Elsevier

Chemosphere

Volume 260, December 2020, 127557
Chemosphere

Transformation of resveratrol under disinfection conditions

https://doi.org/10.1016/j.chemosphere.2020.127557Get rights and content

Highlights

  • Trans-resveratrol becomes more and more popular all over the world as a powerful antioxidant.

  • The first study of transformation of resveratrol and its formulations in aquatic chlorination.

  • Over 80 transformation products were tentatively identified using GC-HRMS and UPLC-HRMS.

  • Toxicity estimation of resveratrol products was carried out using luminescent bacteria V. fischeri.

Abstract

Trans-resveratrol becomes more and more popular all over the world as a powerful antioxidant. Since its positive properties, including antioxidant, anti-inflammatory, anti-tumor are indisputable, nowadays trans-resveratrol is used as a component of various products from nutriceutics to body care formulations, where it is supposed to behave as natural antioxidant and anti-aging compound. It is also added to food packaging materials to increase their stability or/and prevent oxidation. Nevertheless, being released to the environment resveratrol easily forms various transformation products with potentially negative environmental and health effects. The present paper deals with transformation of pure resveratrol and its formulation used as UV-protectors in conditions of aquatic chlorination. Over 80 transformation products were tentatively identified using gas chromatography-high resolution mass spectrometry (GC-HRMS) and ultra pressure liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). Chlorinated phenols and biphenyls are the most relevant among them. Estimation of toxicity of resveratrol products was carried out using luminescent bacteria V. fischeri tests.

Introduction

Photons of UV light cause breakage of covalent bonds and thus induce different oxidation processes leading to aging and weathering of different construction materials, coatings, plastics, rubber, etc. UV-radiation is particularly harmful for biological systems, causing damage to skin cells, resulting in accelerated aging of the skin and the emergence of various diseases, from inflammatory processes to cancer (Velasco et al., 2008; Kullavanijaya and Lim, 2005).

Protection against ultraviolet (UV) radiation is the major function of sunscreen lotions as well as UV-protective coatings for different kind of material. Various substances are used as UV protectors either reflecting or absorbing UV light. In addition to inorganic pigments, efficiently reflecting UV light, organic compounds absorbing UV light are usually called UV filters. Based on the literature survey on the use and effects of old and new formulations, the list of substances permitted by law is regularly updated. The European Union (EU) currently allows 28 organic substances (EC Regulation 1223/2009 on cosmetics, 2009), while some other compounds are allowed in countries around the world, such as Japan and the USA, where they are treated as biological agents, available without prescription (Over-the-Counter (OTC) Drug Monograph Process, 2020; Standards for Cosmetics, 2000). Actually, in 2019 FDA tightened regulation of over-the-counter sunscreen products. Besides that, FDA called for more research on 14 non-prescription sunscreen ingredients and increased maximum SPF values on sunscreen labels from 50 to 60 (FDA advances new proposed regulation to make sure that sunscreens are safe and effective, 2019). Due to fairly broad spectral range, 400-290 nm (UVA and UVB), individual compounds, possessing rather narrow absorption peaks, cannot prevent the exposure to the whole spectrum of UV light. Thus, formulations of different compounds are used.

Sunscreen products are used primarily in special conditions, such as swimming in the sea, open swimming pools, and on the snow and in the mountains, where a really thorough protection is needed. Several recent studies showed that they may decompose by light. Mostly, two types of reactions occur: a) direct photolytic reactions, and b) chlorination of aromatic rings or side chains due to the presence of active chlorine medium (mainly pools).

If we take into account that UV-filters do not afford 100% protection to the skin and that most of UVA-induced damage is mainly mediated by ROS generated after UV exposure (Nichols and Katiyar, 2010; Norval and Wulf, 2009), the addition of antioxidants to sunscreens is needed (Gilaberte and Gonzalez, 2010). Natural antioxidants, mainly polyphenols and carotenoids, are used in sunscreens due to their efficacy in reducing free radical generation and thereby decreasing skin photodamage (Aziz et al., 2005; Bando et al., 2004; Darvin et al., 2011; Huang et al., 2010; Lee et al., 2013; Nichols and Katiyar, 2010), especially after sun exposure, when the levels of endogenous antioxidants are significantly depleted (Godic et al., 2014).

