Determination of free formaldehyde in cosmetics containing formaldehyde-releasing preservatives by reversed-phase dispersive liquid–liquid microextraction and liquid chromatography with post-column derivatization

• Published in: Journal of Chromatography A Vol. 1543; pp. 34 - 39
• Main Authors: Miralles, Pablo, Chisvert, Alberto, Alonso, M. José, Hernandorena, Sandra, Salvador, Amparo
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 30.03.2018
• Subjects: Acetonitriles - chemistry; Chemistry Techniques, Analytical - methods; Chromatography, Liquid; Cosmetic products; Cosmetics - chemistry; Formaldehyde; Formaldehyde - analysis; Formaldehyde-releasing preservatives; Limit of Detection; Liquid chromatography; Liquid Phase Microextraction; Preservatives, Pharmaceutical - analysis; Reproducibility of Results; Reversed-phase dispersive liquid–liquid microextraction; Solvents - chemistry; Toluene - analysis; Water - chemistry; Formaldehyde-releasing preservatives; Liquid chromatography; Formaldehyde; Reversed-phase dispersive liquid–liquid microextraction; Cosmetic products
• ISSN: 0021-9673; 1873-3778
• DOI: 10.1016/j.chroma.2018.02.031

•A new method to determine traces of formaldehyde in cosmetics is presented.•RP-DLLME is used as novel clean-up and enrichment step.•The method uses simple LC–UV instrumentation, suitable for routine analysis.•The method is suitable for the analysis of both lipophilic and hydrophilic samples. An analytical method for the determination of traces of formaldehyde in cosmetic products containing formaldehyde-releasing preservatives has been developed. The method is based on reversed-phase dispersive liquid–liquid microextraction (RP-DLLME), that allows the extraction of highly polar compounds, followed by liquid chromatography–ultraviolet/visible (LC–UV/vis) determination with post-column derivatization. The variables involved in the RP-DLLME process were studied to provide the best enrichment factors. Under the selected conditions, a mixture of 500 μL of acetonitrile (disperser solvent) and 50 μL of water (extraction solvent) was rapidly injected into 5 mL of toluene sample solution. The extracts were injected into the LC–UV/vis system using phosphate buffer 6 mmol L−1 at pH 2 as mobile phase. After chromatographic separation, the eluate merged with a flow stream of pentane-2,4-dione in ammonium acetate solution as derivatizing reagent and passed throughout a post-column reactor at 85 °C in order to derivatize formaldehyde into 3,5-diacetyl-1,4-dihydrolutidine, according to Hantzsch reaction, which was finally measured spectrophotometrically at 407 nm. The method was successfully validated showing good linearity, an enrichment factor of 86 ± 2, limits of detection and quantification of 0.7 and 2.3 ng mL−1, respectively, and good repeatability (RSD < 9.2%). Finally, the proposed analytical method was applied to the determination of formaldehyde in different commercial cosmetic samples containing formaldehyde-releasing preservatives, such as bronopol, diazolidinyl urea, imidazolidinyl urea, and DMDM hydantoin, with good relative recovery values (91–113%) thus showing that matrix effects were negligible. The good analytical features of the proposed method besides of its simplicity and affordability, make it useful to carry out the quality control of cosmetic products containing formaldehyde-releasing preservatives.