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Resumen Introducción: Los vertidos de líquidos inflamables pueden producir accidentes graves, principalmente en plantas industriales y en carretera. Para prevenir la dispersión de derrames, se utilizan diversas formas de recolecta, como la absorción con sólidos porosos. Residuos agroindustriales pueden ser aprovechados como materiales sorbentes de líquidos inflamables. Objetivo: Determinar la capacidad de absorción de las biomasas residuales del pedúnculo de la palma aceitera (Elaeis guineensis) y del endocarpio del fruto de coyol (Acrocomia sp.) para cuatro líquidos orgánicos inflamables. Métodos: Las biomasas residuales de E. guineensis y de Acrocomia sp. se evaluaron como sorbentes para combustibles derramados (diésel, queroseno de aviación, queroseno comercial y gasolina). Se midió la cantidad de líquido absorbida por las biomasas a 24 ºC durante una semana, y su cinética de desorción a 50 ºC, usando balanzas de secado. Resultados: La propiedad sorbente del material de Acrocomia sp. no fue satisfactoria, comparada con el pedúnculo de E. guineensis, debido a diferencias en arquitectura residual del material orgánico. Esta última biomasa muestra una capacidad de absorción para los combustibles de 2.4 ± 0.2 cm3 g-1 a 24 ºC. La diatomita absorbe mayor cantidad de los combustibles estudiados, pero la difusión de estos fluidos a 50 ºC por la matriz mineral es solo 0.26 ± 0.09 veces lo observado para el material de E. guineensis, como resultado del mayor grado de tortuosidad de los poros de la diatomita. Conclusiones: El pedúnculo de palma aceitera (E. guineensis) mostró un adecuado potencial desempeño para la aplicación pasiva en la mitigación de los riesgos de incendio, con respecto a la diatomita. El endocarpio del fruto de Acrocomia sp. no resultó útil para esta operación de recuperación.

Abstract Introduction: Spills of flammable liquids can lead to serious accidents, mainly in industrial plants and on roads. To prevent the spread of spills, various forms of collection are used, such as absorption with porous solids. Agroindustrial waste can be used as sorbent materials for flammable liquids. Objective: To determine the sorption capacity of the residual empty-fruit bunch of oil-palm (Elaeis guineensis) and the macaw palm (Acrocomia sp.) nutshell for four organic flammable liquids. Methods: The residual biomasses of E. guineensis and Acrocomia sp. were assessed as sorbents for spilled fuels (diesel, jet fuel, commercial kerosene, and gasoline). Volumetric measurement of liquid-fuel absorption at 24 ºC was taken during a week. Desorption was measured at 50 ºC as the drying kinetics, by using moisture scales. Results: The sorption capacity of the Acrocomia sp. material was not satisfactory, compared to the E. guineensis residual material, due to differences in the residual architecture of the organic material. This last can absorb 2.4 ± 0.2 cm3 g-1 at 24 ºC, during a one-week period. Diatomite absorbs greater quantities of the organic liquids but, the fluids diffusion at 50 ºC is 0.26 ± 0.09 times more slowly in the mineral matrix, because of the greater pore tortuosity in this mineral matrix. Conclusions: The oil-palm empty fruit bunch of E. guineensis, showed lesser but adequate performance than the sorbing behavior for fire hazard mitigation of diatomite. The nutshell of macaw palm (Acrocomia sp.) did not prove to be useful for this recovery operation.

