Advances in sample preparation techniques for chromatographic analysis of personal care products and their metabolites in human biological matrices: A critical review

• Analysis of PCPs and their metabolites in biological matrices was reviewed. • Urine and nails are the most commonly analyzed biological samples. • LLE and UAE were the most used sample preparation techniques. • LC-MS/MS is the prevailing technique to determine PCPs and their metabolites. • More studies covering the analysis of PCPs metabolites are needed. The extensive use of personal care products (PCPs) — including preservatives, UV filters, insect repellents, antimicrobials, and synthetic musks — has led to widespread human exposure, making them contaminants of emerging concern. They are ingredients of products that are used daily for hygiene and skin care. While biomonitoring studies confirm the presence of both parent PCPs and their metabolites in human tissues and fluids, a critical gap exists in the review of analytical methods for analyzing them simultaneously in complex biological matrices. This review critically examines state-of-the-art analytical techniques published from 2013 to the present for the simultaneous determination of multi-class PCPs and their metabolites in human biological samples, such as urine, blood, plasma, serum, saliva, breast milk, nails, and hair. It highlights advances in sample preparation, including innovative extraction and clean-up strategies, as well as chromatographic methods coupled with mass spectrometry. Special emphasis is placed on evaluating key analytical validation parameters, including accuracy, precision, limits of detection, and limits of quantification. Emerging trends reveal that parabens and their metabolites are the most frequently studied compounds, while synthetic musks remain notably underrepresented. Among biological matrices, urine and nails dominate as the preferred liquid and solid samples, respectively. To our knowledge, this is the first review to synthesize recent advances in the simultaneous analysis of diverse PCP classes and their metabolites in human matrices, offering a valuable resource for toxicologists and analytical chemists engaged in exposure assessment and biomonitoring.