Determination of Selected Phthalates in Some Commercial Cosmetic Products by HPLC-UV

Author(s): Emrah Dural*

Journal Name: Combinatorial Chemistry & High Throughput Screening
Accelerated Technologies for Biotechnology, Bioassays, Medicinal Chemistry and Natural Products Research

Volume 23 , Issue 10 , 2020

Become EABM
Become Reviewer
Call for Editor


Aim and Scope: Due to the serious toxicological risks and their widespread use, quantitative determination of phthalates in cosmetic products have importance for public health. The aim of this study was to develop a validated simple, rapid and reliable high-performance liquid chromatography (HPLC) method for the determination of phthalates which are; dimethyl phthalate (DMP), diethyl phthalate (DEP), benzyl butyl phthalate (BBP), di-n-butyl phthalate (DBP), di(2- ethylhexyl) phthalate (DEHP), in cosmetic products and to investigate these phthalate (PHT) levels in 48 cosmetic products marketing in Sivas, Turkey.

Materials and Methods: Separation was achieved by a reverse-phase ACE-5 C18 column (4.6 x 250 mm, 5.0 μm). As the mobile phase, 5 mM KH2PO4 and acetonitrile were used gradiently at 1.5 ml min-1. All PHT esters were detected at 230 nm and the run time was taking 21 minutes.

Results: This method showed the high sensitivity value the limit of quantification (LOQ) values for which are below 0.64 μg mL-1 of all phthalates. Method linearity was ≥0.999 (r2). Accuracy and precision values of all phthalates were calculated between (-6.5) and 6.6 (RE%) and ≤6.2 (RSD%), respectively. Average recovery was between 94.8% and 99.6%. Forty-eight samples used for both babies and adults were successfully analyzed by the developed method. Results have shown that, DMP (340.7 μg mL-1 ±323.7), DEP (1852.1 μg mL-1 ± 2192.0), and DBP (691.3 μg mL-1 ± 1378.5) were used highly in nail polish, fragrance and cream products, respectively.

Conclusion: Phthalate esters, which are mostly detected in the content of fragrance, cream and nail polish products and our research in general, are DEP (1852.1 μg mL-1 ± 2192.0), DBP (691.3 μg mL-1 ± 1378.5) and DMP (340.7 μg mL-1 ±323.7), respectively. Phthalates were found in the content of all 48 cosmetic products examined, and the most detected phthalates in general average were DEP (581.7 μg mL-1 + 1405.2) with a rate of 79.2%. The unexpectedly high phthalate content in the examined cosmetic products revealed a great risk of these products on human health. The developed method is a simple, sensitive, reliable and economical alternative for the determination of phthalates in the content of cosmetic products, it can be used to identify phthalate esters in different products after some modifications.

Keywords: Phthalates, DEP, DMP, BBP, DBP, DEHP, cosmetics, HPLC-UV, method validation.

