Tri Manh Tran

Main Article Content

Abstract

Benzophenone and its derivatives (BPs) are widely used in various consumer products as effective UV filters. However, they are endocrine-disrupting micropollutants with adverse effects in laboratory animals. In this work, an LC-MS/MS-based method for the determination of BP and nine of its derivatives in settled dust samples was developed. Sample preparation involved extracting with the mixture of methanol/DCM (1/1, v/v), cleaning through a SPE cartridge packed with sodium sulfate and Florisil. The target compounds were eluted with 5 mL of methanol, then  concentrated under a gentle stream of nitrogen to 1 mL before transferring to a LC vial for instrumental analysis. The calibration curves of all target compounds were established in the concentration range of 0.5–500 ng/mL. The mean recoveries of target and surrogate standards ranged from 82.4 to 107%. The method quantification limit (MQL) of individual target compounds in dust samples was in the range of 0.06–0.6 ng/g.

Keywords: Benzophenone; BP-3; LC-MS/MS; Dust sample; Method development, Validation

References

[1] C. Almeida, A. Stepkowska, A. Alegre, J.M.F. Nogueira, Determination of trace levels of benzophenone-type ultraviolet filters in real matrices by bar adsorptive micro-extraction using selective sorbent phases, J. Chromatogr. A Vol. 1311, 2013, 1–10. https://doi.org/10.1016/j.chroma.2013.08.007.
[2] S. Kim, K. Choi, Occurrences, toxicities, and ecological risks of benzophenone-3, a common component of organic sunscreen products: a mini-review, Environ. Int. Vol. 70, 2014, 143–157. https://doi.org/10.1016/j.envint.2014.05.015.
[3] J. Wang, L. Pan, S. Wu, L. Lu, Y. Xu, Y. Zhu, M. Guo, S. Zhuang, Recent advances on endocrine disrupting effects of UV filters, Int. J. Environ. Res. Public Health, Vol. 13, No. 8, 2016, 782–793. https://doi.org/10.3390/ijerph13080782.
[4] IARC, International Agency for Research on Cancer, Benzophenone, in: IARC Monographs on the evaluation of carcinogenic risks to humans, Vol. 101, 2013, 285–304 (accessed July 2023). https://monographs.iarc.who.int/wp-content/uploads/2018/08/14-002.pdf.
[5] European Commission, Regulation (EC) No 1223/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic products. Off. J. Eur. Comm. L342, Vol. 2009, 59–209. http://eur-lex.europa.eu/eli/reg/2009/1223/oj.
[6] I. Jim´enez-Díaz, A. Zafra-Gomez, O. Ballesteros, A. Navalon, ´ Analytical methods for the determination of personal care products in human samples: an overview. Talanta 129, Vol. 2014, 448–458. https://doi.org/10.1016/j.talanta.2014.05.052.
[7] L. Carstensen, S. Beil, H. Bornick, S. Stolte, Structure-related endocrine-disrupting potential of environmental transformation products of benzophenone-type UV filters: a review. J. Hazard. Mater. Vol. 430, 2022, 128495. https://doi.org/10.1016/j.jhazmat.2022.128495.
[8] T. Suzuki, S. Kitamura, R. Khota, K. Sugihara, N. Fujimoto, S. Ohta, Estrogenic and antiandrogenic activities of 17 benzophenone derivatives used as UV stabilizers and sunscreens. Toxicol. Appl. Pharmacol. Vol. 203, 2005, 9–17. https://doi.org/10.1016/j.taap.2004.07.005.
[9] G. Wejnerowska, I. Narloch, Determination of benzophenones in water and cosmetics samples: a comparison of solid-phase extraction and microextraction by packed sorbent methods. Molecules Vol. 26, 2021, 6896–6910. https://doi.org/ 10.3390/molecules26226896.
[10] N.I. Chang, M.Y. Yoo, S.H. Lee, Determination of fourteen sunscreen agents in cosmetics using high-performance liquid chromatography. Int. J. Cosmetic Sci. Vol. 37, 2015, 175–180. https://doi.org/10.1111/ics.12171.
[11] S. Lu, F. Long, P. Lu, B. Lei, Z. Jiang, G. Liu, J. Zhang, S. Ma, Y. Yu, Benzophenone UV filters in personal care products and urine of schoolchildren from Shenzhen, China: exposure assessment and possible source. Sci. Total Environ. Vol. 640–641, 2018, 1214–1220. https://doi.org/10.1016/j.scitotenv.2018.06.015.
[12] G.J. Nohynek, E. Antignac, T. Re, H. Toutain, Safety assessment of personal care products/cosmetics and their ingredients, Toxicol. Appl. Pharmacol. Vol. 243, 2010, 239–259. https://doi.org/10.1016/j.taap.2009.12.001.
[13] C.A. Downs, J.C. Dinardo, D. Stien, A.M.S. Rodrigues, P. Lebaron, Benzophenone accumulates over time from the degradation of octocrylene in commercial sunscreen products. Chem. Res. Toxicol. Vol. 34, 2021, 1046–1054. https://doi.org/10.1021/acs.chemrestox.0c00461.
