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Innovative technologies have been designed to improve efficacy and safety of chemical UV filters. Encapsulation can enhance efficacy and reduce transdermal permeation and systemic exposure. The aims of this work were (i) to determine the cutaneous biodistribution of avobenzone (AVO), oxybenzone (OXY), and octyl methoxycinnamate (OMC) incorporated in mesoporous silica SBA-15 and (ii) to perform preclinical (in vitro) and (iii) clinical safety studies to demonstrate their innocuity and to evaluate sun protection factor (SPF) in humans. Skin penetration studies showed that deposition of OXY and AVO in porcine and human skin after application of stick formulation with incorporated filters (stick incorporated filters) was significantly lower than from a marketed (non-encapsulated) stick. Cutaneous deposition and transdermal permeation of OXY in and across human skin were 3.8-and 13.4- fold lower, respectively, after application of stick entrapped filters. Biodistribution results showed that encapsulation in SBA-15 decreased AVO and OXY penetration reaching porcine and human dermis. Greater deposition (and permeation) of OXY in porcine skin than in human skin, pointed to the role of follicular transport. Stick incorporated filters had good biocompatibility in vivo and safety profiles, even under sun-exposed conditions. Entrapment of UV filters improved the SPF by 26% and produced the same SPF profile as a marketed stick. Overall, the results showed that SBA-15 enabled safety and efficacy of UV filters to be increased.

BACKGROUND Fugacity, the driving force for transdermal uptake of chemicals, can be difficult to predict based only on the composition of complex, non-ideal mixtures such as personal care products. OBJECTIVE Compare the predicted transdermal uptake of benzophenone-3 (BP-3) from sunscreen lotions, based on direct measurements of BP-3 fugacity in those products, to results of human subject experiments. METHODS We measured fugacity relative to pure BP-3, for commercial sunscreens and laboratory mixtures, using a previously developed/solid-phase microextraction (SPME) method. The measured fugacity was combined with a transdermal uptake model to simulate urinary excretion rates of BP-3 resulting from sunscreen use. The model simulations were based on the reported conditions of four previously published human subject studies, accounting for area applied, time applied, showering and other factors. RESULTS The fugacities of commercial lotions containing 3-6% w/w BP-3 were ~20% of the supercooled liquid vapor pressure. Simulated dermal uptake, based on these fugacities, are within a factor of 3 of the mean results reported from two human-subject studies. However, the model significantly underpredicts total excreted mass from two other human-subject studies. This discrepancy may be due to limitations in model inputs, such as fugacity of BP-3 in lotions used in those studies. SIGNIFICANCE The results suggest that combining measured fugacity with such a model may provide order-of-magnitude accurate predictions of transdermal uptake of BP-3 from daily application of sunscreen products.

Organic ultraviolet (UV) filters are used in cosmetic and personal care products (CPCPs) and over‐the‐counter (OTC) sunscreens, due to their ability to absorb solar radiation. When OTC and CPCP ingredients are washed down the drain, they can then enter freshwaters that receive wastewater treatment plant effluents. This paper presents a freshwater environmental safety assessment of a key UV filter, oxybenzone, used in OTC sunscreens and CPCPs in the United States. Exposure was characterized using iSTREEM®, a spatially resolved aquatic exposure model developed for chemicals disposed of down the drain. iSTREEM® provides a comprehensive exposure assessment of oxybenzone concentrations in United States receiving waters through predicted environmental concentration (PEC) distributions representative of conditions across the region. A review of available hazard data was used to derive a predicted no‐effect concentration (PNEC) using aquatic toxicity data and assessment factors. A safety assessment was conducted by comparing the PEC distribution with the PNEC. The results indicate that oxybenzone is of low concern and there is a significant margin of safety as the 90th percentile PEC is two orders of magnitude below the PNEC. These results are instrumental in demonstrating the environmental safety of key organic UV filters in the U.S. freshwater environment and will help prioritize future work. Integr Environ Assess Manag 2021;17:951–960. © 2021 Personal Care Products Council. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC), KEY POINTS A freshwater environmental risk assessment for oxybenzone was conducted that considered available aquatic toxicity data and down‐the‐drain emissions of sunscreen, cosmetic, and personal care products.A nationwide distribution of predicted environmental concentrations was modeled, using the spatially explicit iSTREEM® exposure model, and the median and 90th percentile oxybenzone concentrations were predicted to be 0.01 and 0.15 µg/L, respectively.The 90th percentile exposure prediction (reasonable worst case) is two orders of magnitude below the predicted no‐effect concentration value of 18 µg/L, indicating that risk is negligible.This paper provides a down‐the‐drain freshwater environmental risk assessment framework suitable for over‐the‐counter drugs, cosmetic, and personal care ingredients.

Coupling of membrane distillation with bioreactors containing enzymes such as ‘laccase’ forms an enzymatic membrane bioreactor resulting in complete retention of both trace organic contaminants and enzyme, facilitating simultaneous trace organic contaminants degradation. Integration of enzymatic membrane bioreactor and ultraviolet photolysis may result in further improved degradation of trace organic contaminants in membrane-concentrate. We studied the degradation as well as by-products formation of five selected trace organic contaminants, namely, sulfamethoxazole, diclofenac, bisphenol A, oxybenzone, and carbamazepine by ‘membrane distillation — ultraviolet photolysis’ system and ‘enzymatic membrane bioreactor — ultraviolet photolysis’ system. In the former, the membrane effectively retained the trace organic contaminants and then ultraviolet photolysis of membrane-concentrate resulted in trace organic contaminant degradation in the following order: diclofenac (88 %) > sulfamethoxazole (71 %) > oxybenzone (35 %) > bisphenol A (33 %) > carbamazepine (27 %). By contrast, the enzymatic membrane bioreactor — ultraviolet photolysis system resulted in 100 % degradation of diclofenac, sulfamethoxazole, and bisphenol A and around 70 % degradation of oxybenzone and carbamazepine. This system also resulted in more than 50 % reduction in number of degradation products with 60–70 % lower abundance. Our results indicate that laccase degradation led to products that were more amenable to the post-treatment by ultraviolet photolysis. Overall, it can be concluded that for enzymatic membrane bioreactor — ultraviolet photolysis system, enzymatic pre-treatment not only helped in better degradation of the parent trace organic contaminants but also led to the formation of fewer by-products with lower abundance (i.e., more complete degradation).

The condition of coral reefs in several locations in Indonesia is indeed in critical condition and the impact of damage continues to grow every year. Sunscreen, which is one of the mandatory requirements used for skin protection to prevent sunburn, has dangerous substances oxybenzone and octinoxate, causing unconscious damage. Substances in sunscreens make coral reefs lose their adaptability to climate change which also damages coral reefs and prevents the growth of coral reefs. This topic is important because coral reefs have many ecological, social and economic influences and benefits that are very useful for life. Therefore, it is necessary to design a campaign that is made with the aim that this topic can increase awareness of campaign targets and readers with information that can be accounted for so that the risks of damage to coral reefs can be reduced. This design is carried out through the process of collecting data, formulating strategies, thinking ideas, designing visuals, and applying them to campaigns.

Benzophenones are UV-blockers found in most common sunscreens. The ability of Scyphozoan planula larvae of Cassiopea xamachana and C. frondosa to swim and complete metamorphosis in concentrations 0–228 µg/L benzophenone-3 (oxybenzone) was tested. Planulae of both species swam in erratic patterns, 25–30% slower, and experienced significant death (p < 0.05) in the highest concentrations of oxybenzone tested, whereas the larvae exhibited normal swimming patterns and no death in ≤2.28 µg/L oxybenzone. In addition, metamorphosis decreased 10–30% over 3 days for both species maintained in 228 µg/L oxybenzone. These effects do not involve symbiotic dinoflagellates, as planulae larvae of Cassiopea sp. are aposymbiotic. It is concluded that oxybenzone can have a detrimental impact on these jellyfish.

Oxybenzone (OBZ), a popular additive in sunscreen, can protect human skin by blocking ultraviolet (UV) rays from the sun (Baker et al. 2015). In addition to being used in sunscreens, OBZ is also widely used in perfumes, shampoos, lip balms, and other pharmaceuticals and personal care products (PPCPs) (Aguirre et al. 1992, Emonet et al. 2001, Kasichayanula et al. 2007). OBZ can enter rivers, lakes, groundwater, sewage, and so on through human activities and was identified as an 'emerging environmental pollutant' by the Environmental Protection Agency of the USA (Rodil et al. 2012, Aguera et al. 2013). With the rise in coastal tourism, a large number of coral reefs in coastal areas are being exposed to water containing OBZ (Baron et al. 2013, Tashiro and Kameda 2013). OBZ, as a pseudo-persistent pollutant, has a long-term toxic effect on the environment (Vione et al. 2013).

