, ibuprofen, and carbamazepine are three of the most widely detected and most concerning pharmaceutical residues in aquatic ecosystems. The aim of this study was to identify bacteria that may be involved in their degradation from a bacterial biofilm. Selective enrichment cultures in mineral salt solution containing pharmaceutical compounds as sole source of carbon and energy were set up, and population dynamics were monitored using shotgun metagenome sequencing. Bacterial genomes were reconstructed using genome-resolved metagenomics. Thirty bacterial isolates were obtained, identified at species level, and tested regarding pharmaceutical biodegradation at an initial concentration of 1.5 mg l-1. The results indicated that most probably diclofenac biodegrading cultures consisted of members of genera Ferrovibrio, Hydrocarboniphaga, Zavarzinia, and Sphingopyxis, while in ibuprofen biodegradation Nocardioides and Starkeya, and in carbamazepine biodegradation Nocardioides, Pseudonocardia, and Sphingopyxis might be involved. During the enrichments, compared to the initial state the percentage relative abundance of these genera increased up to three orders of magnitude. Except Starkeya, the genomes of these bacteria were reconstructed and annotated. Metabolic analyses of the annotated genomes indicated that these bacteria harbored genes associated with pharmaceutical biodegradation. Stenotrophomonas humi DIC_5 and Rhizobium daejeonense IBU_18 isolates eliminated diclofenac and ibuprofen during the tests in the presence of either glucose (3 g l-1) or in R2A broth. Higher than 90% concentration reduction was observed in the case of both compounds.

Mechanism analysis of efficient degradation of carbamazepine by chalcopyrite-activated persulfate.

In this study, natural chalcopyrite (NCP) was used to activate peroxymonosulfate (PMS) to degrade carbamazepine (CBZ) oxidatively. Before and after the NCP reaction, the physical and chemical properties were characterized by SEM-EDS, XRD, XPS, XRF, and VSM. The effects of the amount of NCP and PMS, the initial pH value, and the reaction temperature on the catalytic performance of NCP were systematically studied. The research results show that the degradation efficiency of the NCP/PMS system for CBZ can reach 82.34% under the optimal reaction conditions, and the degradation process follows a pseudo-second-order kinetic model. The results of the radical quenching experiment and EPR analysis show that the active species in the system are OH·, SO4-·, and 1O2, of which SO4-· is the main active species. In addition, this study shows that the NCP/PMS system can degrade CBZ with high efficiency of 90.73% only with the assistance of 0.15 g/L Fe0. This study determined the optimal reaction conditions for natural chalcopyrite to activate PMS to degrade CBZ and clarified the activation mechanism, which broadened the application of natural ores in the field of water treatment.

Evaluation of eight psychoactive drugs used in Chinese cities by wastewater-based epidemiology.

With rapid economic development, an increasing number of people suffer from mental health diseases, which are gradually receiving the attention of society. However, basic data from surveys of mental disorders are limited. Composite influent samples were collected from 26 wastewater treatment plants in 23 major cities in China. The concentrations of the psychoactive drugs diphenhydramine, fluoxetine, doxepin, imipramine, sulpiride, zolpidem, carbamazepine, and flunitrazepam in the wastewater were determined. The detection frequency of diphenhydramine, sulpiride, and carbamazepine was close to 100 %, whereas that of the compounds was lower than 35 %. Carbamazepine had the highest mean consumption (31.1 mg/d/1000 people), followed by diphenhydramine (10.4 mg/d/1000 people) and sulpiride (11.3 mg/d/1000 people). Wastewater-based epidemiology (WBE) estimates of the average use of the three drugs were lower than those from the drug statistics data. Consumption of diphenhydramine in northern China was higher than that in southern China. A correlation analysis of psychotropic and illicit drugs revealed a correlation between sulpiride and heroin use, which may be related to the adverse effects of sulpiride treatment after heroin withdrawal. Psychotropic drug use is associated with both economic and social factors. We found associations between the use of the three drugs and age, occupation, and obesity, which are risk factors for mental disorders. The results showed that the monitoring of psychotropic drug using WBE has a certain reference value for public health care and for improving the understanding of mental disorders.

Photodegradation of a mixture of five pharmaceuticals commonly found in wastewater: Experimental and computational analysis.

Photochemical transformation of pharmaceuticals plays an important role in their natural attenuation, especially in lagoon-based wastewater treatment plants and surface waters receiving substantial sunlight. In this study, the photodegradation of five important pharmaceuticals was studied in samples obtained from a wastewater treatment plant and surface water sources. Batch photodegradation studies for a mixture of pharmaceuticals (diclofenac, sulfamethoxazole, acetaminophen, carbamazepine and gemfibrozil) were carried out in a photochemical reactor. Multiple aliquots of samples removed from the reactor during the experiment were analyzed through high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector. Intermediate products formed due to photodegradation were identified by ultra-high-performance liquid chromatography coupled with a time-of-flight mass spectrometry (UHPLC-MS/MS). Diclofenac and sulfamethoxazole were found to undergo direct photodegradation due to strong light absorption, whereas the indirect route of photosensitized degradation in the presence of dissolved organic matter (DOM) and model humic acid was significant for acetaminophen, carbamazepine, and gemfibrozil. The reactive radicals such as hydroxyl (OH•), singlet oxygen (1O2) and excited states of DOM (*DOM) were predominantly responsible for the indirect photodegradation of acetaminophen, gemfibrozil and carbamazepine, respectively. Computational analysis revealed that chlorine and carbon atoms belonging to the benzene ring of diclofenac were more reactive to radical attack. Sulfamethoxazole photodegradation occurred through oxidation of the NH2 group. Acetaminophen was more susceptible to electrophilic radical attack at the O-11, and N-7 positions and carbon atoms ortho to the phenolic oxygen and the amine group. The double bonds between C-7, C-8 and C-13 were the most reactive sites for carbamazepine that participated in the phototransformation pathway. Organic matter plays a critical role in the photodegradation of emerging contaminants. The coupling of DFT calculations with UHPLC-MS/MS analysis provided insights on key functional groups participating in the phototransformation pathway. Thus, both parent pharmaceuticals and the photodegradation intermediates should be considered during wastewater treatment.