UV Filters Research Articles

Electrochemical Oxidation of UV Filters: A First-Principles Molecular Dynamics Study.

A theoretical model is proposed to study the oxidation mechanisms of the organic UV filters BP3 and BP4 during electrochemical water treatment utilizing Car-Parrinello molecular dynamics. Factors such as the amount of solvent to be included and how to design the system with the least possible intervention are discussed. The proposed model consist of the optimization of the geometries by density functional theory methods, the equilibration of the structure immersed in a water box, the inclusion of the reactive species, and the analysis of the reaction energies of each reaction pathway. The ab-initio molecular dynamics simulations lead to several products, and some trends can be identified, in accordance with the well-known reactivity rules of organic chemistry. The products proposed in this work are intermediates in longer oxidative pathways.

Potential hazards of octinoxate (ethylhexyl methoxycinnamate) exposure in the seagrass Posidonia oceanica (L.) Delile: Experimental evidence

Interest has risen in recent years to assess the fate and impacts of organic ultraviolet (UV) filters in aquatic environments, after being recognized as contaminants of emerging concern. Octinoxate, also known as ethylhexyl methoxycinnamate (EHMC), is among the widely used UV filters in sunscreen formulations. Its potential toxicological effects in aquatic biota have led to precautionary actions in some jurisdictions, such as restricting and even banning its presence in commercial sunscreens. However, research data is lacking for effective regulation of sunscreen ingredients in Mediterranean countries. Our study evaluated the response of the seagrass Posidonia oceanica to EHMC under a short-term experimental setup, recreating summer conditions in aquaria subjected to different environmentally relevant concentrations for the Mediterranean Sea (minimum: 30.57 ng L−1, intermediate: 710 ng L−1 and maximum: 1420 ng L−1) and a control (no addition). Negative responses were evidenced in the physiology of P. oceanica due to EHMC exposure, with decreased gross primary production rates, loss of leaf chlorophyll content and inhibition of the overall nitrogen fixation associated with the seagrass tissues. Elevated oxidative stress biomarkers in P. oceanica under EHMC addition (i.e., catalase activity, polyphenols concentrations and alkaline phosphatase activity in leaves) reflect the activation of antioxidant defenses to counteract oxidative damages possibly induced in cellular components by the presence of the contaminant. Our results may conservatively imply the high ecological risk imposed to P. oceanica by maximum concentrations of EHMC in Mediterranean coastal waters. Moreover, they contribute as experimental evidence of the potentially detrimental effects of sunscreen pollution in a keystone species, such as P. oceanica, which is the main structural component of a priority habitat for conservation in the Mediterranean Sea, currently affected by multiple stress factors leading to its recession in recent years.

Dynamic impact of different human activities on the distribution of organic ultraviolet absorbers in coastal aquatic environments: A case study in Beibu Gulf, South China Sea

The increasing environmental concern surrounding organic ultraviolet absorbers (OUVAs) has prompted heightened attention, particularly their presence in personal care products (organic ultraviolet filters, OUVFs) and industrial products (organic ultraviolet stabilizers, OUVSs). This study investigates the impact of human activities and environmental factors on the occurrence, spatiotemporal distribution, and ecological risk of eight commonly utilized OUVFs and OUVSs in the coastal region of Beibu Gulf, South China Sea. The study area is characterized by multiple functional zones with distinct human activities. Results reveal elevated concentrations of OUVAs during summer compared to winter, attributed to increased residential usage, tourist activities, industrial releases, and intensified ultraviolet (UV) radiation. Interestingly, the proportion of OUVFs increases during summer, while OUVSs decrease. Correlation analysis between OUVAs and sampling sites reveals that tourism and domestic wastewater are the main contributors to OUVF contamination in summer, whereas mariculture and port trade significantly impact OUVS contamination in winter. The ecological risk assessment indicates predominantly low or medium risk levels for most OUVAs in both local seawater and freshwater ecosystems. Nevertheless, OUVFs, with a particular focus on 4-methylbenzylidene camphor (4-MBC), and OUVSs, specifically 2-(2-hydroxy-5-methylphenyl) benzotriazole (UV-P), exhibit a heightened risk compared to alternative substances. These findings provide crucial insights into the development of targeted mitigation strategies for OUVAs, taking into account the varying contamination levels of OUVFs and OUVSs resulting from diverse human activities, aiming to protect the health of aquatic ecosystems in diverse functional zones.

