Role of the hydrolytic-acidogenic phase on the removal of bisphenol A and sildenafil during anaerobic treatment.

This paper presents the main results of the removal of two pharmaceutical and personal care products (PPCPs), bisphenol A (BPA) and sildenafil (SDF), by applying anaerobic biological batch tests. The biomass used was previously acclimatized and the experiment lasted 28 days. The effect of factors such as compound (BPA and SDF), concentration and type of inoculum was assessed, considering the factorial experimental design. The results indicated that evaluated factors did not significantly affect the PPCPs elimination in the evaluated range with a confidence level of 95%. On the other hand, the removal percentages obtained with BPA were mainly related to mechanisms, such as sorption and abiotic reactions. Regarding SDF, biodegradation was the predominant mechanism of removal under the experimental conditions of this study; however, the degradation of SDF was partial, with percentages lower than 43% in the tests with hydrolytic/acidogenic inoculum (H/A) and lower than 41% in the tests with methanogenic inoculum (MET). Finally, these findings indicated that hydrolysis/acidogenesis phase is a main contributor to SDF biodegradation in anaerobic digestion. The study provides a starting point for future research that seeks to improve treatment systems to optimize the removal of pollutants from different water sources.

Occurrence and distribution of persistent organic pollutants (POPs) in the atmosphere of the Andean city of Medellin, Colombia.

Passive air sampling (PAS) was used to evaluate organochlorine pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, polybrominated biphenyl, hexabromocyclododecane, polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and perfluoroalkane substances in the atmosphere of Medellin, Colombia. PAS was carried out for three months (four quarters per year) over two consecutive years (2017 and 2018). This study allowed establishing the baseline of some pollutants in the city against which future temporal trends can be assessed. Furthermore, monitoring results suggested releases of DDT in the city or surrounding areas despite this pollutant was banned many years ago in the country. Moreover, this study evidenced the limited scope of the national laboratories to analyze persistent organic pollutants, specially brominated and fluorinated contaminants. However, there is an installed capacity to analyze organochlorine pesticide and indicator PCB in future national monitoring plans. Therefore, it is essential to realize efforts to improve the analytical capacity and increase the scope of the national laboratories. Furthermore, the PAS strategy was valuable for monitoring these pollutants in air. Finally, the results provide an overall view of persistent organic pollutants levels and represent an initial attempt to monitor and surveillance the releases of these pollutants in the city.

Monitoring of cyanobacteria and cyanotoxins in a Colombian tropical reservoir.

Anthropogenic pollution and global climate change have resulted in favorable environmental conditions for increased frequency and duration of cyanobacterial blooms in aquatic systems. Cyanobacteria can produce toxic metabolites called cyanotoxins, which have become a worldwide concern as they threaten human and animal health. The presence of cyanobacteria and four cyanotoxins were evaluated in a Colombian reservoir. The reservoir was monitored for a year, with sampling campaigns every 3 months in seven stations. To identify and quantify cyanotoxins, the ultra-high-performance liquid chromatography coupled with triple quadrupole mass spectrometry (UHPLC-QqQ-MS/MS) technique was used, and the quantification of cyanobacteria was done by quantitative real-time PCR (qPCR) assay using a cyanobacterial-specific 16S rRNA gene fragment as a target. Cyanobacteria concentration was between 4.02 (± 0.11) × 104 and 2.72 (± 0.28) × 107 copies of Cyan 16S/µL, the minimum value corresponds to the station located in the central zone and the maximum to the station at the entrance of one of the tributary rivers. The presence of MC-RR, MC-LR, MC-YR, and NOD was detected in at least six of the seven sampling stations at different times of the year. In all cases, the concentration of the toxins detected was below 0.05 µg/L, so the guideline value established by the WHO for MC-LR was not exceeded.

Individual and synergic effect of carbamazepine and diclofenac in the removal of organic matter from an expanded granular bed anaerobic reactor.

