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Bisphenols are widely used as monomers and additives in plastic production. Thus, bisphenol A (BPA) and its most prominent substitutes have been detected in many environmental and human samples. This study proposes an online solid-phase extraction analytical methodology coupled to liquid chromatography with tandem mass spectrometry for the determination of six bisphenols (BPA and bisphenols F (BPF), S (BPS), AF (BPAF), B (BPB), and E (BPE)) in urine samples as an efficient and automated methodology. The method was developed and validated for all bisphenols with good recoveries (92-112%) and repeatability (RSD ≤ 10%) despite the variable matrix effects, except BPAF (which would require a dedicated internal standard), achieving method quantification limits in the 0.05-2.2 ng mL-1 range. The methodology was subsequently applied to 435 urine samples from a non-occupational exposure population (civil servants for the regional government) from Santiago de Compostela (Galicia, Spain). Only BPA, BPF, and BPS were positively detected; the last two presented higher detection frequencies than BPA. When the urinary concentrations are extrapolated to human intake and compared to the European Food Safety Agency (EFSA) tolerable daily intake (TDI) of 2 × 10-4 µg kg-1 day-1 (TDI), all BPA positively identified samples would surpass this threshold. Although no TDI exists currently for the other two identified bisphenols, it is evident that human exposure to bisphenols should be limited. Finally, the results stratification by gender revealed higher levels of exposure to BPF in the women group.
Assuntos
Compostos Benzidrílicos , Fenóis , Extração em Fase Sólida , Espectrometria de Massas em Tandem , Fenóis/urina , Espectrometria de Massas em Tandem/métodos , Humanos , Extração em Fase Sólida/métodos , Feminino , Masculino , Compostos Benzidrílicos/urina , Cromatografia Líquida/métodos , Adulto , Limite de Detecção , Pessoa de Meia-Idade , Exposição Ocupacional/análise , Reprodutibilidade dos Testes , EspanhaRESUMO
Wastewater-based epidemiology (WBE) has become an invaluable tool for tracking the evolution of use or exposure of/to numerous substances. Bisphenols, commonly utilized in manufacturing plastic goods, have been categorized as endocrine disrupting chemicals, underscoring the critical need for real-time data on their local-level exposure to safeguard public health. In this study, we have developed a novel analytical method and WBE framework for the assessment of population-level exposure to bisphenol A (BPA) and its most prominent substitutes, bisphenols F and S (BPF and BPS), through the determination their Phase II metabolites in wastewater by WBE. Stability and exclusivity tests denoted that glucuronides are not stable in sewage, whereas sulfate metabolites are good biomarkers. Therefore, a solid-phase extraction followed by liquid chromatography-tandem mass spectrometry method was developed for the bisphenols' monosulfates and BPA bissulfate. The analytical method was validated with three different wastewater matrices, providing trueness (as recovery) in the 79-112 % range with relative standard deviations < 12 %, and method quantification limits below 2 ng L-1 for monosulfates, but higher (35 ng L-1) for BPA bissulfate. Subsequently, the method was applied to 24h-composite raw wastewater samples collected over a week in 4 different locations in Spain and Portugal. BPA bissulfate was not detected, but the three monosulfate metabolites of each bisphenol were positively detected in the samples, being the metabolite of BPA the most prevalent, followed by those of BPF and BPS. Community-wide BPA intake was then estimated to be higher than the European Food Safety Agency (EFSA) tolerable daily intake (TDI) of 2 × 10-4 µg kg-1day-1 in all locations. In the case of BPF and BPS, there is not enough metabolism data or even established limit, but they would also surpass safe levels in several locations if a similar metabolism and TDI would be assumed. This innovative method could be used to a larger set of wastewater-treatment plants as an early-warning approach on human exposure to bisphenols.