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The advancement of traditional sample preparation techniques has brought about miniaturization systems designed to scale down conventional methods and advocate for environmentally friendly analytical approaches. Although often referred to as green analytical strategies, the effectiveness of these methods is intricately linked to the properties of the sorbent utilized. Moreover, to fully embrace implementing these methods, it is crucial to innovate and develop new sorbent or solid phases that enhance the adaptability of miniaturized techniques across various matrices and analytes. Graphene-based materials exhibit remarkable versatility and modification potential, making them ideal sorbents for miniaturized strategies due to their high surface area and functional groups. Their notable adsorption capability and alignment with green synthesis approaches, such as bio-based graphene materials, enable the use of less sorbent and the creation of biodegradable materials, enhancing their eco-friendly aspects towards green analytical practices. Therefore, this study provides an overview of different types of hybrid graphene-based materials as well as their applications in crucial miniaturized techniques, focusing on offline methodologies such as stir bar sorptive extraction (SBSE), microextraction by packed sorbent (MEPS), pipette-tip solid-phase extraction (PT-SPE), disposable pipette extraction (DPX), dispersive micro-solid-phase extraction (d-µ-SPE), and magnetic solid-phase extraction (MSPE).

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A film composed of agarose and graphene (G) and magnetic nanoparticles (G-MNPs) is proposed as a sorbent for the extraction and determination of medroxyprogesterone (MED), levonorgestrel (LEV), norethisterone (NOR) and progesterone (PRO) in natural water samples. Both the preparation of the film and the extraction procedure were optimized. The optimal extraction parameters were as follows: isopropyl alcohol as activation solvent, sample pH value of 3.0, extraction time of 30 min, 1.00 mL of acetonitrile as eluent, elution time of 5 min and sample volume of 100.00 mL. HPLC with photodiode array detector was used for the separation and determination. The method presented a linear range between 2.50 and 75.0 µg L-1 for all analytes, and the LODs were between 1.40 and 1.80 µg L-1. The method was applied to natural water samples, obtaining satisfactory recovery values (75-111 %). In conclusion, for the immobilization of the G-MNPs, agarose was used, which is a non-toxic, renewable and biodegradable material. The G-MNPs-agarose film was reused up to 70 times, without losing its extraction capacity significantly and presenting excellent sorbent properties, which allow the extraction and preconcentration of the progestogens under study.

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PURPOSE: We developed and validated a method for quantitative analysis of ten synthetic cathinones in oral fluid (OF) samples, using microextraction by packed sorbent (MEPS) for sample preparation followed by liquid chromatography‒tandem mass spectrometry (LC‒MS/MS). METHOD: OF samples were collected with a Quantisal™ device and 200 µL was extracted using a C18 MEPS cartridge installed on a semi-automated pipette and then analyzed using LC‒M/SMS. RESULTS: Linearity was achieved between 0.1 and 25 ng/mL, with a limit of detection (LOD) of 0.05 ng/mL and a limit of quantification (LOQ) of 0.1 ng/mL. Imprecision (% relative standard deviation) and bias (%) were better than 11.6% and 7.5%, respectively. The method had good specificity and selectivity against 9 different blank OF samples (from different donors) and 68 pharmaceutical and drugs of abuse with concentrations varying between 400 and 10,000 ng/mL. No evidence of carryover was observed. The analytes were stable after three freeze/thaw cycles and when kept in the autosampler (10 °C) for up to 24 h. The method was successfully applied to quantify 41 authentic positive samples. Methylone (mean 0.6 ng/mL, median 0.2 ng/mL), N-ethylpentylone (mean 16.7 ng/mL, median 0.35 ng/mL), eutylone (mean 39.1 ng/mL, median 3.6 ng/mL), mephedrone (mean 0.5 ng/mL, median 0.5 ng/mL), and 4-chloroethcathinone (8.1 ng/mL) were quantified in these samples. CONCLUSION: MEPS was an efficient technique for Green Analytical Toxicology purposes, which required only 650 µL organic solvent and 200 µL sodium hydroxide, and the BIN cartridge had a lifespan of 100 sample extractions.

