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This work presents a sustainable and rapid method for halogenated pesticide analysis without chromatographic separation. The system is composed of a microfluidic open interface (MOI) for solid-phase microextraction (SPME) liquid phase desorption, connected to a liquid electron ionization mass spectrometry interface (LEI-MS). Either a triple quadrupole mass spectrometer (QQQ-MS/MS, (low-resolution) or a quadrupole-time-of-flight tandem MS (QTOF-MS/MS, high-resolution) were employed, each operating in negative chemical ionization (NCI) conditions. The flow rate used (100 µL/min) to rapidly empty the MOI chamber (approximately 2.5 µL) is reduced to the working flow rate of the LEI interface (500 nL/min) by a passive flow splitter (PFS). NCI is an appropriate ionization technique for electrophilic compounds, increasing specificity and reducing background noise. Two halogenated pesticides, dicamba and tefluthrin, were extracted simultaneously from a commercial formulation matrix (CF) using a C18 fiber by direct immersion (3 min under vortex agitation). Analyte desorption occurred in static conditions inside MOI filled with acidified acetonitrile (ACN) (0.2% phosphoric acid, PA). Extraction and desorption steps were optimized to increase efficiency and accelerate the process. No chromatographic separation was involved; therefore, the system fully exploited MS/MS selectivity and HRMS accuracy demonstrating good linearity, repeatability and limits of detection (LODs) and limits of quantification (LOQs) in the pg/mL range (50 and 500 pg/mL, respectively). Low-resolution experiments showed that matrix effects (ME) did not affect the results. The fast workflow (5 min) makes the system suitable for high-throughput analysis observing the principles of green analytical chemistry (GAC).

Extra virgin olive oil (EVOO) is one of the main ingredients of the Mediterranean diet. It is claimed as a functional food for its unique content of health-promoting compounds. Tyrosol (Tyr), Hydroxytyrosol (Htyr), and their phenolic derivatives present in EVOO show beneficial properties, and their identification and quantification, both in their free form and after the hydrolysis of more complex precursors, are important to certify its quality. An alternative method for quantifying free and total Tyr and Htyr in EVOO is presented using an LC–MS interface based on electron ionization (EI), called liquid electron ionization (LEI). This method requires neither sample preparation nor chromatography; the sample is diluted and injected. The selectivity and sensitivity were assessed in multiple reaction monitoring mode (MRM), obtaining confirmation and quantification in actual samples ranging from 5 to 11 mg/Kg for the free forms and from 32 to 80 mg/Kg for their total amount after hydrolysis. Two MS/MS transitions were acquired for both compounds using the Q/q ratios as confirmatory parameters. Standard addition calibration curves demonstrated optimal linearity and negligible matrix effects, allowing a correct quantification even without expensive and difficult to find labeled internal standards. After several weeks of operation, the system’s repeatability was excellent, with an intraday RSD (%) spanning from five to nine and an interday RSD (%) spanning from 9 to 11.