Simultaneous Determination of Trace Levels of 12 Steroid Hormones in Soil Using Modified QuEChERS Extraction Followed by Ultra Performance Liquid Chromatography–Tandem Mass Spectrometry (UPLC–MS/MS)
- 384 Downloads
Steroid hormones, mainly secreted by vertebrates, are discharged into the soil environment through surface runoff and land application of animal manure, sewage sludge, and organic fertilizers. The adequate analytical methods for steroid hormones in soil are lacking due to the requirement of rigorous sample pre-treatment. In this study, a rapid and effective modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was developed for trace simultaneous analysis of 12 steroid hormones (estrogen, androgens, and progestogens) in soil samples using ultra performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS). Samples were extracted by the mixture of acetonitrile and acetate buffer, and then cleaned with PSA/C18 absorbents. The QuEChERS method was validated by evaluating the linearity, repeatability, accuracy and precision. A suitable linear relationship was obtained in the mass concentration range of 1–100 ng g−1 with high correlation coefficients (> 0.9927). The method enabled the determination of the target analytes with limits of detection between 0.0014 and 0.462 ng g−1 and limits of quantification between 0.0047 and 1.54 ng g−1. Soil was spiked at 5, 50 and 100 ng g−1, and the recoveries ranged from 75.17 to 110.33% with relative standard deviations ≤ 9.45. The developed method was successfully applied to the analysis of soil samples collected in Beijing, and five hormones (E1, E3, αE2, And, and Tes) were detected with the concentrations ranging from 0.35 to 7.09 ng g−1.
KeywordsSoil Steroid hormones QuEChERS UPLC–MS/MS
The present work was funded by the Open Project of the Risk Assessment Lab for Agro-products (Beijing) Ministry of Agriculture (ZBZXKFKT201503), Open Project of the Risk Assessment Lab for Agro-products (Beijing) Ministry of Agriculture (ZBZXKFKT201701) and Special projects of construction of science and technology innovation ability of Beijing academy of agriculture and forestry sciences (KJCX20150408).
Compliance with Ethical Standards
Conflict of interest
The authors report no conflicts of interest with this study.
This article does not contain any studies with human participants or animals performed by any of the authors. No compliance with ethical standards was involved.
- 3.Alexandre B, Emmanuelle V (2015) Development of a method for the analysis of hormones and pharmaceuticals in earthworms by quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction followed by liquid chromatography–tandem mass spectrometry (LC–MS/MS). Anal Bioanal Chem 407(26):7995–8008. https://doi.org/10.1007/s00216-015-8972-z CrossRefGoogle Scholar
- 5.Maier RM, Pepper LI, Gerba CP (2000) Environmental microbiology. Academic Press, New York, pp 61–80Google Scholar
- 9.Nieto A, Borrull F, Pocurull E, Marcé RM (2008) Determination of natural and synthetic estrogens and their conjugates in sewage sludge by pressurized liquid extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1213(2):224–230. https://doi.org/10.1016/j.chroma.2008.10.043 CrossRefGoogle Scholar
- 11.Vulliet E, Wiest L, Baudot R et al (2008) Multi-residue analysis of steroids at sub-ng/L levels in surface and ground-waters using liquid chromatography coupled to tandem mass spectrometry. J Chromatogr A 1210(1):84–89. https://doi.org/10.1016/j.chroma.2008.09.034 (Epub 2008 Sep 16) CrossRefGoogle Scholar
- 13.Mokhtari SA, Farzadkia M, Gholami M (2017) Application of dispersive liquid–liquid microextraction as a simple assisted clean-up and preconcentration technique for GC/MS determination of selected PAHs extracted from sewage sludge by Soxhlet and ultrasound assisted extraction method. Desalin Water Treat 66(5):176–183. https://doi.org/10.5004/dwt.2017.20206 CrossRefGoogle Scholar
- 15.Azzouz A, Ballesteros E (2012) Combined microwave-assisted extraction and continuous solid-phase extraction prior to gas chromatography–mass spectrometry determination of pharmaceuticals, personal care products and hormones in soils, sediments and sludge. Sci Total Environ 419:208–215. https://doi.org/10.1016/j.scitotenv.2011.12.058 CrossRefGoogle Scholar
