Direct sample introduction gas chromatography and mass spectrometry for the determination of phthalate esters in cleaning products

• First application of DSI–GC–MS to cleaning products.
• Minimal sample preparation, extraction and clean-up in a single step.
• DSI significantly improves sensibility over classical injection.

A method using direct sample introduction (DSI) coupled to gas chromatography–mass spectrometry (GC–MS) is developed for the determination of six phthalate esters (dimethyl, diethyl, dibutyl, butylbenzyl, diethylhexyl and dioctyl phthalate) in cleaning products. The different variables involved in the DSI step, including venting time and temperature, vaporisation time and temperature, injector heating temperature and gas flow rate and pressure, were evaluated and optimised using Taguchi orthogonal arrays. The proposed method, using calibration against methanolic standards, showed good linearity in the 0.05–15 μg g−1 range and good repeatability, with RSD values ranging from 3.5% to 5.7%. Quantification limits between 0.010 and 0.041 μg g−1, depending on the compound, were attained, while recovery assays provided values from 83% to 115%. Twenty-seven cleaning products were analysed using the DSI–GC–MS method, being four phthalates (dimethyl, diethyl, dibutyl and diethylhexyl phthalate) found in fourteen of them at concentration levels in the 0.1–21 μg g−1 range. Compared with the most common GC injection technique, which uses the split/splitless injector, the proposed DSI procedure provided larger peak areas and lower detection limits, as result of the greater injected volume and reduction in noise.