Sunscreens in Coastal Ecosystems: Occurrence, Behavior, Effect and Risk [1st ed.] 9783030560768, 9783030560775

Table of contents :
Front Matter ....Pages i-xi
Sunscreen Components Are a New Environmental Concern in Coastal Waters: An Overview (David Sánchez-Quiles, Julián Blasco, Antonio Tovar-Sánchez)....Pages 1-14
Sunscreen Regulation in the World (Giulio Pirotta)....Pages 15-35
Chemical UV Filters: Analysis in Marine Waters (M. Silvia Diaz-Cruz)....Pages 37-58
Fate and Behavior of UV Filters in the Marine Environment (Marina G. Pintado-Herrera, Pablo A. Lara Martín)....Pages 59-83
Bioaccumulation and Toxicological Effects of UV-Filters on Marine Species (Clément Lozano, Justina Givens, Didier Stien, Sabine Matallana-Surget, Philippe Lebaron)....Pages 85-130
The Mediterranean Sea (Antonio Tovar-Sánchez, David Sánchez-Quiles, Araceli Rodríguez-Romero)....Pages 131-161
Environmental Risk Assessment of Sunscreens (Julián Blasco, Chiara Trombini, Marta Sendra, Cristiano V. M. Araujo)....Pages 163-184
Sustainable Sunscreens: A Challenge Between Performance, Animal Testing Ban, and Human and Environmental Safety (Sascha Pawlowski, Mechtild Petersen-Thiery)....Pages 185-207

Citation preview

The Handbook of Environmental Chemistry 94 Series Editors: Damià Barceló · Andrey G. Kostianoy

Antonio Tovar-Sánchez David Sánchez-Quiles Julián Blasco  Editors

Sunscreens in Coastal Ecosystems Occurrence, Behavior, Effect and Risk

The Handbook of Environmental Chemistry Volume 94 Founding Editor: Otto Hutzinger Series Editors: Damia Barcelo´ • Andrey G. Kostianoy

Editorial Board Members: Jacob de Boer, Philippe Garrigues, Ji-Dong Gu, Kevin C. Jones, Thomas P. Knepper, Abdelazim M. Negm, Alice Newton, Duc Long Nghiem, Sergi Garcia-Segura

In over three decades, The Handbook of Environmental Chemistry has established itself as the premier reference source, providing sound and solid knowledge about environmental topics from a chemical perspective. Written by leading experts with practical experience in the field, the series continues to be essential reading for environmental scientists as well as for environmental managers and decisionmakers in industry, government, agencies and public-interest groups. Two distinguished Series Editors, internationally renowned volume editors as well as a prestigious Editorial Board safeguard publication of volumes according to high scientific standards. Presenting a wide spectrum of viewpoints and approaches in topical volumes, the scope of the series covers topics such as • • • • • • • •

local and global changes of natural environment and climate anthropogenic impact on the environment water, air and soil pollution remediation and waste characterization environmental contaminants biogeochemistry and geoecology chemical reactions and processes chemical and biological transformations as well as physical transport of chemicals in the environment • environmental modeling A particular focus of the series lies on methodological advances in environmental analytical chemistry. The Handbook of Envir onmental Chemistry is available both in print and online via http://link.springer.com/bookseries/698. Articles are published online as soon as they have been reviewed and approved for publication. Meeting the needs of the scientific community, publication of volumes in subseries has been discontinued to achieve a broader scope for the series as a whole.

Sunscreens in Coastal Ecosystems Occurrence, Behavior, Effect and Risk Volume Editors: Antonio Tovar-Sánchez
David Sánchez-Quiles
Julián Blasco

With contributions by C. V. M. Araujo
J. Blasco
M. S. Diaz-Cruz
J. Givens
P. A. Lara Martı´n
P. Lebaron
C. Lozano
S. Matallana-Surget
S. Pawlowski
M. Petersen-Thiery
M. G. Pintado-Herrera
G. Pirotta
A. Rodrı´guez-Romero
D. Sa´nchez-Quiles
M. Sendra
D. Stien
A. Tovar-Sa´nchez
C. Trombini

Editors Antonio Tovar-Sa´nchez Department of Ecology and Coastal Management Institute of Marine Sciences of Andalusia (CSIC) Ca´diz, Spain

David Sa´nchez-Quiles Department of Ecology and Coastal Management Institute of Marine Sciences of Andalusia (CSIC) Ca´diz, Spain

Julia´n Blasco Department of Ecology and Coastal Management Institute of Marine Sciences of Andalusia (CSIC) Ca´diz, Spain

ISSN 1867-979X ISSN 1616-864X (electronic) The Handbook of Environmental Chemistry ISBN 978-3-030-56076-8 ISBN 978-3-030-56077-5 (eBook) https://doi.org/10.1007/978-3-030-56077-5 © Springer Nature Switzerland AG 2020 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG. The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Series Editors Prof. Dr. Damia Barcelo´

Prof. Dr. Andrey G. Kostianoy

Department of Environmental Chemistry IDAEA-CSIC C/Jordi Girona 18–26 08034 Barcelona, Spain and Catalan Institute for Water Research (ICRA) H20 Building Scientific and Technological Park of the University of Girona Emili Grahit, 101 17003 Girona, Spain [email protected]

Shirshov Institute of Oceanology Russian Academy of Sciences 36, Nakhimovsky Pr. 117997 Moscow, Russia and S.Yu. Witte Moscow University Moscow, Russia [email protected]

Editorial Board Members Prof. Dr. Jacob de Boer VU University Amsterdam, Amsterdam, The Netherlands

Prof. Dr. Philippe Garrigues Universite´ de Bordeaux, Talence Cedex, France

Prof. Dr. Ji-Dong Gu Guangdong Technion-Israel Institute of Technology, Shantou, Guangdong, China

Prof. Dr. Kevin C. Jones Lancaster University, Lancaster, UK

Prof. Dr. Thomas P. Knepper Hochschule Fresenius, Idstein, Hessen, Germany

Prof. Dr. Abdelazim M. Negm Zagazig University, Zagazig, Egypt

Prof. Dr. Alice Newton University of Algarve, Faro, Portugal

Prof. Dr. Duc Long Nghiem University of Technology Sydney, Broadway, NSW, Australia

Prof. Dr. Sergi Garcia-Segura Arizona State University, Tempe, AZ, USA

Series Preface

With remarkable vision, Prof. Otto Hutzinger initiated The Handbook of Environmental Chemistry in 1980 and became the founding Editor-in-Chief. At that time, environmental chemistry was an emerging field, aiming at a complete description of the Earth’s environment, encompassing the physical, chemical, biological, and geological transformations of chemical substances occurring on a local as well as a global scale. Environmental chemistry was intended to provide an account of the impact of man’s activities on the natural environment by describing observed changes. While a considerable amount of knowledge has been accumulated over the last four decades, as reflected in the more than 150 volumes of The Handbook of Environmental Chemistry, there are still many scientific and policy challenges ahead due to the complexity and interdisciplinary nature of the field. The series will therefore continue to provide compilations of current knowledge. Contributions are written by leading experts with practical experience in their fields. The Handbook of Environmental Chemistry grows with the increases in our scientific understanding, and provides a valuable source not only for scientists but also for environmental managers and decision-makers. Today, the series covers a broad range of environmental topics from a chemical perspective, including methodological advances in environmental analytical chemistry. In recent years, there has been a growing tendency to include subject matter of societal relevance in the broad view of environmental chemistry. Topics include life cycle analysis, environmental management, sustainable development, and socio-economic, legal and even political problems, among others. While these topics are of great importance for the development and acceptance of The Handbook of Environmental Chemistry, the publisher and Editors-in-Chief have decided to keep the handbook essentially a source of information on “hard sciences” with a particular emphasis on chemistry, but also covering biology, geology, hydrology and engineering as applied to environmental sciences. The volumes of the series are written at an advanced level, addressing the needs of both researchers and graduate students, as well as of people outside the field of vii

viii

Series Preface

“pure” chemistry, including those in industry, business, government, research establishments, and public interest groups. It would be very satisfying to see these volumes used as a basis for graduate courses in environmental chemistry. With its high standards of scientific quality and clarity, The Handbook of Environmental Chemistry provides a solid basis from which scientists can share their knowledge on the different aspects of environmental problems, presenting a wide spectrum of viewpoints and approaches. The Handbook of Environmental Chemistry is available both in print and online via www.springerlink.com/content/110354/. Articles are published online as soon as they have been approved for publication. Authors, Volume Editors and Editors-in-Chief are rewarded by the broad acceptance of The Handbook of Environmental Chemistry by the scientific community, from whom suggestions for new topics to the Editors-in-Chief are always very welcome. Damia Barcelo´ Andrey G. Kostianoy Series Editors

