Novel ferrofluid based on hydrophobic deep eutectic solvents for separation and analysis of trace estrogens in environmental water and urine samples.

A novel ferrofluid prepared from a hydrophobic deep eutectic solvent (DES) and Fe3O4@graphite composite materials was introduced as a green microextraction medium for the separation and enrichment of trace estrogens in real samples. It was found that the ferrofluid greatly improved the capacity and selectivity of target analytes, benefiting from the enrichment of both DES and Fe3O4@graphite composite materials. Using a combination of high-performance liquid chromatography-fluorescence detection (HPLC-FLD) and vortex-assisted liquid-liquid microextraction (VALLME), a new method was established for simultaneous rapid processing and accurate determination of three estrogens (estradiol [E2], estriol [E3], and ethinyl estradiol [EE2]) in environmental water and urine samples. Key parameters affecting the extraction efficiency were optimized using a single-factor approach and response surface methodology. Under optimal conditions, this method yielded a low limit of detection (1.01 ng L-1, 3.03 ng L-1, and 25.0 ng L-1 for EE2, E2, and E3, respectively), wide linear range (3-200,000 ng L-1), high enrichment factors (9.81-47.2), and satisfactory recovery (73.8-129.0%). Compared with traditional analytical techniques, this method avoids the use of volatile toxic organic extraction solvents and cumbersome phase separation operations.

Development of a "turn off" fluorescent molecularly imprinted nanoparticle-based sensor for selective captopril quantification in synthetic urine and wastewater samples.

The combination of silica nanoparticles with fluorescent molecularly imprinted polymers (Si-FMIPs) prepared by a one-pot sol-gel synthesis method to act as chemical sensors for the selective and sensitive determination of captopril is described. Several analytical parameters were optimized, including reagent ratio, solvent, concentration of Si-FMIP solutions, and contact time. Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and the ninhydrin assay were used for characterization. The selectivity was evaluated against molecules belonging to other drug classes, such as fluoroquinolones, nonacid nonopioids, benzothiadiazine, alpha amino acids, and nitroimidazoles. Under optimized conditions, the Si-FMIP-based sensor exhibited a working range of 1-15 µM, with a limit of detection (LOD) of 0.7 µM, repeatability of 6.4% (n = 10), and suitable recovery values at three concentration levels (98.5% (1.5 µM), 99.9% (3.5 µM), and 99.2% (7.5 µM)) for wastewater samples. The sensor provided a working range of 0.5-15 µM for synthetic urine samples, with an LOD of 0.4 µM and a repeatability of 7.4% (n = 10) and recovery values of 93.7%, 92.9%, and 98.0% for 1.0 µM, 3.5 µM, and 10 µM, respectively. In conclusion, our single-vessel synthesis approach for Si-FMIPs proved to be highly effective for the selective determination of captopril in wastewater and synthetic urine samples.

Paper Spray Mass Spectrometry with On-Paper Electrokinetic Manipulations: Part-Per-Trillion Detection of Per/Polyfluoroalkyl Substances in Water and Opioids in Urine.

We developed a simple, paper-based device that enables sensitive detection by mass spectrometry (MS) without solid phase extraction or other sample preparation. Using glass fiber filter papers within a 3D printed holder, the device employs electrokinetic manipulations to stack, separate, and desalt charged molecules on paper prior to spray into the MS. Due to counter-balanced electroosmotic flow and electrophoresis, charged analytes stack on the paper and desalting occurs in minutes. One end of the paper strip was cut into a sharp point and positioned near the inlet of a MS. The stacked analyte bands move toward the paper tip with the EOF where they are ionized by paper spray. The device was applied to analysis of PFAS in tap water with sub part-per-trillion detection limits in less than ten minutes with no sample pretreatment. Analysis of opioids in urine also occurs in minutes. The crucial parameters to enable stacking, separation, and MS ionization of both positively and negatively charged analytes were determined and optimized. Experimental and computational modeling studies confirm the electrokinetic stacking and analyte transport mechanisms. On-paper separations were carried out by stacking analyte bands at different locations depending on their electrophoretic mobility, achieving baseline separation in some cases.

ARSENIC IN DRINKING WATER AND URINE AND ITS RELATIONSHIP WITH MALIGNANT TUMORS OF URINARY TRACT IN OSIJEK-BARANJA COUNTY, CROATIA.

