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Certain aerobic bacteria produce bacterial cellulose (BC) to protect themselves from UV radiation. Inspired by this natural function, the UV-filtering capacity of wet BC film (BC) and dried BC (BC-Dried) is evaluated and it is concluded that both samples hardly filter UVA, but filter UVB to some extent, especially BC-Dried. Moreover, this filtering capacity does not diminish but significantly increases with time, with efficiencies in the 145-160 min time range equal to or greater than most UV filters of the market. This increase in efficiency is due to the fact that the BC structure is modified by prolonged exposure to UVB radiation. Specifically, UVB causes sintering of the cellulose fibers, making the structure denser and increasing its reflection and scattering of UVB radiation. Remarkably, this UVB filtering ability of BC allows it to protect key skin probiotics, Lactobacillus fermentum (L. fermentum) and Cutibacterium acnes (C. acnes), against UVB damage. While the protection of healthy skin microbiota is not currently a regulatory requirement for sunscreens with UV filters, it may become a key differentiator for future UV filters given the increasing evidence on the role of skin microbiota in health.

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UV light is known to cause damage to biomolecules in living tissue. Tissues of the eye that play highly specialised roles in forming our sense of sight are uniquely exposed to light of all wavelengths. While these tissues have evolved protective mechanisms to resist damage from UV wavelengths, prolonged exposure is thought to lead to pathological changes. In the lens, UV light exposure is a risk factor for the development of cataract, which is a condition that is characterised by opacity that impairs its function as a focusing element in the eye. Cataract can affect spatially distinct regions of the lens. Age-related nuclear cataract is the most prevalent form of cataract and is strongly associated with oxidative stress and a decrease in the antioxidant capacity of the central lens region. Since UV light can generate reactive oxygen species to induce oxidative stress, its effects on lens structure, transparency, and biochemistry have been extensively investigated in animal models in order to better understand human cataract aetiology. A review of the different light exposure models and the advances in mechanistic understanding gained from these models is presented.

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The chemical UV filter 2-ethylhexyl salicylate (EHS) is used in various personal-care products. The dermal and oral metabolism of EHS have already been targeted by different studies. However, toxicokinetic data after a single dermal exposure to EHS was missing. In our study, three volunteers were dermally exposed to a commercial EHS-containing sunscreen for 9 h with an application dose of 2 mg sunscreen per cm2 body surface area. The exposure was performed indoors, and sunscreen was applied on about 75% of the total skin area. Complete urine voids were collected over 72 h and eight blood samples were drawn from each subject. Urine samples were analyzed for EHS and seven known metabolites (5OH-EHS, 4OH-EHS, 2OH-EHS, 6OH-EHS, 4oxo-EHS, 5oxo-EHS, and 5cx-EPS) by online-SPE UPLC MS/MS. The peaks of urinary elimination occurred 10-11 h after application. The elimination half-lives (Phase 1) were between 6.6 and 9.7 h. The dominant urinary biomarkers were EHS itself, followed by 5OH-EHS, 5cx-EPS, 5oxo-EHS, and 4OH-EHS. 2OH-EHS, 6OH-EHS, and 4oxo-EHS were detected only in minor amounts. An enhanced analysis of conjugation species revealed marginal amounts of unconjugated metabolites and up to 40% share of sulfate conjugates for 5OH-EHS, 5oxo-EHS, and 5cx-EPS. The results demonstrated a delayed systemic resorption of EHS via the dermal route. Despite an extensive metabolism, the parent compound occurred as main urinary parameter. The delayed dermal resorption as well as the slow elimination of EHS indicate an accumulation up to toxicological relevant doses during daily repeated dermal application to large skin areas.

