4-methylbenzylidene Camphor Research Articles

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.

Assessing the interaction between 4-methylbenzylidene camphor and microplastic fibers in aquatic environments: Adsorption kinetics and mechanisms

Wastewater treatment plants play a crucial role in managing environmental pollutants, but they often release persistent contaminants like synthetic microplastic fibers (MPFs) into ecosystems. These microplastics, mainly from the textile industry and domestic washing of synthetic fabrics, are a major type of microplastic found in aquatic environments. Some harmful chemicals have an affinity for these microplastics, making them vectors for contaminants. This study investigates the adsorption of 4-methylbenzylidene camphor (4-MBC), an organic UV filter, onto microplastic fibers from two different sources. Batch experiments conducted at room temperature (25 °C) under laboratory conditions assessed the adsorption kinetics and mechanisms. Morphological and visual characterization of the microplastic fibers was done using optical microscopy and scanning electron microscopy (SEM), revealing diverse shapes, types, and colors. Physico-chemical properties were confirmed through thermogravimetric analysis (TGA) and Fourier-transform infrared spectroscopy (FTIR). The data matched well with the PSO kinetic model and Langmuir isotherm, indicating monolayer chemisorption with equilibrium achieved within 24 h. The adsorption mechanisms involved electrostatic attraction, hydrogen bonding, and π-π interactions. Both types of microplastic fibers exhibited a tendency to adsorb 4-MBC, indicating the significance of this research in understanding the interactions between this compound and various fiber types emphasizing the need for further research under the different environmental conditions.

Impacts of UV-filter pollution and low pH: Sperm and adult biomarkers in the mussel Mytilus galloprovincialis in a multi-stressor context.

In an era of unprecedented environmental changes, understanding the combined effects of multiple stressors on species' performance is urgent. The increasing UV-filter incorporation in daily-life products raises concerns about their potential impact on marine-coastal environments upon release. As stressors rarely act alone, global change-induced factors, such as ocean acidification (OA), can amplify ecological hazards promoted by contaminants in coastal realms. This study investigated the combined impacts of UV-filters 4-methylbenzylidene camphor (4-MBC) and benzophenone-3 (BP-3), at ecologically relevant concentrations (1 and 10 µg/L), under two target pH levels (8.2 and 7.7, reflecting a ∆pH of 0 and -0.3 relative to the average pH at the sampling site), on the biological performance and male reproductive health of the mussel Mytilus galloprovincialis. Using sperm and adult assays alongside a multi-biomarker approach, the study revealed that pH was the primary driver of the decline in mussel physiological and biochemical performances, further intensifying UV-filters' impacts. While sperm cells showed adaptive responses to low pH conditions alone, characterized by reduced lipid peroxidation (LPO) levels and superoxide anion overproduction, adult mussels experienced more pronounced effects, particularly under simultaneous exposure to low pH and UV-filters. Specifically, the adults exhibited distinct bioconcentration patterns under low pH, enhanced cellular metabolic activity and energy-demand compensatory processes, activation of biotransformation pathways, and regulation of antioxidant defenses. Given the ecological and socio-economic importance of M. galloprovincialis and its demonstrated vulnerability to these stressors, these findings highlight the need for further studies on potential transgenerational impacts and evolutionary implications for mussel populations.

Advanced HPLC Method with Diode Array Detection Using a Phenyl-Bonded Column for Simultaneous Quantitation of Three Sunscreen Filters in a Moisturizing Sunscreen Cream for Acne-Prone Skin