Due to the negative effects caused to the natural environment by the presence of pharmaceutical-type traces and other pollutants in wastewater, it is necessary to develop and optimize efficient treatment systems. This study evaluated the effect of carbamazepine (CBZ) and diclofenac (DCF) on the behavior of seven EGSB (expanded granular sludge bed) anaerobic reactors at laboratory scale, using chromatographic and physicochemical analyses of the influent, effluent, and the biomass contained in the reactors. The results showed that CBZ had a greater effect on the removal and behavior of microorganisms than DCF, with average efficiencies of 34.04 ± 18.58%, 20.76 ± 8.51% and 16.29 ± 11.08% during stage II, III and IV, respectively, for CBZ, and 92.37 ± 12.74%, 26.77 ± 5.90% and 22.28 ± 9.60% during stage II, III and IV, respectively, for DCF. Additionally, it was found that the interaction of the co-substrate used (sodium acetate) in conjunction with the pharmaceutical compounds decreased the efficiency of the system in terms of the removal of analytes.

Cephalexin removal by persulfate activation using simulated sunlight and ferrous ions.

This study presents the main results related to the use of activated persulfate (PS) in the elimination of the beta-lactam antibiotic cephalexin (CPX). Experiments were done using K2S2O8 and simulated sunlight. A face-centered central composite experimental design was used to analyze the effects of the solution pH and the PS concentration on the reaction, and to determine the optimized conditions that favor the CPX elimination. The results indicated that the removal of CPX is promoted by an acidic pH and under the higher evaluated PS dose (7.5 mg L-1). CPX total removal was achieved in 30 min. The analysis of the effect of the pollutant initial concentration indicated that a pseudo-first-order kinetics model can be used to describe the reaction. Likewise, the use of Fe2+ ions for PS activation (in the dark) was evaluated and established that a higher concentration of ions favors the pollutant removal. Control tests and under the presence of scavenger agents indicated that both HO• and SO4-• radicals would be present in the solution and promote the CPX elimination. The assessment of the solution dissolved organic carbon, nitrates and sulfates was also carried out, and indicated that a portion of the organic matter was mineralized.

Elimination of cephalexin and doxycycline under low frequency ultrasound.

Cephalexin (CPX) and doxycycline (DOX) are two of the most used antibiotics to treat bacterial infections in human medicine, veterinary practices, animal husbandry, agriculture, aquaculture, among others. Nevertheless, due to their excessive consumption and incomplete absorption during their metabolization, they have been detected in different environmental matrices and the effluents of wastewater treatment plants, which reflects that conventional water treatment methods are not enough to eliminate this type of compounds. This paper presents the main results about the removal of the antibiotics CPX and DOX under low frequency (40 kHz) ultrasonic radiation (US). The effects of operational parameters such as the solution initial pH and the applied US power were assessed considering the response surface methodology and a face centered, central composite experimental design. The results indicated that evaluated operational factors significantly affect the pollutants elimination and that US technology is able to remove them completely. In addition, in terms of mineralization, experimental results showed a reduction of the organic carbon present in the solutions and a significant increase of ions (nitrates and sulfates) concentration, suggesting that part of the organic matter was transformed into CO2, H2O and inorganic species. Finally, results regarding the samples toxicity indicated that ultrasonic treatment could promote a significant reduction in this parameter, and the potential negative effect associated to CPX and DOX presence in water bodies.

Updating the use of biochemical biomarkers in fish for the evaluation of alterations produced by pharmaceutical products.

The evaluation of toxic effects in stressful environmental conditions can be determined through the imbalance between exogenous factors (environmental contaminants) and enzymatic and non-enzymatic defenses in biological systems. The use of fish for the identification of alterations in biochemical biomarkers provides a comprehensive vision of the effects that pharmaceutical products cause in the aquatic ecosystem, as they are organisms with high sensitivity to contaminants, filtering capacity, and potential for environmental toxicology studies. A wide range of pharmaceuticals can stimulate or alter a variety of biochemical mechanisms, such as oxidative damage to membrane lipids, proteins, and changes in antioxidant enzymes. This review includes a summary of knowledge of the last 20 years, in the understanding of the different biochemical biomarkers generated by exposure to pharmaceuticals in fish, which include different categories of pharmaceutical products: NSAIDs, analgesics, antibiotics, anticonvulsants, antidepressants, hormones, lipid regulators and mixtures. This review serves as a tool in the design of studies for the evaluation of the effects of pharmaceutical products, taking into account the most useful biomarkers, type of matrix, enzyme alterations, all taking the pharmaceutical group of interest.