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2-Ethylhexyl salicylate (EHS) is an organic UV filter which is used in sunscreen and other personal care products. The dermal uptake of EHS was studied in several dermal-exposure experiments. This paper aims to coherently assess urine samples after dermal exposure for the biomarkers EHS, 5OH-EHS, 5oxo-EHS, and 5cx-EPS as well as further biomarkers of interest, specifically 4OH-EHS, 4oxo-EHS, 2OH-EHS, and 6OH-EHS, for the first time. Samples from 18 participants of a pre-existing dermal exposure study under real-life conditions were reassessed using a comprehensive LC-MS/MS method. EHS accounts for 34 % of the cumulative excretion of all analytes within 24 h after exposure, followed by 5OH-EHS (19 %), 5cx-EPS (18 %), 4OH-EHS (15 %) and 5oxo-EHS (11 %). Further metabolites were only quantified in minor amounts. EHS as the most prominent excretion parameter in this study demonstrates the missing first-pass effect after dermal absorption. Furthermore, the applied novel comprehensive analytical procedure revealed oxidation at the ω (5cx-EPS, 6OH-EHS), ω-1 (5OH-EHS, 5oxo-EHS), and ω-2 positions (4OH-EHS, 4oxo-EHS) in the main chain of the ethylhexyl group as well as oxidation in the side chain (2OH-EHS). The presented data are of high relevance for a reliable toxicological risk assessment of dermal exposure to EHS.

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BACKGROUND: Evidence from animal models suggests a role for the organic ultraviolet filter benzophenone-3's (BP-3) on white blood cells (WBCs). However, BP-3's effect on WBCs in humans is unknown. MATERIALS AND METHODS: We used National Health and Nutrition Examination Survey data from 2003 to 2016. We included participants >6 years with data on urinary BP-3, urinary creatinine, and WBC count. Quintiles of urinary creatinine-normalized BP-3 (CnBP-3) levels were used in linear regression models adjusting for age, gender, race, body mass index (BMI), smoking status, education level, family income to poverty threshold ratio, survey cycle, and season. RESULTS: Of the 16 959 participants, 8564 (50.5%) were females, 6602 (38.9%) were White, and 3870 (22.8%) were Black. The mean (standard deviation) age was 37.6 (22.7) years, BMI was 26.8 (7.40) kg/m2, WBC count was 7.22 (2.53) × 109/L, neutrophil count was 4.15 (1.86) × 109/L, and lymphocyte count was 2.25 (1.33) × 109/L and median (interquartile range) of CnBP-3 was 12.1 (44.9) µg/gm. The highest quintile of CnBP-3 was associated with significantly lower WBC and neutrophil counts compared to the lowest quintile of CnBP-3 (Δ quintiles = -137 × 106/L, 95% CI: -249 to -24, p = 0.02 and = -177 × 106/L, 95% CI: -323 to -30, p = 0.02, respectively). In contrast, we did not observe a difference in lymphocyte count between the lowest and highest quintiles of CnBP-3 in unadjusted or adjusted analyses. CONCLUSION: We found an inverse relationship between BP-3 levels and WBC and neutrophil counts, and not with lymphocyte count. Further research is needed to confirm our findings.

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The benzophenone (BP) family, including oxybenzone (BP-3), a prevalent sunscreen ingredient and environmental contaminant, has raised concerns since the year 2005. This study investigated oxybenzone toxicity in zebrafish (Danio rerio) eleutheroembryos and brine shrimp (Artemia salina) nauplii, focusing on the LC50 and developmental impacts. Zebrafish embryos (0.100-1.50 mg/L BP-3, 96 h) and A. salina (0.100-5.00 mg/L BP-3, 48 h) were tested with ultrasound-assisted emulsified liquid-phase microextraction (UA-ELPME) used for zebrafish tissue analysis. HPLC-DAD determined BP-3 concentrations (highest: 0.74 ± 0.13 mg/L). Although no significant zebrafish embryo mortality or hatching changes occurred, developmental effects were evident. Lethal concentrations were determined (A. salina LC50 at 24 h = 3.19 ± 2.02 mg/L; D. rerio embryos LC50 at 24 h = 4.19 ± 3.60 mg/L), with malformations indicating potential teratogenic effects. A. salina displayed intestinal tract alterations and D. rerio embryos exhibited pericardial edema and spinal deformities. These findings highlight oxybenzone's environmental risks, posing threats to species and ecosystem health.