Facial disbiosis and UV filters.

Acne is a multifactorial inflammatory disease with a robust microbial component and numerous correlations with dysbiosis states. Furthermore, various factors are recognized as triggers for skin dysbiosis, including the use of certain cosmetics. Based on these arguments, we hypothesized that using photoprotective formulations could trigger dysbiosis and the occurrence of acne manifestations. To verify this assumption, six volunteers between 19 and 23 years of age, meeting all the inclusion criteria, received two applications a day of a non-commercial sunscreen formulation developed with the sun filters ethylhexyl methoxycinnamate, ethylhexyl salicylate, methyl anthranilate, and octocrylene dispersed in a base gel, with an estimated protection factor of 28.8. The pure base gel was used as a control. The samples were applied to an area delimited by a standard template (15 cm2) in an amount corresponding to 30mg (2mg cm2) for ten days. At two points in time, pre- and post-sample applications, the facial skin surface was swabbed to collect extracted DNA and processed to verify divergent degrees of 16S RNA coding sequences. The data obtained allowed us to determine the abundance of different bacterial entities at the genus and species levels. The results showed that critical species of the acne process, such as Cutibacterium acnes and Staphylococcus epidermidis, seem to tolerate the evaluated formulation well and are not significantly affected by the formulation, suggesting no interference of its use concerning dysbiosis induction. These findings refute the idea that photoprotectors may cause skin dysbiosis in men.

Novel synthetic UV screen compounds inspired in mycosporine-like amino acids (MAAs): Antioxidant capacity, photoprotective properties and toxicity

The combination of environmental stress on the ozone layer, climate change and a greater sun exposure due to outdoor habits has led to an increase in skin cancer cases and other health issues related with UV radiation. Researchers are searching for new alternative UV filters that could protect our skin from the deleterious effects of UV radiation while also presenting low toxicity and biodegradable character (unlike the UV filters currently available in the market). In this work, two compounds inspired in the natural oxo-mycosporine-like amino acids (MAAs) have been synthesized and their antioxidant and photoprotective properties, as well as their in vitro and in vivo toxicity effects were evaluated. Both compounds featured a strong UV-B absorption together with a high antioxidant capacity, close to 50 μmol TE g−1 DW in the ABTS assay. Compound 1 presented an absorption peak at 285–300 nm, whereas compound 2 showed a wider band with a peak around 295–305 nm and two shoulders at 318 and 342 nm. The addition of 5 % of compound 2 to galenic formulas increased the photoprotection, reaching SPF values of 4. Both compounds were stable under UV radiation exposure. Regarding toxicity, the synthetic compounds did not show cytotoxic activity against healthy human cell lines or significant toxicity over zebrafish embryos. Compound 1 showed a complete lack of toxicity over zebrafish, although compound 2 showed slight, not-significant effects on viability, hatching, pericardial stability or body axis formation over 5 mg mL−1. Moreover, compound 1 presented relatively antitumoral activities against HCT-116 cells (selective index:1.49). The relevant antioxidant and photoprotective ability together with the great advantage provided by the reduced toxicity to health cells or zebrafish embryos, make these compounds promising candidates to be exploited as functional ingredients with specific applications in the biotechnological or pharma sector.

Ethylhexyl triazone sunscreen and its disinfection byproducts obtained after chlorine treatment: Ecofriendliness or ecotoxicity?

In recent years, there has been a growing demand for high-quality sunscreens that combine high efficacy with ecological characteristics. This trend has led to an increased use of triazine compounds, which represent an emerging class of UV filters. While it is well-established that sunscreens can have significant environmental impacts, there is limited data on the degradation of triazine UV filters, despite available information on their environmental persistence, particularly in relation to disinfection processes. This study investigates the chemical fate of ethylhexyl triazone (EHT) under chlorination conditions, typical of swimming pools. Twelve disinfection byproducts (DBPs) were isolated and fully identified using nuclear magnetic resonance and mass spectrometry, with three of these byproducts being identified for the first time. DBP1–DBP12 were isolated at relative percentages of 1.26, 9.68, 1.05, 0.42, 0.84, 3.37, 3.58, 1.89, 0.84, 1.47, 0.42, and 0.63. Additionally, a mechanism for their formation was proposed. The ecotoxicological assessment of EHT and of byproducts (DBP1-DBP4) was conducted using acute, sub-chronic or chronic toxicity tests in producers and primary consumers of the freshwater trophic chain. The organisms included the alga Raphidocelis subcapitata, the rotifer Brachionus calyciflorus, the crustacean anostracan Thamnocephalus platyurus and the benthic ostracod Heterocypris incongruens. EHT caused a lethal median concentration in rotifers, with values in the range of tens of mg/L. EHT, DBP1, and DBP4 exhibited sub-chronic effects in ostracods at concentrations in the μg/L range, with EC50s of 210, 9, 20 μg/L, respectively. Rotifers were slightly affected by DBP3 with a chronic EC50 of 200 μg/L. Algae were not affected by either EHT or byproducts.