Evaluation of ibuprofen and diclofenac in the main rivers of Colombia and striped catfish Pseudoplatystoma magdaleniatum.

This is one of the first studies carried out over three climatic seasons on the determination of ibuprofen and diclofenac, in the main rivers of Colombia and striped catfish Pseudoplatystoma magdaleniatum. Determination of water concentrations was carried out using SPE extraction, while for the analysis of the muscular tissue, the extraction was carried out by QuEChERS. For both matrices, quantification was done by UHPLC-MS/MS. No levels of ibuprofen or diclofenac concentrations were found in the muscle tissue of Pseudoplatystoma magdaleniatum, in any season or sampling site, during the 2 years of sampling. In some sampling sites, concentrations of up to 75 µg/L of diclofenac were detected, corresponding to the sampling carried out in the dry season, being the highest reported so far in surface waters, possibly generated by large concentrations of population or agricultural activities. On the other hand, for ibuprofen, no concentrations above the limit of quantification (0.50 µg/L) were found in the waters of the Cauca and Magdalena rivers, for any season and sampling site.

Enzymatic activity changes in striped catfish Pseudoplatystoma magdaleniatum, induced by exposure to different concentrations of ibuprofen and triclosan.

The present study aimed to evaluate the effects of exposure for four months, with ibuprofen and triclosan at 25 and 50 µg/L in Striped catfish Pseudoplatystoma magdaleniatum, evaluated between sexes and exposure times. Biochemical biomarkers such as lactate dehydrogenase, alanine aminotransferase, aspartate aminotransferase, alkaline phosphatase, gamma-glutamyltransferase, acetylcholinesterase, creatine kinase, lipid peroxidation, albumin, globulins, creatinine, and urea were evaluated. The results of this study suggest that both ibuprofen and triclosan at concentrations of 25 and 50 µg/L can cause alterations to P. magdaleniatum, interfering with the activity of certain enzymes associated with energy production, immune response, architecture, and cellular physiology. Also, we determined the current state of contamination in fish, the concentration of ibuprofen and triclosan in P. magdaleniatum muscle samples from the different places markets located on the banks of the main rivers of Colombia was quantified by UHPLC-QqQ-MS/MS, in three climatic periods; finding triclosan levels in the dry season in some of the sampling points compatible with enzyme-level alterations in this species.

Assessment of chromium, lead and mercury in seawater and some fish species from the Gulf of Urabá, Colombian Caribbean: a baseline study.

The coastline of the department of Antioquia, in Colombia, exhibits a wide variety of aquatic and land ecosystems rich in both diversity and abundance. However, it is exposed to a variety of human activities, including industry, tourism, and mining. Banana cultivation is the main activity carried out in this region, which offers large economic benefits. In addition, there are diverse fishery resources that are main basis of the economy and nutrition for the population. Over the years, the Gulf of Urabá has been affected by serious pollution problems due to elevated contents toxic compounds that deteriorate the aquatic ecosystem, even our laboratory has conducted previous studies in heavy metals in fish from this same area. The aim of this study was to evaluate the contents of chromium (Cr), lead (Pb), and mercury (Hg) in seawater and fish muscle in three fish species from the Gulf of Urabá that are commercialized and consumed by the population of the municipality of Turbo, using microwave-induced plasma optical emission spectrometry (MIP OES). The occurrence of toxic metals in seawater in this area has not been reported, and to the best of our knowledge, this is the first study. Cr and Pb concentrations in seawater from several sampling points were detected ranged from 0.025 to 0.369 mg/L and 0.012-0.165 mg/L, respectively, while Hg levels were below detection limit. Regarding fish samples, Pb and Hg levels range 0.64-1.91 mg/kg and 0.11-1.09 mg/kg, respectively. Sea catfish species exhibited the highest content of metals, followed by stone head catfish and anchovy, it which showed the lowest contamination by metals. In this study, levels that exceed the limits in Colombian regulations regarding metal contents in discharge points to surface water and fishery products for human consumption were found.

