Optimization of Analytical Conditions to Determine Steroids and Pharmaceuticals Drugs in Water Samples Using Solid Phase-Extraction and HPLC

Ramiro Vallejo-Rodríguez, Alberto Lopez-Lopez, Hugo Saldarriaga-Noreña, Mario Murillo-Tovar, Leonel Hernández-Mena

.

DOI: 10.4236/ajac.2011.28099                

Abstract

Two reliable methods were optimized to determine two steroids (17?-Estradiol and 17?-Ethinylestradiol) and two pharmaceutical drugs (ibuprofen and naproxen) using Solid-Phase Extraction (SPE) for sample preparation and High Performance Liquid Chromatography (HPLC) for analysis. SPE (C18) conditions were evaluated varying elution solvent volume, pH conditions and sample mass in the cartridge and reduction techniques of the extract. The efficiency of the analytical methods was evaluated by spiking ultrapure water samples with compounds at three and four levels of concentration for steroids and pharmaceutical drugs, re- spectively. The recoveries were independent (P > 0.05) of added mass of target analytes with a repeatability lower than 6.5% for steroids and 12.1% for pharmaceutical compounds. The recovery factor (coefficient of variation, CV) was higher than 83% for steroids (CV < 3.8%) and >93% for pharmaceuticals (CV < 5.2%). The optimized analytical method was applied for the evaluation of a steroid degradation test using ozone, finding that the estimated limit of detection is sufficient to determine the residual mass (μg?L–1) of 17β-Estradiol after the experiment.

