Enantioselective determination of ibuprofen residues by chiral liquid chromatography: a systematic study of enantiomeric transformation in surface water and sediments
María Eugenia León-González A B and Noelia Rosales-Conrado AA Analytical Chemistry Department, Faculty of Chemistry, Complutense University of Madrid, E-28040 Madrid, Spain.
B Corresponding author. Email: leongon@ucm.es
Environmental Chemistry 13(4) 656-664 https://doi.org/10.1071/EN15146
Submitted: 9 July 2015 Accepted: 8 October 2015 Published: 18 December 2015
Environmental context. Ibuprofen, a common anti-inflammatory drug and one of many pharmaceuticals sold as a mixture of enantiomers, has recently been found in river and surface waters. There are, however, few analytical methods able to separate and accurately measure ibuprofen enantiomers in environmental matrices. This study reports a method for quantifying ibuprofen enantiomers in sediments and surface water, and applies it to shed light on the degradation and fate of the enantiomers in aquatic systems.
Abstract. The enantioselective composition of ibuprofen in sediments in contact with surface water was evaluated over 168 h in the presence and absence of light. Multivariate techniques applied for the evaluation of enantiomeric fraction (EF) and recoveries of enantiomers in water and sediments show differences in the EF and composition of each enantiomer. In sediments, differences in the EF are a result of the presence or absence of light, whereas in water it is attributable to degradation of the two enantiomers with time. To achieve enantioselective separation of ibuprofen in surface water and sediments, a clean-up and preconcentration procedure using solid phase extraction combined with a direct chiral liquid chromatography–ultraviolet method was developed. Quantitation limits of the proposed method were between 0.12 and 0.15 µg g–1 for each enantiomer in sediments, and between 2.4 and 3.0 µg L–1 in surface water. Intra- and inter-day precisions were between 5.1 and 8.9 %. Multivariate techniques can be useful to identify enantiomeric modifications and to select the variables that should be used for modelling such transformations.
Additional keywords: degradation, direct chiral liquid chromatography, enantiomers, environmental matrices, multivariate chemometric techniques
References
[1] M. A. Sousa, C. Gonçalves, E. Cunha, J. Hajšlová, M. F. Alpendurada, Cleanup strategies and advantages in the determination of several therapeutic classes of pharmaceuticals in wastewater samples by SPE-LC-MS/MS. Anal. Bioanal. Chem. 2011, 399, 807.| Cleanup strategies and advantages in the determination of several therapeutic classes of pharmaceuticals in wastewater samples by SPE-LC-MS/MS.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhtlSjtbbK&md5=d1b0b8917037d1259eacb10389418555CAS | 20957470PubMed |
[2] R. López-Serna, B. Kasprzyk-Hordern, M. Petrović, D. Barceló, Multi-residue enantiomeric analysis of pharmaceuticals and their active metabolites in the Guadalquivir River basin (South Spain) by chiral chromatography coupled with tandem mass spectrometry. Anal. Bioanal. Chem. 2013, 405, 5859.
| Multi-residue enantiomeric analysis of pharmaceuticals and their active metabolites in the Guadalquivir River basin (South Spain) by chiral chromatography coupled with tandem mass spectrometry.Crossref | GoogleScholarGoogle Scholar | 23579471PubMed |
[3] P. Paíga, L. H. M. L. M. Santos, C. G. Amorim, A. N. Araújo, M. C. B. S. M. Montenegro, A. Pena, C. Delerue-Matos, Pilot monitoring study of ibuprofen in surface waters of north of Portugal. Environ Sci. Pollut. Res. 2013, 20, 2410.
| Pilot monitoring study of ibuprofen in surface waters of north of Portugal.Crossref | GoogleScholarGoogle Scholar |
[4] H. Chen, X. Li, S. Zhu, Ocurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments: a comparative study of regions in China with different urbanization levels. Environ. Sci. Pollut. Res. 2012, 19, 2381.
| Ocurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments: a comparative study of regions in China with different urbanization levels.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtVShsLjI&md5=7835079dc4fd470c91a244eb1d9b8cc8CAS |
[5] C. Caballo, M. D. Sicilia, Enantioselective determination of representative profens in wastewater by a single step sample treatment and chiral liquid chromatography-tandem mass spectrometry. Talanta 2015, 134, 325.