This study introduces a novel, robust, and efficient method for the simultaneous quantitative determination of three sunscreen filters, namely, 4-methylbenzylidene camphor, octyl methoxycinnamate, and avobenzone, in a moisturizing sunscreen cream specifically designed for acne-prone skin. The method employs high-performance liquid chromatography with photodiode-array detection, providing a reliable separation of the analytes. Chromatographic separation was achieved using a Fortis Phenyl analytical column (150.0 × 2.1 mm, 5 μm), with isocratic elution at a flow rate of 0.4 mL/min. The mobile phase was composed of a 57/43 (v/v) mixture of acetonitrile/45 mM aqueous ammonium formate solution, ensuring sufficient resolution and peak symmetry for the target compounds. The method was validated comprehensively for critical performance parameters, including linearity, precision, accuracy, and robustness. Linearity was established across a suitable range for all three analytes, with high correlation coefficients. Precision was confirmed with intra-run and total precision coefficients of variation of ≤4.6%, while accuracy assessments yielded a percent recovery between 98.6 and 100.4, for all quality control levels. Additionally, the method was able to effectively separate the sunscreen filters from other cosmetic ingredients, such as [β-(1.3), (1.6)-D-glucan], low molecular weight (LMW) hyaluronic acid and plant extracts ensuring specificity in complex formulations. This straightforward and time efficient sample preparation process, involving methanol extraction followed by serial dilution, makes the method suitable for routine quality control in cosmetic laboratories. The method was successfully applied to the analysis of two different lots of a commercial sunscreen cream, achieving excellent recovery for all filters, ranging between 94.6% and 99.8%, thus demonstrating its reliability and applicability for the quality control of cosmetics.

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.

P21-41 Deciphering sex-specific disruption in the nervous and reproductive systems through interactions of 4-methylbenzylidene camphor and nanoplastics in adult zebrafish

P21-41 Deciphering sex-specific disruption in the nervous and reproductive systems through interactions of 4-methylbenzylidene camphor and nanoplastics in adult zebrafish

Distribution and accumulation of UV filters (UVFs) and conservation status of Posidonia oceanica seagrass meadows in a prominent Mediterranean coastal tourist hub

This study investigates the presence and impact of UV filters in Posidonia oceanica meadows in Formentera, a Mediterranean tourist hotspot. It highlights the distribution of inorganic (TiO2 and ZnO) and organic UV filters (UVFs) in different environmental matrices, their accumulation in seagrass tissues and their impact on the seagrass health.In the overlying and canopy waters of P. oceanica, Zn concentrations surpassed Ti, with three organic UVFs (benzophenone-3 [BP-3], avobenzone and homosalate [HMS]) consistently detected. Ti concentrations were generally higher than Zn in rhizosphere sediments, along with recurrent presence of octocrylene, HMS, 2-ethylhexyl methoxycinnamate (EHMC), and 4-methylbenzylidene camphor (4-MBC). Maximum Zn concentrations were found in canopy waters (3052.9 ng L−1). Both Ti and Zn were found in all P. oceanica tissues and leaf epiphytes across all study sites. Additional UVFs like octocrylene, avobenzone, and BP-8 were also detected in P. oceanica tissues and epiphytes. Elevated levels of octocrylene in leaf epiphytes (2112.1 ng g−1 dw) and avobenzone in leaves (364.2 ng g−1 dw) and leaf epiphytes (199.6 ng g−1 dw) were observed in the Port of La Savina, the island's main entry port. Octocrylene concentrations (up to 2575 ng g−1 dw) in rhizosphere sediments near sewage discharge points exceeded reported maxima, highlighting wastewater treatment plants as significant sources of organic UVFs. Correlational analyses suggested that the accumulation of octocrylene, avobenzone, and BP-3 negatively impacted P. oceanica's conservation status, affecting global density, density at 100 % cover, and leaf morphometry. Positive correlations were observed between leaf polyphenols (antioxidants) and concentrations of avobenzone, benzophenone-8 (BP-8), and BP-3, indicating potential oxidative stress induced by UVFs in P. oceanica.Our study underscores the pervasive presence of UV filters in P. oceanica habitats, with implications for seagrass health and conservation, especially in areas of high tourism and sewage discharge.