[14] T. M. Tran, H. T. Le, N. D. Vu, G. H. M. Dang, T. B. Minh, & K. Kannan, Cyclic and linear siloxanes in indoor air from several northern cities in Vietnam: Levels, spatial distribution and human exposure, Chemosphere. Vol. 184, 2017, 1117-1124. http://dx.doi.org/10.1016/j.chemosphere.2017.06.092.
[15] I. Narloch, G. Wejnerowska, An overview of the analytical methods for the determination of organic ultraviolet filters in cosmetic products and human samples, Molecules. Vol. 26, 2021, 4780. https://doi.org/10.3390/molecules26164780.
[16] T.M. Tran, T.M. Le, T.B. Minh, K. Kannan, Occurrence of phthalate diesters in indoor air from several Northern cities in Vietnam, and its implication for human exposure, Sci. Total Environ. Vol. 601, 2017, 1695-1701. https://doi.org/10.1016/j.scitotenv.2017.06.016.
[17] H. K. Joe, Y. Chung, J.K. Ryu, Simultaneous determination of benzophenone-type UV filters in water and soil by chromatography-mass spectrometry, J. Chromatogr. A Vol. 113, 2006, 192-202. https://doi.org/10.1016/j.chroma.2006.07.036.
[18] Z. M. Li and K. Kannan, Comprehensive survey of 14 benzophenone UV filters in sunscreen products marketed in the United States: Implications for human exposure, Environ. Sci. Technol. Vol. 56, 2022, 12473-12482. https://doi.org/10.1021/acs.est.2c03885.
[19] F. Mao, Y. He, and K. Y. H Gin, Occurrence and fate of benzophenone-type UV filters in aquatic environments: a review, Environ. Sci Water Res. Technol, Vol. 2018. https://doi.org/10.1039/C8EW00539G.
[20] H. Frederiksen, M. Krause, N. Jørgensen, A. Rehfeld, N. E. Skakkebæk, A. M. Andersson, UV filters in matched seminal fluid-, urine-, and serum samples from young men, J. Expo. Sci. Environ. Epidemiol. Vol. 2019. https://doi.org/10.1038/s41370-020-0209-3.
[21] N. Negreira, I. Rodríguez, M. Ramil, E. Rubí, R. Cela, Solid-phase extraction followed by liquid chromatography–tandem mass spectrometry for the determination of hydroxylated benzophenone UV absorbers in environmental water samples, Anal. Chim. Acta. Vol. 654, 2009, 162-170. https://doi.org/10.1016/j.aca.2009.09.033.
[22] M. C. Semones, C. M. Sharpless, A. A. Mackay, Y. P. Chin, Photodegradation of UV filters oxybenzone and sulisobenzone in wastewater effluent and by dissolved organic matter, Appl. Geochem. Vol. 2017. https://doi.org/10.1016/j.apgeochem.2017.02.008.
[23] Scientific committee on consumer safety (SCCS) of the European Union issued a find opinion on benzophenone-4, SCCS/1660/23, Vol. 2024. https://health.ec.europa.eu/document/download/3784d1dc-0a4b-4177-ac2c-0a426f68de7d_en?filename=sccs_o_283.pdf.
[24] Scientific committee on consumer safety (SCCS) of the European Union issued a find opinion on benzophenone-1, SCCS/1672/24, Vol. 2025. https://health.ec.europa.eu/publications/sccs-opinion-benzophenone-1-cas-no-131-56-6-ec-no-205-029-4_en.
[25] Scientific committee on consumer safety (SCCS) of the European Union issued a find opinion on benzophenone-2, SCCS/1679/25, Vol. 2026. https://health.ec.europa.eu/publications/sccs-scientific-advice-benzophenone-2-bp-2-and-benzophenone-5-bp-5-substances-potential-endocrine_en.
[26] Benzophenone-6, Ataman Chemicals. https://www.atamanchemicals.com/benzophenone-6_u35097/.
[27] 4-Methoxybenzophenone, Material Safety Data Sheet. https://datasheets.scbt.com/sc-238887.pdf.
[28] Scientific committee on consumer products (SCCP) of the European Union issued a find opinion on 4-Methybenzylidene Camphor, SCCP/104225, Vol. 2006. https://ec.europa.eu/health/ph_risk/committees/04_sccp/docs/sccp_o_141.pdf.
[29] 2-Hydroxy-4-(octyloxy)benzophenone, ChemBK. https://www.chembk.com/en/chem/2-Hydroxy-4-Octyloxy%20Benzophenone.
[30] Screening Assessment Methanone, diphenyl- (Benzophenone), Environment and Climate Change Canada Health Canada, Vol. 2021. https://www.canada.ca/en/environment-climate-change/services/evaluating-existing-substances/screening-assessment-benzophenone.html.
[31] W. Lei, A. G. Asimakopoulos, H. B. Moon, H. Nakta, K. Kannan, Benzotriazole, benzothiazole, and benzophenone compounds in indoor dust from the United States and East Asian countries, Environ. Sci. Technol. Vol, 47, 2013, 4752-4759. dx.doi.org/10.1021/es305000d.