A sensitive method was developed and validated for the determination of UV filters (oxybenzone, octocrylene, 4-methyl-benzylidene camphor, 2-ethylhexyl-4-methoxycinnamate and avobenzone) in tilapia muscle using matrix solid-phase dispersion followed by on-line solid-phase extraction–liquid chromatography/UV. The validation showed good linearity from 100 to 3600 ng g−1 with r2 values > 0.98. Precision values with relative standard deviations were

To provide an up-to-date synopsis of the literature on the safety of sunscreen active ingredients in humans and the environment and highlight regulatory changes in the USA. Currently, as per the US Food and Drug Administration, the only ultraviolet filters generally recognized as safe and effective are inorganic zinc oxide (ZnO) and titanium dioxide (TiO2). In vivo human systemic absorption studies found that common organic filters attain sufficient plasma concentrations to require carcinogenicity and reproductive studies. In vivo human skin penetration studies showed ZnO nanoparticles (ZnO-NP) did not penetrate the stratum corneum. Limited quantities of TiO2-NP may be absorbed systemically. In laboratory settings, corals exposed to oxybenzone manifested concentration-dependent toxicity and bleaching. In response, bills passed in Hawaii and elsewhere ban sales of oxybenzone-containing sunscreens. ZnO-NP, but not TiO2-NP, caused coral bleaching under controlled conditions. The collective knowledge on sunscreen safety is continually evolving, with many preliminary findings. Studies on the effects of systemic absorption of organic filters in humans are forthcoming; importantly, there has been no evidence of harm over decades of use. Organic (less so inorganic) filters caused coral bleaching in controlled environments, but filter concentrations may not have been realistic, and bleaching is predominantly driven by other factors. No present evidence suggests any marketed sunscreens should be avoided. For consumers with concerns, inorganic ZnO and TiO2 are supported by the most reassuring data at the time of writing.

Laccase-catalysed degradation is a promising technology for the degradation of trace organic contaminants (TrOCs). However, depending on their physicochemical properties (e.g., chemical structures), non-phenolic TrOCs appear to be resistant to laccase-catalysed degradation, thus requiring an additional treatment process. In this study, the performance of an integrated laccase and persulfate (PS) mediated oxidation process was explored and elucidated for the first time. Compared to that achieved during treatment with laccase alone, the addition of PS at 1–10 mM concentration into batch enzymatic bioreactors showed concentration-dependent improvement in the degradation of the five TrOCs selected, namely diclofenac, sulfamethoxazole, carbamazepine, bisphenol A and oxybenzone. The results obtained from a series of batch tests also confirmed that the structural components (e.g., carbohydrate moieties in the enzyme) as well as the possibility of PS acting as a final acceptor of electrons from the type II and type III active sites of laccase may have led to PS activation. A continuous treatment system was developed by integrating a nanofiltration (NF) membrane with the laccase/PS process (NF-MBRlaccase/PS), which achieved TrOC-specific degradation. Importantly, the degradation of non-phenolic TrOCs (diclofenac, sulfamethoxazole and carbamazepine) further improved by 10 to 65% in the NF-MBRlaccase/PS system. This improvement could be attributed to: (i) the prolonged contact time between laccase/PS and TrOCs, which was possible due to their complete retention by the NF membrane; and (ii) retention of oxidative cross coupling agents or secondary radicals enhancing TrOC degradation. The NF membrane not only retained the moderately degraded carbamazepine and sulfamethoxazole effectively but also effectively removed toxic transformation products and residual estrogenicity of the final effluent as evaluated by cytotoxicity and estrogenicity assays, respectively. These observations indicate the significance of the high retention membrane in the NF-MBRlaccase/PS system for producing high quality permeate suitable for disposal and potentially for water reuse applications.

Photoprotection, including the use of sunscreen, has been shown to decrease the development of keratinocyte cancers and melanoma. Due to concerns about the environmental effects of some organic UVR filters, several locations across the world have begun to pass legislation banning the use of these ingredients in sunscreens. Furthermore, the health effects of several organic UVR filters have also been called into question and a recent proposal by the US FDA has resulted in public confusion about the safety of sunscreens. The aim of this article is to discuss FDA regulation of sunscreens and to review the environmental and health effects of oxybenzone and octinoxate. Ultimately, as dermatologists, our recommendations are to continue to encourage people to practice proper photoprotection including photoprotective clothing, staying in the shade while outdoors, and applying sunscreen to exposed areas. For those concerned about the potential environmental and health effects of organic UVR filters, inorganic/mineral UVR filter (namely, zinc oxide and titanium dioxide)-based sunscreens can be used.

Experimental studies have suggested benzophenone-3 (BP-3), a sunscreen ingredient, may have endocrine-disrupting properties. A cohort of girls were recruited at ages 6–7 years and returned semi-annually for pubertal maturation staging, provided blood for serum hormone analyses [estradiol, estrone, testosterone, dehydroepiandrosterone-sulfate (DHEA-S)], and urine to measure BP-3 concentrations. We found a significant negative linear association between amount of reported sunscreen use and testosterone levels at the onset of puberty (N = 157, adjusted β = −0.0163, 97.5% CI:-0.0300,-0.0026). The 2nd quartile of the BP-3 biomarker had earlier thelarche compared to the 1st quartile (N = 282, adjusted HR = 1.584, 97.5% CI:1.038,2.415). Results suggest that higher report of sunscreen use may be associated with lower testosterone levels at thelarche and a non-linear relationship between the BP-3 urinary biomarker and onset of puberty, although the clinical significance of the finding is limited and may be a random effect. Improved methods of BP-3 exposure characterization are needed.

Sunscreen and sunblock are crucial skincare products to prevent photoaging and photocarcinogenesis through the addition of chemical filters to absorb or block ultraviolet (UV) radiation. However, several sunscreen and sunblock ingredients, mostly UV filters, have been associated with human and environmental safety concerns. Therefore, the exploration and discovery of promising novel sources of efficient and safer compounds with photoprotection-related activities are currently required. Marine invertebrates, particularly their associated microbiota, are promising providers of specialized metabolites with valuable biotechnological applications. Nevertheless, despite Actinobacteria members being a well-known source of bioactive metabolites, their photoprotective potential has been poorly explored so far. Hence, a set of methanolic extracts obtained from Cliona varians-derived actinomycetes was screened regarding their antioxidant and UV-absorbing capacities (i.e., photoprotection-related activities). The active extract-producing strains were identified and classified within genera Streptomyces, Micrococcus, Gordonia, and Promicromonospora. This is the first report of the isolation of these microorganisms from C. varians (an ecologically important Caribbean coral reef-boring sponge). The in vitro cytotoxicity on dermal fibroblasts of oxybenzone and the selected active extracts revealed that oxybenzone exerted a cytotoxic effect, whereas no cytotoxic effect of test extracts was observed. Accordingly, the most active (SPFi > 5, radical scavenging > 50%) and nontoxic (cell viability > 75%) extracts were obtained from Streptomyces strains. Finally, LC-MS-based characterization suggested a broad chemical space within the test strains and agreed with the reported streptomycetes’ chemodiversity. The respective metabolite profiling exposed a strain-specific metabolite occurrence, leading to the recognition of potential hits. These findings suggest that marine Streptomyces produce photoprotectants ought to be further explored in skincare applications.

There is a rise in concern across the globe over the contaminants of emerging concerns (CECs) such as pharmaceuticals, personal care products (PCPs), UV stabilizers, surfactants, endocrine disrupting compounds (EDCs), etc. In the present study, we have identified some compounds belonging to the classes of pharmaceuticals, PCPs, and EDCs in the water samples collected from the coastal area of Ernakulam district of Kerala (India) (sea and lake). The analysis was carried out using ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-ToF–MS) after enrichment by solid-phase extraction. The nine CECs were identified in both positive and negative electrospray ionization mode (ESI). In both the matrices (sea and lake water), the highest concentration levels were noted for benzophenone (26.5–33.2 µg/l) and dibutyl phthalate (12.65–35.21 µg/l), whereas butyl and propyl parabens occurred at low concentration levels. The normality (Kolmogorov–Smirnov and Shapiro–Wilk) tests indicated that the concentration levels of contaminants among lake water samples were non-normally distributed. Whereas in seawater samples, the contaminant concentration levels were normally distributed. The analysis of homogeneity of variance and ANOVA test revealed no significant relationship between the contaminants detected from the lake and seawater samples. The risk assessment analysis showed that the organisms in the lake are at more risk compared to that of the sea. The results from the risk quotient (RQ) values obtained for each identified compound showed that the presence of dibutyl phthalate, butylparaben, and oxybenzone pose a medium risk to biological populations than other CECs.

