Coated glass capillaries as SPME devices for DART mass spectrometry.

Abstract

Solid-phase microextraction (SPME) provides high-throughput sample cleanup and pre-concentration. Here we demonstrate coated glass capillaries (CGCs) as SPME devices for specific applications in direct analysis in real time (DART) mass spectrometry, referred to as "CGC-DART", for rapid screening of environmental contaminants at low parts-per-trillion detection limits and with accurate identification of analytes. The extraction is performed in a one-step process in minutes by dipping the CGC in solutions containing the analytes, and then placing the CGC in a DART source for analysis. CGCs are disposable and relatively inexpensive in comparison with SPME devices, and can be prepared with hydrophobic, hydrophilic or mixed-mode materials similar to SPME. CGCs were prepared by adsorption coating with incubation of capillaries in saturated solutions of octadecylamine or covalent activation of silanes. Quantitation is shown with perfluorooctanoic acid (PFOA) at 1 ppt to 100 ppb, with the lowest detection at 500 parts-per quadrillion (ppq) in tap water. One-step extraction of contaminated groundwater from Northern Queensland, Australia, revealed perfluorooctane sulfonate (PFOS) and perfluorohexanesulfonamide as well as C4-C8 perfluoroalkyl carboxylic acids. A soil sample taken near a former military air base (New Hampshire, USA) revealed the presence of perfluorononanoic acid (PFNA) at 1 ppb and traces of perfluoroheptanoic acid. CGC-DART enabled one-step extraction of PFASs in minutes with mL sample volumes at low concentrations as shown for the standards and contaminated soil and water samples. DART-MS combined with Kendrick mass defect analysis enabled accurate identification of PFASs without chromatography steps, as fluorinated compounds are mass deficient and easily distinguished over background signal.