The HST Large Programme on ω Centauri

We present a study of the white dwarf (WD) cooling sequence (CS) in the globular cluster (GC) Omega Centauri (or NGC 5139; hereafter, ω Cen), the primary goal of a dedicated Hubble Space Telescope (HST) programme. We find that the peak at the termination of the WD CS is located at mF606W = 30.1 ± 0.2 (equivalent to V ∼ 31). The brighter part of ω Cen’s WD CS is consistent with the presence of massive He-core WDs, in agreement with previous HST analyses with ultraviolet and blue filters. Comparative analyses of the WD luminosity function (LF) and theoretical counterparts show that a single-age population for the cluster is compatible with the data. However, an analysis of only the WD LF cannot entirely exclude the possibility of an age range, due to uncertainties in the present-day WD mass function, with a star formation history potentially spanning up to 5 billion years, predominantly comprising stars about 13 Gyr old, with a minority potentially as young as 8 Gyr. This underscores the need for global spectroscopic and photometric investigations that simultaneously include both the WD populations and the previous evolutionary phases, in order to fully understand the cluster’s diverse chemical compositions and ages.

Clinical Evaluation of Violet Light Filtration and High-Resolution Lathing on a Diffractive Extended Depth of Focus IOL.

This study is a prospective, randomized, subject/evaluator-masked clinical trial in a single-center clinical setting. The purpose of the study is to compare the clinical performance of Tecnis Symfony Optiblue IOL (models ZXR00V and ZXW150) with violet light filter (VLF) and manufacturing improvements versus Tecnis Symfony IOL (models ZXR00 and ZXT150) with ultraviolet light filter (UVF) in patients undergoing cataract surgery. Patients with cataracts aged ≥ 22years were randomly assigned 1:1 to bilateral implantation with ZXR00V/ZXW150 (VLF group) or ZXR00/ZXT150 (UVF group). Key endpoints at 6months postoperative included patient reported nighttime dysphotopsia symptoms, 25% low contrast visual acuity with glare, and patient satisfaction. Sixty patients were implanted with ZXR00V/ZXW150 (30) or ZXR00/ZXT150 (30). At 6months, the VLF group did not show a statistically significant differences in mean monocular photopic uncorrected distance visual acuity (UCDVA), best-corrected distance visual acuity (BCDVA), uncorrected near visual acuity (UCNVA) (40cm), or distance-corrected near visual acuity (DCNVA) (40cm) compared to the UVF group. At 1month, patients in the VLF group reported significantly less difficulty due to halo (p = 0.016) and starburst (p = 0.028) symptoms. By the 6months, dysphotopsia complaints were no longer significantly different between the groups. Although the VLF group trended toward better low contrast visual acuity and patient satisfaction, statistical significance was not reached. Managing the patients' expectations is key to achieving success. At the 1-month visit the patients who reported dysphotopsia complaints in the VLF group had significantly less difficulty with starbursts and halos as compared to the UVF group. By the 6-month visit, there was no significant difference between the two groups in the difficulty with starbursts and halos. ClinicalTrials.gov identifier, NCT06567834.

Nutshell Materials as a Potential Eco-Friendly Biosorbent for the Effective Extraction of UV Filters and Parabens from Water Samples.