Keywords

Steroids, Pharmaceuticals Drugs, Solid-Phase Extraction, HPLC-DAD

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	EEA (European Environment Agency), “Pharmaceuticals in the Environment: Results of an EEA Workshop,” Technical Report No. 1/2010 ISSN 1725-2237, EEA, Copenhagen, 2010.
[2]	K. Kümmerer, “Pharmaceuticals in the Environment: Sources, Fate, Effects and Risks,” Environmental Science and Pollution Research, Vol. 17, No.2, 2010, pp. 519- 521.
[3]	K. Fent, A. A. Weston and D. Caminada, “Ecotoxicology of Human Pharmaceuticals,” Aquatic Toxicology, Vol. 76, No. 2, 2006, pp. 122-159. doi:10.1016/j.aquatox.2005.09.009
[4]	A. M. Vajda, L. B. Barber, J. L. Gray, E. M. López, J. D. Woodling and D. O. Norris, “Reproductive Disruption in Fish Downstream from an Estrogenic Wastewater Efflu- ent,” Environmental Science & Technology, Vol. 42, No, 9, 2008, pp. 3407-3414. doi:10.1021/es0720661
[5]	F. X. M. Casey, G. Larsen, H. Hakk and J. Simunek, “Fate and Transport of 17β-Estradiol in Soil-Water Systems,” Environmental Science & Technology, Vol. 37, No, 11, 2003, pp. 2400-2409. doi:10.1021/es026153z
[6]	R. L. Gomes, M. D. Scrimshaw, E. Cartmell and J. N. Lester, “The Fate of Steroid Estrogens: Partitioning during Wastewater Treatment and onto River Sediments,” Environmental Monitoring and Assessment, Vol. 175, No. 1, 2011, pp. 431-441.
[7]	I. Rodríguez, J. B. Quintana, J. Carpinteiro, A. M. Carro, R. A. Lorenzo and R. Cela, “Determination of Acidic Drugs in Sewage Water by Gas Chromatography―Mass Spectrometry as Tert-Butyldimethylsilyl Derivatives,” Journal of Chromatography A, Vol. 985, No. 1-2, 2003, pp. 265-274.
[8]	X. Peng, Y. Yu, C. Tang, J. Tan, Q. Huang, Z. Wang, “Occurrence of Steroid Estrogens, Endocrine-Disrupting Phenols, and Acid Pharmaceutical Residues in Urban Riverine Water of the Pearl River Delta, South China,” Science of the Total Environment, Vol. 397, No. 1-3, 2008, pp. 158-166. doi:10.1016/j.scitotenv.2008.02.059
[9]	J. Radjenovi?, M. Petrovi? and D. Barceló, “Fate and Distribution of Pharmaceuticals in Wastewater and Sewage Sludge of the Conventional Activated Sludge (CAS) and Advanced Membrane Bioreactor (MBR) Treatment,” Water Research, Vol. 43, No. 3, 2009, pp. 831-841. doi:10.1016/j.watres.2008.11.043
[10]	V. G. Samaras, N. S. Thomaidis, A. S. Stasinakis, G. Gatidou and T. D. Lekkas, “Determination of Selected Non-Steroidal Anti-Inflammatory Drugs in Wastewater by Gas Chromatography―Mass Spectrometry,” International Journal of Environmental Analytical Chemistry, Vol. 90, No. 3-6, 2010, pp. 219-229. doi:10.1080/03067310903243936
[11]	C. Y. Chen, T. Y. Wen, G. S. Wang, H. W. Cheng, Y. H. Lin and G. W. Lien, “Determining Estrogenic Steroids in Taipei Waters and Removal in Drinking Water Treatment Using High-Flow Solid-Phase Extraction and Liquid Chr- omatography/Tandem Mass Spectrometry,” Science of the Total Environment, Vol. 378, No. 3, 2007, pp. 352- 365. doi:10.1016/j.scitotenv.2007.02.038
[12]	A. J. Jafari, R. Pourkabireh-Abasabad and A. Salehzadeh, “Endocrine Disrupting Contaminants in Water Resources and Sewage in Hamadan City of Iran, Iran,” Journal of Environmental Health Science & Engineering, Vol. 6, No. 2, 2009, pp. 89-96.
[13]	M. J. Benotti, B. D. Stanford and S. A. Snyder, “Impact of Drought on Wastewater Contaminants in an Urban Water Supply,” Journal of Environmental Quality, Vol. 39, No. 4, 2010, pp. 1196-1200. doi:10.2134/jeq2009.0072
[14]	M. J. López de Alda and D. Barceló, “Determination of Steroid Sex Hormones and Related Synthetic Compounds Considered as Endocrine Disrupters in Water by Liquid Chromatography-Diode Array Detection―Mass Spectrometry,” Journal of Chromatography A, Vol. 892, No. 1-2, 2000, pp. 391-406.
[15]	J. L. Santos, I. Aparicio, E. Alonso and M. Callejón, “Simultaneous Determination of Pharmaceutically Active Compounds in Wastewater Samples by Solid Phase Extraction and High-Performance Liquid Chromatography with Diode Array and Fluorescence Detectors,” Analytica Chimica Acta, Vol. 550, No. 1-2, 2005, pp. 116-122. doi:10.1016/j.aca.2005.06.064
[16]	R. Gibson, E. Becerril-Bravo, V. Silva-Castro and B. Jiménez, “Determination of Acidic Pharmaceuticals and Potential Endocrine Disrupting Compounds in Wastewaters and Spring Waters by Selective Elution and Analysis by Gas Chromatography―Mass Spectrometry,” Journal of Chromatography A, Vol. 1169, No. 1-2, 2007, pp. 31- 39. doi:10.1016/j.chroma.2007.08.056
[17]	Z. Liu, Y. Kanjo and S. Mizutani, “Removal Mecha- nisms for Endocrine Disrupting Compounds (EDCs) in Wastewater Treatment—Physical Means, Biodegradation, and Chemical Advanced Oxidation: A Review,” Science of the Total Environment, Vol. 407, No. 2, 2009, pp. 731-748. doi:10.1016/j.scitotenv.2008.08.039
[18]	C. Almeida and J. M. F. Nogueira, “Determination of Steroid Sex Hormones in Water and Urine Matrices by Stir Bar Sorptive Extraction and Liquid Chromatography with Diode Array Detection,” Journal of Pharmaceutical and Biomedical Analysis, Vol. 41, No. 4, 2006, pp. 1303- 1311. doi:10.1016/j.jpba.2006.02.037
[19]	Y. K. K. Koh, T. Y. Chiu, A. Boobis, E. Cartmell, J. N. Lester and M.D. Scrimshaw, “Determination of Steroid Estrogens in Wastewater by High Performance Liquid Chromatography-Tandem Mass Spectrometry,” Journal of Chromatography A, Vol. 1173, No. 1-2, 2007, pp. 81- 87. doi:10.1016/j.chroma.2007.09.074
[20]	C. Miège, P. Bados, C. Brosse and M Coquery, “Method Validation for the Analysis of Estrogens Including Conju- gated Compounds) in Various Aqueous Matrices,” Trends in Analytical Chemistry, Vol. 28, No. 2, 2009, pp. 237-244. doi:10.1016/j.trac.2008.11.005
[21]	E. M. Thurman and M. S. Mills, “Solid-Phase Extraction: Principles and Practice,” In: J. D. Winefordner, Ed., Chemical Analysis, A Series of Monographs on Analytical and Its Applications, John Wiley & Sons, Inc., Hoboken, 1998, pp. 1-339.
[22]	E. M. Costi, I. Goryachevab, M. D. Sicilia, S. Rubio and D. Pérez-Bendito, “Supramolecular Solid-Phase Extrac- tion of Ibuprofen and Naproxen from Sewage Based on the Formation of Mixed Supramolecular Aggregates Prior to Their Liquid Chromatographic/Photometric Determination,” Journal of Chromatography A, Vol. 1210, No. 1, 2008, pp. 1-7. doi:10.1016/j.chroma.2008.09.024
[23]	M. Huber, S. Canonica and G. Y. Park, “Oxidation of Pharmaceuticals during Ozonation and Advanced Oxida- tion Processes,” Environmental Science & Technology, Vol. 37, No. 5, 2003, pp. 1016-1024. doi:10.1021/es025896h
[24]	L. S. Clesceri, A. E. Greenberg and A. D. Eaton, “Stan- dard Methods for the Examination of Water and Waste- water,” APHA, AWWA and WEF, New York, 1998.
[25]	H. B. Jakobsen, M. R. N?rrelykkeb, L. P. Christensen and M. Edelenbos, “Comparison of Methods Used for Pre- concentrating Small Volumes of Organic Volatile Solu- tions,” Journal of Chromatography A, Vol. 1003, No. 1-2, 2003, pp. 1-10. doi:10.1016/S0021-9673(03)00847-1
[26]	M. Deborde, S. Rabouan, J. P. Duguet and B Legube, “Kinetics of Aqueous Ozone-Induced Oxidation of Some Endocrine Disruptors,” Environmental Science & Technology, Vol. 39, No. 16, 2005, pp. 6086-6092. doi:10.1021/es0501619
[27]	M. Guedes-Maniero, D. B. Maia and M. Dezotti, “Deg- radation and Estrogenic Activity Removal of 17β-Estradiol and 17α-Ethinylestradiol by Ozonation and O3/ H2O2,” Science of the Total Environment, Vol. 407, No. 1, 2009, pp. 731-748.
[28]	S. Mitra, “Sample Preparation Techniques in Analytical Chemistry,” Wiley Interscience Publication, 2003. doi:10.1002/0471457817