The increased ultraviolet (UV) radiation on the Earth's surface increased the need for UV filters products. One of the most used is oxybenzone, which is indiscriminately released in the environment. Oxybenzone's ecotoxicological effects on physiology have been investigated because of the bioaccumulation and action as an endocrine disruptor. However, little is known about its effects on behavior or cognition. In this study, we approach the effects of short-term oxybenzone exposure on locomotion, anxiety-like, social behavior, and short-term memory in zebrafish (Danio rerio). Adult zebrafish were exposed to oxybenzone 10, 100 and 1000 μg L−1 for 15 days and then tested (novel tank, shoal preference, mirror test, and T-maze with novelty). Fish exposed to oxybenzone showed reduced locomotion, decreased anxiety-like behavior, less time near/interacting with the shoal, fewer interactions with the mirror image, and decreased exploration of the novel arm in the T-maze test. These results suggest that oxybenzone affects perception, increases risk-taking, impairs proper aggressive response, and jeopardizes the animals' ability to retain information. These results reinforce the risk posed by products discarded into the aquatic ecosystems, especially those with underestimated toxic potential.

Hanauma Bay is a 101-acre bay created by the partial collapse of a volcanic cone and once supported a vibrant coral reef system. It is the most popular swimming area in the Hawaiian Islands and has been reported to have averaged between 2.8 and 3.5 million visitors a year between the 1980s and the 2010s, with visitors averaging between 3000-4000 a day and peaking around 10,000-13,000 per day. Concentrations of oxybenzone and other common UV filters were measured in subsurface water samples and in sands from the beach-shower areas in Hanauma Bay. Results demonstrate that beach showers also can be a source of sunscreen environmental contamination. Hydrodynamic modeling indicates that oxybenzone contamination within Hanauma Bay's waters could be retained between 14 and 50 h from a single release event period. Focusing on only oxybenzone, two different Hazard and Risk Assessment analyses were conducted to determine the danger of oxybenzone to Hanauma Bay's coral reef system. Results indicate that oxybenzone contamination poses a significant threat to the wildlife of Hanauma Bay. To recover Hanauma Bay's natural resources to a healthy condition and to satisfactorily conserve its coral reef and sea grass habitats, effective tourism management policies need to be implemented that mitigate the threat of sunscreen pollution., Water and beach sand samples were collected under permit and permission from both the City and County of Honolulu's Department of Parks and Recreation and State of Hawaii's Department of Land and Natural Resources. We thank the BIO2MAR platform (http://bio2mar.obs-banyuls.fr) for providing technical support and access to instrumentation. We thank Wendy Wiltse and her associates for assistance in sample collection. We also greatly appreciate and profusely thank the three anonymous reviewers who improved the quality of this manuscript.

Methylene blue (MB) is a century-old medicine, a laboratory dye, and recently shown as a premier antioxidant that combats ROS-induced cellular aging in human skins. Given MB’s molecular structure and light absorption properties, we hypothesize that MB has the potential to be considered as a sunscreen active for UV radiation protection. In this study, we tested the effects of MB on UVB ray-induced DNA double strand breaks in primary human keratinocytes. We found that MB treatment reduced DNA damages caused by UVB irradiation and subsequent cell death. Next, we compared MB with Oxybenzone, which is the most commonly used chemical active ingredient in sunscreens but recently proven to be hazardous to aquatic ecosystems, in particular to coral reefs. At the same concentrations, MB showed similar broad-spectrum UV light absorption ability as Oxybenzone but significantly outperformed Oxybenzone in the prevention of UVB-induced DNA damage and the clearance of UVA-induced cellular ROS. Furthermore, unlike Oxybenzone, MB-containing seawater did not affect the growth of the coral species Xenia umbellata. Altogether, our study suggests that MB has the potential to be a coral reef-friendly sunscreen active ingredient that can provide broad-spectrum protection against UVA and UVB.

1. 2-Hydroxy-4-methoxybenzophenone (HMB) is a common ingredient in personal care products and used as an UV stabilizer. In these studies, disposition and metabolism of [(14)C]HMB in rats and mice was assessed following single gavage administration (10, 100, or 500 mg/kg), single IV administration (10 mg/kg), or dermal application (0.1, 1, 10, or 15 mg/kg). 2. Following gavage administration, [(14)C]HMB was well absorbed and excreted mainly in urine (39–57%) and feces (24–42%) with no apparent difference between doses, species or sexes. Distribution of HMB in tissues was minimal in rats (0.36%) and mice (

Household dust is a reservoir of various consumer product chemicals. Thus, characterizing comprehensive chemical profiles of house dust may help improve our understanding of residential chemical exposure. We have previously developed a method for detecting a broad spectrum of chemicals in dust by applying a combination of target, suspect screening, and non-target methods with mass spectrometry preceded by liquid chromatography and gas chromatography. Building upon a previous study that detected 271 compounds in 38 dust samples, we presented concentrations of 144 compounds that were confirmed and quantified by standards in the same set of samples. Ten compounds were measured with median concentrations greater than 10000ng/g of dust: cis-hexadec-6-enoic acid, squalene, cholesterol, vitamin E, bis(2-ethylhexyl) phthalate, dioctyl terephthalate, linoleic acid, tricaprylin, tris(1-chloroisopropyl) phosphate, and oxybenzone. We also reviewed in vitro toxicity screening data to identify compounds that were not previously detected in indoor dust but have potential for adverse health effects. Among 119 newly detected compounds, 13 had endocrine-disrupting potential and 7 had neurotoxic potential. Toxicity screening data were not available for eight biocides, which may adversely affect health. Our results strive to provide more comprehensive chemical profiles of house dust and identified information gaps for future health studies.

Two widely used ultraviolet filters, oxybenzone and dioxybenzone, are applied in a variety of areas, particularly in sunscreen cosmetics. Ultrafast femtosecond transient absorption is utilized to trace the excited states and transient states of the nanocrystalline suspension and solution phase of these two molecules. The analysis reveals the intriguing discovery that the transient species of the oxybenzone nanocrystalline suspension have shorter lifetimes than that in solution. The energy dissipation mechanism of these molecules is simulated by density functional theory calculations, and the potential energy surface calculations and the single-crystal structure can well explain the fast decay dynamics of the nanocrystalline transient states of these two molecules.

Ultraviolet (UV) filters such as octocrylene and oxybenzone in topical photoprotection products work effectively in absorbing UV radiation, thus minimizing sun damage to the skin. Antioxidants are incorporated into sunscreen products to enhance the photoprotection ability of the products. However, the effectiveness of the antioxidants on the sun protection factor (SPF) of UV filters is not well established. Hence in this study, the effect of caffeine, nicotinamide, β-carotene, α-tocopherol, and cactus extract on the SPF of octocrylene and oxybenzone were investigated. The UV absorbance of octocrylene (5 µg/mL) and oxybenzone (20 µg/mL) in 95% ethanol, with different concentrations of the antioxidants (0.1–100 µg/mL) and cactus extract were measured from 290-320nm. The UV absorbance values were converted to SPF values by the Mansur equation. Statistical analysis was performed by ANOVA test and Post Hoc test (Dundett T3 test) with a significance level of p

Melanoma, a type of cancer that develops in melanocytes, is usually caused by direct exposure of skin to ultraviolet (UV) radiation resulting in cellular damage. In this study, a procedure to determine the effects of various commercial sunscreens with SPF values ranging from 15 to 100 was developed using pig skin to mimic human skin. These sunscreens contain inorganic filters, such as zinc oxide and titanium dioxide; active organic ingredients, such as octocrylene and oxybenzone; or both. As a model for human skin, pig skin was analyzed before and after UV exposure, and the presence of free radicals was measured using electron paramagnetic resonance (EPR) spectroscopy. Using this method, students were able to quantify radical formation following irradiation and use this as a basis to compare the efficacies of sunscreens against UVA. This experiment allowed undergraduate students to characterize a complex chemical process (light-induced radical formation) and relate it to something they experience every day (sun damage). Interestingly, students found higher levels of postillumination radical formation in sunscreen-treated samples, perhaps indicating sunscreen-induced stabilization of these species. Student outcomes included learning how to collect and interpret EPR data, statistical analysis of these data, and the preparation of reproducible biological samples. Students also consulted literature sources to properly display their measurements.

