Rapid analysis of 65 pharmaceuticals and 7 personal care products in plasma and whole-body tissue samples of fish using acidic extraction, zirconia-coated silica cleanup, and liquid chromatography-tandem mass spectrometry

Abstract

The presence of pharmaceuticals and personal care products (PPCPs) in aquatic systems has raised concern about their potential adverse effects on aquatic organisms. Considering the fact that the physiological/biological effects of PPCPs are triggered when their concentrations in the organism exceeds the respective threshold values, it is important to understand the bioconcentration and toxicokinetics of PPCPs in aquatic organisms. In the present study, we developed a convenient analytical method for the determination of 65 pharmaceuticals and 7 personal care products (log Kow = 0.14–6.04) in plasma and whole-body tissues of fish. The analytical method consists of ultrasound-assisted extraction in methanol/acetonitrile (1:1, v/v,) acidified with acetic acid-ammonium acetate buffer (pH 4), cleanup on a HybridSPE®-Phospholipid cartridge (zirconia-coated silica cartridge), and quantification with liquid chromatography-tandem mass spectrometry (LC–MS/MS). Acceptable accuracy (internal standard-corrected recovery: 70%–120%) and intra- and inter-day precision (coefficient of variation: <15%) were obtained for both plasma and whole-body tissue samples. In addition, low method detection limits were achieved for both plasma (0.0077 to 0.93 ng mL−1) and whole-body tissue (0.022 to 4.3 ng g − 1 wet weight), although the developed method is simple and fast ― a batch of 24 samples can be prepared within 6 h, excluding the time for measurement with LC–MS/MS. The developed method was successfully applied to the analysis of PPCPs in plasma and whole-body tissue samples of fish collected in a treated wastewater-dominated stream, for a comprehensive evaluation of their bioconcentration properties. The analytical method developed in the present study is sufficiently accurate, sensitive, and rapid, and thus highly useful for the comprehensive evaluation of PPCP residues in fish and would aid in future exposome and risk assessment.