A case study on pharmaceutical residues and antimicrobial resistance genes in Costa Rican rivers: A possible route of contamination for feline and other species.

In this investigation, the presence of antibiotics and pharmaceuticals in Costa Rican surface waters, specifically in regions near feline habitats, was examined. The study revealed that 47% of the water samples contained detectable traces of at least one antibiotic. Ciprofloxacin and norfloxacin were the most frequently detected compounds, each with a detection rate of 27%. Other antibiotics, such as erythromycin, roxithromycin, and trimethoprim, were also found but at lower frequencies, around 14%. Notably, all antibiotic concentrations remained below 10 ng/L, with ciprofloxacin, norfloxacin, and erythromycin showing the highest concentrations. Furthermore, the investigation revealed the presence of non-antibiotic pharmaceutical residues in the water samples, typically at concentrations below 64 ng/L. Tramadol was the most frequently detected compound, present in 18% of the samples. The highest concentrations were observed for acetaminophen and tramadol, measuring 64 and 10 ng/L, respectively. Comparing these findings with studies conducted in treated wastewater and urban rivers, it became evident that the concentrations of antibiotics and pharmaceuticals were notably lower in this study. While previous research reported higher values, the limited number of studies conducted in protected areas raises concerns about the potential environmental impact on biodiversity. In summary, these results emphasize the importance of monitoring pharmaceutical residues and antimicrobial resistance genes ARGs in vulnerable ecosystems, especially those in close proximity to feline habitats in Costa Rica. Additionally, the study delved into the detection of (ARGs). All tested water samples were positive for at least one ARG, with the blaTEM gene being the most prevalent at 82%, followed by tetS at 64% and qnrB at 23%. Moreover, this research shed light on the complexity of evaluating ARGs in environmental samples, as their presence does not necessarily indicate their expression. It also highlighted the potential for co-selection and co-regulation of ARGs, showcasing the intricate behaviors of these genes in aquatic environments.

Exploring matrix effects in liquid chromatography-tandem mass spectrometry determination of pesticide residues in tropical fruits.

Tropical fruits are being increasingly consumed around the world because of their appreciated characteristics, particularly their high nutritional value and distinctive taste, which are different from those of traditional fruits. Owing to their introduction into international markets it is necessary to have a reliable analytical methodology available for the sensitive determination of pesticide residues in order to monitor the compliance of maximum residue limits (MRLs). From an analytical point of view, tropical fruits have generally been far less studied than other fruits frequently consumed in the European Union or USA, which are among the most important markets. In this work, LC-MS/MS-based methodology using a triple quadrupole analyzer was developed for the multi-residue determination of selected pesticides and metabolites in tropical fruits, which were selected among the most popular in Colombia, one of the most important suppliers of tropical fruits around the world. After selection of a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe)-based sample treatment, the study focused on the evaluation of matrix effects, in order to find a simple way for their correction. Twelve different food matrices were selected to perform this study: the seven Colombian tropical fruits of highest value for domestic and international markets (uchuva, tamarillo, granadilla, gulupa, maracuya, papaya, and pithaya), and five more matrices highly consumed in Colombia (lulo, carambolo, feijoa, mangostan, and guayaba). Twenty compounds, including pesticides widely applied in tropical fruits pest control and several metabolites considered in residue definition, were used as model compounds in this work. Correction factors were used on the basis of calibration graphs obtained with standards in solvent and in matrix, and their usefulness was supported by validation of the method in all the matrices tested at 0.01 and 0.1 mg/kg. The analysis of real-world samples revealed the presence of several target compounds that were identified by the acquisition of two MS/MS transitions, and by ion intensity ratio and retention time agreement.

LC-QTOF MS screening of more than 1,000 licit and illicit drugs and their metabolites in wastewater and surface waters from the area of Bogotá, Colombia.

A large screening of around 1,000 emerging contaminants, focused on licit and illicit drugs and their metabolites, has been made in urban wastewaters (both influent and effluent) and surface waters from the area of Bogotá, Colombia. After a simple generic solid-phase extraction (SPE) step with Oasis hydrophilic-lipophilic balanced (HLB) cartridges, analyses were made by ultra high-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF MS) under MS(E) mode (sequential acquisition of mass spectra at low energy (LE) and high collision energy (HE)). Accurate mass measurements and the information provided by MS(E) on the presence of the (de)protonated molecule and fragment ions allowed the reliable identification of the compounds detected, even without reference standards being available in some cases (tentative identification). The compounds most frequently found were acetaminophen/paracetamol, carbamazepine and its dihydro-dihydroxylated metabolite, clarithromycin, diclofenac, ibuprofen, gemfibrozil, lincomycin, losartan, valsartan, the two metabolites of metamizole (4-acetamido-antipyrine and 4-formylamino-antipyrine), sucralose, and cocaine and its main metabolite benzoylecgonine. Caffeine, the sweetener saccharin, and two hydroxylated metabolites of losartan were tentatively identified in almost all samples analyzed. Pharmaceutical lidocaine was tentatively identified and subsequently confirmed with reference standard. For the first time, a general overview of the occurrence of drugs and their metabolites in the aquatic environment of Colombia has been reported. In the near future, target methodologies, typically based on liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), will need to be set up for accurate and sensitive quantification of the contaminants selected on the basis on the information provided in the present paper.