Assuntos
Compostos Benzidrílicos , Fenóis , Águas Residuárias , Poluentes Químicos da Água , Águas Residuárias/química , Humanos , Sulfonas , Espectrometria de Massas em Tandem , Exposição Ambiental , Extração em Fase Sólida , Disruptores Endócrinos , Cromatografia LíquidaRESUMO
As global effects of water scarcity raise concerns and environmental regulations evolve, contemporary wastewater treatment plants (WWTPs) face the challenge of effectively removing a diverse range of contaminants of emerging concern (CECs) from municipal effluents. This study focuses on the assessment of advanced oxidation processes (AOPs), specifically UV-C/H2O2 and UV-C/Chlorine, for the removal of 14 target CECs in municipal secondary effluent (MSE, spiked with 10 µg L-1 of each CEC) or in the subsequent MSE nanofiltration retentate (NFR, no spiking). Phototreatments were carried out in continuous mode operation, with a hydraulic retention time of 3.4 min, using a tube-in-tube membrane photoreactor. For both wastewater matrices, UV-C photolysis (3.3 kJ L-1) exhibited high efficacy in removing CECs susceptible to photolysis, although lower treatment performance was observed for NFR. In MSE, adding 10 mg L-1 of H2O2 or Cl2 enhanced treatment efficiency, with UV-C/H2O2 outperforming UV-C/Chlorine. Both UV-C/AOPs eliminated the chronic toxicity of MSE toward Chlorella vulgaris. In the NFR, not only was the degradation of target CECs diminished, but chronic toxicity to C. vulgaris persisted after both UV-C/AOPs, with UV-C/Chlorine increasing toxicity due to potential toxic by-products. Nanofiltration permeate (NFP) exhibited low CECs and microbial content. A single chlorine addition effectively controlled Escherichia coli regrowth for 3 days, proving NFP potential for safe reuse in crop irrigation (<1 CFU/100 mL for E. coli; <1 mg L-1 for free chlorine). These findings provide valuable insights into the applications and limitations of UV-C/H2O2 and UV-C/Chlorine for distinct wastewater treatment scenarios.
Assuntos
Cloro , Filtração , Peróxido de Hidrogênio , Fotólise , Raios Ultravioleta , Eliminação de Resíduos Líquidos , Águas Residuárias , Poluentes Químicos da Água , Peróxido de Hidrogênio/química , Águas Residuárias/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Eliminação de Resíduos Líquidos/métodos , Cloro/química , Filtração/métodos , Purificação da Água/métodos , Chlorella vulgaris/efeitos dos fármacos , Escherichia coli/efeitos dos fármacos , OxirreduçãoRESUMO
Abstract Introduction Suicide has shown an international and national trend to increase, mainly in young people, together with seasonal behavior associated with high temperatures. Although Chihuahua saw the highest number of suicides and suicide attempts in 2016, there are no studies documenting their seasonal and trend behavior. Objective This study sought to analyze the trend and seasonality of completed suicides in the state of Chihuahua from 2008 to 2018. Method The number of deaths from intentionally self-inflicted injuries was obtained from INEGI. The absolute suicide rate was estimated, and a time series model applied to identify its trend and seasonality. In addition, environmental temperature was used as a predictor variable for the number of suicides through a Poisson model. Results A trend was found in the completed suicide rate from 2008 to 2018 in men and women, both separately and together (stationary R2 .73, .66 and .69, respectively), together with seasonality in both sexes (p < .002), with the highest figures being recorded in June and July. An increase of 1,028 suicides was found for every 1°C rise in temperature. In the 10-24 and 25-34 age groups, a linear increase in the suicide rate was observed during the period studied (R² > .7, p = .001). Discussion and conclusion Between 2008 and 2018, the suicide rate increased in the state of Chihuahua, mainly among those aged between 10 and 34. Moreover, suicide rates tend to increase during the months of June and July because of temperature.
Resumen Introducción El suicidio ha presentado una tendencia a la alta a nivel internacional y nacional, principalmente en jóvenes, y un comportamiento estacional, asociado a altas temperaturas. Aunque Chihuahua presentó la mayor cantidad de suicidios e intentos de suicidio durante 2016; no hay estudios que evidencien su comportamiento tendencial y estacional. Objetivo El objetivo fue analizar la tendencia y estacionalidad de suicidios consumados en el estado de Chihuahua de 2008 a 2018. Método Se obtuvieron las defunciones por lesiones autoinfligidas intencionalmente del repositorio del INEGI. Se estimó la tasa de suicidio absoluta y se aplicó un modelo de series de tiempo para identificar su tendencia y estacionalidad; además, se utilizó la temperatura ambiental como variable predictora en el número de suicidios por medio de un modelo Poisson. Resultados Se encontró una tendencia en la tasa de suicidios consumados de 2008 a 2018 en hombres, mujeres y en conjunto (R2 estacionaria .73, .66 y .69, respectivamente); y estacionalidad en ambos sexos (p < .002), donde los mayores registros fueron en junio y julio. Se encontró una asociación en un incremento de 1,028 suicidios por cada incremento de 1°C de la temperatura. En los grupos etarios de 10-24 y 25-34 se observó un incremento lineal en la tasa de suicidio durante el periodo estudiado (R2 > .7, p = .001). Discusión y conclusión De 2008 a 2018, la tasa de suicidios se ha incrementado en el estado de Chihuahua, principalmente entre los 10 y 34 años de edad. Además, la tasa de suicidio tiende a incrementarse durante los meses de junio y julio, asociándose a la temperatura.
