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Two analytical methods were developed using electrochemical and spectrometric techniques for the simultaneous determination of endocrine disruptors triclosan and methylparaben in the monitoring of personal care products. For the electroanalytical analyses, a sensitive electrode based on graphene quantum dots supported in chitosan was employed. Under optimized conditions and a working potential of typically + 0.60 V for triclosan and + 0.81 V (vs. Ag/AgCl) for methylparaben, the calibration plots obtained by differential pulse voltammetry were linear in the range 0.10 to 10.0 µmol L-1. The detection limits were 0.03 and 0.04 µmol L-1 for triclosan and methylparaben, respectively. For the spectrometric method, UV/VIS spectrometry was used with a mathematical processing of non-linear deconvolution. This processing was used to solve the problem of overlapping absorption bands of triclosan (282 nm) and methylparaben (257 nm), which enabled simultaneous determination. The calibration plots by UV/VIS spectrometry were linear in the range 1.0 to 14.0 µmol L-1 with detection limits of 0.42 and 0.37 µmol L-1, respectively, for triclosan and methylparaben. Similar results obtained from the calibration plots of individual analytes suggest that the methods can be applied for individual or simultaneous determination of these species. Both methods were employed in the analysis of five samples of personal care products: toothpaste, antiseptic soap, antiseptic deodorant, shampoo, and a bath kit (soap and shampoo). The statistical tests indicated that there were no significant differences regarding the accuracy and precision of the data provided by the two methods described herein. Graphical abstract Schematic representation for simultaneous determination of triclosan and methylparaben: electrochemical method employing an electrode modified with graphene quantum dots supported in chitosan and spectrometric method applying a non-linear deconvolution of spectrum.

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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.

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This review aims to gather and summarize information about the occurrence of emerging contaminants and antibiotic resistance genes in environmental matrices in Latin America. We aim to contribute to future research by compiling a list of priority pollutants adjusted to the needs and characteristics of Latin America, according to the data presented in this study. In order to perform a comprehensive research and secure a representative and unbiased amount of quality data concerning emerging contaminants in Latin America, the research was performed within the Scopus® database in a time frame from 2000 to July 2019. The countries with higher numbers of published articles were Brazil and México, while most studies were performed in the surroundings of Mexico City and in Southern and Southeastern Brazil. The main investigated environmental matrices were drinking water and surface water. The presence of antibiotic resistance was frequently reported, mainly in Brazil. Monitoring efforts should be performed in other countries in Latin America, as well as in other regions of Brazil and México. The suggested priority list for monitoring of emerging contaminants in Latin America covers: di(2-ethylhexyl) phthalate (DEHP), bisphenol-A (BP-A), 4-nonylphenol (4-NP), triclosan (TCS), estrone (E1), estradiol (E2), ethinylestradiol (EE2), tetracycline (TC), amoxicillin (AMOX), norfloxacin (NOR), ampicillin (AMP) and imipenem (IMP). We hope this list serves as a basis for the orientation of the future research and monitoring projects to better understand the distribution and concentration of the listed emerging substances.

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OBJECTIVES: To determine the effect of triclosan-containing fluoride toothpaste on the clinical parameters and the osteo-immunoinflammatory mediators in the peri-implant fluid when applied in a stent during experimental peri-implant mucositis in smokers. MATERIALS AND METHODS: Twenty-six smokers with an implant-supported crown were enrolled in this double-blind, randomized, crossover study. During the two 3-week periods without mechanical toothbrushing (washout period: 30 days), patients were randomly assigned to triclosan/fluoride (n:13) or fluoride toothpaste (n:13), three times/day. Clinical and immunoenzymatic assays were performed at baseline, 3, 7, 14 and 21 days. RESULTS: Both groups showed increase in the Plaque Index throughout the study (p = 0.001), without inter-group differences at 21 days (p > 0.05). No intra- or inter-group differences were observed for IFN-γ, IL10, IL-1ß, IL8, IL-17, IL-6, TNF-α, MMP-2, MMP-9, TGF-ß, OC, OPN, ICTP, OPG and RANKL (p > 0.05). However, the RANKL/OPG ratio was significantly higher in fluoride toothpaste-treated sites when compared to triclosan/fluoride-treated sites at the end of period without mechanical toothbrushing, on the 21st day (p = 0.041). CONCLUSION: Triclosan-containing toothpaste favorably modulated osteo-immunoinflammatory mediators during the experimental peri-implant mucositis in smokers, decreasing the ratio of RANKL/OPG.

