Online coupling of matrix solid-phase dispersion to direct analysis in real time mass spectrometry for high-throughput analysis of regulated chemicals in consumer products

The current work is the first study on online coupling of matrix solid-phase dispersion (MSPD) to direct analysis in real time mass spectrometry (DART-MS) bridging with solid-phase analytical derivatization (SPAD) based on a graphene oxide nanosheets (GONs)-coated cotton swab. Proof-of-concept demonstrations were explored for high-throughput analysis of a diversity of regulated chemicals in consumer products such as textiles, toys, and cosmetics. On-demand sorbent combinations were blended with samples, packed into MSPD columns, and mounted on a homemade 3D-printed rack module for automated sample feeding. To achieve good synergy between MSPD and DART-MS, a cotton swab with a conical tip deposited with GONs was attached to the bottom of the MSPD column. The swabs serve as a solid-phase microextraction probe for convenient enrichment of the eluted analytes from MSPD, thermal desorption of the enriched analytes by DART, and sensitive detection by a hybrid quadrupole-Orbitrap mass spectrometer. Furthermore, the utility of an on-swab SPAD strategy was demonstrated for the detection of formaldehyde by use of the derivatizing reagent of dansyl hydrazine, contributing to improved ionization efficiency without compromising the overall coherence of the analytical workflow. The MSPD-DART-MS methodology was systematically optimized and validated, obtaining acceptable recovery (71.7-110.3%), repeatability (11.8-19.3%), and sensitivity (limits of detection and quantitation in the ranges of 6.2-19.5 and 23.7-75.9 μg/kg) for 32 target analytes. The developed protocol streamlined sample extraction, clean-up, desorption, ionization, and detection, highlighting the appealing potential for high-throughput analysis of samples with complex matrices.