UV filters and parabens, as ingredients of cosmetics, are commonly occurring water pollutants. In our work, nutshells were used as biosorbents in the developed analytical procedure for the determination of UV filters and parabens in water samples. The shells obtained from walnuts, hazelnuts, peanuts and pistachios were applied as biosorbents. The proposed analytical method can be used as a powerful alternative to other methods for the analysis of UV filters and parabens in water samples. A method of carrying out the sorption step and its parameters, i.e., the effect of time, pH, and salt addition, was developed. A method for the desorption of analytes was also developed, in which the type and volume of solvent, and the desorption time, were established. The recoveries were in the range of 59-117% for benzophenones and lower recoveries from 14 to 75% for parabens. The results showed that nutshells can be used as low-cost, efficient and eco-friendly biosorbents for the determination of parabens and UV filters in water samples. These materials can be used as a 'greener' replacement for the commercially available adsorbents for the extraction of cosmetic ingredients from the environment.

Photoinitiated Degradation Kinetics of the Organic UV Filter Oxybenzone in Solutions and Aerosols: Impacts of Salt, Photosensitizers, and the Medium.

Organic UV filters like oxybenzone (BP3) in sunscreens are seawater pollutants suspected to transfer to the atmosphere via sea spray aerosol (SSA). This study examines the photoinitiated degradation of BP3 in artificial and real seawater compared to SSA mimics containing NaCl and 4-benzoylbenzoic acid (4-BBA). We investigated pure, binary, and ternary mixtures of BP3, NaCl, and 4-BBA using solar-simulated light to isolate the effects of salt and photosensitization on BP3 degradation. Results showed significantly faster degradation in the aerosol phase (J eff,env ≈ 10-3-10-2 s-1 or t 1/2 < 10 min) compared to bulk solutions (J eff,env ≈ 10-6 s-1 or t 1/2 > 1 day). The photosensitizer enhanced BP3 photodegradation in both phases more than when mixed with salt or all three components in solutions. BP3 photodegradation was most enhanced by salt in the aerosol phase. High-resolution molecular analysis via Orbitrap LC-MS/MS revealed more acutely toxic compounds (benzophenone, benzoic acid, and benzaldehyde) in irradiated aerosols than in solution, supported by electronic structure and toxicity modeling. These findings highlight that seawater may serve as a reservoir for BP3 and other organic UV filters and that upon transfer into SSA, BP3 rapidly transforms, increasing aerosol toxicity.

UV and blue light cut-off filters using phosphorus doped carbon quantum dots extracted from raw egg yolk

Abstract Using raw egg yolk and phosphoric acid, a simple hydrothermal treatment for synthesizing carbon quantum dots (CQDs) has been developed for the manufacture of UV and blue light-blocking filters. Several samples with different doping ratios of phosphoric acid were prepared. Namely: reference (REF.), 25%, 50%, 75% and 100%. The synthesized CQDs were embedded in polyvinyl alcohol (PVA) to produce blocking-light films with desired optical properties. Six films were prepared, one of which was PVA alone, and the other five samples were the prepared CQDs, with different phosphorus doping levels, mixed with PVA in a 1:1 ratio. We aimed to test the ability of these films to block ultraviolet rays and blue light. The experimental results revealed that the prepared films were able to block the blue light, emitted from a 450 nm blue LED, with blocking ratios of 7%, 17.5%, 27%, 30%, 37% and 70% for the films: PVA alone, REF., 25%, 50%, 75% and 100%, respectively. Moreover, it was found that these phosphorus-doped CQDs films can prevent destructive UV light with substantial value reaching 86%. These results suggest that carbon dots, derived from raw egg yolk, can be effectively applied to block harmful UV and blue lights.

ZnO Nanoparticles as Potent Inducers of Dermal Immunosuppression in Contact Hypersensitivity in Mice.

Nanosized zinc oxide (nZnO) metal particles are used in skin creams and sunscreens to enhance their texture and optical properties as UV filters. Despite their common use, little is known about the molecular mechanisms of nZnO exposure on damaged skin. We studied the effects of topically applied nZnO particles on allergic skin inflammation in an oxazolone (OXA)-induced contact hypersensitivity (CHS) mouse model. We investigated whether exposure to nZnO during the sensitization or challenge phase would induce immunological changes and modulate transcriptional responses. We followed skin thickness, cellular infiltration, and changes in the local transcriptome up to 28 days after the challenge. The responses peaked at 24 h and were fully resolved by 28 days. Co-exposure to nZnO and hapten did not interfere with the formation of the sensitization process. Conversely, during the hapten challenge, the application of nZnO fully suppressed the development of the CHS response by the inhibition of pro-inflammatory pathways, secretion of pro-inflammatory cytokines, and proliferation of immune cells. In differentiated and stimulated THP-1 cells and the CHS mouse model, we found that nZnO particles and Zn ions contributed to anti-inflammatory responses. The immunosuppressive properties of nZnO in inflamed skin are mediated by impaired IL-1R-, CXCR2-, and LTB4-mediated pathways. nZnO-induced dermal immunosuppression may be beneficial for individuals with contact allergies who use nZnO-containing cosmetic products. Our findings also provide a deeper understanding of the mechanisms of nZnO, which could be considered when developing nanoparticle-containing skin products.