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The occurrence, partitioning, and spatio-temporal distribution of seven pharmaceuticals for human use, three steroid hormones and one personal care product were determined in surface water, suspended particulate matter (SPM), and sediment of Piraí Creek and Jundiaí River (Jundiaí River Basin, São Paulo, Brazil). The maximum average detected concentrations of the compounds in the Piraí River samples were < 30 ng L-1, except for caffeine (222 ng L-1). In Jundiaí River samples, most of the compounds were frequently detected, wherein caffeine had the highest concentration, with maximum average concentrations of 14,050 ng L-1, followed by atenolol (431 ng L-1), ibuprofen (268 ng L-1) and diclofenac (214 ng L-1). Atenolol, propranolol, estrone, and triclosan were the contaminants most frequently detected in sediment and SPM samples. Triclosan had the highest average proportion of SPM as opposed to in the aqueous phase (> 75%). Contaminants with acid functional groups showed, in general, a lower tendency to bind to particulate matter and sediments. In addition, hydrophobicity had an important effect on their environmental partitioning. The spatial distribution of contaminants along the Jundiaí River was mainly affected by the higher concentration of contaminants in water samples collected downstream from a sewage treatment plant (STP). The results obtained here clearly showed the importance of the analysis of some contaminants in the whole water, meaning both dissolved and particulate compartments in the water, and that the partitioning is ruled by a set of parameters associated to the physicochemical characteristics of contaminants and the matrix properties of the studied, which need be considered in an integrated approach to understand the fate of emerging chemical contaminants in aquatic environments.

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The guidelines for the Environmental Risk Assessment (ERA) of pharmaceuticals and personal care products (PPCP) recommend the use of standard ecotoxicity assays and the assessment of endpoints at the individual level to evaluate potential effects of PPCP on biota. However, effects at the sub-individual level can also affect the ecological fitness of marine organisms chronically exposed to PPCP. The aim of the current study was to evaluate the environmental risk of two PPCP in marine sediments: triclosan (TCS) and ibuprofen (IBU), using sub-individual and developmental endpoints. The environmental levels of TCS and IBU were quantified in marine sediments from the vicinities of the Santos submarine sewage outfall (Santos Bay, São Paulo, Brazil) at 15.14 and 49.0 ng g-1, respectively. A battery (n = 3) of chronic bioassays (embryo-larval development) with a sea urchin (Lytechinus variegatus) and a bivalve (Perna perna) were performed using two exposure conditions: sediment-water interface and elutriates. Moreover, physiological stress through the Neutral Red Retention Time Assay (NRRT) was assessed in the estuarine bivalve Mytella charruana exposed to TCS and IBU spiked sediments. These compounds affected the development of L. variegatus and P. perna (75 ng g-1 for TCS and 15 ng g-1 for IBU), and caused a significant decrease in M. charruana lysosomal membrane stability at environmentally relevant concentrations (0.08 ng g-1 for TCS and 0.15 ng g-1 for IBU). Chemical and ecotoxicological data were integrated and the risk quotient estimated for TCS and IBU were higher than 1.0, indicating a high environmental risk of these compounds in sediments. These are the first data of sediment risk assessment of pharmaceuticals and personal care products of Latin America. In addition, the results suggest that the ERA based only on individual-level and standard toxicity tests may overlook other biological effects that can affect the health of marine organisms exposed to PPCP.

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The main objective of this study is to propose a new sorbent phase based on a commercial epoxy resin, for use as an alternative sorbent in the stir bar sorptive extraction (SBSE) technique. The analytes triclosan (TCS) and methyl-triclosan (MTCS) were selected in order to demonstrate the application of the bars, using some water samples as matrices. The extraction conditions of sample volume, stirring time, pH, temperature and ionic strength were evaluated, and for the back extraction, the bars were sonicated using 1.00 mL of acetonitrile for 10 min. The technique of liquid chromatography using a diode array detector was employed for the quantitation. Analytical curves of between 2.50 and 50.0 µg L-1 with r2 of 0.9894 (TCS) and 0.9933 (MTCS), and limit of detection (LOD) values of 0.6 µg L-1 (TCS) and 2.0 µg L-1 (MTCS) were observed. Recovery values between 100.4% and 121.6% were verified for ultrapure water and between 50.3% and 93.8% for wastewater samples, thereby suggesting the possibility of employing the bars for quantitation of TCS and MTCS in aqueous samples. This is the first time that this resin has been applied without the need for the adhesion of any additional sorbent phase, thereby providing a simple and low-cost method. Another feature is that only eight bars were employed in the entire work, and each bar was used approximately 40 times with the same performance without memory effects.