Preface

Sunscreens are employed as protective agents of UV radiation for more than 70 years and their use has increased along the time. Although they play an essential role against ageing of the skin and serious illness as melanoma, they are harmful to the environment. Research into the impact of sunscreens on the marine environment began in the first decade of the twenty-first century. Since then, analytical techniques for quantifying UV filters in the marine environment have been developed and improved, and a significant number of studies have been carried out to find out the toxicity of these sunscreens (using the whole sunscreen or their active ingredients) in a wide range of organisms. These investigations have led to an increasing concern about the use of these products and some states and countries have made new laws prohibiting the use of sunscreens with certain UV filters to protect their marine ecosystems. This volume has been written by renowned experts in the field and covers the subject from both a social and scientific perspective through the study of current global regulations on the use of UV filters; advances in analytical methods for their determination in complex samples; the occurrence, fate, behaviour, toxicity and risk of these compounds in the marine ecosystem; the paradigmatic case of the Mediterranean Sea, a unique ecosystem threatened by its intense population growth, mainly in its coastal areas; and, finally, an approach for developing more sustainable UV filters for sunscreen formulations. We hope that this volume will become a useful book as its multidisciplinary approach can be of interest to experts in various fields of expertise such as analytical and environmental chemistry, marine ecology and toxicology, among others. This book is also of interest to environmental managers specializing in coastal areas, the tourism industry concerned with coastal conservation, cosmetics companies interested in developing new sustainable sunscreens and the society in general.

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Preface

We would like to express our sincere gratitude to all the authors who have contributed their knowledge, time and effort to each chapter of this book. We thank the editorial team for its continuous help and support through the editorial process. Ca´diz, Spain Ca´diz, Spain Ca´diz, Spain

Antonio Tovar-Sa´nchez David Sa´nchez-Quiles Julia´n Blasco

Contents

Sunscreen Components Are a New Environmental Concern in Coastal Waters: An Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . David Sa´nchez-Quiles, Julia´n Blasco, and Antonio Tovar-Sa´nchez

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Sunscreen Regulation in the World . . . . . . . . . . . . . . . . . . . . . . . . . . . . Giulio Pirotta

15

Chemical UV Filters: Analysis in Marine Waters . . . . . . . . . . . . . . . . . M. Silvia Diaz-Cruz

37

Fate and Behavior of UV Filters in the Marine Environment . . . . . . . . Marina G. Pintado-Herrera and Pablo A. Lara Martı´n

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Bioaccumulation and Toxicological Effects of UV-Filters on Marine Species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cle´ment Lozano, Justina Givens, Didier Stien, Sabine Matallana-Surget, and Philippe Lebaron

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The Mediterranean Sea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131 Antonio Tovar-Sa´nchez, David Sa´nchez-Quiles, and Araceli Rodrı´guez-Romero Environmental Risk Assessment of Sunscreens . . . . . . . . . . . . . . . . . . . 163 Julia´n Blasco, Chiara Trombini, Marta Sendra, and Cristiano V. M. Araujo Sustainable Sunscreens: A Challenge Between Performance, Animal Testing Ban, and Human and Environmental Safety . . . . . . . . . . . . . . . 185 Sascha Pawlowski and Mechtild Petersen-Thiery

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Sunscreen Components Are a New Environmental Concern in Coastal Waters: An Overview David Sánchez-Quiles, Julián Blasco, and Antonio Tovar-Sánchez

Contents 1 Brief History of Sun Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2 Previous Concepts of UV Radiation and Sunscreen’s Composition and Use Habits . . . . . . . 2 3 Source of UVFs in Coastal Ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 3.1 Directly from the Bathers’ Skin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 3.2 Indirectly Through the WWTP Effluents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 3.3 Atmospheric Depositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 4 Occurrence and Fate of UVFs in Coastal Ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 5 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

Abstract Since ancient times, humans have felt the need to protect their skin from the harmful effects of the sun: first with the use of vegetable oils or mud that were applied on the skin and then with the wearing of clothes, hats, or umbrellas. Today, the use of sunscreens around the world has become widespread. It has been shown that the use of these cosmetics can release large quantities of chemicals into coastal waters, either directly through bathing or indirectly through waste water treatment plants and atmospheric depositions. Due to the nature of the active ingredients of sunscreens, organic and inorganic UV filters, it has been proven that they can bioaccumulate and bioconcentrate in sediments and biota and can enter the food chain, being a problem whose true magnitude is still unknown. Keywords Coastal tourism, Solar radiation, Sunscreen, UV filters

D. Sánchez-Quiles (*), J. Blasco, and A. Tovar-Sánchez Department of Ecology and Coastal Management, Institute of Marine Sciences of Andalusia (CSIC), Puerto Real, Cádiz, Spain e-mail: [email protected] Antonio Tovar-Sánchez, David Sánchez-Quiles, and Julián Blasco (eds.), Sunscreens in Coastal Ecosystems: Occurrence, Behavior, Effect and Risk, Hdb Env Chem (2020) 94: 1–14, DOI 10.1007/698_2019_439, © Springer Nature Switzerland AG 2020, Published online: 8 March 2020

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1 Brief History of Sun Protection Throughout the history of human beings, they have felt the need to protect their skin from sunlight: in ancient Egypt, Mesopotamia, China, India, Greece, and Rome, they used any kind of clothes and umbrellas to protect their skin from the sun; even in ancient Egypt, pale skin was ideal among women, who also used a mixture of clay and mineral powders, especially between people with high social status [1–3]. But it was many centuries after, in 1801, when Johann Wilhelm Ritter discovered the ultraviolet radiation (UV) [4]. Some years later, in 1820, an experiment by Sir Everard Home corroborated that some component of sunlight could be more damaging to the skin than heat: he put his hands under the sunlight and covered one of them with a black cloth. His results showed how the uncovered hand burned even when the hand under the black cloth reached a higher temperature [5]. And, in 1889, Dr. E. J. Widmark proved that UV radiation was responsible for sunburn [6]. All these findings led to the commercialization of the first sunscreen in 1928 in the USA which contains two active ingredients: benzyl salicylate and benzyl cinnamate [3]. From this date the sequence of events accelerated: in 1933 the first commercialized sunscreen in Germany contains benzimidazole sulfonic acid. In France, the first sunscreen became available in 1936. During World War II, it was very famous among the soldiers a sunscreen called Red Vet Pet (Red Veterinary Petrolatum), a disagreeable red sticky cream which was produced in 1944. After the war, a great number of compounds were synthetized, tested, and commercialized. But it was during the 1970s when coastal tourism became more and more popular, and consequently there was an increase of the sunscreen demand. The first waterproof sunscreen was commercialized in 1977, and during the 1980s the broadspectrum sunscreens became available [3]. Today, the growth of the sunscreen industry is determined by a few factors: the knowledge of the harmful effects of UV radiation on the skin; the large number of different sunscreen formulations on the market; longevity, which increases the time of exposure; and, therefore, the time of use of sunscreens and the growth of coastal population and coastal tourism worldwide.