Structure, Property, and Functionality of 2D ZnO Microplatelets with Low Photocatalytic Activity for Application as UV Filters in Sunscreens for Photoprotection

Structure, Property, and Functionality of 2D ZnO Microplatelets with Low Photocatalytic Activity for Application as UV Filters in Sunscreens for Photoprotection

Combined toxic effects of polystyrene microplastic and benzophenone-4 on the bioaccumulation, feeding, growth, and reproduction of Daphniamagna

The potential toxicity of microplastics (MPs) and UV filter Benzophenone-4 (BP4) to aquatic organisms has caused widespread concern among the public. However, the combined effects of MPs and BP4 on aquatic organisms are not well understood. This study sought to examine the combined impacts of 10 μg/L BP4, 1 mg/L Polystyrene (PS, 10 μm), and a mixture of both on the feeding, behavior, growth, and reproduction of Daphnia magna (D. magna) over a period of 21 days. The results showed that the combined exposure led to a reciprocal facilitation of bioaccumulation, along with a decrease in the second antenna beats frequency in D. magna. While the co-exposure did not change the body size or growth rate of D. magna, it did affect their feeding efficiency, leading to a decrease in Chlorella ingestion within a 24-h period. Furthermore, there was a high occurrence of malformations in two generations of D. magna exposed to BP4 and PS. The combined exposure also negatively affected reproductive parameters, such as the cumulative number of neonates and the days of first brood, suggesting a decline in overall reproductive success possibly due to feeding inhibition, with available energy potentially being redistributed between reproduction and growth in the daphnids. Co-exposure to BP4 and PS also led to elevated levels of Reactive Oxygen Species (ROS), Malonydialdehyde (MDA), and Glutathione (GSH) levels, as well as mRNA levels related to reproduction, growth, and detoxification in D. magna. Overall, this study delved into the consequences of BP4 and PS on bioaccumulation, feeding, behavior, growth, and reproduction, demonstrating that simultaneous exposure to BP4 and PS could pose a synergistic ecological hazard, potentially threatening aquatic organisms. These findings are critical and should be taken into account for accurate environmental risk assessments.

Toxic Beauty: Parabens and benzophenone-type UV Filters linked to increased non-alcoholic fatty liver disease risk

The prevalence of non-alcoholic fatty liver disease (NAFLD) has increased concomitantly with heightened exposure to environmental chemicals, such as benzophenone-type ultraviolet (BP-type UV) filters and parabens, which are prevalent in personal care products. This study aimed to investigate the potential link between the exposure to these chemicals and the risk of developing NAFLD. We conducted a case-control study involving 228 participants from South China, encompassing individuals diagnosed with NAFLD and healthy controls. Blood samples were collected and analyzed for the presence of 11 parabens and 8 BP-type UV filters. The findings revealed significantly elevated concentrations of several parabens and BP-type UV filters in the blood of patients with NAFLD compared with the healthy cohort. Notably, methylparaben (MeP), ethylparaben (EtP), isopropylparaben (iPrP), butylparaben (BuP), isobutylparaben (iBuP), 3,4-dihydroxybenzoic acid (3,4-DHB), total parabens (Σparabens), BP1, BP3, BP4, and 4-hydroxybenzophenone (4-OH-BP) were identified as significant predictors of NAFLD prevalence. Through multiple regression analyses, the blood levels of iBuP, Σparabens, and BP4 were found to be significantly associated with elevated triglycerides (TG) (β = 0.59 mmol/L, 95% CI = 0.11–1.59), total bilirubin (TBIL) (β = 2.81 μmol/L, 95% CI = 0.46–15.6) or direct bilirubin (DBIL) (β = 1.89 μmol/L, 95% CI = 0.47–10.2), and reduced globulins (GLB) (β = −0.29 g/L, 95% CI = −0.07 to −5.45), respectively, which are indicators of liver damage. Moreover, TBIL and DBIL were found to mediate 26.7% and 24.6% of the increase in NAFLD prevalence associated with Σparabens, respectively. In conclusion, this study offers pioneering insights into human exposure to parabens and BP-type UV filters as well as their hepatotoxic potential.