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An automated microextraction by packed sorbent followed by liquid chromatography-tandem mass spectrometry (MEPS-LC-MS/MS) method was developed for the determination of four endocrine disruptors-parabens, benzophenones, and synthetic phenolic antioxidants-in wastewater samples. The method utilizes a lab-made repackable MEPS device and a multi-syringe robotic platform that provides flexibility to test small quantities (2 mg) of multiple extraction phases and enables high-throughput capabilities for efficient method development. The overall performance of the MEPS procedure, including the investigation of influencing variables and the optimization of operational parameters for the robotic platform, was comprehensively studied through univariate and multivariate experiments. Under optimized conditions, the target analytes were effectively extracted from a small sample volume of 1.5 mL, with competitive detectability and analytical confidence. The limits of detection ranged from 0.15 to 0.30 ng L-1, and the intra-day and inter-day relative standard deviations were between 3 and 21%. The method's applicability was successfully demonstrated by determining methylparaben, propylparaben, butylated hydroxyanisole, and oxybenzone in wastewater samples collected from the São Carlos (SP, Brazil) river. Overall, the developed method proved to be a fast, sensitive, reliable, and environmentally friendly analytical tool for water quality monitoring.

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Hybrid membranes with three different thicknesses, PMDS_C1, PMDS_C2, and PMDS_C3 (0.21 ± 0.03 mm, 0.31 ± 0.05 mm, and 0.48 ± 0.07 mm), were synthesized by the sol-gel method using polydimethylsiloxane, hydroxy-terminated, and cyanopropyltriethoxysilane. The presence of cyano, methyl, and silicon-methyl groups was confirmed by FTIR analysis. Contact angle analysis revealed the membranes' hydrophilic nature. Solvent resistance tests conducted under vortex and ultrasonic treatments (45 and 60 min) demonstrated a preference order of acetonitrile > methanol > water. Furthermore, the membranes exhibited stability over 48 h when exposed to different pH conditions (1, 3, 6, and 9), with negligible mass losses below 1%. The thermogravimetric analysis showed that the material was stable until 400 °C. Finally, the sorption analysis showed its capacity to detect furfural, 2-furylmethylketone, 5-methylfurfural, and 2-methyl 2-furoate. The thicker membrane was able to adsorb and slightly desorb a higher concentration of furanic compounds due to its high polarity provided by the addition of the cyano groups. The results indicated that the membranes may be suitable for sorbent materials in extracting and enriching organic compounds.

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A procedure of direct magnetic sorbent sampling in flame atomic absorption spectrometry (DMSS-FAAS) was developed in this work. Metal-loaded magnetic sorbents were directly inserted in the flame of the FAAS for direct metal desorption/atomization. Magnetic graphene oxide aerogel (M-GOA) particles were synthesized, characterized, and used as a proof-of-concept in the magnetic dispersive solid phase extraction of Pb2+ ions from water samples. M-GOA was selected because is a light and porous sorbent, with high adsorption capacity, that is quickly burned by the flame. Magnetic particles were directly inserted in the flame by using a metallic magnetic probe, thereby avoiding the need for a chemical elution step. As all the extracted Pb2+ ions arrive to the flame without passing through the nebulization system, a drastic increase in the analytical signal was achieved. The improvement in the sensitivity of the proposed method (DMSS-FAAS) for Pb2+ determination was at least 40 times higher than the conventional procedure in which the Pb2+ is extracted, eluted, and analyzed by conventional flame atomic absorption spectrometry (FAAS) via the nebulization system. The analytical curve was linear from 5.0 to 180.0 µg L-1 and the limit of detection was found to be 1.30 µg L-1. Background measurements were insignificant, and the atomic absorption peaks were narrow and reproducible. Precision assessed as a percentage of the relative standard deviation %RSD was found to be 17.4, 7.1, and 7.8% for 10, 70, and 180 µg L-1 levels, respectively. The method showed satisfactory results even in the presence of other ions (Al3+, Cr3+, Co2+, Cu2+, Fe3+, Mn2+, Ba2+, Mg2+, and Li+). The performance of the new system was also evaluated for Cd2+ ions, as well as by using other magnetic particles available in our lab: magnetic carbon nanotubes (M-CNTs), magnetic restricted access carbon nanotubes (M-RACNT), magnetic poly (methacrylic acid-co-ethylene glycol dimethacrylate) (M-PMA), magnetic nanoparticles coated with orange powder peel (M-OPP), and magnetic nanoparticles covered with SiO2 (M - SiO2). Analytical signals increased for both analytes in all sorbents (increases of about 4-37 times), attesting the high potential and applicability of the proposed method. Simplicity, high analytical frequency, high detectability and reproducibility, low cost, and possibility of being totally mechanized are the most relevant advantages.