Determination of 16 ultraviolet–absorbing compounds in marine invertebrates by using LC-USI-MS/MS coupled with QuEChERS

In this study, we examined multiple endocrine-disrupting ultraviolet-absorbing compounds (UVACs) in marine invertebrates used in personal care products and packaging. Modified QuEChERS and liquid chromatography UniSpray ionization tandem mass spectrometry were used to identify 16 UVACs in marine invertebrates. Matrix-matched calibration curves revealed high linearity (r ≥ 0.9929), with limits of detection and quantification of 0.006–1.000 and 0.020–3.000 ng/g w.w., respectively. In oysters, intraday and interday analyses revealed acceptable accuracy (93%–120%) and precision (≤18%), except for benzophenone (BP) and ethylhexyl 4-(dimethylamino) benzoate. Analysis of 100 marine invertebrate samples revealed detection frequencies of 100%, 98%, 89%, 64%, and 100% for BP, 4-hydroxybenzophenone, 4-methylbenzophenone, 4-methylbenzylidene camphor, and benzophenone-3 (BP-3), respectively. BP and BP-3 were detected at concentrations of 4.40–27.39 and < 0.020–0.560 ng/g w.w., respectively, indicating their widespread presence. Overall, our proposed method successfully detected UVACs in marine invertebrates, raising concerns regarding their potential environmental and health effects.

New Insight into the Degradation of Sunscreen Agents in Water Treatment Using UV-Driven Advanced Oxidation Processes

This study evaluates, for the first time, the effects of UV/PMS and UV/H2O2/PMS processes on the degradation of sunscreen agents in synthetic and natural water matrices and compares their effectiveness with the more conventional UV/H2O2. Investigations were conducted using a mixture of organic UV filters containing 4-methylbenzylidene camphor (4-MBC) and 2-ethylhexyl-4-methoxycinnamate. Among the investigated UV-driven AOPs, UV/PMS/H2O2 was the most effective in synthetic water, while in natural water, the highest degradation rate was observed during the degradation of EHMC by UV/PMS. The degradation of UV filters in the UV/PMS system was promoted by sulfate radical (68% of the degradation), with hydroxyl radical contributing approximately 32%, while both radical species contributed approximately equally to the degradation in the UV/H2O2/PMS system. The Vibrio fischeri assay showed an increase in inhibition (up to 70%) at specific stages of UV/H2O2 treatment when applied to natural water, which further decreased to 30%, along with an increase in UV fluence and progressive degradation. The Pseudomonas putida test recorded minor toxicity (&lt;15%) after treatments. Magnetic biochar utilized in conjunction with UV-driven AOPs exhibited superior performance in eliminating residual contaminants, providing an efficient and sustainable approach to mitigate sunscreen agents in water treatment.

Organic UV filters: Occurrence, risks and (anti-)progestogenic activities in samples from the Czech aquatic environment and their bioaccumulation in fish

The occurrence, environmental risks and contribution of organic UV filters to detected (anti-)progestogenic activities were examined in samples of wastewater treatment plant influents and effluents, various surface waters and fish from the Czech Republic. Of the 20 targeted UV filters, 15 were detected in the WWTP influent samples, 11 in the effluents, and 13 in the surface water samples. Benzophenone-3, benzophenone-4, and phenyl benzimidazole sulfonic acid (PBSA) were found in all water samples. Octocrylene, UV-327 and 4-methylbenzylidene camphor exceeded the risk quotient of 1 at some sites. In the anti-progestogenic CALUX assay, 10 out of the 20 targeted UV filters were active. Anti-progestogenic activities reaching up to 7.7 ng/L, 3.8 ng/L, and 4.5 ng/L mifepristone equivalents were detected in influents, effluents, and surface waters, respectively. UV filters were responsible for up to 37 % of anti-progestogenic activities in influents. Anti-progestogenic activities were also measured in fish tissues from the control pond and Podroužek (pond with the highest number of detected UV filters) and ranged from 2.2 to 9.5 and 1.9 to 8.6 ng/g dw mifepristone equivalents, respectively. However, only benzophenone was found in fish, but it does not display anti-progestogenic activity and thus could not explain the observed activities.