A density functional theory study of a series of symmetric dibenzylideneacetone analogues as potential chemical UV-filters

The aim of this research was to provide valuable insights on symmetrical α,β-unsaturated ketones as potential chemical ultraviolet (UV) filters from experimental data and theoretical aspects. Towards this end, density functional theory (DFT/B3LYP) calculations on a series of symmetrical α,β-unsaturated ketones, (1E,4E)-1,5-bis[4-(R)phenyl]penta-1,4-diene-3-one (R = methylthio, 1; R = dimethylamino, 2; R = ethyl, 3), were performed to determine the effect of different electron-donating substituents on their stability when exposed to solar UV radiation. Their molecular structures, and UV-visible, infrared (IR) and NMR (1H and 13C) spectra were theoretically obtained from their optimized geometries with the B3LYP/6-311++ G (d, p) basis set and were compared with the experimental results. Conformational analysis was performed and the most stable conformer of each compound was identified as the trans-trans conformer, which was further supported by experimental NMR data. The UV spectra and effect of solvent polarity and proticity were studied by the time-dependent-DFT (TD-DFT) approach with the B3LYP/6-311++G (d, p) level of theory. Furthermore, various molecular parameters like dipole moment, frontier molecular orbital (FMO) energies, ΔEHOMO-LUMO gap, lifetime of the first excited state (τ), global chemical reactivity descriptors, and natural bond orbital analysis were predicted at the same level of theory and compared with the experimental data. Inspection of the active FMOs revealed the photoinstability trends of 1 and 3 under UV irradiation. However, introducing a -N(CH3)2 substituent to 2 at the para-position improves its photostability towards simulated UV radiation. Thus, compound 2 has the potential to provide efficient broad-spectrum protection against UV radiation. This work has shown that molecular modelling strategies can assist to rationalize experimental findings and also support the identification of photoproducts of 1 and 3.

Single and mixture toxicity of benzophenone-3 and its metabolites on Daphnia magna

Benzophenone-3 (BP-3) is one of the organic ultraviolet (UV) filters widely used in personal care products, resulting in its ubiquitous occurrence in aquatic systems. This study discovered the potential risks of benzophenone-3 and its metabolites (BP-1 and BP-8) in aquatic environments. This study investigated the toxicity of three single BPs and their mixtures' effects on the survival of Daphnia magna. All three BP types were found to have toxic effects on D. magna, with median effective concentration (EC50) values of 22.55 mg/L for BP-1, 1.89 mg/L for BP-3, and 2.36 mg/L for BP-8, after 48 h of exposure. When the three BPs were binary and ternary mixtures, the EC50 values fell within 2.74–32.26 mg/L. Binary and tertiary mixtures of the three BPs indicated no strong synergistic or antagonistic effects. The mixture toxicity predictions using the classical mixture concept of concentration addition and measured toxicity data showed good predictability. The ecological risks of BPs were assessed using the maximum measured environmental concentrations of BPs collected from a river in Taiwan, divided by their respective predicted no-effect concentration (PNEC) values derived from the assessment factor (AF) method. The result showed a low ecological risk for the sum of three BPs. However, BP-3 had the highest potential risk, while BP-1 was the lowest among the three BPs. Therefore, BP-3 should pay attention to long-term environmental monitoring and management. This study provides valuable information for establishing scientifically-based water quality criteria for BPs and evaluating and managing the potential risk of BPs in the aquatic environment.

Embryonal exposure to 4-methylbenzylidene camphor induces reproduction impairment in adult zebrafish (Danio rerio)