Koo, H.J.; Lee, B.M. Estimated exposure to phthalates in cosmetics and risk assessment. J. Toxicol. Environ. Heal. - Part A, 2004, 67, 1901-1914.
[] [PMID: 15513891]
Preziosi, P. Endocrine disrupters as environmental signallers: an introduction. Pure Appiled Chem., 1998, 70, 1617-1631.
De Orsi, D.; Gagliardi, L.; Porrà, R.; Berri, S.; Chimenti, P.; Granese, A.; Carpani, I.; Tonelli, D. A environmentally friendly reversed-phase liquid chromatography method for phthalates determination in nail cosmetics. Anal. Chim. Acta, 2006, 555, 238-241.
[] [PMID: 17723678]
Arcadi, F.A.; Costa, C.; Imperatore, C.; Marchese, A.; Rapisarda, A.; Salemi, M.; Trimarchi, G.R.; Costa, G. Oral toxicity of bis (2-Ethylhexyl) phthalate during pregnancy and suckling in the long ± Evans Rat. Food Chem. Toxicol., 1998, 36, 963-970.
[]] [PMID: 9771559]
Latini, G. Monitoring phthalate exposure in humans. Clin. Chim. Acta, 2005, 361, 20-29.
[] [PMID: 16004980]
Fabjan, E.; Hulzebos, E.; Mennes, W.; Piersma, A.H. A category approach for reproductive effects of phthalates. Crit. Rev. Toxicol., 2006, 36, 695-726.
[] [PMID: 17050082]
Hubinger, J.C. A survey of phthalate esters in consumer cosmetic products. J. Cosmet. Sci., 2010, 61, 457-465.
[PMID: 21241635]
Kleinsasser, N.H.; Wallner, B.C.; Kastenbauer, E.R.; Weissacher, H.; Harreus, U.A. Genotoxicity of di-butyl-phthalate and di-iso-butyl-phthalate in human lymphocytes and mucosal cells. Teratog. Carcinog. Mutagen., 2001, 21, 189-196.
[] [PMID: 11301413]
Duty, S.M.; Singh, N.P.; Silva, M.J.; Barr, D.B.; Brock, J.W.; Ryan, L.; Herrick, R.F.; Christiani, D.C.; Hauser, R. The relationship between environmental exposures to phthalates and DNA damage in human sperm using the neutral comet assay. Environ. Health Perspect., 2003, 111, 1164-1169.
[] [PMID: 12842768]
Ema, M.; Miyawaki, E.; Kawashima, K. Further evaluation of developmental toxicity of di-n-butyl phthalate following administration during late pregnancy in rats. Toxicol. Lett., 1998, 98, 87-93.
[] [PMID: 9776565]
Gangolli, S.D. Testicular effects of phthalate esters. Environ. Health Perspect., 1982, 45, 77-84.
[] [PMID: 6754364]
Huber, W.W.; Grasl-Kraupp, B.; Schulte-Hermann, R. Hepatocarcinogenic potential of di(2-ethylhexyl)phthalate in rodents and its implications on human risk. Crit. Rev. Toxicol., 1996, 26, 365-481.
[] [PMID: 8817083]
Tomonari, Y.; Kurata, Y.; David, R.; Gans, G.; Kawasuso, T.; Katoh, M. Effect of di(2-ethylhexyl) phthalate (DEHP) on genital organs from juvenile common marmosets: I. morphological and biochemical investigation in 65-week toxicity study. J. Toxicol. Environ. Heal. - Part A Curr. Issues, 2006, 69, 1651-1672.
[] [PMID: 16854791]
Chen, H.; Wang, C.; Wang, X.; Hao, N.; Liu, J. Determination of phthalate esters in cosmetics by gas chromatography with flame ionization detection and mass spectrometric detection. Int. J. Cosmet. Sci., 2005, 27, 205-210.
[] [PMID: 18492189]
Batlle, R.; Nerín, C. Application of single-drop microextraction to the determination of dialkyl phthalate esters in food simulants. J. Chromatogr. A, 2004, 1045, 29-35.
[] [PMID: 15378876]
Prokůpková, G.; Holadová, K.; Poustka, J.; Hajšlová, J. Development of a solid-phase microextraction method for the determination of phthalic acid esters in water. Anal. Chim. Acta, 2002, 457, 211-223.
Teirlynck, O.A.; Rosseel, M.T. Disposition of orally administered di-(2-ethylhexyl) phthalate and mono-(2-ethylhexyl) phthalate in the rat. J. Chromatogr. A, 1985, 342, 399-405.
[] [PMID: 4091646]