- 17.Albero B, Sánchez-Brunete C, Miguel E (2013) Analysis of natural-occurring and synthetic sexual hormones in sludge Sánchez-Brunete-amended soils by matrix solid-phase dispersion and isotope dilution gas chromatography –tandem mass spectrometry. J Chromatogr A 1283:39–45. https://doi.org/10.1016/j.chroma.2013.01.113 CrossRefGoogle Scholar
- 19.Andreu V, Ferrer E, Rubio JL et al (2007) Quantitative determination of octylphenol, nonylphenol, alkylphenol ethoxylates and alcohol ethoxylates by pressurized liquid extraction and liquid chromatography–mass spectrometry in soils treated with sewage sludges. Sci Total Environ 378(1–2):124–129. https://doi.org/10.1016/j.scitotenv.2007.01.024 CrossRefGoogle Scholar
- 21.Durán-Alvarez JC, Becerril-Bravo E, Castro VS (2009) The analysis of a group of acidic pharmaceuticals, carbamazepine, and potential endocrine disrupting compounds in waste water irrigated soils by gas chromatography–massspectrometry. Talanta 78(3):1159–1163. https://doi.org/10.1016/j.talanta.2009.01.035 CrossRefGoogle Scholar
- 23.Anastassiades M, Lehotay SJ, Stajnbaher D (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solid-phase extraction for the determination of pesticide residues in produce. AOAC Int 86(2):412–431 (PMID:12723926) Google Scholar
- 26.Salvia MV, Vulliet E, Wiest L et al (2012) Development of a multi-residue method using acetonitrile-based extraction followed by liquid chromatography–tandem mass spectrometry for the analysis of steroids and veterinary and human drugs at trace levels in soil. J Chromatogr A 1245(6):122–133. https://doi.org/10.1016/j.chroma.2012.05.034 CrossRefGoogle Scholar
- 27.Fülöp I, Vari CE, Miklos A (2017) LC–MS/MS ESI Methods for the determination of oestrogens and androgens in biological matrix—a minireview. FARMACIA 65(4):485–493Google Scholar
- 29.Zhang K, Fent K (2018) Determination of two progestin metabolites (17α-hydroxypregnanolone and pregnanediol) and different classes of steroids (androgens, estrogens, corticosteroids, progestins) in rivers and wastewaters by high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS). Sci Total Environ 610–611:1164–1172. https://doi.org/10.1016/j.scitotenv.2017.08.114 CrossRefGoogle Scholar
- 30.ICH (2005) Harmonised tripartite guideline, Q2B validation of analytical procedures: text and methodology, p 9Google Scholar
- 34.Padilla-Sánchez JA, Plaza-Bolaños P, Romero-González R et al (2010) Application of a quick, easy, cheap, effective, rugged and safe-based method for the simultaneous extraction of chlorophenols, alkylphenols, nitrophenols and cresols in agricultural soils, analyzed by using gas chromatography–triple quadrupole-mass spectrometry/mass spectrometry. J Chromatogr A 1217:5724–5731. https://doi.org/10.1016/j.chroma.2010.07.004 CrossRefGoogle Scholar
- 35.AFNOR (NF EN 15662) (2009) Determination of pesticide residues using GC-MS and/or LC–MS/MS) following acetonitrile extraction/partitioning and clean-up by dispersive SPE—QuEChERS-method. France, p 11Google Scholar
- 36.AOAC Official Method 2007.01 (2007) Pesticides residues in food by acetonitrile extraction and partitioning with magnesium sulphate. AOAC Int 9Google Scholar
- 37.Han YT, Song L, Zou N et al (2016) Multi-residue determination of 171 pesticides in cowpea using modified QuEChERS method with multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction materials. J Chromatogr B 7(43):99–108. https://doi.org/10.1016/j.jchromb.2016.07.043 CrossRefGoogle Scholar
- 41.Han Y, Song L, Zhao P (2016) Residue determination of glufosinate in plant origin foods using modified Quick Polar Pesticides (QuPPe) method and liquid chromatography coupled with tandem mass spectrometry. Food Chem 197(Part A):730–736. https://doi.org/10.1016/j.foodchem.2015.11.021 CrossRefGoogle Scholar
- 45.Pérez RL, Escandar GM (2016) Multivariate calibration-assisted high-performance liquid chromatography with dual UV and fluorimetric detection for the analysis of natural and synthetic sex hormones in environmental waters and sediments. Environ Pollut 209:114–122. https://doi.org/10.1016/j.envpol.2015.11.024 CrossRefGoogle Scholar