Treatment of wastewater effluents from Bogotá - Colombia by the photo-electro-Fenton process: Elimination of bacteria and pharmaceutical.

In this work, the occurrences of bacteria families and relevant pharmaceuticals in municipal wastewater effluents from Bogotá (Colombia), and their treatment by the photo-electro-Fenton process were studied. Twenty-five representative pharmaceuticals (azithromycin, carbamazepine, ciprofloxacin, clarithromycin, diclofenac, enalapril, gabapentin, iopromide, metoprolol, sulfamethoxazole, trimethoprim, valsartan, clindamycin, erythromycin, levamisole, lincomycin, norfloxacin, oxolinic acid, phenazone, primidone, salbutamol, sulfadiazine, tetracycline, tramadol, and venlafaxine) were quantified in the effluent by LC-MS/MS analysis. Four of these target compounds (azithromycin, diclofenac, trimethoprim, norfloxacin) were found at concentrations that represent an environmental risk. In addition, several bacteria families related to water and foodborne diseases were identified in such effluents (e.g., Pseudomonadaceae, Campylobacteraceae, Aeromonadaceae, Enterobacteriaceae, and Bacteroidaceae), via shotgun-metagenomic technique. Then, a bench-scale photo-electro-Fenton (PEF) system equipped with a DSA anode (Ti/IrO2-SnO2) and a GDE cathode was applied to treat such effluents. After 60 min, this treatment led to a decrease in the ratio of the bacterial content in the original samples, ~150 thousand times, and a pondered removal of 66.12% for the pharmaceuticals. The study of the process pathways indicated that the bacteria and pharmaceuticals elimination mainly occurred through attacks of hydroxyl and chlorine radicals. Interestingly, in the case of pharmaceuticals, their environmental risk quotients were diminished after the PEF application. Furthermore, the prolonged action of this electrochemical process induced ~15% of mineralization and a significant reduction of the total DNA (removal >85%). Hence, the photo-electro-Fenton process showed to be a promising alternative to deal with municipal effluents for limiting the waterborne diseases, pollution by pharmaceuticals, and mobility/availability of genetic material coming from microorganisms.

Effective elimination of fifteen relevant pharmaceuticals in hospital wastewater from Colombia by combination of a biological system with a sonochemical process.

This work presents the treatment of selected emerging concern pharmaceuticals in real hospital wastewater (HWW) from Tumaco-Colombia by combination of a biological system with a sonochemical process. Fifteen compounds, commonly present in HWW, were considered: acetaminophen, diclofenac, carbamazepine, venlafaxine, loratadine, ciprofloxacin, norfloxacin, valsartan, irbesartan, sulfamethoxazole, trimethoprim, clarithromycin, azithromycin, erythromycin and clindamycin. Initially, HWW was characterized in terms of global parameters and the pharmaceuticals content. HWW contained a moderate amount of organic matter (i.e., total organic carbon: 131.56 mg L-1 (C)) mainly associated to biodegradable components. However, the most of pharmaceuticals were found at levels upper than their predicted no effect concentration (PNEC). Then, a conventional biological treatment was applied to the HWW. After 36 h, such process mainly removed biodegradable substances, but had a limited action on the pharmaceuticals. The resultant biotreated water was submitted to the sonochemical process (375 kHz and 88 W L-1, 1.5 h), which due to its chemical (i.e., radical attacks) and physical (i.e., suspended solids disaggregation) effects induced a considerable pharmaceuticals degradation (pondered removal: 58.82%), demonstrating the complementarity of the proposed combination. Afterwards, Fe2+ (5 ppm) and UVC light (4 W) were added to the sonochemical system (generating sono-photo-Fenton process), which significantly increased up to 82.86% the pondered pharmaceuticals removal. Subsequently, to understand fundamental aspects of the pharmaceuticals degradations, a model compound (norfloxacin) in distilled water was treated by sonochemical system, sono-photo-Fenton process and their sub-systems (i.e., sono-Fenton and UVC alone). This allowed proving the hydroxyl radical action in sonochemical treatment, plus the contribution of Fenton reaction and direct photodegradation in the pharmaceuticals removal by sono-photo-Fenton. Finally, it was found that 91.13% of the initial pharmaceuticals load in HWW was removed by the biological/sono-photo-Fenton combination. The high pollutants abatement evidenced that this combination is a powerful alternative for removing pharmaceuticals from complex-matrix waters, such as raw HWW.