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2-ethylhexyl salicylate (EHS) is used as a UV filter in personal-care products, such as sunscreen, to prevent skin damage through UV radiation. The application of EHS-containing products leads to systemic EHS absorption, metabolization and excretion. To measure EHS and its corresponding metabolite levels in urine, a comprehensive analytical procedure based on an extended enzymatic hydrolysis, on-line-SPE, and UPLC-MS/MS was developed. The method covers a large profile of seven metabolites (including isomeric structures) as well as EHS itself in a run time only of 18 min. Easy sample preparation, consisting of a 2-h hydrolysis step, followed by on-line enrichment and purification, add to the efficiency of the method. An update, compared to a previous method for the determination of EHS and metabolites in urine, is that, during hydrolysis, both glucuronide and sulfate conjugates are considered. The method was furthermore applied to urine samples after a real-life exposure scenario to EHS-containing sunscreen. The method is highly sensitive with limits of detection ranging from 6 to 65 ng/L. Moreover, it is characterized by good precision data, accuracy, and robustness to matrix influences. Application of the method to urine samples following dermal exposure to an EHS-containing sunscreen revealed EHS as the main biomarker after dermal exposure, followed by the major biomarkers 5OH-EHS, 5cx-EPS, 4OH-EHS and 5oxo-EHS. The expansion and optimization of this method decisively contributes to the research on the dermal metabolism of EHS and can be applied in exposure studies and for human biomonitoring.

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Factors affecting the in vitro Sun Protection Factor (SPF) and Ultraviolet-A Protection Factor (UVA-PF) of sunscreens were analyzed for verifying the validity and reliability of the ISO24443 evaluation method. UV absorbance measurements by different spectrophotometers did not lead to the large difference in in vitro SPF/UVA-PF, although the UV absorbance determined by each spectrophotometer exhibited relatively large difference when it was larger than 2. On the other hand, relatively large difference was found in in vitro SPF/UVA-PF by utilizing European Cosmetic and Perfumery Association (Colipa) 1994 or UV-solar simulated radiation (UV-SSR) for the spectral irradiance. Appropriateness of employing the coefficient of adjustment for the determination of in vitro UVA-PF was also found to be reexamined.

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Titanium dioxide (TiO2) nanoparticles are extensively used as a sunscreen filter due to their long-active ultraviolet (UV)-blocking performance. However, their practical use is being challenged by high photochemical activities and limited absorption spectrum. Current solutions include the coating of TiO2 with synthetic polymers and formulating a sunscreen product with additional organic UV filters. Unfortunately, these approaches are no longer considered effective because of recent environmental and public health issues. Herein, TiO2-metal-phenolic network hybrid nanoparticles (TiO2-MPN NPs) are developed as the sole active ingredient for sunscreen products through photochemical suppression and absorption spectrum widening. The MPNs are generated by the complexation of tannic acid with multivalent metal ions, forming a robust coating shell. The TiO2-MPN hybridization extends the absorption region to the high-energy-visible (HEV) light range via a new ligand-to-metal charge transfer photoexcitation pathway, boosting both the sun protection factor and ultraviolet-A protection factor about 4-fold. The TiO2-MPN NPs suppressed the photoinduced reactive oxygen species by 99.9% for 6 h under simulated solar irradiation. Accordingly, they substantially alleviated UV- and HEV-induced cytotoxicity of fibroblasts. This work outlines a new tactic for the eco-friendly and biocompatible design of sunscreen agents by selectively inhibiting the photocatalytic activities of semiconductor nanoparticles while broadening their optical spectrum.