Trans-resveratrol (RES) is a biologically important stilbene showing antioxidant (Džeba et al., 2012; Gülcin, 2010), anti-inflammatory (Xiao et al., 2013) and anti-tumor (Chao et al., 2014; Wang et al., 2012; Yin et al., 2013) properties. It is a phytoalexin produced by various plants to protect them in stress conditions due to micobacterial infections, extremal temperatures, and dryness (Piñeiro et al., 2006).

Nowadays trans-resveratrol is used as a component of various products from nutriceutics (Rossi et al., 2012) to body care formulations (Soby et al., 2003), where it is supposed to behave as a natural antioxidant and antiaging compound. Additionally, resveratrol may be added to plastic films for the food packaging in order to increase their stability or/and prevent oxidation (Agustín-Salazar et al., 2014; Barbosa-Pereira et al., 2014). The related problem involves low stability of resveratrol and possible products of its transformation with unknown chemical and biological properties. Thus the number of products forming from resveratrol in chlorinated water may be rather high. Our earlier studies on the aquatic chlorination of the known UV-protectors diethylaminohydroxybenzoyl hexyl benzoate (DHHB) (Grbović et al., 2013) and especially avobenzone (Trebše et al., 2016; Wang et al., 2017; Detenchuk et al., 2019; Lebedev et al., 2020) demonstrated formation of various disinfection products mainly with the unknown biological activity. Belonging to the classes of halogenated phenols, aldehydes, acetophenones, these compounds may be rather harmful for humans.

This study was focused on stability of resveratrol as a pure substance as well as a sunscreens’ ingredient after aquatic chlorination as a common disinfection processes for swimming pool waters. Given that the use of sunscreen products is essential, with resveratrol being an antioxidant and a substance of benefit in such formulations, we investigated resveratrol aquatic chlorination products. For the identification of the corresponding DBPs (disinfection by-products) gas chromatography-high resolution mass spectrometry (GC-HRMS) with electron ionization for the determination of semi volatile compounds and ultra pressure liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) with electrospray ionization for the determination of polar and non volatile ones have been used.

Section snippets

Chlorination experiments

Resveratrol standard or sunscreen, containing resveratrol and oxybenzone (10 mg of sunscreen, containing 1% resveratol and 5% oxybenzone), was dissolved in 25 mL of chlorine water, prepared by dissolving one chlorine tablet containing 17,0 mg of sodium dichloroisocyanurate anhydrous in 1L of distilled water and producing 10 mg L−1 of active chlorine. According to the producer’s instructions, 10 min are needed for solution to become saturated with chlorine. That time, when we dissolved studied

Resveratrol persistence under conditions of aquatic chlorination

Fig. 1 illustrates the persistence of pure resveratrol and resveratrol in a sunscreen during aquatic chlorination process. Chlorination of resveratrol is very fast and there is practically no difference in case of resveratrol formulation or pure resveratrol chlorination rate. In fact, a decrease of resveratrol concentration was observed immediately after dissolving resveratrol standard or resveratrol sunscreen in chlorine water. After 120 min less than 10% of the resveratrol remained in both

Conclusions

The study of trans-resveratrol and its UV-protecting formulations demonstrated the fast transformation of that compound under aquatic chlorination conditions. The toxicity of the resveratrol aquatic chlorination products is substantially higher than that of pure resveratrol or its sunscreen formulatons. GC-HRMS and LC-HRMS allowed tentatively identifying 82 aquatic chlorination products of resveratrol, including chlorophenols and polychlorinated biphenyls. The principal mechanisms of the

CRediT author statement

Albert Lebedev: Methodology, Software, Validation, Resources, Writing - Review & Editing, Supervision, Funding acquisition. Mojca Bavcon Kralj: Conceptualization, Methodology, Visualization, Supervision. Aleksandra Marjanović: Investigation. Elena A.Detenchuk: Investigation. Dmitry Kosyakov: Formal analysis. Nikolay Uljanovskii: Formal analysis. Polonca Trebše: Methodology, Resources, Writing - Review & Editing, Project administration, Funding acquisition.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

The reported study was funded by RFBR, project number 19-33-90042. This work was performed using instrumentation of the Core Facility Center “Arktika” of the Northern (Arctic) Federal University under financial support of the Ministry of Science and Higher Education of the Russian Federation (state assignment project No. 0793-2020-0007).

The authors acknowledge the financial support from the Slovenian Research Agency, the research core funding No. P3-0388 (Mechanisms of health maintenance), No.

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