Simultaneous determination of UV-filters and estrogens in aquatic invertebrates by modified quick, easy, cheap, effective, rugged, and safe extraction and liquid chromatography tandem mass spectrometry

Ke He; Anne Timm; Lee Blaney

doi:10.1016/j.chroma.2017.06.039

Simultaneous determination of UV-filters and estrogens in aquatic invertebrates by modified quick, easy, cheap, effective, rugged, and safe extraction and liquid chromatography tandem mass spectrometry

J Chromatogr A. 2017 Aug 4:1509:91-101. doi: 10.1016/j.chroma.2017.06.039. Epub 2017 Jun 15.

Authors

Ke He¹, Anne Timm², Lee Blaney³

Affiliations

¹ University of Maryland Baltimore County, Department of Chemical, Biochemical and Environmental Engineering, 1000 Hilltop Circle, Engineering 314, Baltimore, MD 21250, USA.
² USDA Forest Service, Northern Research Station, 5523 Research Park Drive, Suite 350, Baltimore, MD 21228, USA.
³ University of Maryland Baltimore County, Department of Chemical, Biochemical and Environmental Engineering, 1000 Hilltop Circle, Engineering 314, Baltimore, MD 21250, USA. Electronic address: blaney@umbc.edu.

PMID: 28647144
DOI: 10.1016/j.chroma.2017.06.039

Abstract

Ultraviolet-filters (UV-filters) and estrogens have attracted increased attention as contaminants of emerging concern (CECs) due to their widespread occurrence in the environment. Most of these CECs are hydrophobic and have the potential to accumulate in aquatic organisms. To date, co-analysis of UV-filters and estrogens has not been reported due, in part, to the complex environmental matrices. Here, a multi-residue method has been developed for simultaneous determination of five UV-filters and three estrogens in tissue from aquatic and marine organisms. The procedure involved a modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction with a novel reverse-solid-phase extraction (reverse-SPE) cleanup in place of dispersive-SPE, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis. The tissue mass, acetonitrile content, and salt conditions for QuEChERS extraction, along with the reverse-SPE cartridge material and elution conditions, were thoroughly investigated and optimized. Five UV-filters (i.e., 3-(4-methylbenzylidene) camphor, benzophenone-3, ethylhexylmethoxycinnamate, homosalate, and octocrylene) and three estrogens (i.e., estrone, 17β-estradiol, and 17α-ethinylestradiol) were simultaneously analyzed by taking advantage of wrong-way-round ionization in LC-MS/MS. The optimized analytical protocol exhibited good recoveries (>80%) for target compounds and enabled their detection at concentrations as low as 0.2ng/g in 50mg tissue samples. The method was applied to determine concentrations of target analytes in four invertebrates (i.e., Orconectes virilis, Procambarus clarkii, Crassostrea virginica, and Ischadium recurvum). All eight target analytes were detected at least once in the tissue samples, with the highest concentration being 399ng/g of homosalate in O. virilis. These results highlight the ubiquitous bioaccumulation of CECs in aquatic and marine invertebrates.

Keywords: Estrogens; Invertebrates; QuEChERS; Reverse-solid-phase extraction; UV-filters; Wrong-way-round ionization.

Publication types

Evaluation Study

MeSH terms

Animal Structures / chemistry*
Animals
Chromatography, Liquid / methods*
Estrogens / chemistry*
Estrogens / isolation & purification*
Invertebrates / chemistry*
Solid Phase Extraction / methods*
Tandem Mass Spectrometry / methods*

Substances

Estrogens