Universidad de Almería

Tris(1,3-dichloro-2-propyl) phosphate (TDCPP) is an emerging environmental contaminant of concern due to its widespread presence and potential toxicity. Its metabolite, bis(1,3-dichloro-2-propyl) phosphate (BDCPP), plays a critical role in mediating TDCPP-induced toxicities and may exacerbate aging-related processes. In this study, we quantitatively compared the bioconcentration and toxicity of TDCPP and BDCPP in Caenorhabditis elegans. BDCPP exhibited higher environmental persistence and bioaccumulation potential than TDCPP. Exposure to 0.1-1000 μg/L TDCPP and BDCPP increased Oil red O staining (7.88%-55.44%, 6.42%-33.92%), lipofuscin levels (5.44%-35.98%, 3.54%-28.66%), and reduced the mean lifespan (3.09%-10.31%, 1.84%-8.74%). Overall, TDCPP caused greater triglyceride (TG) accumulation, lipofuscin formation, and lifespan reduction compared to BDCPP. TDCPP reduced brood size by 5.30%-18.95%, while BDCPP exposure increased brood size by up to 13.90%. Mechanism investigations revealed that TDCPP and BDCPP induce aging through distinct pathways. The adverse outcome pathways revealed that BDCPP disrupted germline stem cells (GSCs) apoptosis, transmitting reproductive signals through the kri-1-daf-16-lipl-4 signaling cascade, impairing TG hydrolysis and lifespan, while TDCPP acted through a GSC-independent route. These findings underscore the central role of GSCs in BDCPP-induced aging, enhance our understanding of BDCPP as a secondary pollutant, and provide critical data for assessing the ecological and health risks of chlorinated organophosphate esters.

This study presents the development and validation of an automated pressurized liquid extraction (PLE) method using the EXTREVA ASE system for the determination of 233 pesticide residues in coffee, a matrix considered challenging due to its complex composition. The method was evaluated at three fortification levels (10, 20, and 50 μg/kg), with nine replicates per level distributed over three days to assess inter-day reproducibility. At 20 and 50 μg/kg, all compounds met the established performance criteria of 70-120 % recovery and relative standard deviations (RSDs) below 20 %. At the 10 μg/kg level, only 12 compounds (5.2 %) were outside these criteria, primarily due to known issues such as co-elution with matrix components or the acidic nature of certain analytes. All analytes exhibited excellent linearity (R² ≥ 0.99) across a five-point procedural calibration from 0.005 to 0.1 mg/L (0.005, 0.01, 0.02, 0.05, 0.1 mg/L), confirming the method's suitability for quantitative analysis. Matrix effect evaluation showed that 44 % of analytes experienced low or negligible effects, 42 % moderate effects, and only 14 % were strongly affected. Real sample analysis confirmed the method's applicability for routine monitoring, while participation in the EUPT-FV-SC07 proficiency test for coffee demonstrated high analytical performance, with z-scores ranging from -0.7 to 0.3 and RSDs below 20 % for all compounds. Overall, this work provides a validated, reproducible and automation-ready solution for multiresidue pesticide control in complex matrices such as coffee, meeting regulatory standards and suited for high-throughput laboratories.

A quantitative quadrupolar nuclear magnetic resonance (qQNMR) method based on sulfur-33 (³³S) NMR has been developed for the direct, dilution-free determination of taurine in human urine, addressing matrix challenges in biofluid analysis. The 1D³³S approach exhibited linearity (14-70 mg mL^-1; R² = 0.9993), LOD = 6.78 ± 0.66 mg mL^-1, LOQ = 10.84 ± 0.69 mg mL^-1, precision <1.1 % CV, and recoveries of 96.95-101.58 % with negligible matrix effect (-3.15 %). External calibration using ammonium sulfate yielded similar results. Critically, 2D ¹H-³³S gHMBC experiments reduced LOD/LOQ to 1.2/4.0 mg mL^-1 by leveraging ¹H sensitivity. The method enables rapid (<12 min), robust analysis without sample pretreatment, offering a practical alternative to chromatographic techniques for high-concentration urinary taurine quantification.