Andersen, K.S.; Lam, J. Simple and direct method for quantitative gas chromatographic determination of di(2-ethylhexyl) phthalate in edible oils. J. Chromatogr. A, 1979, 169, 101-106.
Brossa, L.; Marcé, R.M.; Borrull, F.; Pocurull, E. Application of on-line solid-phase extraction-gas chromatography-mass spectrometry to the determination of endocrine disruptors in water samples. J. Chromatogr. A, 2002, 963, 287-294.
[] [PMID: 12187982]
Chaler, R.; Cantón, L.; Vaquero, M.; Grimalt, J.O. Identification and quantification of N-octyl esters of alkanoic and hexanedioic acids and phthalates as urban wastewater markers in biota and sediments from estuarine areas. J. Chromatogr. A, 2004, 1046, 203-210.
[PMID: 15387189]
Cortazar, E.; Zuloaga, O.; Sanz, J.; Raposo, J.C.; Etxebarria, N.; Fernández, L.A. MultiSimplex optimisation of the solid-phase microextraction-gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and phthalates from water samples. J. Chromatogr. A, 2002, 978, 165-175.
[] [PMID: 12458953]
Luks-Betlej, K.; Popp, P.; Janoszka, B.; Paschke, H. Solid-phase microextraction of phthalates from water. J. Chromatogr. A, 2001, 938, 93-101.
[]] [PMID: 11771850]
Hubinger, J.C.; Havery, D.C. Analysis of consumer cosmetic products for phthalate esters. J. Cosmet. Sci., 2006, 57, 127-137.
Blount, B.C.; Silva, M.J.; Caudill, S.P.; Needham, L.L.; Pirkle, J.L.; Sampson, E.J.; Lucier, G.W.; Jackson, R.J.; Brock, J.W. Levels of Seven Urinary Phthalate Metabolites in a Human Reference Population. Environ. Health Perspect., 2000, 108, 979-982.
Calafat, A.M.; Slakman, A.R.; Silva, M.J.; Herbert, A.R.; Needham, L.L. Automated solid phase extraction and quantitative analysis of human milk for 13 phthalate metabolites. J. Chromatogr. B Anal. Technol. Biomed. Life Sci., 2004, 805, 49-56.
[] [PMID: 15113539]
Mitani, K.; Narimatsu, S.; Izushi, F.; Kataoka, H. Simple and rapid analysis of endocrine disruptors in liquid medicines and intravenous injection solutions by automated in-tube solid-phase microextraction/high performance liquid chromatography. J. Pharm. Biomed. Anal., 2003, 32, 469-478.
[] [PMID: 14565551]
Cai, Y.Q.; Jiang, G. Bin; Liu, J.F.; Zhou, Q.X. Multi-walled carbon nanotubes packed cartridge for the solid-phase extraction of several phthalate esters from water samples and their determination by high performance liquid chromatography. Anal. Chim. Acta, 2003, 494, 149-156.
Kambia, K.; Dine, T.; Azar, R.; Gressier, B.; Luyckx, M.; Brunet, C. Comparative study of the leachability of di(2-ethylhexyl) phthalate and tri(2-ethylhexyl) trimellitate from haemodialysis tubing. Int. J. Pharm., 2001, 229, 139-146.
[] [PMID: 11604266]
Houlihan, J.; Brody, C.; Schwan, B. Not Too Pretty. Phthalates, Beauty Prod. FDA. Accessed May, 2002, 11, 2008.
Koniecki, D.; Wang, R.; Moody, R.P.; Zhu, J. Phthalates in cosmetic and personal care products: concentrations and possible dermal exposure. Environ. Res., 2011, 111, 329-336.
[] [PMID: 21315328]
ICH Topic Q2 (R1) Validation of Analytical Procedures: Methodology Text and Methodology. In International Conference on Harmonization of Technical Requirements for Registration of Pharmaceuticals for Human Use, 2005.
Shen, H.Y.; Jiang, H.L.; Mao, H.L.; Pan, G.; Zhou, L.; Cao, Y.F. Simultaneous determination of seven phthalates and four parabens in cosmetic products using HPLC-DAD and GC-MS methods. J. Sep. Sci. 2007, 30, 48-54.
[] [PMID: 17313141]

Rights & PermissionsPrintExport Cite as

Article Details

Year: 2020
Page: [1010 - 1022]
Pages: 13
DOI: 10.2174/1386207323666200630113850
Price: $65

Article Metrics

PDF: 25