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Estimar el grado de remoción de contaminantes emergentes en el proceso de tratamiento de aguas residuales es de importancia para evaluar la efectividad de las técnicas empleadas en la actualidad. El triclosán (TCS) es un agente antimicrobiano sintético de amplio espectro, estudios recientes sugieren que presenta elevado potencial como interruptor endocrino. Se determinó la concentración de TCS en cuatro muestras de aguas residuales obtenidas en diferentes etapas del proceso de tratamiento de aguas en la Planta Piloto para el Tratamiento de Aguas Residuales Ingeniero Arturo Pazos Sosa (IAPS). Las muestras de agua fueron filtradas en membrana, tratadas por adición de TCS estándar y formación de un compuesto complejo coloreado amarillo-café cuya absorbancia a 475 nm fue registrada en un espectrofotómetro Cary® 50 UV-Vis. Se identificó la presencia de TCS en concentraciones por arriba de 200 µg/L en tres diferentes etapas del tratamiento de aguas residuales en la planta piloto IAPS lo que permitió concluir que el grado de remoción de TCS en esta planta de tratamiento de aguas osciló entre 31 y 95% dependiendo de la etapa de tratamiento, sin embargo el agua del efluente de la planta no puede considerarse como potable ya que la concentración de TCS determinada en este estudio sobrepasa por al menos un orden de magnitud de diez los niveles a los cuales no se han reportado efectos adversos hacia organismos vivos.

Estimating the degree of contaminants' removal during wastewater treatment is important to evaluate the effectiveness of the current treatment techniques. Triclosan (TCS) is a synthetic broad spectrum antimicrobial agent and recent investigations suggest that this compound has high potential as endocrine disruptor. The concentration of TCS was measured in four wastewater samples obtained at different processing steps at the Ingeniero Arturo Pazos Sosa (IAPS) pilot plant. The wastewater samples were treated by membrane filtration, standard addition of TCS and the subsequent formation of a brown-yellow colored complex, whose absorbance at 475nm was measured in a Cary 50® UV-Vis spectrophotometer. TCS was found at concentrations over 200 µg/L in three different phases of the wastewater treatment at the IAPS plant. In conclusion, the degree of TCS removal in this plant was between 31 and 95% depending on the treatment stage. However plant effluent cannot be considered potable since the TCS concentration found in this study is at least ten times higher than those at which adverse effects to living organisms have not been detected.

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Triclosan is a broad-spectrum biocide used in personal-care products that is suspected to be linked to the emergence of antibiotic-resistant bacteria. In the present work, the enzymes horseradish peroxidase and laccase from Trametes versicolor were evaluated for the conversion of triclosan in an aqueous matrix. The removal of antibacterial activity by the enzymatic processes was evaluated by an assay based on the growth inhibition of Escherichia coli K12. The horseradish peroxidase (HRP) process appears more advantageous than the laccase process in removing triclosan from an aqueous matrix, considering the reaction parameters pH, temperature, catalytic efficiency, and enzyme concentration. The highest conversion of triclosan catalysed by laccase was observed at pH 5.0, that is, lower than the typical pH range (6.5-7.5) of sewage treatment plants' effluents. The efficiency of laccase process was much more impacted by variations in the temperature in the range of 10-40°C. Kinetic studies showed that triclosan is a substrate more specific for HRP than for laccase. The protein content for the HRP-catalysed process was 14 times lower than that for the laccase process. Decay kinetics suggest that reaction mechanisms depend on enzyme concentration and its concentration. Both processes were able to reduce the antibacterial activity, and the residual activity of the treated solution is probably due to non-converted triclosan and not due to the reaction products. The laccase-catalysed conversion of triclosan in an environmental relevant concentration required a higher amount of enzyme than that required in the HRP process.

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Lab-scale photolysis, biodegradation and transport experiments were carried out for naproxen, carbamazepine and triclosan in soil, wastewater and surface water from a region where untreated wastewater is used for agricultural irrigation. Results showed that both photolysis and biodegradation occurred for the three emerging pollutants in the tested matrices as follows: triclosan>naproxen>carbamazepine. The highest photolysis rate for the three pollutants was obtained in experiments using surface water, while biodegradation rates were higher in wastewater and soil than in surface water. Carbamazepine showed to be recalcitrant to biodegradation both in soil and water; although photolysis occurred at a higher level than biodegradation, this compound was poorly degraded by natural processes. Transport experiments showed that naproxen was the most mobile compound through the first 30cm of the soil profile; conversely, the mobility of carbamazepine and triclosan through the soil was delayed. Biodegradation of target pollutants occurred within soil columns during transport experiments. Triclosan was not detected either in leachates or the soil in columns, suggesting its complete biodegradation. Data of these experiments can be used to develop more reliable fate-on-the-field and environmental risk assessment studies.

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