A skin irritation test using in vitro reconstructed human epidermis (RhE) models was established for hazard identification of irritant chemicals in accordance with UN Globally Harmonized System of Classification and Labelling of Chemicals (GHS) category. In this study, EpiDerm™ was used to assess skin irritation by oxybenzone and N,N-diethyl-m-toluamide (DEET), which are widely used sunscreen and insect repellent components, respectively. EpiDerm™ was applied with oxybenzone and DEET, combined and sequentially with each single dose. Epidermal morphology and differentiation/proliferation were examined microscopically. Oxybenzone and sequential administration groups were determined as nonirritant with cell viability >50% and the morphology was comparable to the human epidermis. Contrastingly, the DEET and coadministration groups exhibited cell viability

The occurrence of UV-filters in the environment has raised concerns over potentially adverse impacts on corals. In this study, the concentrations of 13 UV-filters and 11 hormones were measured in surface seawater, sediment, and coral tissue from 19 sites in Oahu, Hawaii. At least eight UV-filters were detected in seawater, sediment, and coral tissue and total mass concentrations of all UV-filters were octisalate (OS) > benzophenone-3 (BP-3, also known as oxybenzone) > octocrylene (OC); sediment, HMS > OS > OC > BP-3; coral, OS ≈ HMS > OC ≈ BP-3. BP-3 concentrations in surface seawater were

The mutagenicity of four organic UV filters namely oxybenzone (benzophenone-3), dioxybenzone (benzophenone-8), avobenzone, and octyl methoxycinnamate, in chlorinated bromide-rich water (artificial seawater) was investigated. Mutagenicity was evaluated using Ames test in Salmonella typhimurium TA98 without S9 mix. Chemical analysis using high-resolution mass spectrometry was carried out to elucidate the mutagenic transformation products. Among the studied UV filters, only dioxybenzone exhibited a clear mutagenic activity following chlorination in seawater at ratio 1:10 (UV filter:chlorine). In contrast, no mutagenic activity was detected when chlorine was added at higher doses (ratio 1:1000). High-resolution mass spectrometry analysis showed that mutagenic extracts contained several brominated transformation products of dioxybenzone. Time course analysis of the transformation products at increasing chlorine doses showed that they were unstable and disappeared more quickly at higher chlorine doses. This instability explained the absence of mutagenic activity of dioxybenzone when 1000-fold excess chlorine was added, as no transformation products were detected. Relevance of these findings to the context of swimming pool is discussed. Further investigations taking into consideration the mutagenicity of not only the intermediate transformation products but also the final disinfection byproducts are needed to determine the overall impact of high levels of chlorine on the overall mutagenicity. This study highlights the importance of considering the reactivity of organic UV filters and their transformation products in disinfected recreational waters when sunscreen formulations are prepared.

Background: Lack of established criteria for sunscreen product recommendations and potentially allergenic ingredients in sunscreens pose an issue for physicians and patients with autoimmune skin conditions. Objective: We reviewed popular sunscreens for effectiveness and potential allergenicity for recommendation and use in the autoimmune skin condition population. Methods: In this cohort study, we selected sunscreens from the bestseller lists of Amazon, Target, and CVS. Of those, sunscreens with sun protection factor of 50 to 99 and 100 that met our effectiveness criteria (52 sunscreens) were analyzed for allergenic ingredients. An allergen list was developed from the North American Contact Dermatitis Group core data and stratified into low-prevalence and high-prevalence allergens. Results: The allergenicity of popular sunscreens that met our effectiveness criteria are organized in a table by number of tiered potential allergens. Although no sunscreen was allergen-free, several products contained a minimal number of low-prevalence allergens. The most common low-prevalence allergens were chemical sunscreen ingredients avobenzone, octocrylene, and oxybenzone, and the most common high-prevalence allergen was fragrance. A limitation is that not all U.S. sunscreens were analyzed. Conclusion: With the wide range of sunscreens available, physicians and patients should be aware of the effectiveness and potential allergenicity of sunscreens and make recommendations and consumption choices accordingly. Keywords: dermatology, sunscreen, photosensitivity, allergens, contact dermatitis, autoimmune skin

Given the prevalence of skin cancer, sunscreens are recommended by dermatologists including the American Academy of Dermatology to protect skin from harmful ultraviolet rays. Unfortunately, this leads to an estimated 14,000 tons of sunscreen entering waterways each year. Many of the chemicals in sunscreens, such as oxybenzone and benzophenone-2, are indicated to have adverse effects on corals and other aquatic life. As an eco-conscious alternative, physical barrier sunscreens, such as non-nano-titanium dioxide (TiO2), have been suggested as a replacement. This study examines the impact of a non-nano-TiO2-based sunscreen over a nationally sold brand of sunscreen containing oxybenzone, on clownfish (Amphiprion ocellaris). Animals were evaluated for mortality, swimming behavior, and feeding behavior. Our data indicate that at an exposure level of 100 mg/L oxybenzone-containing sunscreen had a negative impact on mortality, leading to 25% death by the end of the 97-h testing period. Negative impacts on behavior were even more dramatic for the 100 mg/L oxybenzone-containing sunscreen, with 100% of the animals failing to feed over the first 49 h of testing and 100% of animals demonstrating abnormal swimming behavior over the entire testing period. By comparison, the non-nano-(TiO2) sunscreen at 100 mg/L had little (6.7%) negative impact on mortality and feeding. While swimming behavior was disrupted during the first 25 h of testing (26.7% abnormal movement), animals recovered well over the remainder of the testing period (out to 97 h).

The benzophenone (BP) organic ultraviolet (UV) filters have been measured in seawater at ng/L to μg/L levels, but more data on their effects in non-target marine organisms are needed. Corals can be exposed to BPs due to wastewater discharges and coastal recreational activities. In this study, toxicities and bioaccumulation of BP-1 (2,4-dihydroxybenzophenone), BP-3 (oxybenzone), BP-4 (sulisobenzone) and BP-8 (dioxybenzone) to larvae and adults of two coral species, Pocillopora damicornis and Seriatopora caliendrum, were assessed at concentrations ranging from 0.1–1000 μg/L. BP-1 and BP-8 exposure caused significant settlement failure, bleaching and mortality of S. caliendrum larvae [lowest observed effect concentration (LOEC): ≥10 μg/L] compared to the other BPs, while none of the tested compounds and concentrations affected P. damicornis larvae. Nubbins were more sensitive to BP-3, BP-1 and BP-8 than larvae. Overall, BP-1 and BP-8 were more toxic to the two tested species than BP-3 and BP-4, which matches the relative bioaccumulation potential of the four BPs (BP-8 > BP-1 ≈ BP-3 > BP-4). A conservative risk assessment using the effect concentrations derived from this study showed that BP-3, BP-1 and BP-8 pose high or medium risk to the health of corals in popular recreational areas of Taiwan and Hong Kong. Our study suggests that future ecotoxicological studies of corals should take their sensitivities, life stages and metabolic capacities into consideration.

In this study, copper sulfide/carboxylated graphene oxide nanohybrid (CuSG) blended polyethersulfone hollow fiber membranes (P HFMs) were developed for efficient separation of oxybenzone and bisphenol A from water. The composite HFMs showed remarkable improvement in hydrophilicity, mechanical strength, thermal stability, bulk porosity, and surface charge. The notably high pure water permeability (528.2 ± 44.6 mL/m2/h/mmHg) and 90.1% flux recovery were measured for HFMs blended with 1 wt % CuSG nanohybrid. Also, significantly high removal of oxybenzone (98 ± 1%) and bisphenol A (95 ± 2%) from EDCs-spiked water was measured by these composite HFMs. Thus, the experimental results demonstrated the potential efficacy of the novel composite polymeric HFMs for the separation applications.