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Benzophenone-3 (BP3) is a common ingredient in personal care products (PCPs) due to its well-established effectiveness in absorbing UV radiation. Sunscreen products are among the most widely used PCPs-containing BP3 applied to the skin, resulting in significant human exposure to BP3 primarily through a dermal application. In the present work, we have tested the action of three environmentally relevant concentrations of BP3 (2, 20 and 200 µg/L) on an in vitro model of implantation of murine blastocysts and on migration ability of the human trophoblast cell line Swan 71. We showed that BP3 caused a significant reduction of blastocyst expansion and a delayed hatching in a non-monotonic way. Besides, embryos displayed a delayed attachment in the three BP3 groups, resulting in a smaller implantation area on the 6th day of culture: BP3(2) (0.32 ± 0.07 mm2); BP3(20) (0.30 ± 0.08 mm2) and BP3(200) (0.25 ± 0.06 mm2) in comparison to the control (0.42 ± 0.07 mm2). We also found a reduced migration capacity of the human first-trimester trophoblast cell line Swan 71 in a scratch assay when exposed to BP3: the lowest dose displayed a higher uncovered area (UA) at 6h when compared to the control, whereas a higher UA of the wound was observed for the three BP3 concentrations at 18 and 24 h of exposure. The changes in UA provoked by BP3 restored to normal values in the presence of flutamide, an androgen receptor (AR) inhibitor. These results indicate that a direct impairment on early embryo implantation and a defective migration of extravillous trophoblast cells through the androgen receptor pathway can be postulated as mechanisms of BP3-action on early gestation with potential impact on fetal growth.

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The adverse effects of microplastics (MPs) on Daphnia magna have been extensively studied; however, their population-level effects are relatively unknown. This study investigated the effect of polyethylene MP fragments (33.90 ± 17.44 µm) and benzophenone-3 (BP-3), which is a widely used plastic additive (2.91 ± 0.02% w/w), on D. magna population dynamics in a 34-day microcosm experiment. In the growth phase, neither MP nor MP/BP-3 fragments changed the population size of D. magna compared with the control. However, MP/BP-3 fragments significantly reduced (p < 0.05) the population biomass compared to that of the control, whereas MP fragments did not induce a significant reduction. The MP/BP-3 group had a significantly higher (p < 0.05) neonate proportion than that in the control and MP groups. MP/BP-3 fragments upregulated usp and downregulated ecrb, ftz-f1, and hr3, altering gene expression in the ecdysone signaling pathway linked to D. magna growth and development. These findings suggested that BP-3 in MP/BP-3 fragments may disrupt neonatal growth, thereby decreasing population biomass. In the decline phase, MP fragments significantly decreased (p < 0.05) the population size and biomass of D. magna compared with the control and MP/BP-3 fragments. This study highlights the importance of plastic additives in the population-level ecotoxicity of MPs.

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Previously, we found that the ultraviolet filter benzophenone-3 (BP3) causes fetal growth restriction in mice when is applied when implantation occurs (first week of gestation). However, whether BP3 can affect gestation and fertility after implantation period is unknown. We aimed to study the effects on reproductive physiology of the offspring caused by perinatal exposure to BP3. C57BL/6 pregnant mice were dermally exposed to 50 mg BP3/kg bw.day or olive oil (vehicle) from gestation day 9 (gd9) to postnatal day 21 (pnd1). We observed no differences in mother's weights, duration of gestation, number of pups per mother, onset of puberty or sex ratio. The weights of the pups exposed to benzophenone-3 were transiently lower than those of the control. Estrous cycle was not affected by perinatal exposure to BP3. Besides, we performed a fertility assessment by continuous breeding protocol: at 10 weeks of age, one F1 female and one F1 male mouse from each group was randomly chosen from each litter and housed together for a period of 6 months. We noticed a reduction in the number of deliveries per mother among dams exposed to BP3 during the perinatal period. To see if this decreased fertility could be associated to an early onset of oocytes depletion, we estimated the ovarian reserve of germ cells. We found reduced number of oocytes and primordial follicles in BP3. In conclusion, perinatal exposure to BP3 leads to a decline in the reproductive capacity of female mice in a continuous breeding protocol linked to oocyte depletion.