Monitoring of chlorine decay in public swimming pools in Medellín (Colombia).

The present work shows the evaluation of the decay of free residual chlorine in several public swimming pools in the city of Medellín, observing that a decrease in residual chlorine does occur. Some factors accelerate the decrease in the concentration of free residual chlorine in recreational water, such as the number of bathers in the pool, the pH, and the temperature of the water. For this reason, the concentration of the disinfectant rapidly decreases to an extent that the health of swimmers could be put at risk. The Authority of Health of Medellín carries out inspection, surveillance and quality control activities of water for recreational use. These purposes of these include guaranteeing the reduction of risk factors to the health of the users of said pools.

Methyl Paraben and Carbamazepine in Water and Striped Catfish (Pseudoplatystoma magdaleniatum) in the Cauca and Magdalena Rivers.

Between 2017 and 2019, samplings were carried out in the San Jorge, Cauca and Magdalena River basins in Colombia, to determine the presence of methyl paraben and carbamazepine in water and Pseudoplatystoma magdaleniatum. For the analysis of the samples, a validation of the analytical method was performed, following the EPA method 1694 (Pharmaceutical and personal care products in water), with slight modifications. This was done by liquid-chromatography tandem mass spectrometry, for quantification of methyl paraben and carbamazepine, including parameters of linearity, accuracy precision and veracity. Carbamazepine was found in the Magdalena River at 8.03 ± 0.01 µg/L in transition season. In fish samples, methyl paraben and carbamazepine were detected in a range between 32 and 90.80 µg/kg in transition and dry seasons.

Occurrence and removal of pharmaceutical and personal care products using subsurface horizontal flow constructed wetlands.

A significant number of emerging pollutants resulting from point source and diffuse pollution are present in the aquatic environment. These are chemicals that are not commonly monitored, but have the potential to cause adverse effects on human and ecological health. One form of emerging pollutants, pharmaceutical and personal care products (PPCPs), are becoming a serious problem in the discharge of domestic wastewater. Therefore, the aim of this study was to determine their occurrence in wastewater and surface waters, and to evaluate the efficiency of subsurface horizontal flow constructed wetlands (planted in polyculture and unplanted), in removing two pharmaceuticals: carbamazepine (Cbz) and sildenafil (Sil); and a personal care product: methylparaben (Mp), present in domestic wastewater. The mixed PPCPs were added to wetlands, at nominal concentrations of 200 µg / L for each compound. The working flow of the reactors was 15 mL / min and the hydraulic retention time was three days. The physicochemical parameters evaluated were: organic load, dissolved oxygen, temperature, conductivity, redox potential, dissolved solids, pH and PPCPs concentration. The presence of the three compounds became evident in all sampled sites, with concentrations of up to 10.66 µg / L, 7.24 µg / L and 2.64 µg / L for Cbz, Mp and Sil, respectively. In planted wetlands, removal efficiencies of up to 97% were achieved for Sil, while in the unplanted these were 30% lower. Removal efficiencies greater than 97% were achieved for Mp, however, for Cbz they were less than 10%, evaluated in both treatments. The average removal efficiency for organic load was 95%. It was determined that constructed wetlands can efficiently remove simple molecular structure compounds such as Mp, and complex structures such as Sil. However, Cbz remained as a recalcitrant contaminant.

Use of low frequency ultrasound for water treatment: Data on azithromycin removal.