Sunscreens provide vital protection against the photodamaging effects of UV radiation, however, many fundamental questions remain about the detailed mechanisms by which they dissipate UV energy. One such issue is the extent to which the pH environment of an organic sunscreen molecule alters its effectiveness, both in terms of ability to absorb UV radiation, and also its potential to photodegrade. Here, we use gas-phase laser photodissociation spectroscopy for the first time to measure the intrinsic UVA-UVC absorption spectra and associated photodegradation products of protonated and deprotonated oxybenzone, away from the complications of bulk mixtures. Our results reveal that protonation state has a dramatic effect on the absorption and photodissociation properties of this sunscreen. While the UV absorption profile of oxybenzone is only modestly affected by protonation across the range from 400-216 nm, deprotonated oxybenzone displays a significantly modified absorption spectrum, with very low photoabsorption between 370-330 nm. Protonated oxybenzone primarily photofragments by rupture of the bonds on either side of the central carbonyl group, producing cationic fragments with m/z 151 and 105. Additional lower mass photofragments (e.g. m/z 95 and 77) are also observed. The production spectra for the photofragments from protonated oxybenzone fall into two distinct categories, which we discuss in the context of different excited state decay pathways. For deprotonated oxybenzone, the major photofragments observed are m/z 211 and 212, which are associated with the ejection of methane and the methyl free radical from the parent ion, respectively. Implications for the suitability of oxybenzone in its protonated and deprotonated forms as an optimum sunscreen molecule are discussed.

Recent legislative measures restricting the sale of sunscreens containing certain ultraviolet light filtering ingredients (UVFs) have been based on a perception of risk to aquatic life despite the lack of a robust data set to support these decisions. Concerns were focused on the potential for recreational swimmers' and divers' sunscreen use to result in exposures to coral already stressed due to climate change, disease, and other local conditions. In published environmental risk assessments for UVFs, exposure estimates were based on episodic environmental monitoring or estimates of typical sunscreen use, arbitrarily assuming the portion rinsed off from skin in seawater. To improve the accuracy of exposure estimates and thereby develop more robust risk assessments, we measured the amount of the UVFs, avobenzone, homosalate, octisalate, octocrylene, and oxybenzone released to seawater from four sunscreen products (two lotions, one spray, one stick) in a novel porcine skin model of typical human sunscreen use. Sunscreen was applied to porcine skin, allowed to briefly dry, then exposed to four rinse cycles in artificial seawater. The mass of each UVF in seawater, partitioned from seawater onto glassware, and extractable from skin after rinsing were determined. The proportion rinsed from skin varied by UVF, by formula type, and by application rate. Less than 1.4% of applied octisalate, homosalate, and octocrylene was detected in seawater samples (independent of formula) increasing to an average of 4% and 8% for avobenzone in stick and lotion forms, and to 24% for oxybenzone in lotions. The initial data show substantial differences in rinse‐off among formulation types and sunscreen application rates, and stress the importance of using UVF‐specific rinse‐off values rather than a single value for all UVFs. This new method provides a tool for more robust exposure estimates, with initial data supporting lower rinse‐off values than adopted in published risk assessments. Integr Environ Assess Manag 2021;17:961–966. © 2021 Johnson & Johnson Consumer Companies Inc. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC)., KEY POINTS Regulatory decisions on sunscreen use have been made on the basis of potential risk to coral, but published risk assessments for sunscreens' ultraviolet light filter (UVF) ingredients lack empirical data to establish their rinse‐off rate from swimmers' skin into seawater.A method was developed to reproducibly simulate rinse‐off of UVFs in sunscreen from skin into seawater, and the method was tested for stick, lotion, and spray formula types.Rinse‐off of the five UVFs in these formulas—octocrylene, octisalate, homosalate, avobenzone, and oxybenzone—varied substantially and depended on the sunscreen formula type and application rate.The initial results suggest that published risk assessments adopted artificially high rinse‐off rates, and future assessments should account for differences among UVFs and for the sunscreen formula types used.

The use of Benzophenone-3 (BP3), also known as oxybenzone, a common UV filter, is a growing environmental concern in regard to its toxicity on aquatic organisms. Our previous work stressed that BP3 is toxic to Epibacterium mobile, an environmentally relevant marine α-proteobacterium. In this study, we implemented a label-free quantitative proteomics workflow to decipher the effects of BP3 on the E. mobile proteome. Furthermore, the effect of DMSO, one of the most common solvents used to vehicle low concentrations of lipophilic chemicals, was assessed to emphasize the importance of limiting solvent concentration in ecotoxicological studies. Data-independent analysis proteomics highlighted that BP3 induced changes in the regulation of 56 proteins involved in xenobiotic export, detoxification, oxidative stress response, motility, and fatty acid, iron and amino acid metabolisms. Our results also outlined that the use of DMSO at 0.046% caused regulation changes in proteins related to transport, iron uptake and metabolism, and housekeeping functions, underlining the need to reduce the concentration of solvents in ecotoxicological studies.