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The degradation kinetics, reaction pathways, and disinfection by-products formation of an organic UV filter, benzophenone-4 (BP4) during UV/persulfate oxidation were investigated. BP4 can hardly be degraded by UV alone, but can be effectively decomposed by UV/persulfate following pseudo-first order kinetics. BP4 degradation rate was enhanced with increasing persulfate dosage and decreasing pH from 8 to 5. However, the degradation rate of BP4 at pH 9 was higher than that at pH 8 because of the presence of phenolic group in BP4 structure. and SO4-⋅ were confirmed as the major contributors to BP4 decomposition in radical scavenging experiments, and the second-order rate constants between HO⋅ and BP4 as well as those between SO4-⋅ and BP4 were estimated by establishing and solving a kinetic model. The presence of Br- and humic acid inhibited the decomposition of BP4, while NO3- promoted it. The mineralisation of BP4 was only 9.1% at the persulfate concentration of 50 µM. Six degradation intermediates were identified for the promulgation of the reaction pathways of BP4 during UV/persulfate oxidation were proposed as a result. In addition, the formation of DBP in the sequential chlorination was evaluated at different persulfate dosages, pH values, and water matrix. The results of this study can provide essential knowledge for the effective control of DBP formation with reducing potential hazard to provide safe drinking water to the public.

BP4 can be effectively degraded by UV/persulfate process, following pseudo-first order kinetics.OH⋅ and SO4−⋅ were identified as the main contributors to BP4 degradation during UV/persulfate process.The degradation pathways of BP4 during UV/persulfate process were proposed.Initial persulfate concentration and solution pH both affected the yield of DBPs.The higher toxic DBPs can be generated in the presence of Br− or NO3−.

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BACKGROUND: Understanding the interaction mechanisms and the relevant binding constants between humic acids and emerging or regulated pollutants is of utmost importance in predicting their geochemical mobility, bioavailability, and degradation. Fluorescence spectroscopy, UV-vis spectroscopy, equilibrium dialysis, and solid-phase extraction combined with liquid chromatography-mass spectrometry have been employed to elucidate interactions of humic acids with organic micropollutants, especially pharmaceutical drugs. These methods demand large sample volumes, long equilibration times, and laborious extraction steps which may imply analytical errors. Monolithic high-performance affinity chromatography is an alternative and simpler method to investigate these interactions and determine the binding constants. RESULTS: Polymer monoliths based on aminated glycidyl methacrylate and ethylene glycol dimethacrylate served to immobilize Cu(II) and then humic acid to produce monolithic affinity chromatography columns with humic acid as the active interaction phase. About 86.5 mg of humic acid was immobilized per gram of polymer. The columns enabled a comparison of the binding strength of humic acid with herbicides and emerging pollutants at 25 °C and pH 6.0 ± 0.1. Paracetamol, acetylsalicylic acid, and salicylic acid did not retain. Among the compounds that interacted with humic acid, the order of increasing affinity, estimated by the global affinity constant (nKa) or partition coefficient (KD) was: caffeine < simazine < atrazine âˆ¼ propazine < benzophenone. The nKa (L mol-1) values ranged from (4.9 ± 0.3) × 102 for caffeine to (1.9 ± 0.3) × 103 for benzophenone, whereas KD (L kg-1) varied from 14 ± 1 to 56 ± 8 for the same compounds. SIGNIFICANCE AND NOVELTY: To our knowledge, this is the first paper demonstrating the use of a monolithic platform to immobilize supramolecular structures of humic acids exploiting immobilized metal affinity to comparatively evaluate their affinity towards emerging pollutants exploiting the concepts of high-performance affinity chromatography. The proposed approach needs only small amounts of humic acid, which is a relevant feature in preparing columns with humic substances isolated and purified from remote areas.