Azithromycin (AZT) is a broad-spectrum antibiotic present in different aqueous matrices due to its incomplete removal using conventional water treatments. Ultrasound (US) is an advanced oxidation technology that has demonstrated its capacity to degrade different types of organic molecules due to the generation of cavitation bubbles or cavities that promote the generation of radicals. In this paper, data regarding the use of low-frequency US (40 kHz) in the removal of AZT are presented. Tests were carried out at lab scale for 60 min considering a reaction volume of 300 mL (pollutant initial concentration 1.0 mg L -1). The effect of operational parameters such as pH, ultrasound power, the presence of external agents like ferrous ions, hydrogen peroxide, and UV radiation were evaluated. In general, obtained data show that under the experimental reaction conditions, it is feasible to reach extents of AZT removal ∼50.0%, and that the presence of other species in the medium could inhibit the reaction, mainly due to scavenging effects. This information is relevant to future applications of US, at pilot or real scale, in the treatment of water with presence of AZT or similar organic pollutants.

Presence of Disinfection Byproducts in Public Swimming Pools in Medellín, Colombia.

The quality of water in swimming pools is essential to avoid risks to the health of users. Medellín has more than 1000 public swimming pools, which are supervised by the Medellín Health Authority to monitor and ensure compliance with relevant regulations. The Health Authority has financed several studies related to the quality of drinking and recreational water in Medellín in order to protect consumers and users. One such study involves the evaluation of the presence of disinfection byproducts (DBP). The best known DBPs resulting from disinfection with chlorine are trihalomethanes (THMs) and halogenated acetic acids (HAAs), as well as other minorities such as chloramines or halophenols (HPs). DBPs pose a greater risk in swimming pool water because there is a greater possibility of ingestion, since exposure occurs through several routes at the same time (direct ingestion of water, inhalation of volatile or aerosol solutes, dermal contact and absorption through skin). In the present work, high concentrations of THMs and HAAs were detected in the public swimming pools selected in the study, but the presence of HPs was not detected in the pools.

Monitoring pharmaceuticals and personal care products in water and fish from the Gulf of Urabá, Colombia.

Gulf of Urabá is considered a tourist zone of Antioquia Department attracts a large number of visitors to explore the aquatic ecosystem and beaches thus offering a large economic benefit. However, this region has been affected by various anthropogenic effects thus generating an environmental problematic that affect aquatic ecosystem. Over the years, several research has been evaluated pollutant such as pesticides, metals and physicochemical parameters, even our laboratory had found several toxic metals in fish from this same area. The presence of emerging pollutant in matrices such as seawater and fish from Gulf of Urabá have not been reported, and to the best of our knowledge, this is the first study. This work presents important aspects relating to sampling, monitoring and surveillance of seawater and several fish species caught in the area in order to determinate the content of emerging pollutant (triclosan, ibuprofen, diclofenac) using UPLC-QqQ/MS. In general, all three pharmaceuticals in different sampling sites were detected and total concentrations ranged from 0.10 to 1.54 µg/L in surface water. However, emerging pollutants content in fish muscle was not detected. In addition, a high variability in triclosan, ibuprofen and diclofenac concentrations according to the season of sampling was found. Regarding to seasonal variations, most emerging pollutant in the surface water had variation in levels both dry and wet season. Better removal was presented in the dry season, due to stronger irradiation and greater activity of microorganisms.

Photolysis of a mixture of anthracene and benzo[a]pyrene at ultra-trace levels in natural water with disinfection purposes.

The photodegradation of anthracene (AN) and benzo[a]pyrene (BaP), two priority polycyclic aromatic hydrocarbons (PAHs), was examined at ultra-trace levels in surface water to elucidate their behaviour under several irradiance values and types of radiation. The emitting flux and the spectrum of the lamps were found to develop a crucial role in AN and BaP degradation since removal efficiencies of the target contaminants higher than 99% were found after 15 min of irradiation under an ultraviolet C (UVC) irradiance of 0.63 mW/cm2, corresponding to a fluence of 560.25 mJ/cm2. On the other hand, although ultraviolet A (UVA) lamps exhibited a higher irradiance compared to that of UVC lamps, they were not efficient for degrading the target PAHs. The removal kinetic studies corroborated these findings, being the AN elimination rate in surface water higher than that in deionized water at optimal operating conditions. Disinfection potential was also measured. A rapid microbial load inactivation, in terms of total coliforms naturally contained in the water matrix studied, was evidenced within 15 min of treatment for the fluence referred. However, after 24 hr in the dark, a regrowth was observed. Additionally, photolysis products more toxic than the parent compounds were found, which were not removed even by extending the treatment time. In this regard, it can be concluded that the individual action of UVC light for removing AN and BaP with disinfection purposes is not an efficient treatment; therefore, the use of radiation in combination with other kinds of treatments is required.