[ES] El espectro de la luz solar está compuesto por una amplia gama de radiaciones electromagnéticas las cuales tienen diferentes impactos sobre la vida en la tierra. Entre ellas, las pertenecientes a la región ultravioleta toman un papel principal cuando nos referimos a la fotobiología, ya que pueden interactuar con las biomoléculas por medio de procesos tanto directos como fotosensibilizados. Como resultado, estas biomoléculas pueden sufrir modificaciones que no siempre tienen efectos beneficiosos. En este contexto, los daños fotoinducidos al ADN son de gran relevancia ya que están estrechamente relacionados con la creciente incidencia de cáncer de piel. Por ello, es necesario investigar tanto los mecanismos involucrados en dichos procesos como el desarrollo de nuevas estrategias para combatirlos. En la presente tesis se da respuesta a estas necesidades mediante el desarrollo y empleo de grupos protectores fotolábiles (PPG). En una primera parte se avanza en el desarrollo de nuevos PPG basados en filtros solares. Estos ofrecen la ventaja de actuar, una vez liberados, como un escudo protector frente a la radiación ultravioleta. En este contexto, en el Capítulo 3 se profundiza en las propiedades fotofísicas y fotoquímicas de los sistemas formados por la avobenzona como PPG de ácidos carboxílicos, más concretamente del ketoprofeno (KP) y del naproxeno (NPX). En este estudio se analiza por medio de modelado molecular y técnicas espectroscópicas la influencia que tiene la energía relativa del triplete de la avobenzona en su forma dicetónica, 3AB(K)*, respecto a la de los compuestos protegidos en el proceso de liberación. Siguiendo en esta misma línea de trabajo, en el Capítulo 4 se ha desarrollado un nuevo PPG capaz de liberar el filtro solar oxibenzona (OB) junto con compuestos carbonílicos. En una segunda parte, el foco de atención se ha puesto en el concepto de "Caballo de Troya", el cual establece que ciertas lesiones del ADN pueden actuar a su vez como fotosensibilizadores endógenos generando así nuevas lesiones en su entorno. En este contexto, en el Capítulo 5 se han estudiado, mediante métodos tanto experimentales como teóricos, las propiedades fotosensibilizantes de dos de los daños oxidativos del ADN, el 5-formiluracilo (ForU) y la 5-formilcitosina (ForC), poniendo especial énfasis en la capacidad de estos para poblar sus estados tripletes, así como de inducir la formación fotosensibilizada de dímeros ciclobutánicos de pirimidina (CPD). Por último, en el Capítulo 6 se ha desarrollado una nueva alternativa sintética para la incorporación del ForU en oligonucleótidos. Debido a la inestabilidad del grupo aldehído, esta síntesis se lleva a cabo generalmente mediante la incorporación de un precursor el cual es posteriormente convertido en el ForU mediante la acción de un agente oxidante. Por el contrario, en la nueva alternativa planteada el aldehído es protegido con un PPG, de manera que una vez insertado en el ODN, el aldehído es liberado de forma selectiva mediante el empleo de luz. Este trabajo supone un avance en el estudio de las propiedades fotosensibilizantes del ForU ofreciendo una nueva herramienta para la evaluación de las mismas en un entorno más cercano al del ADN., [CA] L'espectre de la llum solar està compost per una àmplia gamma de radiacions electromagnètiques les quals tenen diferents impactes sobre la vida en la terra. Entre elles, les pertanyents a la regió ultraviolada prenen un paper principal quan ens referim a la fotobiologia, ja que poden interactuar amb les biomolècules per mitjà de processos tant directes com fotosensibilitzats. Com a resultat, aquestes biomolècules poden patir modificacions que no sempre tenen efectes beneficiosos. En este context, els danys fotoinduits a l'ADN són de gran rellevància ja que estan estretament relacionats amb la creixent incidència de càncer de pell. Per això, és necessari tant d'investigar els mecanismes involucrats en els processos com el desenvolupament de noves estratègies per a combatre'ls. En la present tesi es dóna resposta a aquestes necessitats per mitjà del desenvolupament i ús de grups protectors fotolàbils (PPG). En una primera part s'avança en el desenvolupament de nous PPG basats en filtres solars. Estos ofereixen l'avantatge d'actuar, una vegada alliberats, com un escut protector enfront de la radiació ultraviolada. En este context, en el capítol 3 s'aprofundeix en les propietats fotofísiques i fotoquímiques dels sistemes formats per l'avobenzona com PPG d'àcids carboxílics, més concretament del ketoprofé (KP) i del naproxé (NPX). En este estudi s'analitza per mitjà de modelatge molecular i tècniques espectroscòpiques la influència que té en el procés d'alliberament l'energia relativa del triplet de l'avobenzona en la seua forma dicetònica, 3AB(K)*, respecte a la dels compostos protegits. En esta mateixa línia de treball, en el capítol 4 s'ha desenvolupat un nou PPG capaç d'alliberar el filtre solar oxibenzona (OB) junt amb compostos carbonílics. En una segona part, el focus d'atenció s'ha posat en el concepte de "Cavall de Troia", el qual estableix que certes lesions de l'ADN poden actuar al seu torn com fotosensibilitzadors endògens generant així noves lesions en el seu entorn. En este context, en el capítol 5 s'han estudiat, per mitjà de mètodes tant experimentals com teòrics, les propietats fotosensibilitzants de dos dels danys oxidatius de l'ADN, el 5-formiluracil (ForU) i la 5-formilcitosina (ForC), posant especial èmfasi tant en la capacitat d'estos per a poblar els seus estats triplet, com d'induir la formació fotosensibilitzada de dímers ciclobutànics de pirimidina (CPD). Finalment, en el capítol 6 s'ha desenvolupat una nova alternativa sintètica per a la incorporació del ForU en oligonucleòtids. A causa de la inestabilitat del grup aldehid, esta síntesi es duu a terme generalment per mitjà de la incorporació d'un precursor el qual és posteriorment convertit en el ForU per mitjà de l'acció d'un agent oxidant. Al contrari, en la nova alternativa plantejada l'aldehid és protegit amb un PPG, de manera que una vegada inserit en l'oligonucleòtid, l'aldehid és alliberat de forma selectiva per mitjà de l'ús de llum. Este treball suposa un avanç en l'estudi de les propietats fotosensibilitzants del ForU i ofereix una nova ferramenta per a l'avaluació de les mateixes en un entorn més pròxim al de l'ADN., [EN] The solar spectrum is composed of a wide range of electromagnetic radiations which have different impacts on life on earth. Among them, those belonging to the ultraviolet region are of utmost importance when we refer to photobiology, since they can interact with biomolecules through both direct and photosensitized processes. As a result, these biomolecules can undergo modifications that do not always have beneficial effects. In this context, photoinduced DNA damage is of great relevance as it is closely related to the increasing incidence of skin cancer. Therefore, it is necessary both to investigate the mechanisms involved in these processes and to develop new strategies to avoid them. In this Thesis these issues have been addressed through the development and use of photolabile protecting groups (PPG). The first part of this Thesis involves the development of new PPG based on solar filters. Once released, these PPG offer the advantage of acting as ultraviolet shields. In this context, Chapter 3 looks into the photophysical and photochemical properties of those systems formed by avobenzone as PPG of carboxylic acids, more specifically ketoprofen (KP) and naproxen (NPX). In this study, the influence on the photorelease process of the relative energetic location of the avobenzone triplet manifold in its diketo form, 3AB(K)*, with respect to that of its caged compound, is duly analyzed by means of molecular modeling and spectroscopic techniques. Following this same line of work, a new PPG capable of releasing oxybenzone (OB) solar filter along with carbonyl compounds has been developed in Chapter 4. The second part of this Thesis focuses on the "Trojan Horse" concept, which establishes that certain DNA lesions can act as endogenous photosensitizers, thus generating new lesions in their neighborhood. In this context, in Chapter 5 the photosensitizing properties of two oxidatively generated DNA damages, namely 5-formyluracil (ForU) and 5-formylcytosine (ForC), have been studied by means of experimental and theoretical approaches. Here, special emphasis has been placed on unraveling their capacity to photoinduce the formation of cyclobutane pyrimidine dimers (CPD). Finally, in Chapter 6 a new synthetic alternative for the incorporation of ForU into oligodeoxynucleotides (ODN) has been developed. Due to the instability of the aldehyde group, this synthesis is generally carried out by incorporating a precursor which is subsequently converted into ForU by the action of an oxidative agent. On the contrary, in the new approach, the aldehyde is protected with a PPG, so that once inserted into the ODN, the aldehyde is selectively released through the use of light. This work entails a step forward in the study of the photosensitizing properties of ForU, offering a new tool for their evaluation within the DNA environment.

euskaraKoralezko uharriak ur azpiko ekosistemarik dibertsoenetarikoak dira, ingurumeneko aldaketa txikiekiko sentikorrak direnak. Hala, urteetan zehar gizakiek eragindako mehatxu lokal zein mundu-mailakoek koralen heriotza eragin dute eta, horrekin batera, biodibertsitatearen murrizketa. Mehatxu lokalen artean, eguzkitako kremak daude, haien konposatua den oxibentzona barne. Iragazki organiko hori, azalaren babeserako ez ezik, azalaren eta ilearen zaintze-produktuetan, kosmetikarako eta perfumeen konposaketarako ere erabili izan da. Itsasoan sartzean, krema bertan murgildu, eta koraletan metatzen da, haien zuritzea eta ondoriozko heriotza eraginez. Konposatu horren eragin toxikoak azterturik, ekosistemaren babeserako alternatibak bilatu beharko dira, zink oxidoaren, titanio dioxidoaren eta horien gisako iragazki mineralen ezaugarriak baloratuz. EnglishCoral reefs are one of the most diverse underwater ecosystems, sensitive to small changes in the environment. Thus, over the years both local and global threats have led to the death of corals and, in turn, an important reduction on biodiversity. Among local threats, there are sunscreens, including oxybenzone compound. This organic filter has been used not only for skin protection, but also for skin and hair care products, cosmetics and perfume. Upon entering the sea, suncreams are submerged and deposited in the corals, causing their bleaching and death. When examining the toxic effects of this compound, alternatives to ecosystem protection should be found, assessing the characteristics of mineral filters such as zinc oxide or titanium dioxide.

UV filters are potentially harmful to marine organisms. Given their worldwide dissemination and the scarcity of studies on marine fish, we evaluated the toxicity of an organic (oxybenzone) and an inorganic (titanium dioxide nanoparticles) UV filter, individually and in a binary mixture, in the turbot (Scophthalmus maximus). Fish were intraperitoneally injected and a multi-level assessment was carried out 3 and 7 days later. Oxybenzone and titanium dioxide nanoparticles induced mild effects on turbot, both isolated and in mixture. Neither oxidative stress (intestine, liver and kidney) nor neurotoxicity (brain) was found. However, liver metabolic function was altered after 7 days, suggesting the impairment of the aerobic metabolism. An increased motility rate in oxybenzone treatment was the only behavioural alteration (day 7). The intestine and liver were preferentially targeted, while kidney and brain were unaffected. Both infra- and supra-additive interactions were perceived, with a toxicodynamic nature, resulting either in favourable or unfavourable toxicological outcomes, which were markedly dependent on the organ, parameter and post-injection time. The combined exposure to the UV filters did not show a consistent increment in toxicity in comparison with the isolated exposures, which is an ecologically relevant finding providing key information towards the formulation of environmentally safe sunscreen products.

Sunscreens have now been around for decades to mitigate the Sun’s damaging ultraviolet (UV) radiation which, although essential for the existence of life, is a recognized prime carcinogen. Accordingly, have suncreams achieved their intended purposes towards protection against sunburns, skin photo-ageing and the like? Most importantly, however, have they provided the expected protection against skin cancers that current sunscreen products claim to do? In the last two decades, there have been tens, if not hundreds of studies on sunscreens with respect to skin protection against UVB (280‒320 nm)—traditionally sunscreens with rather low sun protection factors (SPF) were intended to protect against this type of radiation—and UVA (320‒400 nm) radiation; a distinction between SPF and UVA protection factor (UVA-PF) is made. Many of the studies of the last two decades have focused on protection against the more skin-penetrating UVA radiation. This non-exhaustive article reviews some of the important facets of what is currently known about sunscreens with regard (i) to the physical UV filters titanium dioxide (TiO2) and zinc oxide (ZnO) and the mostly photo-unstable chemical UVB/UVA filters (e.g., octinoxate (OMC) and avobenzone (AVO), among others), (ii) to novel chemical sunscreen agents, (iii) to means that minimize the breakdown of chemical filters and improve their stability when exposed to UV sunlight, (iv) to SPF factors, and (v) to a short discussion on non-melanoma skin cancers and melanoma. Importantly, throughout the article we allude to the safety aspects of sunscreens and at the end ask the question: do active ingredients in sunscreen products pose a risk to human health, and what else can be done to enhance protection? Significant loss of skin protection from two well-known commercial suncreams when exposed to simulated UV sunlight. Cream I: titanium dioxide, ethylhexyl triazone, avobenzone, and octinoxate; Cream II: octyl salicylate, oxybenzone, avobenzone, and octinoxate.

