TY  - JOUR
T1  - Gas Chromatography-Mass Spectrometry (GC-MS) was Used for The Determination of Cyclic Volatile Dimethylsiloxane (D4) in Personal Care Products
AU  - Özdemir, Elif
AU  - Neşetoğlu, Neşet
AU  - Ergün, Barkın
AU  - Ünal, Durişehvar Özer
PY  - 2025
DA  - September
Y2  - 2025
DO  - 10.26650/IstanbulJPharm.2025.1515130
JF  - İstanbul Journal of Pharmacy
JO  - iujp
PB  - Istanbul University
WT  - DergiPark
SN  - 2587-2087
SP  - 260
EP  - 266
VL  - 55
IS  - 2
LA  - en
AB  - Background and Aims: Compounds of low-molecular-weight cyclic volatile dimethylsiloxane (cVMS) are widely used in per sonal care products due to their beneficial properties for consumer goods. However, the European Chemicals Agency (ECHA) has proposed restrictions on two cyclic siloxanes, octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), in rinse-off Personal care products that are rinsed off and discharged into drains. The main concerns with D4 and D5 are their persistence and accumulation in the water bodies. The goal of this restriction is to reduce their discharge into surface waters. According to the ECHA, these substances should not be sold or used in concentrations of 0.1% or more by weight in rinse-off personal care products. Analysing cyclic siloxanes in these products is vital for understanding human exposure to these substances. ECHA mandates dependable analytical methods for manufacturers and government agencies to verify adherence to the restrictions. A simple, fast, and easily applicable extraction method using gas chromatography mass spectrometry (GC-MS) for the precise measurement of D4 at around 0.1% by weight of the total formulation in personal care products (PCPs) is proposed in this article.Methods: Detection was performed using a GC-MS instrument equipped with an electron impact (EI) ion source and operated using the selected ion monitoring (SIM) mode. The mass-to-charge ratios (m/z) monitored for D4 were 281.0, 282.0, and 283.0. The monitored mass-to-charge ratios (m/z) for D4 were 281.0, 282.0, and 283.0.Results: The proposed method showed excellent linearity, with a coefficient of determination (r²) exceeding 0.999. The limit of detection (LOD) and limit of quantification (LOQ) were 0.2320 μg/mL and 0.7735 μg/mL, respectively. The precision and accuracy of D4 were evaluated at concentrations of 3.0 µg/mL, 15.0 µg/mL, and 25.0 µg/mL. The coefficients of variation (CV) were 5.07%, 7.24%, and 4.95%, respectively, while the accuracy values were 103.17±0.16, 100.44±1.09, and 101.13±0.07, respectively, for these concentrations. These values are within the acceptable limit of ±15%. The results show that this GC MS method meets the regulatory standards and demonstrates satisfactory accuracy and precision. Real samples, such as beard oil and hair conditioner, were successfully analysed using this method.Conclusion: The developed GC-MS method provides a simple, accurate, and sensitive approach for detecting D4 in rinse-off personal care products. It meets regulatory requirements and is suitable for routine analysis, supporting efforts to control environmental exposure to cyclic siloxanes.