Experimental data on antibiotic cephalexin removal using hydrogen peroxide and simulated sunlight radiation at lab scale: Effects of pH and H2O2.

Cephalexin (CPX) is a ß-lactam antibiotic widely used to treat bacterial infections in the respiratory tract, skin, bones, and ear; a situation that has contributed to its discharge into wastewater (mainly through excretion after ingestion) and its accumulation in water bodies. CPX presence on environmental compartments could interfere in the physiological functions of animals and humans due to the induction of mutagenic and carcinogenic effects. Different technologies have been evaluated to remove CPX from aqueous matrices. In this way, this work presents the main data regarding the use of the combination of hydrogen peroxide and simulated sunlight radiation in CPX removal. Effects of H2O2 initial concentration and solution pH were evaluated using a face-centered, central composite design and the response surface methodology. Optimized conditions, under the evaluated experimental range, were established. In addition, data about the total organic carbon and anions content in treated samples were collected. These data can be useful for the evaluation of the use of H2O2 and light radiation on organic pollutants removal, the comparison of the effectiveness of different technologies on CPX elimination, and as a starting point to carry out this type of process at pilot or real scale.

Effect of Benzophenone-3 on performance, structure and microbial metabolism in an EGSB system.

Benzophenone-3 is an organic compound widely used as a UV filter, which has been reported as water pollutant and is connected with endocrine disruption in humans and animals. Expanded granular sludge beds (EGSB) are a form of an anaerobic digestion system, which has been successfully evaluated for wastewater treatment, and the removal of different compounds, however little is known about the effect of compounds as Benzophenone-3 in the performance of EGSB systems. In this study, we evaluate the effect of BP-3 on the performance, microbial structure and metabolism of EGSB reactors. For this purpose, biogas production, removal efficiencies of BP-3 and DQO were monitored. Changes in bacteria and archaea microbial structure were investigated using PCR-DGGE, and the effect on anaerobic metabolism was evaluated by measuring the expression of mcrA and ACAs genes through qRT-PCR. The systems remained stable and efficient throughout the operation stages, with CH4 percentages greater than 55% and COD and BP-3 removal percentages greater than 90%. The presence of different concentrations of Benzophenone-3 influenced the organization of microbial communities, especially archaea. However, this did not affect the stability and performance of the EGSB systems.

Comparison of microbial and physicochemical behavior of expanded granular sludge bed system during methylparaben and triclosan removal.

Methylparaben and triclosan are antimicrobial agents widely used as preservatives in a variety of personal care and pharmaceutical products. Wastewater is considered the main source of these compounds in the environment. Expanded granular sludge bed (EGSB) reactors are a high rate technology for wastewater treatment based on biological processes and have been shown to be efficient in removing different types of compounds; however, little is known about the effect of contaminants such as methylparaben and triclosan on their behavior and effectiveness. In this study, we evaluate and compare the microbial and physicochemical behavior of EGSB systems during methylparaben and triclosan removal. The presence of different concentrations of pollutants had an influence on the cluster organization of microbial communities, especially bacteria. However, this did not affect the stability and performance of the EGSB systems. The banding patterns of the denaturing gradient gel electrophoresis of archaea demonstrated the constant presence and abundance of Methanosaeta concilii throughout all stages of operation, showing that this microorganism played a fundamental role in the stability of the reactors for the production of methane. The type of compound and its concentration influenced the expression of the mcrA and ACAs genes; however, these changes did not alter the stability and performance of the EGSB systems.