2 Previous Concepts of UV Radiation and Sunscreen’s Composition and Use Habits In the solar light spectra, UV radiation comprises the wavelength between 400 and 100 nm and is mainly divided into three subtypes: UV-A with a wavelength range between 400 and 320 nm which is the main component of the UV radiation reaching the Earth’s surface (approximately 95% of the UV radiation), UV-B between 320 and 280 nm which constitutes the remaining 5%, and UV-C between 280 and 100 nm which is filtered off from the ozone layer in the atmosphere and does not reach the Earth’s surface (Fig. 1).

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Fig. 1 Schematic spectrum of solar radiation over the Earth’s surface. Wavelengths below 290 nm do not reach the Earth

Short exposure to UV radiation (between 5 and 10 min) has therapeutic effects in humans, e.g., increase the calcium absorption by improving the production of vitamin D preventing rickets in children and osteoporosis in adults [7]. However, it is well known that longer exposures to UV radiation cause molecular damage, including different degenerative changes in the skin that lead to sunburn, photoaging, and melanoma [7, 8]. For that reason, every year, dermatologists’ associations give recommendations to people, some of which are the following: protect your skin with clothing, wear a hat and sunglasses, keep yourself out of direct sunlight (specially between 11:00 a.m. and 15:00 p.m.), and use a suitable sunscreen in an appropriate manner (broad-spectrum protection, SPF higher than 30, repeat application every 2 h, etc.). Sunscreen can be defined as a cosmetic product with an active component that can act as a filter of the UV radiation [9]. These components, with a light absorption in the range of UV-A and/or UV-B, are the organic and inorganic UV filters (UVFs). On the one hand, the organic UVFs (O-UVFs) are compounds from different families (e.g., benzophenones, p-aminobenzoates, salicylates, camphor derivatives, etc.), with different solubilities (i.e., water-soluble or lipid-soluble) but generally with at least one aromatic ring and/or carbonyl group that help in the electron delocalization providing them with a high molar absorptivity in UV-A and/or UV-B radiation [10]. Currently, there are around 50 different O-UVFs permitted by the different legislations [11]. On the other hand, the inorganic UVFs (I-UVFs) are metallic oxides, generally titanium dioxide (TiO2) and zinc oxide (ZnO) formulated as nanoparticles to avoid the whitening effects on the skin [12]. The action mode of the I-UVFs implies reflection, scattering, and absorption of the UV radiation [13]. Some studies have demonstrated that these nanoparticles can be toxic for aquatic life due to its reactive oxygen species (ROS) generation under sunlight [14, 15]. In order to obtain a broad-spectrum protection, sunscreen’s composition requires the mixture of two or more UVFs, both organic and inorganic.

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In addition to the UVFs, sunscreens are cosmetics made by many other components: sensory enhancers (e.g., silica or nylon-based compounds), emulsifiers (e.g., potassium cetyl phosphate or PEG-30 dipolyhydroxystearate), emollients (e.g., benzoate esters, butyloctyl salicylates, or dicaprylyl carbonate), preservatives (e.g., methylparaben or propylparaben), film-forming agents (e.g., acrylates copolymer, or silicones), and fragrances among others [12]. Some of these ingredients have been detected in coastal waters elsewhere [16–18]. The use of sunscreen has been shown to be very effective in preventing the health problems caused by UV radiation [19]. As a consequence, the use of sun lotions has been growing since the first one was marketed in 1928. A 10-year study (from 1990 to 2000) performed in 13 European countries shows an increase in the use of sun protection in both men (from 52 to 63%) and women (from 80 to 87%) [20]. Sunscreen is a cosmetic mainly used during holydays especially at the beach [21]. According to a recent survey in France, almost all adults (98% of women and 89% of men) and children (97%) use sunscreen during their summer holidays, with the spray being the preferred dosage form [22]. Today, the sunscreen market is the fastest growing sales sector in the cosmetics industry, with a continuous increase in sales [12]. Every year, the market is flooded with more efficient sunscreens, with components that modify their rheology and make them easier to spread on the skin. Moreover, sunscreens are increasingly used in beauty products: in 2016, the global market of sunscreen ingredients reached 44,000 tons, with a forecasted annual growth rate of 4% over 2016–2021, being North America and Europe the largest markets followed by Asia Pacific [23]. The global sun care market value amounted to 15.83 billion US dollars and is forecasted to reach almost 25 billion by 2024 [24].

3 Source of UVFs in Coastal Ecosystems Coastal areas are under intense anthropogenic pressure: more than 600 million people (around 10% of the world’s population) live in coastal areas that are less than 10 m above sea level, and almost 40% of the worldwide population lives within 100 km of the coast, which suppose a population density twice the global average [25]. In addition, coastal and maritime tourism is considered the most important component of the tourism industry, being one of the most important marine economic activities and with a growing trend toward greater development [26]. The use of sunscreen in many of these coastal tourist areas is the focus of new regulations. For example, the Xel-Há Natural Park in Quintana Roo (Mexico) advises tourists to use an O-UVF’s free sunscreen, and the US National Park Services suggests reducing the amount of sunscreen use [27]. Recently, the State of Hawaii has banned the sale and distribution of any sunscreen that contains benzophenone-3 (BP-3) and octyl methoxycinnamate (OMC) to protect coral reefs [28], being an example for Key West (Florida), the archipelago national of Palau, and the Caribbean islands of Bonaire and Aruba, which recently have followed Hawaii in this ban [29–32].

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Fig. 2 Main sources of UVFs in the marine environment: direct release, WWTP effluents, and atmospheric depositions

Release of UVFs may originate from point sources, such as production facilities, landfills, or wastewater treatment plants, or from nonpoint sources, such as the washoff during the bath on the beach. UVFs are mainly used in the cosmetics industry but also in many other consumer products. On the one hand, O-UVFs are used as protection of several materials from the sunlight such as plastics, paint, car maintenance products, and shoe shine among others [33]. On the other hand, nano-TiO2 and nano-ZnO are used in many industrial applications, i.e., paints, plastics, cleaning agents, electronics, etc. [34–36]. A comprehensive database with more than 3,000 products containing nanoparticles in Europe and their potential risks for humans and the environment can be found at “The Nanodatabase Website” [37]. This widespread use of sunscreens has led to understanding and assessing the three potential sources of UVFs in the marine environment: directly from the bather’s skin or indirectly through the effluents of wastewater treatment plants (WWTPs) and atmospheric depositions (Fig. 2).

3.1

Directly from the Bathers’ Skin

The main use of UVFs is in the cosmetics industry, mainly in the composition of sunscreens. The usage of these cosmetics on coastal areas can reach the aquatic ecosystem directly after it has been washed off from the skin of the bathers.