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The direct magnetic sorbent sampling flame atomic absorption spectrometry (DMSS-FAAS), recently proposed by our research group, was applied to determine the lead in soy-based juice, whole grape juice, reconstituted grape juice, and orange nectar samples. A dispersive solid phase extraction (d-SPE) of lead was carried out using a magnetic orange peel powder, developed and optimized by Gupta et al (2012), that was inserted into flame by FAAS with a magnetic probe. The limits of quantification (<4.6 µg L-1) were smaller than maximum residue limits established in Brazil. Good precisions and accuracies were obtained. DMSS-FAAS presented a sensitivity at least 14 times greater than the d-SPE followed by conventional FAAS analysis, wherein the analytes were extracted and desorbed, and the eluate was introduced in FAAS via nebulization system. Lead was easily quantified in juice samples at very low concentrations, with satisfactory figures of merit, and without the need of a mineralization step.

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Increasing discharges of synthetic antimicrobial agents from industrial and municipal sewage, as well as from agricultural runoffs into water bodies, is still a global challenge. Here, an unmodified low-cost sorbent was prepared in an ecofriendly manner from Pyracantha koidzumii leaves for the removal of enrofloxacin (ENR). Sorbent characterization was accomplished using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), BET surface area, zeta potential, and point of zero charge. Biosorption assays were carried out via batch mode concerning the impact of adsorbent dosage, contact time, solution pH, solution ionic strength, adsorbate concentration, and temperature. In general, ENR adsorption was significantly correlated with pH and ionic strength. At a neutral pH, the sorbent had a theoretical maximal ENR uptake of 138.89 mg/g. However, the adsorption capacity was significantly affected by the presence of high concentrations of divalent cations (Ca2+ and Mg2+). The findings from the kinetics and isotherms showed that the pseudo-second-order kinetic and Langmuir isotherm models best fit the experimental data. Electrostatic interactions, hydrogen bonding, and π-π stacking were the most important mechanisms of adsorption of ENR onto the P. koidzumii sorbent. Overall, this study suggests the promising application of this agricultural residue for the efficient removal of ENR from water.

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The detection of eicosanoids in saliva samples can assist pharmacokinetic/pharmacodynamic studies due to the facility of obtaining samples, minimal discomfort and high adherence of volunteers to the study. The present study enabled determine prostaglandin E2 concentrations in saliva samples, using a microextraction by packed sorbent methodology and subsequent detection in liquid chromatography-tandem mass spectrometry. Twelve volunteers underwent scaling and coronary-radicular polishing of the upper molars and sequential saliva collections: 0.25-96 h after ingestion of a 600 mg ibuprofen tablet, to quantify prostaglandin E2 concentrations. There was an increase in the level of prostaglandin E2 with a significant difference after the dental procedure (0.25 h) compared to 11, 24, 48 and 72 h (*p < 0.05). After taking the drug, these levels begin to decrease up to 5 h, returning to normal in the subsequent hours. The method was developed and validated with linearity between 2.4 and 1250 ng/mL and r2 above 0.9932. The limit of quantitation was about 2.4 ng/mL. The coefficients of variation and the relative standard errors of the accuracy and precision analyzes were < 15%. The proposed extraction and analysis methodology proved to be efficient, fast and promising for pharmacokinetic/pharmacodynamic assays after using anti-inflammatory drugs.

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