| Enantioselective determination of representative profens in wastewater by a single step sample treatment and chiral liquid chromatography-tandem mass spectrometry.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXitFCjtw%3D%3D&md5=4d2245888754ef5d5cd1df547eca91a9CAS | 25618675PubMed |
[6] P. Vazquez-Roig, V. Andreu, C. Blasco, Y. Picó, Risk assessment on the presence of pharmaceuticals in sediments, soil and water of the Pego-Oliva Marshlands (Valencia, eastern Spain). Sci. Total Environ. 2012, 440, 24.
| Risk assessment on the presence of pharmaceuticals in sediments, soil and water of the Pego-Oliva Marshlands (Valencia, eastern Spain).Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhsVWmtb7I&md5=7d080b5e8f5891e88a9e08b1193aaf54CAS | 23021792PubMed |
[7] I. Ali, S. Prashant, Y. A. Hassan, S. Bhavtosh, Chiral analysis of ibuprofen residues in water and sediments. Anal. Lett. 2009, 42, 1747.
| Chiral analysis of ibuprofen residues in water and sediments.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXps1Cgurg%3D&md5=54d652470aff0136d64490c48e5685b4CAS |
[8] A. R. Ribeiro, P. M. L. Castro, M. E. Tiritan, Chiral pharmaceuticals in the environment. Environ. Chem. Lett. 2012, 10, 239.
| Chiral pharmaceuticals in the environment.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtF2gtLrI&md5=dcb3d7995778f863950f301f16804971CAS |
[9] S. Ortiz de García, G. Pinto Pinto, P. García Encina, R. Irusta Mata, Consumption and occurrence of pharmaceutical and personal care products in the aquatic environment in Spain. Sci. Total Environ. 2013, 444, 451.
| Consumption and occurrence of pharmaceutical and personal care products in the aquatic environment in Spain.Crossref | GoogleScholarGoogle Scholar | 23287535PubMed |
[10] K. M. Nowak, C. Girardi, A. Miltner, M. Gehre, A. Schäffer, M. Kästner, Contribution of microorganism to non-extractable residue formation during biodegradation of ibuprofen in soil. Sci. Total Environ. 2013, 445–446, 377.
| Contribution of microorganism to non-extractable residue formation during biodegradation of ibuprofen in soil.Crossref | GoogleScholarGoogle Scholar | 23361042PubMed |
[11] C. Girardi, K. M. Nowak, O. Carranza-Diaz, B. Lewkow, A. Miltner, M. Gehre, A. Schäffer, M. Kästner, Microbial degradation of the pharmaceutical ibuprofen and the herbicide 2,4-D in water and soil – use and limits of data obtained from aqueous systems for predicting their fate in soil. Sci. Total Environ. 2013, 444, 32.
| Microbial degradation of the pharmaceutical ibuprofen and the herbicide 2,4-D in water and soil – use and limits of data obtained from aqueous systems for predicting their fate in soil.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXitlartbg%3D&md5=c9cb91e0077283b1ee6a0eda9ed7d99cCAS | 23262323PubMed |
[12] V. Matamoros, M. Hijosa, J. M. Bayona, Assessment of the pharmaceutical active compounds removal in wastewater treatment systems at enantiomeric level. Ibuprofen and naproxen. Chemosphere 2009, 75, 200.
| Assessment of the pharmaceutical active compounds removal in wastewater treatment systems at enantiomeric level. Ibuprofen and naproxen.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXjt1Kmsbo%3D&md5=714e2f8ce7251664d6f2193953aa89abCAS | 19155040PubMed |
[13] M. Stuart, D. Lapworth, E. Crane, A. Hart, Review of risk from potential emergeing contaminants in UK groundwater. Sci. Total Environ. 2012, 416, 1.
| Review of risk from potential emergeing contaminants in UK groundwater.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhsVyrtbs%3D&md5=f9d9f847a7825d367505be3673151663CAS | 22209399PubMed |
[14] N. H. Hashim, S. J. Khan, Enantioselective analysis of ibuprofen, ketoprofen and naproxen in wastewater and environmental water samples. J. Chromatogr. A 2011, 1218, 4746.
| Enantioselective analysis of ibuprofen, ketoprofen and naproxen in wastewater and environmental water samples.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXotVGisbg%3D&md5=b0359b89bcb31fadd97daa79dc6830c6CAS | 21645900PubMed |
[15] Study on the environmental risks of medicinal products. Final report 2013 (Executive Agency for Health and Consumers). Available at http://ec.europa.eu/health/files/environment/study_environment.pdf [Verified 10 November 2015].