Increased values of arsenic in potable water in eastern Croatia has been a matter of scientific interest for the past two decades due to numerous health effects, including carcinogenic ones. This study investigated whether prolonged exposure to increased arsenic from water could be detectable through increased arsenic in urine, and whether it influenced the incidence of kidney and bladder cancer in Osijek-Baranja County. Inductively coupled plasma mass spectrometry (ICP-MS) was used for analysis of water samples from available water sources (wells, aqueducts). In addition, examinees from Osijek, Nasice, Vladislavci, Cepin and Dalj gave their urine samples for analysis. Data on cancer incidence were obtained from the Institute for Public Health Registry and cumulative incidence of kidney and bladder cancer was calculated for the period between January 1, 2000 and December 31, 2018. Elevated arsenic concentration in drinking water was recorded in Vladislavci, Cepin and Osijek area with values above the allowed maximum according to the EU standards (10 µg L-1) and as a result, arsenic levels in urine of the inhabitants were also elevated. Cumulative incidence for bladder cancer showed correlation between increased arsenic in water and urine in the areas affected by increased arsenic in water. Epidemiologic data suggest a conclusion that elevated arsenic could be considered at least as a cofounding factor for urinary tract cancer.

Ultrasound probe enhanced enzymatic hydrolysis for rapid separation of ß2-adrenergic agonists from animal urine and livestock wastewater: Applicability to biomonitoring investigation.

BACKGROUND: An increasing number of ß2-adrenergic agonists are illicitly used for growth promoting and lean meat increasing in animal husbandry in recent years, but the development of analytical methods has lagged behind these emerging drugs. RESULTS: Here, we designed and developed an ultrasound probe enhanced enzymatic hydrolysis reactor for quick separation and simultaneously quantification of 22 ß2-adrenergic agonists in animal urine and livestock wastewater. Owing to the enhancement of the conventional enzymatic digestion through the ultrasound acoustic probe power, only 2 min was required for the comprehensively separation of ß2-adrenergic agonists from the sample matrices, making it a much more desirable alternative tool for high-throughput investigation. The swine, bovine and sheep urines (n = 287), and livestock wastewater (n = 15) samples, collected from both the north and south China, were examined to demonstrate the feasibility and capability of the proposed approach. Six kinds of ß2-adrenergic agonists (clenbuterol, salbutamol, ractopamine, terbutaline, clorprenaline and cimaterol) were found in animal urines, with concentrations ranged between 0.056 µg/L (terbutaline) and 5.79 µg/L (clenbuterol). Up to nine ß2-adrenergic agonists were detected in wastewater samples, of which four were found in swine farms and nine in cattle/sheep farms, with concentration levels from 0.069 µg/L (tulobuterol) to 2470 µg/L (clenbuterol). SIGNIFICANCE: Interestingly, since ß2-adrenergic agonists are usually considered to be abused mainly in the pig farms, our data indicate that both the detection frequencies and concentrations of these agonists in the ruminant farms were higher than the pig farms. Furthermore, the findings of this work indicated that there is a widespread occurrence of ß2-adrenergic agonists in livestock farms, especially for clenbuterol and salbutamol, which may pose both food safety and potential ecological risks. We recommend that stricter controls should be adopted to prevent the illegally usage of these ß2-adrenergic agonists in agricultural animals, especially ruminants, and they should also be removed before discharging to the environment.

Feasibility of sulfated BPA and BPS as wastewater-based epidemiology biomarkers: Insights from wastewater and reported human urine analysis.

In wastewater-based epidemiology (WBE), the selection of appropriate biomarkers presents a significant challenge. Recently, sulfated bisphenols have garnered attention as potential WBE biomarkers due to their increased stability in wastewater compared to glucuronide conjugates. This study aims to comprehensively assess the feasibility of employing sulfated BPA and BPS as WBE biomarkers by analyzing both WBE and human biomonitoring data. To conduct this research, wastewater samples were collected from six domestic wastewater treatment plants in Guangzhou, China, and urinary concentration of BPA and BPS were obtained from peer-reviewed literature. The results revealed that mean urinary concentrations of BPA and BPS, calculated using Monte Carlo simulations, significantly exceeded those reported in human biomonitoring studies. Furthermore, the per capita mass load ratio of sulfated BPA and BPS in human urine to the mass load in wastewater was found to be below 10 %. This outcome suggests that the excretion of BPA-S and BPS-S in urine does not make a substantial contribution to wastewater, hinting at the existence of other notable sources. Consequently, our study concludes that sulfated BPA-S and BPS-S are not suitable candidates as WBE biomarkers. This work provides a referenceable analytical framework for evaluating the feasibility of WBE biomarkers and emphasizes the necessity for caution when utilizing WBE to assess human exposure to chemicals.

