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Simultaneous determination of twelve natural estrogens in dairy milk using liquid–liquid extraction and solid-phase extraction coupled with gas chromatography-mass spectrometry

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Abstract

There have been many analytical methods for natural estrogens in commercial dairy milk samples, but in most of which, only four major estrogens (estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-estradiol (αE2)) were included. This work developed an effective GC–MS analytical method for simultaneous analysis of twelve natural estrogens in commercial dairy milk sample, in which eight far-less well-known natural estrogens (2-hydroxyestone (2OHE1), 4-hydroxyestrone (4OHE1), 2-hydroxyestradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 16-epiestriol (16epiE3), 16α-hydroxyestrone (16αOHE1), 16-ketoestradiol (16ketoE2) and 17epiestriol (17epiE3)) were included besides the four major natural estrogens. With liquid–liquid extraction and solid phase extraction, twelve natural estrogens in commercial dairy milk could be effectively extracted. The established method showed good linearity (R2 > 0.9991), low limits of detections (LODs, 0.02–0.11 ng/g), as well as excellent recoveries (64–117%) with satisfactory low relative standard deviations (RSDs, 0.8–14.7%). This established method was applied to seven commercial dairy milk samples, and all the twelve natural estrogens were frequently detected except for 4OHE2 without detection in any sample. Our results showed that the concentration contribution ratios of the eight far-less well-known natural estrogens in commercial dairy milk samples contributed to 32–83%, while the corresponding contribution ratios based on estrogen equivalence (EEQ) were 21–62%. This work highlighted the high abundance of the eight far-less well-known natural estrogens in commercial dairy milk based on both concentration and EEQ, which has been neglected for a long time.

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Funding

This work was financially supported by National Natural Science Foundation of China (21107025; 21577040), Special funds for public welfare research and capacity building in Guangdong Province (2015A020215003), Science and Technology Program of Guangzhou, China (201510010162; 201904010100), Guangdong Science and Technology Program (2020B121201003), National High-end Foreign Expert Introduction Program (111001300920228000), and Key-Area Research and Development Program of Guangdong (2020B1111350002).

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Authors and Affiliations

  1. School of Environment and Energy, South China University of Technology, Guangzhou, 510006, Guangdong, China

    De-ming Kong, Zhao Tang, Ze-hua Liu & Zhi Dang

  2. Guangdong Provincial Key Laboratory of Chemical Measurement and Emergency Test Technology, Institute of Analysis, Guangdong Academy of Sciences, Guangzhou, 510070, China

    De-ming Kong, Peng-ran Guo & Yu-mei Song

  3. Key Lab Pollution Control & Ecosystem Restoration in Industry Cluster, Ministry of Education, Guangzhou, 510006, Guangdong, China

    Ze-hua Liu

  4. Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, Guangzhou, 510006, Guangdong, China

    Ze-hua Liu

  5. School of Civil and Engineering, Nanyang Technological University, Singapore, 639798, Singapore

    Yu Liu

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  1. De-ming Kong
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  2. Zhao Tang
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  3. Ze-hua Liu
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Contributions

De-ming Kong: methodology, validation, manuscript writing; Zhao Tang: methodology, Ze-hua Liu: supervision, conceptualization, funding support, writing—reviewing and editing; Zhi Dang: writing—reviewing and editing; Peng-ran Guo: funding support; Yu-mei Song: equipment maintenance and analysis support; Yu Liu: writing—reviewing and editing.

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Correspondence to Ze-hua Liu.

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Kong, Dm., Tang, Z., Liu, Zh. et al. Simultaneous determination of twelve natural estrogens in dairy milk using liquid–liquid extraction and solid-phase extraction coupled with gas chromatography-mass spectrometry. Environ Sci Pollut Res 30, 112908–112921 (2023). https://doi.org/10.1007/s11356-023-30330-0

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