[16] C. Caballo, M. D. Sicilia, S. Rubio, Enantioselective analysis of non-steroidal anti-inflammatory drugs in freshwater fish based on microextraction with a supramolecular liquid and chiral liquid chromatography-tandem mass spectrometry. Anal. Bioanal. Chem. 2015, 407, 4721.
| Enantioselective analysis of non-steroidal anti-inflammatory drugs in freshwater fish based on microextraction with a supramolecular liquid and chiral liquid chromatography-tandem mass spectrometry.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXmsVCntrs%3D&md5=8adfe086b4ba1ce2cc661b19974a9e96CAS | 25869485PubMed |
[17] L. E. Jacobs, R. L. Fimmen, Y. Chin, H. E. Mash, L. K. Weavers, Fulvic acid mediated photolysis of ibuprofen in water. Water Res. 2011, 45, 4449.
| Fulvic acid mediated photolysis of ibuprofen in water.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXpt1altLg%3D&md5=cbb043fa1721906836befe395155d246CAS | 21714984PubMed |
[18] H. Hühnerfuss, M. Raza Shah, Enantioselective chromatography – a powerful tool for the discrimination of biotic and abiotic transformation processes of chiral environmental pollutants. J. Chromatogr. A 2009, 1216, 481.
| Enantioselective chromatography – a powerful tool for the discrimination of biotic and abiotic transformation processes of chiral environmental pollutants.Crossref | GoogleScholarGoogle Scholar | 18838139PubMed |
[19] K. B. Borges, A. R. Moraes de Oliveira, T. Barth, V. A. Polizel Jabor, M. Tallarico Pupo, P. Sueli Bonato, LC-MS-MS determination of ibuprofen, 2-hydroxyibuprofen enantiomers and carboxyibuprofen stereoisomers for application in biotransformation studies employing endophytic fungi. Anal. Bioanal. Chem. 2011, 399, 915.
| LC-MS-MS determination of ibuprofen, 2-hydroxyibuprofen enantiomers and carboxyibuprofen stereoisomers for application in biotransformation studies employing endophytic fungi.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsVWqtbvL&md5=63ce3386f89ff45e4529258d2d74f981CAS | 21079932PubMed |
[20] B. Vermeulen, J. P. Remon, Validation of a high-performance liquid chromatographic method for the determination of ibuprofen enantiomers in plasma of broiler chickens. J. Chromatogr. B Biomed. Sci. Appl. 2000, 749, 243.
| Validation of a high-performance liquid chromatographic method for the determination of ibuprofen enantiomers in plasma of broiler chickens.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXot12ltbk%3D&md5=de3b5179ecdfd74ec4afbf70c858e6abCAS | 11145061PubMed |
[21] M. Rambla-Alegre, J. Esteve-Romero, S. Carda-Broch, Is it really necessary to validate an analytical method or not? That is the question. J. Chromatogr. A 2012, 1232, 101.
| Is it really necessary to validate an analytical method or not? That is the question.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XjsFKmsbc%3D&md5=cb12d823019e52c59721f0031a7df641CAS | 22099221PubMed |
[22] Harmonised tripartite guideline: validation of analytical procedures: text and methodology, Q2 (R1) 2005 (ICH: Geneva). Available at http://www.ich.org/fileadmin/Public_Web_Site/ICH_Products/Guidelines/Quality/Q2_R1/Step4/Q2_R1__Guideline.pdf [Verified 10 November 2015].
[23] V. Guillén-Casla, J. Magro-Moral, N. Rosales-Conrado, L. V. Pérez-Arribas, M. E. León-González, L. M. Polo-Díez, Direct chiral liquid chromatography determination of aryloxyphenoxypropionic herbicides in soil: deconvolution tools for peak processing. Anal. Bioanal. Chem. 2011, 399, 915.