Determination of alkylphenols and bisphenol A in seawater samples by dispersive liquid–liquid microextraction and liquid chromatography tandem mass spectrometry for compliance with environmental quality standards (Directive 2008/105/EC)

A fast, simple, sensitive and green analytical chemistry method for the simultaneous determination of alkylphenols (4-tert-octylphenol, 4-octylphenol, 4-n-nonylphenol, nonylphenol) and bisphenol A in seawater was developed and validated. The procedure was based on a dispersive liquid–liquid microextraction (DLLME) of a small volume of seawater sample (30 mL) using only 100 μL of 1-octanol, combined with liquid chromatography–electrospray ionization tandem mass spectrometry in negative mode (LC–ESI-MS/MS). The matrix effect was studied and compensated using deuterated labelled standards as surrogate standards for the quantitation of target compounds. The analytical features of the proposed method were satisfactory: repeatability and intermediate precision were <10% and recoveries were around 84–104% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) ranged between 0.005 and 0.03 μg L−1, therefore the levels established in the Directive 2008/105/EC were achieved. The applicability of the proposed method was demonstrated analyzing seawater samples from different sites of A Coruña (Northwest of Spain). The analyses showed the presence of all compounds at levels between 0.035 (bisphenol A) and 0.14 μg L−1 (nonylphenol).

► Fast, simple and sensitive method for APs and BPA determination in seawater.
► DLLME of 30 mL of sample with only 100 μL of 1-octanol (Green Chemistry principles).
► Ultratrace determination with lower sample volumes than literature.
► Compliance of the Directive 2008/105/EC.