Multi-Spheres Adsorptive Microextraction (MSAμE)—Application of a Novel Analytical Approach for Monitoring Chemical Anthropogenic Markers in Environmental Water Matrices

Abstract

Multi-spheres adsorptive microextraction using powdered activated carbons (ACs) was studied as a novel enrichment approach, followed by liquid desorption and high-performance liquid chromatography with diode array detection (MSAµE(AC)-LD/HPLC-DAD) to monitor caffeine (CAF) and acetaminophen (ACF) traces in environmental matrices. In this study, commercial activated carbons (N, NOX, and R) were tested, with the latter showing a much better performance for the analysis of both anthropogenic drugs. The main parameters affecting the efficiency of the proposed methodology are fully discussed using commercial AC(R). Textural and surface chemistry properties of the ACs sample were correlated with the analytical results. Assays performed on 30 mL of water samples spiked at 10 µg L−1 under optimized experimental conditions, yielding recoveries of 75.3% for ACF and 82.6% for CAF. The methodology also showed excellent linear dynamic ranges for both drugs with determination coefficients higher than 0.9976, limits of detection and quantification of 0.8–1.2 µg L−1 and 2.8–4.0 µg L−1, respectively, and suitable precision (RSD < 13.8%). By using the standard addition method, the application of the present method to environmental matrices, including superficial, sea, and wastewater samples, allowed very good performance at the trace level. The proposed methodology proved to be a feasible alternative for polar compound analysis, showing to be easy to implement, reliable, and sensitive, with the possibility to reuse and store the analytical devices loaded with the target compounds for later analysis.

Green Extraction Techniques as Advanced Sample Preparation Approaches in Biological, Food, and Environmental Matrices: A Review

“…AµE can appear in two geometrical configurations, namely, bar adsorptive microextraction (BAµE) and multisphere adsorptive microextraction (MSAµE). Nevertheless, previous experimental data [17,18] showed that MSAµE devices present much better stability compared with BAµE, especially when they are exposed to an aggressive sample matrix because, in this case, thermal supporting promotes much higher robustness from the fixation point of view. The MSAµE showed several advantages, namely, high recovery for polar analytes, easiness to prepare, economicalness, and selectiveness, as sorbent can be selected based on the target analyte of interest.…”

“…A new adsorptive microextraction (AµE) technique was proposed by Nogueira et al [17,18], which represents a great alternative for the enrichment of a wide range of polar analytes at trace levels in aqueous media, selecting appropriate sorbent phases. The new AµE approach can be used through different analytical devices presenting suitable geometry, where specific sorbents are simply sustained through sticking-based technologies.…”

“…This methodology has also been reported in the preparation of soil samples to increase the extraction efficiency of triazine herbicides [179]. Multisphere adsorptive microextraction (MSAµ) has been applied in the extraction of caffeine, acetaminophen [18], pharmaceuticals, sexual steroid hormones, and antibiotics [17] in water samples. QuECh-ERS is known as the Swiss knife of extraction.…”