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ABSTRACT Introduction: Regression modeling is a statistical method commonly used in health research, especially by observational studies. Objective: The objectives of this paper were to 1) determine the frequency of reporting of regression modeling in original biomedical and public health articles that were published in Biomédica between 2000 and 2017; 2) describe the parameters used in the statistical models, and 3) describe the quality of the information reported by the studies to explain the statistical analyses. Materials and methods: We conducted a critical assessment review of all original articles published in Biomédica between 2000 and 2017 that used regression models for the statistical analysis of the studies main objectives. We generated a 20-item checklist based on four good practice guidelines for the presentation of statistical methods. Results: Most of the studies were observational studies related to public health sciences (65.7%). Less than half (37.2%) of them reported using a combination of conceptual frameworks and statistical criteria for the selection of variables to be included in the regression model. Less than one quarter (22.1%) reported the verification of the assumptions of the model. The most frequently used uncertainty measure was the p-value (73.5%). Conclusion: There are significant limitations in the quality of the reports of statistical regression models, which reviewers and readers need in order to correctly assess and interpret the statistical models. The results, herein, are provided as an invitation to researchers, reviewers, and editors of biomedical journals to develop, promote, and control an appropriate culture for statistical analysis and reporting in Colombia.
RESUMEN Introducción. Los modelos de regresión son métodos estadísticos comúnmente utilizados en la investigación en salud, especialmente en estudios observacionales. Objetivos. Determinar la frecuencia de uso de modelos de regresión en los artículos originales de biomedicina y salud pública publicados en Biomédica entre 2000 y 2017, describir los parámetros utilizados en los modelos estadísticos, así como la calidad de la información reportada por los estudios para explicar el análisis estadístico. Materiales y métodos. Se hizo una revisión y evaluación crítica de todos los artículos originales publicados en la revista Biomédica entre 2000 y 2017 que utilizaron modelos de regresión en el análisis estadístico. Se construyó una lista de verificación de 20 ítems sobre la base de cuatro guías de buenas prácticas para la presentación de los métodos estadísticos. Resultados. La mayoría de los estudios incluidos eran estudios observacionales relacionados con las ciencias de la salud pública (65,7 %). En menos de la mitad (37,2 %) de ellos se informó sobre el uso de una combinación de marco conceptual y criterios estadísticos para la selección de las variables incluidas en el modelo de regresión; en menos de una cuarta parte (22,1 %) se informó de la verificación de los supuestos del modelo, y la medida de incertidumbre reportada con mayor frecuencia fue el valor de p (73,5 %). Conclusión. Hay limitaciones importantes en la calidad de los informes de los modelos de regresión estadísticos necesarios para la correcta evaluación y la interpretación de los modelos estadísticos por parte de los revisores y lectores. Los resultados se ofrecen como una invitación a investigadores, revisores y editores de revistas biomédicas a que promuevan el desarrollo de una cultura adecuada de análisis estadístico y presentación de informes en Colombia.
Assuntos
Publicações Periódicas como Assunto , Editoração , Análise de Regressão , Pesquisa Biomédica , ColômbiaRESUMO
En este artículo se presenta la metodología de análisis de aguas residuales con fines epidemiológicos (wastewater-based epidemiology, WBE) y su potencial para abordar diversos aspectos relacionados con la salud pública. Esta metodología permite obtener datos a una escala temporal y espacial relativamente pequeña (típicamente datos diarios-semanales sobre un municipio) de hábitos de consumo de sustancias de abuso, ilegales (como la cocaína o el cannabis) o legales (como el alcohol) a través de la determinación de biomarcadores de consumo (el compuesto original no metabolizado o alguno de sus metabolitos) en el agua residual. Aparte de discutir los fundamentos, ventajas y limitaciones de WBE, se comentan los precedentes más relevantes a nivel internacional, y las actividades más destacables en España en este ámbito. Finalmente, se exponen, los objetivos de la Red Española de Análisis de Aguas Residuales con Fines Epidemiológicos (ESAR-Net), una "Red de Excelencia " que agrupa a investigadores españoles con amplia experiencia en el área de WBE, así como las perspectivas de futuro de esta metodología puede tener para mejorar las competencias de la Salud Pública en España