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Exposure to organic ultraviolet (UV) filters has raised concerns due to their potential adverse effects on environments. However, their toxic mechanisms on plants remain elusive. In this study, using integrative physiological and transcriptomic approaches we investigated the physiological and molecular responses to three representative UV filters, namely oxybenzone (OBZ), avobenzone (AVB), and octinoxate (OMC), in an agricultural model plant tobacco. The exposure to UV filters disrupts the functionality of photosystem reaction centers and the light-harvesting apparatus. Concurrently, UV filters exert a suppressive effect on the expression of genes encoding Rubisco and Calvin-Benson cycle enzymes, resulting in a decreased efficiency of the Calvin-Benson cycle and consequently hampering the process of photosynthesis. Exposure to UV filters leads to significant generation of reactive oxygen species within tobacco leaves and downregulation of oxidoreductase activities. Moreover, UV filters promote abscisic acid (ABA) accumulation by inducing the expression of ABA biosynthesis genes whereas repress indole-3-acetic acid (IAA) biosynthesis gene expression, which induce leaf yellowing and slow plant growth. In summary, the organic UV filters exert toxic effects on tobacco growth by inhibiting chlorophyll synthesis, photosynthesis, and the Calvin-Benson cycle, while generating excessive reactive oxygen species. This study sheds light on the toxic and tolerance mechanisms of UV filters in agricultural crops.

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Ultraviolet filters (UV-filters) are compounds extensively used in personal care products. These compounds are produced at increasing rates and discharged into marine ecosystems in unknown quantities and with no regulation, making them emerging contaminants. Among those, the UV-filter 4-Methylbenzylidene camphor (4-MBC) is used in a variety of personal care products such as sunscreens, soaps, or lipsticks. This high consumption has resulted in its presence in various environmental matrices at in concentrations ranging from ng to µg L-1. Very little is known, however, about the possible adverse effects in exposed non-target organisms. Our study presents novel data on the bioconcentration, toxicokinetics, and molecular effects of 4-MBC in a marine bivalve species of commercial interest, Ruditapes philippinarum (Manila clam). Organisms were exposed at two different concentrations (1.34 and 10.79 µg L-1) of 4-MBC for 7 days, followed by a 3-day depuration period (clean sea waters). Bioconcentration factors (BCF) were 3562 and 2229 L kg-1 for the low and high exposure concentrations, respectively, making this pollutant bioaccumulative according to REACH criteria. Up to six 4-MBC biotransformation products (BTPs)were identified, 2 of them for the first time. Transcriptomic analysis revealed between 658 and 1310 differently expressed genes (DEGs) after 4-MBC exposure. Functional and enrichment analysis of the DEGs showed the activation of the detoxification pathway to metabolize and excrete the bioconcentrated 4-MBC, which also involved energy depletion and caused an impact on the metabolism of carbohydrates and lipids and in the oxidative phosphorylation pathways. Oxidative stress and immune response were also evidenced through the activation of cathepsins and the complement system. Such elucidation of the mode of action of a ubiquitous pollutant such as 4-MBC at the molecular level is valuable both from an environmental point of view and for the sustainable production of Manila clam, one of the most cultivated mollusk species worldwide.

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Polyelectrolyte multilayer (PEM) deposition conditions can favorably or adversely affect the membrane filtration performance of various pollutants. Although pH and ionic strength have been proven to alter the characteristics of PEM, their role in determining the buildup interactions that control filtration efficacy has not yet been conclusively proved. A PEM constructed using electrostatic or non-electrostatic interactions from controlled deposition of a weak polyelectrolyte could retain both charged and uncharged pollutants from water. The fundamental relationship between polyelectrolyte charge density, PEM buildup interaction, and filtration performance was explored using a weak-strong electrolyte pair consisting of branching poly (ethyleneimine) and poly (styrene sulfonate) (PSS) across pH ranges of 4-10 and NaCl concentrations of 0 M-0.5 M. PEI/PSS multilayers at acidic pH were dominated by electrostatic interactions, which favored the selective removal of a charged solute, phosphate over chloride, while at alkaline pH, non-electrostatic interactions dominated, which favored the removal of oxybenzone (OXY), a neutral hydrophobic solute. The key factor determining these interactions was the charge density of PEI, which is controlled by pH and ionic strength of the deposition solutions. These findings indicate that the control of buildup interactions can largely influence the physico-chemical and transport characteristics of PEM membranes.