Benzophenones are widely used as organic UV filters in many personal care products, especially sunscreen, to protect humans from UV radiation. The increasing use of benzophenone class UV filters has raised concerns about the potential effects on the aquatic environment. These organic UV filters are designed to absorb UV light. However, to date, studies have not considered the potential of UV light to potentiate the toxicity of benzophenones in aquatic organisms. In this study using zebrafish embryos, we assessed the median lethal concentration (LC50) and sub-lethal effects of benzophenone and oxybenzone either under natural levels of UV light or under laboratory light conditions. The LC50 value in zebrafish embryos under both light conditions of oxybenzone was lower when compared to benzophenone. Interestingly, UV light significantly decreased the LC50 values (increased toxicity) of both benzophenone and oxybenzone. The presence of UV light induced a significant increase in hydroxyl radical formation and this was reflected in both increased SOD activity and lipid peroxidation in oxybenzone treated groups. Exposure to either benzophenone or oxybenzone also delayed hatching between 60 and 96 hpf when comparing to the control group while UV exposure further delayed hatching only in oxybenzone-exposed embryos. The results demonstrate the importance of involving UV light in toxicity testing for UV filters and provide much-need information on the UV-induced toxicity of benzophenone and oxybenzone under ecologically realistic conditions.

Oxybenzone (OBZ), an ultraviolet light filter that is widely used in sunscreens and cosmetics, is an emerging contaminant found in humans and the environment. Recent studies have shown that OBZ has been detected in women's plasma, urine, and breast milk. However, the effects of OBZ exposure on oocyte meiosis have not been addressed. In this study, we investigated the detrimental effects of OBZ on oocyte maturation and the protective roles of melatonin (MT) in OBZ-exposed mouse models. Our in vitro and in vivo results showed that OBZ suppressed oocyte maturation, while MT attenuated the meiotic defects induced by OBZ. In addition, OBZ facilitated H3K4 demethylation by increasing the expression of the Kdm5 family of genes, elevating ROS levels, decreasing GSH, impairing mitochondrial quality, and disrupting spindle configuration in oocytes. However, MT treatment resulted in significant protection against OBZ-induced damage during oocyte maturation and improved oocyte quality. The mechanisms underlying the beneficial roles of MT involved reduction of oxidative stress, inhibition of apoptosis, restoration of abnormal spindle assembly and up-regulation of H3K4me3. Collectively, our results suggest that MT protects against defects induced by OBZ during mouse oocyte maturation in vitro and in vivo.

A key decay pathway by which organic sunscreen molecules dissipate harmful UV energy involves excited-state hydrogen atom transfer between proximal enol and keto functional groups. Structural modifications of this molecular architecture have the potential to block ultrafast decay processes, and hence promote direct excited-state molecular dissociation, profoundly affecting the efficiency of an organic sunscreen. Herein, we investigate the binding of alkali metal cations to a prototype organic sunscreen molecule, oxybenzone, using IR characterization. Mass-selective IR action spectroscopy was conducted at the free electron laser for infrared experiments, FELIX (600-1800 cm-1), on complexes of Na+, K+ and Rb+ bound to oxybenzone. The IR spectra reveal that K+ and Rb+ adopt binding positions away from the key OH intermolecular hydrogen bond, while the smaller Na+ cation binds directly between the keto and enol oxygens, thus breaking the intramolecular hydrogen bond. UV laser photodissociation spectroscopy was also performed on the series of complexes, with the Na+ complex displaying a distinctive electronic spectrum compared to those of K+ and Rb+, in line with the IR spectroscopy results. TD-DFT calculations reveal that the origin of the changes in the electronic spectra can be linked to rupture of the intramolecular bond in the sodium cationized complex. The implications of our results for the performance of sunscreens in mixtures and environments with high concentrations of metal cations are discussed.

An electrode composed of an epoxy resin and graphite powder is fast and convenient to fabricate. The performance as a working e lectrode for cyclic voltammetry measurement of hexacyanoferrate(III) in aqueous and nonaqueous systems is compared with a paraffin carbon paste electrode. Well defined current-potential curves, and well linearity of current-root scan rate and current-concentrat ion system are reported. The electroanalytical studies of the octyl methoxycinnamate, oxybenzone , benzophenone, octyl salicylate, and butyl m ethoxy dizenzoyl methane, that are often used as sunscreens in commercial cosmetic products, were described at the carbon-epoxy compos ite electrodes in nonaqueous solvent.

Organic ultraviolet filters (OUVFs) are used in a wide range of manufactured products including personal care (e.g. sunscreens) and plastic items. This review summarizes the available data regarding the toxic effects of OUVFs on marine and freshwater organisms and generates the predicted no-effect concentration (PNEC) values necessary for assessing ecological risk. Through a systematic search of the literature, 89 studies were identified and ecotoxicological data extracted. Collectively, these studies described toxicity testing with 39 OUVF from 10 structural classes, with derivatives of benzophenones (49%) and camphors (16%) most studied. There was a bias towards selecting freshwater species (61%), and evaluating single OUVF effects (87%) rather than OUVF mixtures. Short-term (acute) experimentation (58%) was marginally more common than long-term (chronic) testing (42%). Reproductive, developmental, genetic, and neurological toxicity were the most commonly identified effects in aquatic organism, and were associated with molecular interactions with steroid receptors, DNA, or the production of reactive oxygen species. Species sensitivity distribution and/or assessment factors were used to calculate PNECs for 22 OUVFs and the risk quotients for 12 OUVFs. When using maximum concentrations, high risk was observed for six OUVFs in marine environments (4-methylbenzylidene-camphor, octocrylene, padimate-O, benzophenone-1, and oxybenzone, ethylhexyl-4-methoxycinnamate), and for four OUVFs in freshwater environments (ethylhexyl-4-methoxycinnamate, octocrylene, avobenzone and oxybenzone). When using median concentrations, a risk to marine environments was observed for oxybenzone. The results of this review underline that there is limited knowledge of the pathological effects of OUVFs and their metabolites in aquatic environments, and this inhibits the development of informed water-quality guidelines.

[EN] Photolabile protecting groups (PPGs) have been exploited in a wide range of chemical and biological applications, due to their ability to provide spatial and temporal control over light-triggered activation. In this work, we explore the concept of a new photocage compound based on the commercial UVA/UVB filter oxybenzone (OB; 2-hydroxy-4-methoxybenzophenone) for photoprotection and controlled release of carbonyl groups. The point here is that oxybenzone not only acts as a mere PPG, but also provides, once released, UV photoprotection to the carbonyl derivative. This design points to a possible therapeutic approach to reduce the severe photoadverse effects of drugs containing a carbonyl chromophore., This work was supported by the Spanish Government (project PGC2018-096684-B-I00) and the Universitat Politecnica de Valencia (FPI grant to M.L.-R.). Carmen Clemente Martínez is acknowledged for her technical help during the UPLC-HRMS experiments.

The occurrence of Pharmaceutical and Personal Care Products (PPCPs) in the aquatic environment has raised concerns due to their accumulation in the ecosystem. This study aims to explore the feasibility of using a Revolving Algal Biofilm (RAB) reactor for PPCPs removal from waterbody. Five model PPCP compounds including ibuprofen, oxybenzone, triclosan, bisphenol A and N, N-diethyl-3-methylbenzamide (DEET) were mixed and added to the culture medium. It shows that PPCP removal efficiencies of the RAB reactor ranged from 70% to 100%. The degradation of PPCPs by the RAB reactor contributed 90% PPCP removal while 10% PPCPs removal was due to accumulation in the algal biomass. The nutrients removal performance of the RAB reactor was not affected by exposing to the PPCPs. The extracellular polysaccharides content of the biomass increased when exposing to PPCPs, while the extracellular proteins content remained constant. The Chl a content maintained constant in the PPCPs-treated biomass, but decreased in the biomass without PPCP treatment. It was also found that the microbial consortium of the RAB reactor was enriched with PPCPs degradation microorganisms with the progressing of feeding PPCPs. Collectively, this work demonstrates that the RAB system is a promising technology for removing PPCPs from wastewater.