This manuscript introduces Wastewater-Based Epidemiology (WBE) and its potential in the assessment of diverse aspects related to public health. This methodology can provide data in a relatively short temporal and local scale (typically dialy-weekly at the municipal level) on consumption patterns of illicit drugs (e.g. cocaine or cannabis), licit substances of abuse (e.g. alcohol) by measuring their consumption biomarkers (i.e. the original unmetabolized substance or some of its metabolite) in wastewater. Besides discussing the fundaments, advantages and shortcomings of WBE, it reviews some of the main precedents at international level and most remarkable activities that have been taken place in this field in Spain. Finally, the Spanish Network of Wastewater-Based Epidemiology (ESAR-Net) as is presented. ESAR-Net is an Excellence Network that sums up the efforts of the most relevant Spanish researchers in the field of WBE, aiming to investigate future perspectives of this methodology and its impact on Public Health competences in Spain
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Humanos , 24961 , Características Biológicas de Águas Residuárias/estatística & dados numéricos , Detecção do Abuso de Substâncias/métodos , Drogas Ilícitas/isolamento & purificação , Etanol/isolamento & purificação , Nicotina/isolamento & purificação , Biomarcadores/análise , Problemas Sociais/estatística & dados numéricos , Comportamento de Procura de Droga/tendências , Uso de Tabaco/epidemiologiaRESUMO
Glyphosate is noted for being non-toxic in fishes, birds and mammals (including humans). Nevertheless, the degree of genotoxicity is seriously controversial. In this work, various concentrations of a glyphosate isopropylamine salt were tested using two methods of genotoxicity assaying, viz., the pink mutation assay with Tradescantia (4430) and the comet assay with nuclei from staminal cells of the same plant. Staminal nuclei were studied in two different forms, namely nuclei from exposed plants, and nuclei exposed directly. Using the pink mutation assay, isopropylamine induced a total or partial loss of color in staminal cells, a fundamental criterion utilized in this test. Consequently, its use is not recommended when studying genotoxicity with agents that produce pallid staminal cells. The comet assay system detected statistically significant (p < 0.01) genotoxic activity by isopropylamine, when compared to the negative control in both the nuclei of treated plants and directly treated nuclei, but only the treated nuclei showed a dose-dependent increase. Average migration in the nuclei of treated plants increased, when compared to that in treated nuclei. This was probably due, either to the permanence of isopropylamine in inflorescences, or to the presence of secondary metabolites. In conclusion, isopropylamine possesses strong genotoxic activity, but its detection can vary depending on the test systems used.
Assuntos
Ensaio Cometa , Dano ao DNA , Mutação Puntual , TradescantiaRESUMO
Se han seleccionado 25 muestras de alimentos derivados de maíz entre lasprincipales marcas y las de mayor consumo del mercado español.Éstas se han analizado para detectar la presencia natural de deoxinivalenol(DON), toxina T-2, zearalenona (ZEA) y afa- y ß-zearalenoles (ZOL). Loscontenidos de micotoxinas se han determinado por cromatografía de gasescon detector de ionización de llama, confirmando la presencia de zearalenonapor cromatografía líquida de alta resolución con detector de fluorescencia.La incidencia de DON, ZEA y alfa-ZOL en las 25 muestras fue del 68, 44 y 24%,respectivamente; los niveles detectados variaron entre 29-195, 34-216,y 36-71 μg/kg, respectivamente. La toxina T-2 sólo se detectó en una de lasmuestras (< 50 μg/kg). Por último la micotoxina ß-ZOL no fue detectada porencima del límite de detección en ninguna de las muestras analizadas.La presencia de micotoxinas en este tipo de productos supone un riesgo parala salud de los consumidores e indica la necesidad de controlar estosproductos finales antes de ser consumidos. Este trabajo constituye el primerestudio sobre la presencia natural de estas micotoxinas en alimentosderivados de maíz presentes en el mercado español(AU)
Among the main Spanish commercially available trademarks, we have selecteda total of 25 samples of corn-based foods, which have the highest consumerate, to carry out the analysis of deoxynivalenol (DON), T-2 toxin, zearalenone(ZEA) and zearalenols (ZOL). The contents of mycotoxins were determined bygas chromatography with flame ionization detection, and those of ZEA wereconfirmed by HPLC with fluorescence detection. Of the 25 analyzed samples,the incidence of DON, ZEA and alpha-ZOL was 68, 44 and 24%, respectively;levels detected ranged from 29-195, 34-216, and 36-71 μg/kg, respectively.T-2 toxin was only detected in one sample (< 50 μg/kg). ß-ZOL was notpresent in excess of the detection limit in the investigated samples.The results suggest a risk for consumers of corn products and the need tomonitor the final products before consumption. This is the first report in Spainon natural contamination with these mycotoxins in corn-based foods