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Organic ultraviolet filters (OUVFs) are extensively released into aquatic environments, where they undergo complex phototransformation. However, there is little knowledge regarding their transformation products (TPs) and associated endocrine disruption potentials. In the present study, we characterized the chemical and toxicological profiles of TPs for two common OUVFs, oxybenzone (BP3) and ethylhexyl methoxycinnamate (EHMC), by photooxidation under environmentally relevant conditions. It is hypothesized that TPs of the tested OUVFs will show varied estrogenicity at different reaction times. High-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) identified 17 TPs of 7 m/z for BP-3 and 13 TPs of 8 m/z for EHMC at confidence levels ≤2. Five novel TPs of 2 m/z were reported for the first time with structure-diagnostic MS/MS spectra. Estrogenicity assessment using the MCF-7-luc cell line showed discrepant estrogenic activities exhibited by OUVF-TPs over time. Specifically, BP3-TPs exhibited significantly greater estrogenicity than the parent at several reaction times, whereas EHMC-TPs displayed fluctuating estrogenicity with a declining trend. Correlation analysis coupled with molecular docking simulations further suggested several TPs of BP3 as potential endocrine disruptive compounds. These findings underscore the necessity of considering mixtures during chemical testing and risk assessment and highlight the potentially greater risks associated with post-transformation cocktails.

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Skin cancer continues to increase in incidence year-on-year and represents the most common form of cancer across the globe. Every human undergoes premature ageing, particularly on the face, neck and hands. Both phenomena are driven primarily by chronic, daily exposure to solar ultraviolet radiation (UVR). While sunscreen products play a primary role in the prevention of UVR skin damage, the active ingredients, i.e., UVR filters, are facing unprecedented challenges in the coming 10 years and their future is by no means certain. This article, therefore, reviews afresh the facts around photoprotection and the role of sunscreen products in the prevention of acute (sunburn) and chronic (cancer, photoageing) skin damage and compares/contrasts these with various emerging questions and opinions around UVR filter technology. We present a passionate defence of this remarkable technology, but also attempt to imagine a world without it.

L'incidence du cancer de la peau continue d'augmenter année après année, et ce cancer est le plus fréquent dans le monde. Tous les êtres humains connaissent un vieillissement prématuré, en particulier au niveau du visage, du cou et des mains. Les deux phénomènes sont causés principalement par une exposition quotidienne chronique aux rayons ultraviolets (UVR) du soleil. Bien que les protections solaires jouent un rôle essentiel dans la prévention des lésions cutanées dues aux UVR, les principes actifs, c'est-à-dire les filtres UVR, seront confrontés à des difficultés sans précédent dans les 10 prochaines années, et leur avenir n'est en aucun cas certain. Cet article examine donc les faits concernant la photoprotection et le rôle des produits de protection solaire dans la prévention des lésions cutanées aiguës (coups de soleil) et chroniques (cancer, photovieillissement) ; et les compare/oppose aux différentes questions et opinions émergentes concernant la technologie des filtres UVR. Nous présentons une défense passionnée de cette technologie remarquable, mais nous essayons également d'imaginer un monde sans elle.

