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.

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.

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.

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.

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.

Phytoremediation of soil contaminated with PCBs using different plants and their associated microbial communities.

In this work, we evaluate the abilities of the plants Brassica juncea, Avena sativa, Brachiaria decumbens, and Medicago sativa to uptake polychlorinated biphenyls (PCBs) and induce degradation of soil microorganisms from contaminated soil. Removal of PCBs 44, 66, 118, 153, 170, and 180 was evaluated in both rhizospheric and nonrhizospheric soils. Microbial and bphA1 gene quantifications were performed by real-time PCR. The PCB concentrations in plant tissues and soil were determined, and a fluorescein diacetate (FDA) hydrolysis assay was used to measure microbial activity in soil. The removal percentages for all PCB congeners in planted soil versus unplanted control soil were statistically significant and varied between 45% and 63%. PCBs 118, 153, 138, and 170 were detected in Brachiaria decumbens roots at different concentrations. In planted soil, an increase in the concentration of bacteria was observed compared to the initial concentration and the concentration in unplanted control soil; however, no significant differences were identified between plants. The number of copies of the bphA1 gene was higher in rhizospheric versus non- rhizospheric soil for all plants at the end of the experiment. However, alfalfa and oat rhizospheric soil showed significant differences in the copy number of the bphA1 gene. In general, the concentration of fluorescein in the rhizospheric soil was greater than that in the nonrhizospheric soil. Although the plants had a positive effect on PCB removal, this effect varied depending on the type of PCB, the plant, and the soil.

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.

Application of solar photo-Fenton for benzophenone-type UV filters removal.

Benzophenones (BPs) family is one of the most frequently used groups of UV-filters. However, it has been reported by different authors that this kind of chemical compounds could be associated with some endocrine disrupting activity, genotoxicity and reproductive toxicity. In addition, different studies have evidenced the presence of BPs in several environmental matrices, indicating that conventional technologies of water treatment are not able to remove them, which generates the necessity of evaluating new alternatives of remediation. In this way, the main objective of this paper was to consider the potential removal of the benzophenone-type compounds, Benzophenone-1 and Benzophenone-2 in aqueous solutions using photo-Fenton under simulated sunlight radiation. Effects of different operational parameters, including H2O2 and Fe2+ initial concentrations, on pollutants elimination were assessed, and conditions that allow to get higher degradation rates were established. In general, results indicated that evaluated photo-catalytic system is able to remove completely the studied benzophenones, and to increase the samples biodegradability after a notable reduction of the organic carbon present in the solutions. Additionally, the identification of some of the reaction byproducts showed that hydroxylation of the substrates molecules is one of the main stages that conduct to its elimination under the evaluated experimental conditions.

Application of batch tests to assess antibiotic loads in anaerobic processes.

The presence of antibiotics in drinking water and wastewater has not been widely studied because the sanitary engineering sector mainly focuses on the removal of organic matter and nutrients. There is a lack of environmental regulations for pollutants like antibiotics. Batch tests analyse biodegradability to measure the anaerobic degradation potential of the substrate, or they can be used as toxicity tests. Oxytetracycline, florfenicol (FLO), ceftiofur (CEF) and penicillin G (PEN), commonly used in Colombia for the treatment of livestock diseases, were added in different concentrations to anaerobic sludge contained in serological glass bottles. The production of methane stored in the empty spaces of the bottles was monitored in order to determine the effect of the aforementioned antibiotics on the anaerobic process. It was found that CEF did not have any inhibitory effect on methanogenic activity, while PEN showed inhibition at all concentrations evaluated.

Heterogeneous photocatalytic degradation of the endocrine-disrupting chemical Benzophenone-3: Parameters optimization and by-products identification.

Benzophenone-3 (BP3) is one of the most used UV filters. Its disruptive effect on the endocrine system of different living beings has been demonstrated by several research groups. Present work addresses on a photocatalytic degradation of BP3 using particles of titanium dioxide in aqueous solutions considering the effect of operating parameters such as pH, catalyst and pollutant initial concentrations, and the presence of hydrogen peroxide, acetonitrile and isopropanol in the solution. In this way, a face centered, central composite design was carried out for the identification of significant factors or interactions that allow the determination of the conditions under which the pollutant suffers the highest rates of degradation. A solution initial pH of 9.0, a TiO2 concentration of 1.184 g L(-1) and an H2O2 concentration of 128.069 mg L(-1) were established as the optimal conditions for the substrate removal. In aqueous solutions and low concentrations of the pollutant (<2 mg L(-1)) photocatalytic degradation followed a pseudo-first order kinetics. After 300 min of treatment, ∼67% of the dissolved organic carbon was removed, which together with a reduction in toxicity and an increase in biodegradability confirmed that photocatalysis with TiO2 is a potential method to remove BP3 from water. Additionally, tests using acetonitrile as solvent and isopropanol as hydroxyl radical (OH(.)) scavenger suggested that, OH(.) was the main agent responsible of substrate degradation. Finally, ten process by-products were identified and a degradation route was proposed.