This study investigated how early exposure to xenobiotics can lead to disease in adulthood, which is challenging for toxicologists. We employed a ‘cradle to grave’ approach using zebrafish (Danio rerio) embryos exposed to 4-methylbenzylidene camphor (4-MBC), a commonly used organic UV filter. Molecular docking and simulation studies confirmed the predictive toxicity and stable interaction of 4-MBC with androgen and estrogen receptors, with binding energies of −9.28 and −9.01 kcal/mol, respectively. Exposure to 4-MBC at 5, 50, and 500 μg/L concentrations resulted in significantly altered transcriptional and translational responses of ar, esr1, and vtg1 genes in embryos at 120 h post-fertilization (hpf). The exposure induced a non-monotonic dose-response pattern (NMDR), a characteristic feature of endocrine-disrupting chemicals. Additionally, a significant decrease in fertilization was observed in adults. Although fecundity was not affected in inter- and intra-breeding performances, developmental deformities were observed in F1 progenies with impaired survival at 10 days post-fertilization. The findings of this study show that embryonic exposure to 4-MBC is likely to induce reproductive and transgenerational toxicity in D. rerio and exhibit endocrine disruption in aquatic non-target organisms. This work is the first to elucidate the low-level long-term effects of 4-MBC from the embryonic stage to adulthood.

Sun-protection factor of zinc-oxide sunscreens: SPFin vitro too low compared to SPFin vivo—a brief review

Sunscreens are mainly characterized by their sun-protection factor (SPF), which is measured according to the in vivo gold standard ISO 24444. Although the SPF concept is simple, SPF values are difficult to measure, due to the rather high variability caused by the complex interaction of light and skin. For half a century, there have been attempts to correlate the costly and ethically controversial in vivo procedure with a non-invasive (in vitro) method. After decades of development, alternative non-invasive SPF methods are expected to become available as ISO standards in early 2025. In particular, sunscreen manufacturers who use zinc oxide (ZnO) in higher concentrations (conc.) (10–25%) in their formulations, are concerned that these new in vitro methods would not confirm the SPF-values on their labels that have been determined in vivo, according to ISO 24444. This brief review reveals that sunscreen formulations with high conc. of ZnO often yield SPFin vitro values that are lower than the SPFin vivo values. This can be explained by the fact that in vitro methods have been developed for conventional emulsions products with organic UV filters, but not for highly concentrated ZnO-alone sunscreens. Fortunately, there seems to be a fix for this problem. There is a difference in density between ordinary emulsions with organic filters (density of the residual oil phase ~ 1.0 g/ml) and highly concentrated ZnO-alone formulations (~ 1.3–1.7 g/ml). As the application of current standards is weight-based, this makes the film on the PMMA plate much thinner, which is likely to lead to lower SPFin vitro values. Preliminary experiments show that using the same volume on the PMMA plates instead of the same weight as organic UV filters gives a much better correlation between in vitro and in vivo SPF results. A recent evaluation of three samples of highly concentrated ZnO sunscreens by the Dutch NVWA seems to confirm these findings. Further experimental evidence is required to fully understand this phenomenon and to adapt the in vitro method for higher conc. ZnO formulations accordingly.

Quantifying the sediment sorption of organic ultraviolet filter chemicals using solvophobic theory

Hydrophobic organic chemicals (HOCs) that enter the aquatic environment often negatively impact organisms, endangering aquatic biodiversity. Understanding sediment sorption equilibria for these chemicals can properly direct mitigation efforts. In addition, many HOCs of environmental concern lack sufficient environmental fate data to adequately assess their risk to ecosystems and humans. In this study, a sorption method addressing solvophobic effects was used to quantify the sorption of an HOC of current environmental concern, OD-PABA (padimate O, 2-ethylhexyl-4-(dimethylamino)benzoate), to a variety of sediments. OD-PABA is an organic ultraviolet filter chemical used in commercial sun protection products; it has been shown to exhibit cytotoxic effects and is known to photochemically transform under natural sunlight conditions. Given its commercial use, it enters the aquatic environment via recreational use and wastewater treatment plant effluent. OD-PABA is strongly hydrophobic; to mitigate the adsorption of OD-PABA to the container walls during sorption experiments, a precise concentration of methanol was used to avoid solvophobic effects. This sorption method was used to determine the sorption capacities for OD-PABA of four sediment samples, each with unique geochemical characteristics. Sediment-water distribution coefficients (Kd) were quantified and were normalized to various sediment characteristics to assess the main driving force(s) for sorption of OD-PABA. Organic carbon content was found to be a main driving force, with organic carbon-normalized distribution coefficients (log Koc) ranging from 4.4 to 4.6 for sediments with total organic carbon (TOC) > 10%); the clay fraction was also found to be important, especially for sediments with low TOC. The sorption of para-aminobenzoic acid (PABA), a water-soluble analog of OD-PABA was also investigated to assess the experimental approach, yielding a log Koc of 2.1 for the sediment with the greatest TOC.