High exposure to boron in drinking water and sperm parameters in Chilean young people / Exposición elevada a boro en el agua potable y parámetros de esperma en gente joven chilena

Our aim was to describe sperm parameters in residents from Northern Chile. We evaluated in 101 volunteers (18 and 30 years old) urinary and drinking water Boron levels using Inductively Coupled Plasma Mass Spectrometry; semen parameters were measured with standardized methods. Each individual was categorized in 3 levels of exposure: low (B levels in urine 2.94 mgL-1 or tap water 3.0 mgL-1), medium (urinary B between 2.95-7.4 mgL-1 and B in tap water with 3.0-7.0 mgL-1) and high (urinary B > 7.4 mgL-1 or tap water > 7.0 mgL-1). We found no significant differences among groups by pH, sperm concentration (45.1; 48.2 and 38 million/mL), motility 1th hour (38.1; 40.0 and 45.5 %) and vitality 1th hour (88.6; 88.0 and 76.9 %) respectively. Abnormal morphology was significant different (83.3; 90 and 83 %). Young men exposed to B in drinking water present sperm variations associated with the level of exposure. Most of these changes are positive at intermediate levels of B. For the highest exposures were observed negative changes in sperm morphology, concentration, motility and vitality, all relevant parameters of fertility. Beneficial effect is observed at medium exposure, like a "U curve".

El objetivo de este trabajo fue describir los parámetros espermáticos en residentes del norte de Chile. Se evaluaron en 101 voluntarios (18 y 30 años), los niveles urinarios y de agua potable de boro, usando "Inductively Coupled Plasma Mass Spectrometry". Los parámetros del semen se midieron con métodos estandarizados. Cada individuo se clasificó en 3 niveles de exposición: bajo (niveles B en la orina 2,94 mgL-1 o agua potable 3,0 mgL-1), medio (B urinario entre 2,95-7,4 mgL-1 y B en agua de beber con 3,0- 7,0 mgL-1) y alto (B urinario >7,4 mgL-1 o agua potable > 7,0 mgL-1). No se encontraron diferencias significativas entre los grupos por pH, concentración de espermatozoides (45,1; 48,2 y 38 millones/mL), motilidad a 1 hora (38,1; 40,0 y 45,5%) y vitalidad 1 hora (88,6; 88,0 y 76,9%) respectivamente. La morfología anormal fue significativamente diferente (83,3; 90 y 83%). Los hombres jóvenes expuestos a B en el agua potable presentan variaciones espermáticas asociadas con el nivel de exposición. La mayoría de estos cambios son positivos en niveles intermedios de B. Para las exposiciones más altas se observaron cambios negativos en la morfología, concentración, motilidad y vitalidad del esperma, parámetros relevantes de la fertilidad. Un efecto beneficioso se observa en la exposición media, como una "curva U".

Cuantificacion de arsenico por inyeccion en flujo-generacion de hidruros-espectrometria de absorcion atomica (IF-GH-EAA) previa derivatizacion con L-cisteina. Validacion y comparaci¨®o intermetodologica utilizando dos tecnicas de referencia / Arsenic quantitation by flow injection-hydride generation- atomic absorption spectrometry (FI-HG-AAS) after L-cysteine derivatization. Validation and inter-methodological comparison using two reference techniques

La presencia de Arsenico (As) en aguas de consumo representa una problematica para la salud publica en muchas regiones del mundo, incluida la Argentina. La cuantificacion de arsenico en agua de bebida y en orina se utiliza para evaluar la exposicion a este contaminante. El presente trabajo tuvo como objetivo la validacion metodologica de una tecnica para la cuantificacion de especies del As [AsV + AsIII + acido monometilarsonico (MMA) + acido dimetilarsinico (DMA)] por inyeccion en flujo-generacion de hidruros-espectrometria de absorcion atomica (IF-GH-EAA), previa derivatizacion con L-cisteina. Los resultados fueron comparados con los obtenidos utilizando dos metodologias de referencia, generacion de hidruros-espectrometria de absorcion atomica (GH-EAA) para muestras de aguas y orina, y cromatografia de alta resolucion ¨Cgeneracion de hidruros-espectrometr¨ªa de absorcion atomica (HPLC-GH-EAA) para muestras de orina. Ademas, se evaluo la selectividad de la cuantificacion por IF-GH-EAA, en presencia de otras especies quimicas del As, provenientes del consumo de alimentos producto de la pesca, a traves de un ensayo biologico. Los niveles de As hallados en las muestras de agua y de orina utilizando las tecnicas de referencia presentaron un rango de 6 a 176 ¦Ìg/L y de 143 a 3312 ¦Ìg/g de creatinina, respectivamente. Los coeficientes de Pearson resultantes de la comparacion de los datos obtenidos por IF-GH-EAA, con los logrados por los metodos de referencia fueron r = 0,9976 y r = 0,9422, para agua y orina, respectivamente. Los resultados de la prueba biologica indicaron un mayor nivel de As, debido al consumo de alimentos producto de la pesca, cuando las muestras de orina fueron previamente mineralizadas (GH-EAA), con la consecuente sobreestimacion del contenido de As proveniente del consumo de As inorganico. Este aumento no se observo cuando estas fueron analizadas por IF-GH-EAA ...