Degradation of ethylparaben under simulated sunlight using photo-Fenton.

Ethylparaben (EPB) has been classified by different research groups as a potential endocrine-disrupting chemical, implying that it can potentially interfere with the normal balance of the endocrine system of living beings, which with its presence in different effluents, including drinking water, generates the need to seek methods that allow its removal from different water bodies. Advanced oxidation processes have been employed widely to remove organic compounds from different matrices. In this way, Fenton technology (process based on the reaction between ferrous ions and hydrogen peroxide) has been able to degrade different substrates, but due to the Fe(2+) requirements to carry out the reaction optimally, combination of the conventional Fenton process with visible light radiation (photo-Fenton) is an alternative used in the treatment of pollution due to the presence of chemicals. In this way, the effectiveness of photo-Fenton on EPB degradation was assessed using a face-centered central composite experimental design that allowed assessment of the effects of Fe(2+) and H2O2 initial concentrations on process. In general, results indicated that after 180 min of reaction almost all EPB was eliminated, the dissolved organic carbon in solution was reduced and the sample biodegradability index was increased.

Evaluation of biostimulation and Tween 80 addition for the bioremediation of long-term DDT-contaminated soil.

The bioremediation of a long-term contaminated soil through biostimulation and surfactant addition was evaluated. The concentrations of 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) and its metabolites 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (DDE) were monitored during an 8-week remediation process. Physicochemical characterization of the treated soil was performed before and after the bioremediation process. The isolation and identification of predominant microorganisms during the remediation process were also carried out. The efficiency of detoxification was evaluated after each bioremediation protocol. Humidity and pH and the heterotrophic microorganism count were monitored weekly. The DDT concentration was reduced by 79% after 8 weeks via biostimulation with surfactant addition (B+S) and 94.3% via biostimulation alone (B). Likewise, the concentrations of the metabolites DDE and DDD were reduced to levels below the quantification limits. The microorganisms isolated during bioremediation were identified as Bacillus thuringiensis, Flavobacterium sp., Cuprivadius sp., Variovorax soli, Phenylobacterium sp. and Lysobacter sp., among others. Analysis with scanning electron microscopy (SEM) allowed visualization of the colonization patterns of soil particles. The toxicity of the soil before and after bioremediation was evaluated using Vibrio fischeri as a bioluminescent sensor. A decrease in the toxic potential of the soil was verified by the increase of the concentration/effect relationship EC50 to 26.9% and 27.2% for B+S and B, respectively, compared to 0.4% obtained for the soil before treatment and 2.5% by natural attenuation after 8 weeks of treatment.

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.

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.

Isolation of a selected microbial consortium capable of degrading methyl parathion and p-nitrophenol from a contaminated soil site.

A bacterial consortium with the ability to degrade methyl parathion and p-nitrophenol, using these compounds as the only carbon source, was obtained by selective enrichment in a medium with methyl parathion. Samples were taken from Moravia, Medellin; an area that is highly contaminated, owing to the fact that it was used as a garbage dump from 1974 to 1982. Acinetobacter sp, Pseudomonas putida, Bacillus sp, Pseudomonas aeruginosa Citrobacter freundii, Stenotrophomonas sp, Flavobacterium sp, Proteus vulgaris, Pseudomonas sp, Acinetobacter sp, Klebsiella sp and Proteus sp were the microorganisms identified within the consortium. In culture, the consortium was able to degrade 150 mg L⁻¹ of methyl-parathion and p-nitrophenol in 120 h, but after adding glucose or peptone to the culture, the time of degradation decreased to 24 h. In soil, the consortium was also able to degrade 150 mg L⁻¹ of methyl parathion in 120 h at different depths and also managed to decrease the toxicity.

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.

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.

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.