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This nonpoint source of UVFs could be considered as the major input. In an interesting work, Poiger et al. [38] evaluated the data both from the direct release from the skin and the indirect way via WWTPs in two recreational lakes, one with many WWTPs discharging points and the other with no emitting points. They concluded that the action of the bathers directly on the lake could be the major input pathway of UVFs into the water, at least during the summer season [38]. Many efforts have been done in trying to quantify the amounts of sunscreen or UVFs that could be released during swim. Danovaro et al. [39] estimated that around 25% of the sunscreen applied on the skin could be washed off over a 20-min swimming, which suppose between 4,000 and 6,000 tons of sunscreen per year are potentially released into reef areas of the world [39]. Based on the number of swimmers and the sunscreen that could be washed off during the swim, Sharifan et al. [40] have estimated the input of different O-UVFs to surface waters on the Texas coastline: 1,874 kg/year of OMC, 1,249 kg/year of octocrylene (OCR), 1,015 kg/year of butyl methoxydibenzoylmethane (BDM), and 625 kg/year of BP-3 [40]. Sánchez-Quiles and Tovar-Sánchez [14] calculated that 4 kg of nanoTiO2 could be released on a small Spanish beach during a summer day [14]. Wong et al. [41] estimated that around 250 tons of nanoparticles from sunscreens can be potentially discharged in the marine environment directly after swim [41]. Moreover, some works have corroborated a direct relationship between beachgoers’ affluence and concentrations of UVFs in seawater during a summer day in different countries such as Spain, France, and Japan [42–44].

3.2

Indirectly Through the WWTP Effluents

Although recreational activities are direct inputs of UVFs into the marine environment, other important sources are the effluents from WWTPs [45]. Some daily activities (i.e., laundering clothes such as towels, showering, or even urinating) are sources of UVFs through the domestic sewage, increasing the concentrations of UVFs in the influent of the WWTPs [46–52]. For example, a study carried out in Australia reported a mean concentration of 61.5 μg/L for BP-3 in urine samples of 24 pools of 100 individuals of different age groups [53]; in the Canary Island, reuse of towels and bed linen in hotels depend on how “sweaty” or “oily” are perceived by tourists due to the use of sunscreen [54]; and Lambropoulou et al. [55] found in wear pipes of showers concentrations of BP-3 and octyl dimethyl PABA (ODP) up to 9.9 and 6.2 μg/L, respectively [55]. It is not easy to give the removal efficiencies of each O-UVF in WWTPs as it depends largely on their nature (more than 50 compounds with different low octanolwater partition coefficient [log KOW]), the population that each WWTP serves (i.e., domestic, industrial, hospital, etc.), and the technology employed (with different primary, secondary, and tertiary treatments) [45]. In fact, tertiary treatments are the most efficient in the removal processes, being the reverse osmosis the one that presents the best removal rates. However, these treatments are still uncommon in

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the majority of the WWTPs [47], which means that a considerable amount of these compounds will be part of the effluents or of the sludges depending on its own nature. Thus, in general, the most hydrophilic compounds (i.e., BP-3) will be found in elevated concentrations in both the influent and the effluent, while compounds like 4-methylbenzylidene camphor (4-MBC) or OCR tend to be incorporated into the sludge because of their lipophilicity [45, 47]. In the concern of inorganic nanoparticles, there are little empirical data concerning the release of sunscreens’ nanoparticles in the environment, and many estimates are based on models. For example, Gottschalk et al. [56], using a probabilistic material flow analysis, estimated that approximately up to 4% of nano-TiO2 and 2% of nano-ZnO that enter into the US WWTPs end up in the effluent, which means predicted concentrations in effluents ranged between 1.37 and 6.70 μg/L for nano-TiO2 and between 0.22 and 0.74 μg/L for nano-ZnO [56]. A similar study carried out recently in Europe showed that estimated concentrations of nano-TiO2 in WWTP effluents ranged between 2.77 and 76.1 μg/L [57]. Although WWTP effluents discharged into the sea through submarine outfalls have never been evaluated as a source of UVFs in coastal waters, it is presumable that they are, as they are a source of many organic micropollutants [58, 59].

3.3

Atmospheric Depositions

Atmospheric aerosol containing UVFs may occur from different sources: from the WWTPs, from the incineration of the sludges, and directly after spraying sunscreen over the skin. UVFs have been detected in air samples from different locations. Shoeib et al. [60] have investigated urban and rural WWTPs from Ontario (Canada) as a source of seven O-UVFs into the atmosphere (octyl salicylate (OS), homosalate (HS), BP-3, 4-MBC, OMC, OCR, and BDM). They found these UVFs in all the WWTPs studied with higher concentrations during the summer season compared with the winter and higher in towns than in villages [60]. For example, the average concentrations for HS were 32.5
23.2 ng/m3 during the summer season and 8.61
2.85 ng/m3 in the winter at urban WWTPs, while concentrations in rural WWTPs were 80 times lower, showing a relationship between the use of sunscreens and the concentration of O-UVFs in the atmosphere. Although the atmospheric deposition of UVFs has never been evaluated as an input to the ocean, some works point out that these compounds can be accumulated in coastal organisms potentially exposed to them. Ribeiro et al. [61] investigated the use of coastline plants as biomonitor of two O-UVFs (4-MBC and OCR). Five different plant species were collected from 15 beaches in Portugal, and 71% of the samples were reported to contain UVFs in concentrations ranging from 12 to 240 ng/g dw, with those plants with a high lipid content, such as Euphorbia paralias (sea spurge), capable of concentrating more UVFs from the atmosphere than plants with a higher water content [61]. This work suggests the importance of the atmospheric transport of these organic contaminants to coastal areas.

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Quantitative estimates of nanoparticles in the atmosphere have been made in Europe using a dynamic probabilistic model. This model has predicted concentrations of nano-TiO2 and nano-ZnO in air ranged between 0.43 and 3.98 ng/m3 and between 0.08 and 1.67 ng/m3, respectively [57].

4 Occurrence and Fate of UVFs in Coastal Ecosystems Due to the widespread use of sunscreens worldwide, the high lipophilicity and poor biodegradability of many UVFs, and the importance of their source into the environment, they are present in different environmental matrices. Organic UVFs will have a different fate on the environment depending on their n-octanol/water partition coefficient (log KO/W). Most of the O-UVFs have log KO/W between 4 and 8, which means they are highly lipophilic and may accumulate in sediments and biota [62]. In fact O-UVFs have been found in highly impacted environments such as seawater, sand, and sediments from crowed beaches and densely populated coastal areas from the Mediterranean region, Asia, and North America [42, 63–66], sediments and waters from rivers and lakes from Europe and Asia [38, 50, 52, 67, 68], and in aquatic biota such as mussels, fish, dolphins, coral communities, bird eggs, and cormorants among others around the globe [43, 69–72]. They can also be found in remote places far from high human pressure such as the Tuamotu Archipelago (around 80 French Polynesian islands and atolls) in the middle of the Pacific Ocean, where Goksøyr et al. [73] detected in the sea surface microlayer (SML) concentrations of OMC, 4-MBC, BP-3, and 3-benzylidene camphor (3-BC) in the range of 5–55 ng/L [73]. In open areas of the Arctic Sea, Tsui et al. [74] detected six O-UVFs with concentrations up to 70 ng/L for BDM giving two possible pathways: oceanic transport via oceanic currents or atmospheric transport [74]. Also, Emnet et al. [75] have found O-UVFs in Antarctic waters, ice, and biota associated with effluents from WWTPs of two research stations [75]. As for inorganic nanoparticles, these can be released into the ecosystem throughout their entire life cycle: production, incorporation into products, use of these products and during their transport and fate between WWTP, waste incineration plants, landfill, and recycling processes [34]. Regardless of whether the particles are released directly into water or the atmosphere, once in the environment, these nanoparticles can migrate between the different compartments to eventually form aggregates and accumulate in sediments or biota. Sun et al. [57] have used a dynamic probabilistic material flow modelling to predict the flow of nano-TiO2 and nano-ZnO to the environment and quantify their concentrations in their final sinks (e.g., soils and sediments). In the worst scenario, they estimated in sediments concentrations about 40 mg/kg of nano-TiO2 and 6 mg/kg of nano-ZnO [57]. In addition, these nanoparticles can interact with aquatic biota by being adsorbed on the surface of microorganisms or by being assimilated by phytoplankton, filtering organisms, benthic fauna, and fish [76] and may bioaccumulate or bioconcentrate in different trophic levels.