The presence of arsenic (As) in drinking water is a public health concern in many regions of the world, including Argentina. Quantification of arsenic in drinking water and urine are used to assess exposure to this pollutant. This study aimed to validate a methodology for the quantification of As species [AsV + AsIII + acid monometilarsonico (MMA) + dimetilarsinico acid (DMA)] by flow injection-hydride generation-atomic absorption spectrometry (FI-HG-AAS), after derivatization with L-cysteine. The results were compared with those obtained using two methods of reference, hydride generation-atomic absorption spectrometry (HG-AAS) for water and urine samples, and high performance liquid chromatography-hydride generation-atomic absorption spectrometry (HPLC-HG-AAS) for urine samples. In addition, the selectivity of quantification by FI-HG-AAS in the presence of other chemical species of As, from fishery products intake, was evaluated through a biological assay.The As level found in water and urine samples, using the techniques of reference, showed a range from 6 to 176 ¦Ìg/L and from 143 to 3312 ¦Ìg/g creatinine, respectively. Pearson coefficients resulting from the comparison of data obtained by FI-HG-AAS with those achieved by the reference methods were r = 0.9976 and r = 0.9422 for water and urine, respectively. The results of the biological test showed a higher level of As, due to consumption of food fishery product, when urine samples were previously mineralized (HG-AAS), with consequent overestimation of the inorganic arsenic consumption. When these samples were analyzed by FI-HG-AAS this fact was not observed, and the values were comparable to baseline level prior to consumption ...

Optimización y validación metodológica de la cuantificación de arsénico por inyección en flujo -generación de hidruros- espectrometría de absorción atómica (IF-GH-EAA) previa derivatización con L-cisteína / Optimization and validation method for arsenic quantification by flow injection-hydride generation - atomic absorption spectrometry (FI-HG-AAS) after L-cysteine derivatization

El arsénico (As) es un contaminante natural que afecta una amplia zona de Argentina. El nivel de As en agua de consumo es utilizado para evaluar la fuente de exposición y en orina para evaluar exposición a este tóxico. El presente trabajo tuvo como objetivo la optimización y validación metodológica de una técnica para la cuantificación de As [As suma = As inorgánico (AsI) + especies metiladas: ácido monometilarsónico (MMA) y ácido dimetilarsónico (DMA)], producto del metabolismo del AsI, por inyección en flujo- generación de hidruros- espectrometría de absorción atómica (IF-GH-EAA), previa derivatización con L-cisteína. La recuperación de las especies estudiadas: AsI (AsIII y AsV), MMA y DMA fue cercana al 100% en todos los casos. Los límites de detección y cuantificación encontrados fueron para agua y orina: 2 y 3 µg/L; 5 y 8 µg/L respectivamente y el rango dinámico de trabajo establecido fue desde 5 a 75 µg/L, permitiendo cuantificar As en muestras de agua cercanos a los estándares internacionales vigentes para valores máximos de As en agua de consumo y en orina en niveles comparables con los establecidos en población laboralmente no expuesta. Esta propuesta metodológica es una alternativa para evaluar la exposición al As en muestras de agua y orina, sin necesidad de utilizar prolongados pre-tratamientos de muestra, de forma más rápida y económica.

Arsenic (As) is a natural contaminant that affects a large area of Argentina. Quantification of As in drinking water has been used to evaluate the source of exposure and As in urine to assess exposure to this toxic. This study aimed to optimize and validate a methodological technique for the quantification of As [As sum = inorganic As (AsI) + methylated species: monometilarsonic acid (MMA) and dimetilarsinic acid (DMA)], product of AsI metabolism by flow injection hydridegeneration-atomic absorption spectrometry (FI-GH-AAS), after derivatization with L-cysteine. The recovery of the studied species: AsI (AsIII and AsV), MMA and DMA was close to 100% in all cases. The limits of detection and quantitation were foundfor water and urine: 2 and 3 µg/L; 5 and 8 µg/L respectively and a linear working range from 5 to 75 µg/L, allowing quantify As in water close to international standards of maximum As values for drinking water and urine samples with levels comparables with those found in people non exposed ocupacionally . This methodology is a valid alternative for assessing exposure to As in water and urine samples without the need of prolonged pre-treatment sample, more quickly and inexpensively.