Bogotá River anthropogenic contamination alters microbial communities and promotes spread of antibiotic resistance genes.

The increase in antibiotic resistant bacteria has raised global concern regarding the future effectiveness of antibiotics. Human activities that influence microbial communities and environmental resistomes can generate additional risks to human health. In this work, we characterized aquatic microbial communities and their resistomes in samples collected at three sites along the Bogotá River and from wastewaters at three city hospitals, and investigated community profiles and antibiotic resistance genes (ARGs) as a function of anthropogenic contamination. The presence of antibiotics and other commonly used drugs increased in locations highly impacted by human activities, while the diverse microbial communities varied among sites and sampling times, separating upstream river samples from more contaminated hospital and river samples. Clinically relevant antibiotic resistant pathogens and ARGs were more abundant in contaminated water samples. Tracking of resistant determinants to upstream river waters and city sources suggested that human activities foster the spread of ARGs, some of which were co-localized with mobile genetic elements in assembled metagenomic contigs. Human contamination of this water ecosystem changed both community structure and environmental resistomes that can pose a risk to human health.

Degradation of seventeen contaminants of emerging concern in municipal wastewater effluents by sonochemical advanced oxidation processes.

The simultaneous degradation of seventeen emerging concern pollutants in effluent from the municipal wastewater treatment plant (MWTP) of Bogotá-Colombia was studied using high frequency ultrasound (375 kHz). The considered compounds in the effluent corresponded to pharmaceuticals (diclofenac, carbamazepine, venlafaxine, ciprofloxacin, norfloxacin, valsartan, losartan, irbesartan, sulfamethoxazole, clarithromycin, azithromycin, erythromycin, metronidazole, trimethoprim and clindamycin); cocaine and its major metabolite benzoylecgonine. Due to limitation of the MWTP for the pollutants elimination, ultrasound was applied to remove these compounds. Interestingly, ultrasonic physical action led to releasing of ciprofloxacin, norfloxacin, diclofenac and sulfamethoxazole from suspended solids, whereas the chemical effects induced degradation of the rest of compounds. For the latter ones, an interesting correlation between the sonodegradation and arithmetic multiplication between hydrophobicity and concentration of pollutants was established. Afterwards, the sonochemical process was complemented with ferrous ions (sono-Fenton), ferrous ions plus light (sono-photo-Fenton) or ferrous ions plus light in presence of oxalic acid (sono-photo-Fenton/oxalic acid). Additionally, to clarify fundamental aspects of the different systems, individual treatments in distilled water of a model pollutant (valsartan) were performed. The complemented processes significantly enhanced all compounds degradation, following the order: sono-photo-Fenton/oxalic acid > sono-photo-Fenton ∼ sono-Fenton > sonochemistry. The Fe2+ addition improved the pollutants elimination by generation of more hydroxyl radicals in the solution bulk. Meanwhile, oxalic acid avoided Fe3+ precipitation favoring the iron catalytic cycle. Thus, the work demonstrates the high potentiality of the sono-photo-Fenton/oxalic acid system for the pollutants elimination in real-world wastewater matrices.

Monitoring pharmaceuticals and personal care products in reservoir water used for drinking water supply.

In this work, the presence of selected emerging contaminants has been investigated in two reservoirs, La Fe (LF) and Rio Grande (RG), which supply water to two drinking water treatment plants (DWTPs) of Medellin, one of the most populated cities of Colombia. An analytical method based on solid-phase extraction (SPE) of the sample followed by measurement by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated for this purpose. Five monitoring campaigns were performed in each reservoir, collecting samples from 7 sites (LF) and 10 sites (RG) at 3 different depths of the water column. In addition, water samples entering in the DWTPs and treated water samples from these plans were also analysed for the selected compounds. Data from this work showed that parabens, UV filters and the pharmaceutical ibuprofen were commonly present in most of the reservoir samples. Thus, methyl paraben was detected in around 90% of the samples collected, while ibuprofen was found in around 60% of the samples. Water samples feeding the DWTPs also contained these two compounds, as well as benzophenone at low concentrations, which was in general agreement with the results from the reservoir samples. After treatment in the DWTPs, these three compounds were still present in the samples although at low concentrations (<40 ng/L), which evidenced that they were not completely removed after the conventional treatment applied. The potential effects of the presence of these compounds at the ppt levels in drinking water are still unknown. Further research is needed to evaluate the effect of chronic exposure to these compounds via consumption of drinking water.