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Fig. 3 Conceptual diagram transfer of UVFs in coastal environments

The SML has been defined as the top 1,000 μm of the ocean surface playing a key role as air-water interface. In this narrow fraction of the water column, many processes take place such as atmospheric inputs, solar energy fluxes, and gas exchange with the atmosphere, and many surface-active organic and inorganic chemicals tend to be concentrated [77, 78]. The SML could therefore be the main gateway for UVFs into the marine environment. Once in the water column, under UV radiation, O-UVFs can degrade well by direct or indirect photolysis through photoisomerization [11]. Some studies have shown that in aqueous solution and under UV radiation, UVFs can undergo photooxidation processes generating ROS which could produce damage to lipids, proteins, and DNA generating high levels of stress in marine organisms [14, 79–84] (Fig. 3). Therefore, this environmental compartment should be considered in any study that aims to address the distribution, accumulation, transformation, rates, mobilization, and bio-uptake of UVFs in marine waters.

5 Concluding Remarks Since ancient times, humans have been protected from UV radiation: first with natural products such as mud or vegetable oils, then with clothing and umbrellas, and finally with sunscreens. Today there is a great variety of sunscreens on the market with an almost infinite combination of chemical compounds that can potentially end up in the coastal environment all over the world (i.e., UVFs, emulsifiers, emollients, preservatives, fragrances, etc.). Due to the widespread use of sunscreens and the chemical nature of their active ingredients, their entry into the environment may occur directly after they are released from the skin or indirectly through WWTPs and atmospheric depositions.

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Nowadays these chemicals are present in a wide variety of environmental matrices (i.e., seawater, marine sediments, marine organisms, etc.) and have reached a wide dispersion, being present even in remote areas such as the Arctic and Antarctic oceans. Because of their chemical nature, UVFs are able to bioaccumulate in sediments and bioconcentrate in biota, becoming part of the food chain. Moreover, these compounds have been shown to be a threat to coral reefs; therefore, some countries, states, and local authorities have recently banned their sale and distribution. Nowadays, the real magnitude and potential effects of the input of these chemicals into marine ecosystems are still unknown, as a better understanding of their mobility, bioavailability, and toxicity is required. It is therefore necessary to address this issue from three perspectives: social, scientific, and regulatory, with the aim of becoming socially aware of the environmental consequences of UVFs in the marine ecosystem and ensuring the sustainable growth of coastal communities.

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69. Gago-Ferrero P, Alonso MB, Bertozzi CP et al (2013) First determination of UV filters in marine mammals. Octocrylene levels in Franciscana dolphins. Environ Sci Technol 47:5619–5625. https://doi.org/10.1021/es400675y 70. Tsui MMP, Lam JCW, Ng TY et al (2017) Occurrence, distribution, and fate of organic UV filters in coral communities. Environ Sci Technol 51:4182–4190. https://doi.org/10.1021/acs. est.6b05211 71. Molins-Delgado D, Máñez M, Andreu A et al (2017) A potential new threat to wild life: presence of UV filters in bird eggs from a preserved area. Environ Sci Technol 51:10983–10990. https://doi.org/10.1021/acs.est.7b03300 72. Gago-Ferrero P, Díaz-Cruz MS, Barceló D (2015) UV filters bioaccumulation in fish from Iberian river basins. Sci Total Environ 518–519:518–525. https://doi.org/10.1016/j.scitotenv. 2015.03.026 73. Goksøyr A, Tollefsen KE, Grung M et al (2009) Balsa raft crossing the Pacific finds low contaminant levels. Environ Sci Technol 43:4783–4790. https://doi.org/10.1021/es900154h 74. Tsui MMP, Leung HW, Wai T-C et al (2014) Occurrence, distribution and ecological risk assessment of multiple classes of UV filters in surface waters from different countries. Water Res 67:55–65. https://doi.org/10.1016/j.watres.2014.09.013 75. Emnet P, Gaw S, Northcott G et al (2015) Personal care products and steroid hormones in the Antarctic coastal environment associated with two Antarctic research stations, McMurdo Station and Scott Base. Environ Res 136:331–342. https://doi.org/10.1016/j. envres.2014.10.019 76. Baker TJ, Tyler CR, Galloway TS (2014) Impacts of metal and metal oxide nanoparticles on marine organisms. Environ Pollut 186C:257–271. https://doi.org/10.1016/j.envpol.2013.11. 014 77. Manodori L, Gambaro A, Piazza R et al (2006) PCBs and PAHs in sea-surface microlayer and sub-surface water samples of the Venice Lagoon (Italy). Mar Pollut Bull 52:184–192. https:// doi.org/10.1016/j.marpolbul.2005.08.017 78. Tovar-Sánchez A, Arrieta JM, Duarte CM, Sañudo-Wilhelmy SA (2014) Spatial gradients in trace metal concentrations in the surface microlayer of the Mediterranean Sea. Front Mar Sci 1:79. https://doi.org/10.3389/fmars.2014.00079 79. Hanson KM, Gratton E, Bardeen CJ (2006) Sunscreen enhancement of UV-induced reactive oxygen species in the skin. Free Radic Biol Med 41:1205–1212. https://doi.org/10.1016/j. freeradbiomed.2006.06.011 80. Serpone N, Dondi D, Albini A (2007) Inorganic and organic UV filters: their role and efficacy in sunscreens and suncare products. Inorg Chim Acta 360:794–802. https://doi.org/10.1016/j.ica. 2005.12.057 81. Serpone N, Salinaro A, Emeline AV et al (2002) An in vitro systematic spectroscopic examination of the photostabilities of a random set of commercial sunscreen lotions and their chemical UVB/UVA active agents. Photochem Photobiol Sci 1:970–981. https://doi.org/10. 1039/B206338G 82. Inbaraj JJ, Bilski P, Chignell CF (2002) Photophysical and photochemical studies of 2-phenylbenzimidazole and UVB sunscreen 2-phenylbenzimidazole-5-sulfonic acid. https://doi.org/10.1562/0031-8655(2002) Photochem Photobiol 75:107–116. 0750107PAPSOP2.0.CO2 83. Allen JM, Gossett CJ, Allen SK (1996) Photochemical formation of singlet molecular oxygen in illuminated aqueous solutions of several commercially available sunscreen active ingredients. Chem Res Toxicol 9:605–609. https://doi.org/10.1021/tx950197m 84. Lesser MP (2006) Oxidative stress in marine environments: biochemistry and physiological ecology. Annu Rev Physiol 68:253–278. https://doi.org/10.1146/annurev.physiol.68.040104. 110001

Sunscreen Regulation in the World Giulio Pirotta

Contents 1 The European Union, Switzerland, Norway, and Iceland . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 The USA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Canada . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 ASEAN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Hong Kong . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Korea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Taiwan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Australia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 New Zealand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Russia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 MERCOSUR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 Israel and the Middle East . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Abstract Sunscreens are regulated in different ways in the world; this chapter will outline how sunscreens are limited or allowed. Limits on the use are also the key to understand the environmental origin of these ingredients and may help to understand and compare results from different areas in the world. Keywords Cosmetics, Cosmetics regulation, FDA sunscreens, Sunscreens, Sunscreen regulations, World sunscreen regulation

G. Pirotta (*) NEOVITA consulting, Uboldo, VA, Italy e-mail: [email protected] Antonio Tovar-Sánchez, David Sánchez-Quiles, and Julián Blasco (eds.), Sunscreens in Coastal Ecosystems: Occurrence, Behavior, Effect and Risk, Hdb Env Chem (2020) 94: 15–36, DOI 10.1007/698_2019_440, © Springer Nature Switzerland AG 2020, Published online: 24 April 2020