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OBJECTIVE: A 2-year sampling campaign was realized on French Mediterranean beach (Palavas-les-Flots Hérault) in order to measure the concentration of UV filters released from the sunscreen used by bathers. Multiple factors suspected of playing determining roles in the UV filter pattern in water were explored, such as the seasonal and daily time evolutions, or the vertical and horizontal distributions, and they were regarded through the UV filter characteristics. METHODS: The beach was monitored during periods of high and low tourist attendance, typically before, during and after the summer peak. The beachgoers attendance was counted. Bathing water was sampled distinctly from the bulk column and from the top surface layer, testing different sampling tools. Sediments and mussels were also sampled and analysed as potential UV filter sinks. Three organic UV filters (octocrylene OCR, avobenzone BMDBM and octyl methoxycinnamate OMC) and one mineral (titanium dioxide TiO2 ) were studied here as representatives of the current cosmetic market. RESULTS: Summer peak attendance on the beach was confirmed associated with peak levels of UV filter concentration in the bathing water, even more pronounced during a heat wave period. This relation was also observed at day scale with an afternoon peak, suggesting a rapid evolution of the UV filter pattern in water. Contrasted fates were measured between the four studied UV filters, that could be mainly explained by their respective characteristics, i.e. particulate or dissolved, hydrophilic or lipophilic, lifetime. Generally, this resulted in a concentration ranking TiO2 > OCR > OMC > BMDBM, ranging from 0.5 to 500 µg/L. The most lipophilic and recalcitrant OCR was found most vertically differentiated and over concentrated in the top surface layer of water. Finally, a large horizontal heterogeneity was also observed in the UV filter concentration pattern, raising the need for sample replicates that cover a significant area. CONCLUSION: This work fulfils some knowledge gaps on the issue of UV filter release in coastal environments, not only by providing original field data and methodological recommendations but also importantly in the comparison made of organic and mineral UV filters, which are often considered separately and rarely evaluated at the same time.

OBJECTIF: Une campagne d'échantillonnage de deux ans a eu lieu sur une plage de la Méditerranée en France (Palavas-les-Flots dans l'Hérault) afin de mesurer la concentration de filtres UV libérés par la protection solaire utilisé par les baigneurs. Plusieurs facteurs suspectés de jouer des rôles déterminants dans le modèle de filtre UV dans l'eau ont été étudiés, comme les évolutions saisonnières et quotidiennes, ou les distributions verticales et horizontales, et ils ont été examinés à travers les caractéristiques du filtre UV. MÉTHODES: La plage a été surveillée pendant les périodes de fréquentation touristique élevée et faible, généralement avant, pendant et après le pic estival. La présence des baigneurs a été comptabilisée. L'eau de baignade a été prélevée distinctement de la colonne principale et de la couche superficielle supérieure, en testant différents outils de prélèvement d'échantillons. Des sédiments et des moules ont également été prélevés et analysés comme réservoirs de filtre UV potentiels. En l'occurrence, trois filtres UV organiques (octocrylène OCR, avobenzone BMDBM et octyl méthoxycinnamate OMC) et un minéral (dioxyde de titane TiO2 ) ont été étudiés comme représentants du marché cosmétique actuel. RÉSULTATS: Les pics estivaux de présence de baigneurs sur la plage ont été confirmés comme étant associés à des pics de concentration du filtre UV dans l'eau de baignade, encore plus prononcés pendant une période de vague de chaleur. Cette relation a également été observée à l'échelle d'une journée, avec un pic l'après-midi, suggérant une évolution rapide du profil de filtre UV dans l'eau. Les effets de contraste ont été mesurés entre les quatre filtres UV étudiés, ce qui pourrait s'expliquer principalement par leurs caractéristiques respectives, c'est-à-dire particulaires ou dissous, hydrophiles ou lipophiles, tout au long de la vie. En général, cela a donné lieu à un classement de la concentration : TiO2 > OCR > OMC > BMDBM, comprise entre 0,5 et 500 ug/L. Il est apparu que c'est l'OCR le plus lipophile et le plus récalcitrant qui est le plus différencié verticalement et sur-concentré dans la couche supérieure de l'eau. Enfin, on a observé une grande hétérogénéité horizontale dans le profil de concentration du filtre UV, ce qui a nécessité des réplicats d'échantillons couvrant une zone significative. CONCLUSION: Ce travail comble certaines lacunes en matière de connaissances sur la libération des filtres UV dans les environnements côtiers, non seulement en fournissant des données originales sur le terrain et des recommandations méthodologiques, mais également en comparant des filtres UV organiques et minéraux, qui sont souvent pris en compte séparément et rarement évalués en même temps.

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