KW  - Gas Chromatography
KW  - Octamethylcyclotetrasiloxane (D4)
KW  - Personal Care Products
KW  - Analytical Method Validation
CR  - Aspromonte J., Giacoppo G., Wolfs K., & Adams E. (2020). Headspace gas chromatography for the determination of volatile methylsiloxanes in personal care products. Analytical and Bioanalytical Chemistry, 412(11), 2537–2544. https:// doi.org/10.1007/s00216-020-02478-y. google scholar
CR  - Biesterbos J. W., Beckmann G., Anzion R. B., Ragas A. M., Russel F. G., & Scheepers P. T. (2014). Sensitive method for quantification of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in end-exhaled air by thermal desorption gas chromatography mass spectrometry. Analytical Chemistry, 86(12), 5794–5799. https://doi.org/10.1021/ac5004695. google scholar
CR  - bin Abdullaha A. F. L., Marimuthua Y., Hawa C. K., Fatihah N., Yaacoba H., & Hooic Y. C. (2011). Forensic discrimination of lipsticks by thin layer chromatography and gas chromatography-mass spectrometry. Malaysian Journal of Forensic Sci, 2(1), 22-28. google scholar
CR  - Brothers Jr H. M. Bovens E., Bruni A., Habitz T. M., Hamachi T., Han Y., & Tecklenburg Jr R. E. (2016). A practical gas chromatography flame ionization detection method for the determination of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in silicone emulsions. Journal of Chromatography A, 1441, 116-125. 10.1016/j.chroma.2016.02.069. google scholar
CR  - Brothers Jr H. M., Boehmer T., Campbell R. A., Dorn S., Kerbleski J. J., Lewis S., Mund C., Pero D., Saito K., Wieser M., & Zoller W. (2017). Determination of cyclic volatile methylsiloxanes in personal care products by gas chromatography. Interna- tional Journal of Cosmetic Science, 39(6), 580–588.https://doi.org/10.1111/ics. 12411 google scholar
CR  - Capela D., Homem V., Alves A., & Santos L. (2018). Reply to comments on “volatile methylsiloxanes in personal care products–Using QuEChERS as a “green” analytical approach” Talanta, 174, 156–157. https://doi.org/10.1016/j.talanta.2017. 11.023 google scholar
CR  - Dekant W., Scialli A. R., Plotzke K., & Klaunig J. E. (2017). Biological relevance of effects following chronic administration of octamethylcyclotetrasiloxane (D4) in Fischer 344 rats. Toxicology letters, 279 (1), 42–53. https://doi.org/10.1016/j. toxlet.2017.01.010. google scholar
CR  - European Commission Scientific Committee on Consumer Safety, Opinion on Cyclomethicone Octamethylcyclotetrasiloxane (Cyclotetrasiloxane, D4) and Decamethylcyclopentasiloxane (Cyclopentasiloxane, D5). Report No. SCCS/1241/10. google scholar
CR  - Feng D., Zhang X., Wang, W. Li Z., & Cao X. (2019). Development, validation and comparison of three detection methods for 9 volatile methylsiloxanes in foodcontact silicone rubber products. Polymer Testing, 73, 94-103. https://doi.org/ 10.1016/j.polymertesting.2018.10.014 google scholar
CR  - Franzen A., Greene T., Van Landingham C., & Gentry R. (2017). Toxicology of octamethylcyclotetrasiloxane (D₄). Toxicology Letters, 279(1), 2–22. https://doi.org/10.1016/ j.toxlet.2017.06.007 google scholar
CR  - Horii Y., & Kannan K. (2008). Survey of organosilicone compounds, including cyclic and linear siloxanes, in personal-care and household products. Archives of Environmental contamination and Toxicology, 55(4), 701–710. https://doi.org/ 10.1007/s00244-008-9172-z google scholar
CR  - Lu Y., Yuan T., Wang W., & Kannan K., (2011). Concentrations and assessment of exposure to siloxanes and synthetic musks in personal care products from China. Environmental Pollution (Barking, Essex: 1987), 159(12), 3522–3528. https://doi.org/10.1016/j.envpol.2011.08.015 google scholar
CR  - Neşetoglu N., Kaplan C., Aslan S. S., & Ünal D. Ö. (2020). A Simple and Rapid LC-MS/MS Method for Therapeutic Drug Monitoring of Lenalidomide. Pakistan Journal of Analytical & Environmental Chemistry, 21(1), 19-26. http://dx.doi.org/10.21743/ pjaec/2020.06.03 google scholar
CR  - Sigma-Aldrich Chemie GmbH Eschenstrasse 5 D-82024 TAUFKIRCHEN, ‘’Octamethylcyclotetrasiloxane’’, 235695 Datasheet, Nov. (2021). google scholar
CR  - Vaparrath S., Seaton M., MNcett D., Cao L., & Plotzke K. P. (2000). Quantitative determination of octamethylcyclotetrasiloxane (D4) in extracts of biological matrices by gas chromatography-mass spectrometry. International Journal of Environmental Analytical Chemistry, 77(3), 203-219.https://doi.org/10.1080/ 03067310008032683. google scholar
CR  - Wang R., Moody R. P., & Koniecki D. Zhu, J. (2009). Low molecular weight cyclic volatile methylsiloxanes in cosmetic products sold in Canada: implication for dermal exposure. Environment International, 35(6), 900–904, https://doi.org/10.1016/ j.envint.2009.03.009. google scholar
UR  - https://doi.org/10.26650/IstanbulJPharm.2025.1515130
L1  - https://dergipark.org.tr/en/download/article-file/4065937
ER  -