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The need for protection from sunrays and their damages is ancient, more or less as the history of mankind; early civilizations used a variety of substances: olive oil, powders, and clays used as itself or in more complex mixtures. After World War I, the white skin was no longer attractive, and during the 1930s, some oils were those used with no real protection [1]. We should regard to Eugene Schueller (founder of L’Oréal) for the first formulated product with the sunscreen protection goal. He formulated the first “filtering” oil, Ambre Solaire, and soon after other brands also began producing similar products. The need for protection previously limited to specific geographical areas or periods became a request during World War II when the overexposure of soldiers appeared as a new hazard. A specific product similar to petroleum jelly acting as the physical blocker was developed for army men but with many disagreeable aspects when applied (by the way with a basic SPF of 2). After World War II, some pioneering products were brought to the market (the first Piz Buin product appeared in 1946) with a progressive development of new UV filter substances. In a 40-year period, a number of different chemicals were introduced for sunscreen purposes: tannic acid (1925), benzyl salicylate (1931), paraaminobenzoic acid derivatives and 2-phenyl imidazole derivatives (1942), anthranilic acid (1950), various cinnamates (1954), chloroquine (1962), benzophenones (1965), and many more since then [2]. As a consequence of the rising market and the new category of products, new regulations came in place during the time in the second half of the last century. Linked to the different regulatory approaches from the various authorities in the world, sunscreen products have been subjected to various degrees of regulatory tightening. UV filters or UV absorbers may be used in many products, such as plastic polymers, textiles, paintings, and other products; all these applications are usually subject to specific rules, and usually, the substances are embedded into materials with a limited dispersion into the environment. In this chapter, we will assume that the main application of these molecules is for personal care products, and thus we will focus on the assumption that almost 100% (let’s say more than 90%) of the total amount of each UV filter on the market is used in personal care products describing the worldwide regulations for these ingredients. Another side that should be considered in discussing UV filters is that they are subject to the general regulations of chemicals and many of the environmental aspects are treated in this area; the chemical regulation (the most complex is REACH in Europe that has been regarded as a model in many areas) is quite huge and won’t be the subject of this chapter. At first, we should clarify what is a sunscreen for this discussion. The term sunscreen is usually referred to as both the ingredients and the final preparations used to protect the skin; UV filter, UV absorber, or sun filter are more referred to as a single ingredient. In order to have a starting point, let’s consider the following:

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General definition: Sunscreen – a substance that helps protect the skin from the sun’s harmful rays. Sunscreens reflect, absorb, and scatter both ultraviolet A and B radiation to provide protection against both types of radiation [3]. Regulatory definition: The definition adopted for regulatory purposes may be different according to the specific country; as main terms of reference regulations, basically let’s consider the USA and Europe. In the USA as defined in the Sunscreen Innovation Act (SIA) [4], the term “sunscreen active ingredient” refers to an active ingredient that is intended for application to the skin of humans for purposes of absorbing, reflecting, or scattering ultraviolet radiation. In Europe the adopted definition is [5] “UV-filters” means substances which are exclusively or mainly intended to protect the skin against certain UV radiation by absorbing, reflecting, or scattering UV radiation. This definition is quite similar and this is valid also in the rest of the world. UV filters are usually broadly classified according to their way of action into physical sunscreens (i.e., those that reflect the sunlight/inorganic particles) or chemical sunscreens (i.e., those that absorb the UV light/organic molecules). Allowed sunscreens are subject to the limitation in their use, specific warnings alongside toxicity, and environmental concerns. In order to override these limits, there is constant research for new molecules able to enhance or boost the protection of allowed sunscreens or with intrinsic protection capability. The only two regulatory approved inorganic particulates used are zinc oxide and titanium dioxide. Both are regarded as broad-spectrum since they absorb, scatter, and reflect UVB and UVA rays. Research is made for new forms [6] of the Zn and Ti derivatives: nano, combined with cerium, hydroxyapatite, glass, and silicone spheres are cited; actually, these ingredients are regulated only as cosmetic ingredients, but not specifically as sunscreen agents. As previously noted, organic UV filters have a long history of development, and new molecules are still under search; according to the natural and sustainable trends, many extracts are investigated, and also new organic molecules are promising. Due to the regulatory burdens and the long and costly process for the approval of a new ingredient, many of them are marketed as SPF booster or incorporated in the new formula side by side to sunscreens as simple cosmetic ingredients. Among cosmetics, the category of sunscreen products is surely a fascinating one for a cosmetologist (you know that guy who has knowledge of chemistry, toxicology, dermatology, rheology, marketing, regulatory, etc.). It is a product with a lot of technical and toxicological issues related to the need to have in the same formula opposite needs and contrasting ingredients. A good spreadability is in contrast with the water resistance, the right level of filters is in contrast with the quality of texture and solvents needed or its stability, and so on. Once imagined how to solve some of these points, the brief for developing a new product is complicated by marketing and regulatory issues. Many useful and practical (and let’s say safe) ingredients cannot be used due to a bad reputation they gained in blogs and forums or simply because of the marketing scare so that we are forced to avoid parabens, alumina, and nano-ingredients (the list is wide and the

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Table 1 Common ingredients of a sunscreen and its functions Ingredients Water Silicone, powders Hollow sphere, VP and MA derivatives, acrylic, silicone, polyurethane polymers Waxes, polymeric thickeners O/W anionic – non-ionic W/O emulsifiers Polar emollients/alcohol UV filter system

% 60– 80 2 2 0.3– 3 5 15 10– 20

Function Solvent, the base of the formula Aesthetics improvement, spreadability, texture UV performance boosters, filmforming water resistance activity To adjust viscosity for specific textures (sprays, creams, sticks) Emulsifiers for the structure of formulation Solubilization of UV filters/sensorial Combination of the UV filter activity

citations are only given as an example; every ingredient you can search on Google may have some issues; simply as example of this, check the website www.ewg.org). Before focusing on the regulatory, let’s summarize what you can generally find inside a sunscreen product (Table 1). The list is non-exhaustive; according to the specific form, other ingredients may be added. Functional ingredients may be part of the formula for specific functions (antiaging, hydrating, coloring, functional or marketing added value); the average percentage in these cases is no more than 2%. It should be noted that actually, due to the high request of antiaging products, it is quite common to have UV filters added to everyday creams (up to SPF 15/20) in order to achieve protection for the photoaging. A standard reference to understand typical formulas can be found in the European system of centralized notification for cosmetics (cosmetic products notification portal, CPNP) [7]. The notification can be made also according to standard formulas or “frame formula” that can be found publicly [8]. It is clear that looking at the environmental impact, sunscreen products are the source of many ingredients; it is also clear that the UV percentage is quite high, amounting up to 25% of the total products. Thus, the interest for them and their fate in the environment is mainly in rivers, lakes, and sea waters. With this point, it is also clear that limits to and allowed usage are one key element to better understand how these substances may interact or affect the environment. From the regulatory perspective, we can identify, due to historical, cultural, and political reasons, some major geographic areas to keep into consideration [9] (Table 2). In this context, the European approach (and this is easily understood due to the dimension of the market) is having the way for many other areas that have adopted the same concept and set of rules. It’s not easy to make a comparison among every single regulatory framework, because cosmetic products are defined in different ways. Moreover, in the case of sunscreen products, these are classified as “over-the-counter” (OTC) products in the

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Table 2 For our discussion we can identify Europe

Europe

European Union

European Economic Area – EAA Switzerland European Union candidate countries or potential

USA Canada Japan Australia New Zealand South Korea China Hong Kong Macao South Africa