This research investigates the performance of four types of constructed wetlands (CWs): free water surface CW (FWSCW), horizontal flow CW (HFCW), vertical flow CW (VFCW), and hybrid CW (HCW) for the removal of 20 personal care products (PCPs), based on secondary data compiled for 137 CWs reported in 39 peer reviewed journal papers. In spite of considerable variation in the re-moval efficiency of PCPs, CWs prove to be a promising treatment technology. The average removal efficiency of 15 widely studied PCPs ranged from 9.0% to 84%. Although CWs effectively reduced the environmental risks caused by many PCPs, triclosan was still classified under high risk category based on effluent concentration. Five other PCPs were classified under medium risk category (triclocarban > methylparaben > galaxolide > oxybenzone > methyl dihydrojasmonate). In most of the examined PCPs, adsorption and/or sorption is the most common removal mechanism followed by biodegradation and plant uptake. The comparatively better performance of HCW followed by VFCW, HFCW, and FWSCW might be due to the co-existence of aerobic and anaerobic conditions, and longer hydraulic retention time enhancing the removal of PCPs (e.g., triclosan, methyl dihydro-jasmonate, galaxolide, tonalide, and oxybenzone), which are removed under both conditions and by adsorption/sorption processes.

BACKGROUND: Recent evidence of high systemic absorption of sunscreen ingredients has raised concerns regarding the safety of sunscreen products. Oxybenzone (BP-3) and octinoxate (OMC), two common sunscreen ingredients, were recently banned in Key West and Hawaii due to their toxic effects on marine ecosystems. Their impact on human health requires a careful assessment. OBJECTIVE: To summarize the current evidence on the association between the systemic level of BP-3 or OMC and its health impact. METHODS: A primary literature search was conducted using PubMed database in February 2019. RESULTS: There are 29 studies that address the impact of these ingredients on human health. Studies show that elevated systemic level of BP-3 has no adverse effect on male and female fertility, female reproductive hormone level, adiposity, fetal growth, child’s neurodevelopment and sexual maturation. However, the association of BP-3 level on thyroid hormone, testosterone level, kidney function and pubertal timing has been reported and prompts further investigations to validate a true association. The systemic absorption of OMC has no reported effect on thyroid and reproductive hormone levels. CONCLUSIONS: Current evidence is not sufficient to support the causal relationship between the elevated systemic level of BP-3 or OMC and adverse health outcomes. There are either contradictory findings among different studies or insufficient number of studies to corroborate the observed association. To accurately evaluate the long-term risk of exposure to BP-3 and OMC from sunscreen, a well-designed longitudinal randomized controlled trial needs to be conducted.

Rationale Exposure to UV light can induce adverse effects on human health, such as photo-aging, immunosuppression, and cancer. Sunscreens are used to prevent the absorption of UV rays, but certain UV-filtering compounds have been shown to disrupt endocrine systems or act as carcinogens. To assess the effects of the exposure to such compounds, it is important to study the pathways by which they are biotransformed in the body. Methods Liquid chromatography coupled to high-resolution tandem mass spectrometry (LC/HRMS/MS) was employed to evaluate the oxidative metabolism and, specifically, the formation of reactive metabolites of six active ingredients commonly used in sunscreen formulations: oxybenzone, avobenzone, homosalate, octisalate, octocrylene, and octinoxate. In vitro incubations were performed with human and rat liver microsomes in the presence of β-nicotinamide adenine dinucleotide phosphate and glutathione. An LC/HRMS/MS method was developed to identify metabolites employing a biphenyl reversed-phase column for separating parent molecules, metabolites, and glutathione (GSH) adducts. Results Each tested compound resulted in the formation of several metabolites, including at least one GSH adduct. Compounds containing ester groups were hydrolyzed, and some metabolites of the free acid forms were also detected. High-resolution MS/MS data was crucial for the structural elucidation of metabolites and GSH adducts. Fragmentation pathways were proposed for all parent compounds, as well as each described metabolite and adduct. Conclusions The results of this study will help better understand the metabolism and detoxification pathways of these xenobiotics.

Microplastics (MPs) lipophilic nature and widespread distribution raises concerns due to their increasing presence in the marine environment and their ability to adsorb organic contaminants, as being potential vehicles for transport and potential source of accumulation of organic contaminants by marine organisms. The organic UV-filter, oxybenzone (BP-3) is a constituent of sunscreens and personal care products, entering the marine environment either by direct contact with swimmers or by wastewater effluents. In this study the ecotoxicological effects of exposure to low-density polyethylene (LDPE) microplastics with and without adsorbed BP-3 were investigated in the peppery furrow shell clam, Scrobicularia plana. LDPE microplastics with a size range of 11–13 μm were previously contaminated with an environmentally relevant concentration of BP-3 (82 ng g−1 ). S. plana individuals were exposed to a concentration of 1 mg L−1 of microplastics with and without BP-3 adsorbed in a water-sediment exposure system for 14 days. Clams were sampled at the beginning of the experiment and after 3, 7, and 14 days of exposure. Multiple biomarkers were analysed to investigate the effect of exposure in different clam tissues, gills, digestive gland, and haemolymph. Antioxidant (superoxide dismutase, catalase, glutathione peroxidase) and biotransformation (glutathione-S-transferases) enzyme activities, oxidative damage (lipid peroxidation), genotoxicity (single and double strand DNA breaks), and neurotoxicity (acetylcholinesterase activity) were assessed along with two biomarker indexes to assess the overall health status. Results indicate that after 7 days of exposure MPs with adsorbed BP-3 induced oxidative stress and damage, when compared to exposure to virgin MPs and control treatments. Neurotoxic effects were also noted in MPs with adsorbed BP-3 after 14 days exposure, while some evidence points to increased genotoxicity with exposure time. Overall results indicate that gills were more affected by exposure to microplastics than digestive gland and that biomarkers alterations are apparently more related to the toxicity of BP-3 adsorbed than virgin MPs alone. EPHEMARE project, (FCT JPIOCEANS/0005/2015; BELPSO), info:eu-repo/semantics/publishedVersion

International audience; Organic UV filters are of emerging concern due to their occurrence and persistence in coastal ecosystems. Because marine bacteria are crucial in the major biogeochemical cycles, there is an urgent need to understand to what extent these microorganisms are affected by those chemicals. This study deciphers the impact of five common sunscreen UV filters on twenty-seven marine bacteria, combining both photobiology and toxicity analysis on environmentally relevant species. Seven bacteria were sensitive to different organic UV filters at 1000 μg L−1, including octinoxate and oxybenzone. This is the first report demonstrating inhibition of bacterial growth from 100 μg L−1. None of the UV filters showed any toxicity at 1000 μg L−1 on stationary phase cells, demonstrating that physiological state was found to be a key parameter in the bacterial response to UV-filters. Indeed, non-growing bacteria were resistant to UV filters whereas growing cells exhibited UV filter dependent sensitivity. Octinoxate was the most toxic chemical at 1000 μg L−1 on growing cells. Interestingly, photobiology experiments revealed that the toxicity of octinoxate and homosalate decreased after light exposure while the other compounds were not affected. In terms of environmental risk characterization, our results revealed that the increasing use of sun blockers could have detrimental impacts on bacterioplanktonic communities in coastal areas. Our findings contribute to a better understanding of the impact of the most common UV filters on bacterial species and corroborate the importance to consider environmental parameters such as solar radiation in ecotoxicology studies.

We studied the effect of chronic oxybenzone exposure and elevated temperature on coral health. Microcolonies of Stylophora pistillata and Acropora tenuis were cultured in 20 flow-through aquaria, of which 10 were exposed to oxybenzone at a field-relevant concentration of ~0.06 μg L−1 at 26 °C. After two weeks, half of the corals experienced a heat wave culminating at 33 °C. All S. pistillata colonies survived the heat wave, although heat reduced growth and zooxanthellae density, irrespective of oxybenzone. A. tenuis survival was reduced to 0% at 32 °C, and oxybenzone accelerated mortality. Oxybenzone and heat significantly reduced photosynthetic yield in both species, causing a 5% and 22−33% decrease, respectively. In addition, combined oxybenzone and temperature stress altered the abundance of five bacterial families in the microbiome of S. pistillata. Our results suggest that oxybenzone adds insult to injury by further weakening corals in the face of global warming.Highlights➢Chronic effect study on corals combining oxybenzone and elevated temperature➢Oxybenzone affected photosystem II of coral photosymbionts and altered coral microbiome➢Temperature effects were stronger than oxybenzone effects➢Sensitivities were species-dependent➢Oxybenzone adds insult to injury by weakening corals in the face of global warming