USA Canada Japan Australia New Zealand South Korea China Hong Kong Macao

India Kuwait Mexico Israel Turkey Brazil Taiwan Egypt MERCOSUR

India Kuwait Mexico Israel Turkey Brazil Taiwan Egypt Mercado Común del Sur

ASEAN

Association of Southeast Asian Nation

EAEU

Eurasian Economic Union

Comunidad Andina Caribbean Community

South Africa

Austria, Belgium, Bulgaria, Croatia, Republic of Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, UKa Norway, Iceland Switzerland Albania, The former Yugoslav Republic of Macedonia, Montenegro, Serbia, Turkey Bosnia and Herzegovina, Kosovoa USA Canada Japan Australia New Zealand South Korea People’s Republic of China Hong Kong Macao South Africa Botswana, Lesotho, Namibia, South Africa, Swaziland India Kuwait Mexico Israel Turkey Brazil (MERCOSUR) Taiwan Egypt Argentina, Brazil, Paraguay, Uruguay, Venezuela, Bolivia, Guyana, Suriname Brunei Darussalam, Cambodia, Indonesia, Laos, Malaysia, Myanmar, Philippines, Singapore, Thailand, Vietnam + (Papua New Guinea) Armenia, Belarus, Kazakhstan, Kyrgyzstan, Russia + Tajikistan Bolivia, Colombia, Ecuador, Perù + (Cile) Antigua+Barbuda, Bahamas, Barbados, Belize, Cuba, Dominica, Dominican Republic, Grenada, Guyana, Haiti, Jamaica, Suriname, Saint Lucia, St. Christopher and Nevis, St. Vincent and the Grenadines, Suriname, Trinidad+Tobago (continued)

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Table 2 (continued) East African Community SICA

WAEMU ECOWAS

AMU GCC

Burundi, Kenya, Rwanda, Tanzania, Uganda. Central American Integration System West African Economic and Monetary Union Economic Community of West African States

Arab Maghreb Union Gulf Cooperation Council

Costa Rica, El Salvador, Guatemala, Honduras, Nicaragua, Panamá, Belize, The Dominican Republic Benin, Burkina Faso, Ivory Coast, Guinea Bissau, Mali, Niger, Senegal, Togo Benin, Burkina Faso, Cabo Verde, Côte d’Ivoire, The Gambia, Ghana, Guinea, Guinea Bissau, Liberia, Mali, Niger, Nigeria, Senegal, Sierra Leone, Togo Algeria, Libya, Mauritania, Morocco, Tunisia Bahrain, Kuwait, Oman, Qatar, Saudi Arabia, United Arab Emirates.

Notice: At time when this text is written, the UK is part of the European Union; due to the BREXIT vote, the UK will leave the European Union at the end of the transition period – changes in the regulation after this date cannot be evaluated due to the uncertainty of political situation; it can be imagined that in the initial period, rules will still be the same, while changes may happen during years a UK will leave the European Union at the end of the transition period (31 December 2020)

USA (this means they are regarded as drug and not as cosmetics) or under specific provisions like in Australia or in a different way in Canada. The classification of the final product is not the only critical point and the main obstacle to developing a worldwide formula since each authority has developed specific lists of allowed UV filters, while different systems to calculate, test, and label the SPF factor are enforced. It is quite a large job to go into detail for each of the above-listed regulatory areas; we will provide a track for the main markets and a frame useful to understand how these ingredients are regulated and managed in order to understand their origin and fate. We will detail the regulation of consumer products based on UV filters; it has to be underlined that the wider regulation on chemicals is overlapping some of these rules, mainly in the industrial use, worker protection, and environmental fate.

1 The European Union, Switzerland, Norway, and Iceland We can start with the European Union. The current EU Regulation [10] CE/1223/09 has taken the place of the previous system based on Directive 76/768 providing to all Member States a uniform text and the same legal framework based on the negative and positive lists of ingredients. The same framework is also applied in New Zealand, some of the Middle East/Arabic countries, Turkey, and ASEAN countries; in these areas the EU regulation is accepted and applied as it is or with

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minor changes. The main point, in this case, is to check whether the local legislative status of some of the ingredients is updated following the EU decisions. Accordingly to the definition given by the regulation, “cosmetic product” means any substance or mixture which is intended to be placed in contact with the external parts of the human body (the epidermis, hair system, nails, lips, and external genital organs) or with the teeth and the mucous membranes of the oral cavity with a view exclusively or mainly to cleaning them, perfuming them, changing their appearance, protecting them, keeping them in good condition, or correcting body odors. Among these functions, the protection of the skin from the damages due to sun exposure is referred to as a cosmetic action. Therefore, in Europe sunscreen products are considered as cosmetics. In Europe, the system is constantly updated as the technical progress evolves, based on the Scientific Committee on Consumer Safety (SCCS) opinions relating to the safety of ingredients. The committee provides opinions on health and safety risks (chemical, biological, mechanical, and other kinds of physical risks) of non-food consumer products (e.g., cosmetic products and their ingredients, toys, textiles, clothing, personal care, household products, etc.) and services (e.g., tattooing, artificial sun tanning, etc.). The outcome of these opinions usually leads to an update of the annexes of the regulation; the annexes to be considered for formulating a sunscreen product are: I. Cosmetic product safety report II. List of substances prohibited in cosmetic products III. List of substances which cosmetic products must not contain except subject to the restrictions laid down IV. List of colorants allowed in cosmetic products V. List of preservatives allowed in cosmetic products VI. List of UV filters allowed in cosmetic products The actual list has 30 filters listed along with specific limits of concentration and with some specific warnings for the labeling of the products. Note that titanium dioxide and zinc oxide in the nano-form are listed as a specific entry. The testing guidelines and labeling for this category of products are also included in the Commission Recommendation of September 22, 2006, on the efficacy of sunscreen products and the claims made relating thereto. This recommendation sets some specific guidelines referred to the UVA/UVB ratio of protection, specific labeling warnings, and the labeled category of protection starting from low protection (SPF 6) to very high protection (SPF 50+). European sunscreens should be formulated according to these basic points: minimum efficacy, lowest allowed claim SPF 6, 1/3 of the protection is for UVA (ratio UVA/UVB); critical wavelength for testing is at least 370 nm; precautions and usage instructions, suggestions for protection, four protection categories (low, medium, high, very high); and testing accordingly SPF + UVA (in vitro preferred for ethical reasons).

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2 The USA The sunscreen products are classified in the USA as “over-the-counter” (OTC) drugs, and the main reference documents are the final rule published in 2011 and the Sunscreen Innovation Act published in 2014 [11]. The classification as OTC means that all the limits due to the approval process and strict definition of labeling have their effect in this category of products. The Sunscreen Innovation Act has been approved with the declared purpose to make available to the US market some of the new filters already in use in the EU and in other countries. The Act has also been developed to support the “time and extent application system” (TEA) that allows actives that have been marketed “to a material extent and for a material time” in a foreign market, obviously when supporting safety data, to be added to an OTC (therefore to sunscreens) drug monograph. The decision made in 1970 by the FDA to fix sunscreen products in the OTC category is blocking some of the new sunscreens available in Europe. It has been a long time since the FDA approved a new sunscreen claiming the lack of data on safety and (also) not having enough funds. The Sunscreen Innovation Act didn’t change the situation too much, and the perspective to see miloxate, bemotrizinol, bisoctrizole, drometrizole trisiloxane, ecamsule, enzacamene, iscotrizinol, and octyl triazone approved in the US market is still far away. The complex work of a formulator of sunscreens is surely not easy because some of the allowed filters are any more useful for the actual textures due to their technical characteristics. Many of the aspects that are treated in the final rule are labeling concerns. A punctual definition of the wording is provided, where and how to write some relevant information like for the water resistance or like in the case of the sunscreens with a broad-spectrum SPF >15 which can display on the label the claim “if used as directed with other sun protection measures, (sunscreens) decrease the risk of skin cancer and early skin aging caused by the sun.” One part of the system for sunscreen is represented by the monograph, which essentially provides a standard for active ingredients. If a monograph has been issued for a product, all that a company must do to be allowed on the market is to demonstrate that it has met the standards of that monograph. This method allows to get new formulas on the market and represents a different point than the one related to the new ingredients. Twenty-four ingredients are regulated by the FDA under its various final monographs. A new monograph is on the way, but we’ll have to wait until 2019–2020 looking forward to solving some of the open questions relating to sprays and other forms (powders, wipes), ingredients, high SPF values, etc. At the beginning of 2019, the FDA published the proposed rule “Sunscreen Drug Products for Over-the-Counter Human Use,” which describes the conditions under which over-the-counter (OTC) sunscreen monograph products are generally

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recognized as safe and effective (GRASE) and not misbranded. This proposal seeks additional information on sunscreen ingredients so that FDA can evaluate their GRASE status considering the actual sunscreen usage and exposure and added information about the potential toxicological risks associated with these ingredients. The proposal should be a final monograph on sunscreens, which would substantially amend or substitute the 1999 final rule on sunscreens. The document published states that there is still not enough evidence to determine the GRASE status of most of the ingredients listed in the 1999 final sunscreen rule and should be noted that the active ingredients that have been submitted under FDA’s time and extent application regulations are not discussed. The FDA proposes that two sunscreen ingredients are GRASE (Category I, zinc oxide and titanium dioxide), and two are not GRASE (Category II, paraaminobenzoic acid (PABA) and trolamine salicylate) and cannot be used anymore in sunscreen products. It can be noted that the Category II filters are not actually used in the market of the USA. The proposal refers also other points: • Proposed maximum SPF and broad-spectrum requirements. The maximum value could be 60+ or even 80, and the FDA proposes that all sunscreen products with SPF values of 15 and above satisfy broad-spectrum requirements and meet UVAI/UV ratio of 0.7 (basically the same as the EU guidelines). • Proposed PDP (principal display panel) labeling requirements with a list of the sun filters. • Proposed requirements related to final formulation testing process and recordkeeping. • Proposed status of sunscreen – insect repellent combination products. These products will be no more allowed as Category II. • Proposed actions to effectuate lifting of stay and harmonize impacted regulations. • Proposed requirements related to dosage forms. After the previous Advanced Notice of Proposed Rulemaking (2011) identifying sunscreen dosage forms, this new proposal identifies the following dosage forms as Category I: oils, lotions, creams, gels, butter, pastes, ointments, sticks, and sprays (for these additional testing required). Category III will be populated by “powders” and sunscreens in all other dosage forms, including “wipes, towelettes, body wash, and shampoos,” due to the lack of data showing that they were marketed prior to 1972, as required for inclusion in the monograph. The main open point is about the remaining 12 ingredients (from 1999 rule), listed as Category III. For these ingredients, the FDA is seeking more information. It appears that there is a lack of data about their absorption or concerns about the effect of absorption. The 12 ingredients are cinoxate, dioxybenzone, esulizone, homosalate, meradimate, octinoxate, octisalate, octocrylene, padimate O, sulisobenzone, oxybenzone, and avobenzone. These ingredients are currently marketed in sunscreen products in the USA. It is not clear the fate at the end of the observation period for these ingredients if the data gap is still there. The data gaps that the FDA has identified for these products are

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Table 3 Sunscreen ingredients regulated by OTC monograph (21 CFR 352.10) (6) Ingredient Aminobenzoic acid (PABA) Avobenzone Cinoxate Dioxybenzone Homosalate Menthyl anthranilate Octocrylene Octyl methoxycinnamate Octyl salicylate Oxybenzone Padimate O Phenylbenzimidazole sulfonic acid Sulisobenzone Titanium dioxide Trolamine salicylate Zinc oxide Ensulizole Meradimate Octinoxate Octisalate

% Up to 15% Up to 3% Up to 3% Up to 3% Up to 15% Up to 5% Up to 10% Up to 7.5% Up to 5% Up to 6% Up to 8% Up to 4% Up to 10% Up to 25% Up to 12% Up to 25% Up to 4% Up to 5% Up to 7.5% Up to 5%

Proposed rule category II III III III III III

III III III I II I III III III III

significant and are not likely to be resolved before the FDA finalizes this rule as required by the statutory deadline. When the FDA publishes the final sunscreen rule, the agency will have two choices for each of these Category III ingredients: FDA can either (1) determine that the ingredients are not GRASE, which will require an NDA for continued marketing, or (2) defer rulemaking for these ingredients to allow the necessary research to be conducted, submitted, and evaluated. As this situation is evolving, we won’t go into further detail as it appears, according to many comments, that the FDA’s goal to finalizing the sunscreen monograph by November 26, 2019, is totally unrealistic. It’s quite difficult that there will be a single company that will supply the necessary safety data required by the FDA to reclassify a Category III UV filter as GRASE without the protection of a patent. Perhaps avobenzone from this list of 12 may be the only such ingredient. This situation may evolve in favor of the pending TEA ingredients, or new filters resulting from the easing of the approval pathway; this hope of formulators won’t be for the near future (Table 3). In some cases in single States of the Union, e.g., in California, an additional burden is provided by specific state rules like the Proposition 65 of the State of California of January 1, 2015, requiring to print the following warning on labels of products containing the cancer-causing chemical, benzophenone: “WARNING: This product contains benzophenone, a chemical known to the State of California to cause cancer.”

Sunscreen Regulation in the World

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Mixed in this situation, there is the (growing in popularity) ordinances from Hawaii; the island of Palau; Key West, FL; and others banning oxybenzone and octinoxate from use in sunscreen products, mostly for environmental concerns. These environmental bans are very local and sometimes not exactly clear as they allow, for instance, “prescribed” products anyway. The typical label for a sunscreen product has a layout that is detailed defined in the drug fact labeling.

3 Canada Health Canada has issued a regulatory framework for cosmetics which represents a bridge between EU and US positions. Cosmetics are regulated under a framework with resembling European one (e.g., with a hotlist of ingredients), while sunscreens are classified in different ways accordingly the single ingredient and may fall either under the natural health products or the drug product regulations. A monograph (last revision issued on 23/06/2015) entitled “sunscreen monograph” collects all the points referred to in this class of products. For the marketing of a product, a Product License Application must be filed. We can check two lists: the one in Table 4 is for the natural health products and Table 5 for those classified as medicinal agents. The Canada monograph includes sprays and powders. It refers to all products including those referred to as secondary sunscreens. Actually, specific provisions are defined for labeling broad-spectrum, UVA protection, and some claims not permitted or allowed only clear supporting data.

4 ASEAN As previously stated, the cosmetic directive for ASEAN countries (Brunei, Cambodia, Indonesia, Laos, Malaysia, Myanmar, the Philippines, Singapore, Thailand, Vietnam) is quite the same as the EU regulatory framework. The list of approved ingredients can be found in the annexes of the directive, and it is the same as the EU regulation. Points of difference may arise due to a delay in adopting the EU approach and decisions and a specific provision of warning, i.e., “Do not stay too long in the sun, even while using a sunscreen product” that must be put onto products sold as primary sunscreens. The ASEAN scientific committee acts like the SCCS; the adoption of the directive is not homogeneous over the member countries. A point to be highlighted is that no claim should be made that implies that a “100% protection against UV A & B” is granted and that “reapplication of the product is unnecessary,” e.g., whole-day protection. Other recommended warnings are specific to this area.

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G. Pirotta

Table 4 NHP medicinal ingredients, source ingredients, and concentrations

Ingredient Titanium dioxide Zinc oxide 4-Aminobenzoic acid

UV protection UVA UVB UVA UVB UVB

Concentration