UV filters in beach sands from beaches along the Atlantic Ocean coastline in Lagos, Nigeria: Occurrence and risk assessment

Ultra violet (UV) filters are commonly used as ingredients in sunscreens and cosmetics to protect skin or hair against sun damage, and also in industrial products to prevent photo-degradation. In spite of the benefits provided, some UV filters pose serious threats to the environment. There is currently little information on the occurrence and potential ecological risk of UV filters in beach sands. We investigated, for the first time, the occurrence and ecological risk of seven UV filters in beach sands (offshore, shoreline and sand dune samples) of selected beaches along the Atlantic Ocean coastline in Lagos, Nigeria. Sample extraction and analysis were carried out by ultrasonic-assisted extraction and high performance liquid chromatography, respectively. Overall recoveries ranged from 91% for benzophenone-3 (BP-3) to 109% for 2-ethylhexylsalicylate (EHS) at the spiking concentration 125 ng.g−1. Limits of detection ranged between 5.0 ng.g−1 (for BP-3) to 54.3 ng/g (EHS). Although all studied UV filters were detected in the sand dune sample of Oniru beach and four compounds in Elegushi beach sand dune, none of the UV filters was detected in the beach sands (offshore, shoreline and sand dune samples) collected from Landmark and Lekki Leisure beaches. The highest concentrations of the UV filters were all found in Oniru beach sand dune, up to 191 ng.g−1 for p-aminobenzoic acid (PABA) which was detected in beach sands for the first time. BP-3, EHS, 2-ethylhexyl-4-methoxycinnamate (EHMC), 3-(4-methylbenzylidene) camphor (4-MBC) and octocrylene (OCR) were likely to cause adverse effects to benthic/pelagic organisms.

From cradle to grave: Deciphering sex-specific disruptions of the nervous and reproductive systems through interactions of 4-methylbenzylidene camphor and nanoplastics in adult zebrafish

4-methylbenzylidene camphor (4-MBC) and micro/nanoplastics (MNPs) are common in personal care and cosmetic products (PCCPs) and consumer goods; however, they have become pervasive environmental contaminants. MNPs serve as carriers of 4-MBC in both PCCPs and the environment. Our previous study demonstrated that 4-MBC induces estrogenic effects in zebrafish larvae. However, knowledge gaps remain regarding the sex- and tissue-specific accumulation and potential toxicities of chronic coexposure to 4-MBC and MNPs. Herein, adult zebrafish were exposed to environmentally realistic concentrations of 4-MBC (0, 0.4832, and 4832 μg/L), with or without polystyrene nanoplastics (PS-NPs; 50 nm, 1.0 mg/L) for 21 days. Sex-specific accumulation was observed, with higher concentrations in female brains, while males exhibited comparable accumulation in the liver, testes, and brain. Coexposure to PS-NPs intensified the 4-MBC burden in all tested tissues. Dual-omics analysis (transcriptomics and proteomics) revealed dysfunctions in neuronal differentiation, death, and reproduction. 4-MBC-co-PS-NP exposure disrupted the brain histopathology more severely than exposure to 4-MBC alone, inducing sex-specific neurotoxicity and reproductive disruptions. Female zebrafish exhibited autism spectrum disorder-like behavior and disruption of vitellogenesis and oocyte maturation, while male zebrafish showed Parkinson's-like behavior and spermatogenesis disruption. Our findings highlight that PS-NPs enhance tissue accumulation of 4-MBC, leading to sex-specific impairments in the nervous and reproductive systems of zebrafish.

Bioconcentration, biotransformation, and transcriptomic impact of the UV-filter 4-MBC in the manila clam Ruditapes philippinarum

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.

4-Methylbenzylidene camphor induced neurobehavioral toxicity in zebrafish (Danio rerio) embryos

4-Methylbenzylidene camphor (4-MBC) is a widely used organic UV filter in personal care products. Extensive use of 4-MBC and its frequent detection in aquatic ecosystems defile the biota with muscular and neuronal impairments. This study investigates the neurobehavioral toxicity of 4-MBC using Danio rerio as a model organism. Embryos were exposed semi-statically to 4-MBC at 5, 50, and 500 μg/L concentrations for 10-day post fertilization (dpf). Embryos exhibited a significant thigmotaxis and decreased startle touch response with altered expression of nervous system mRNA transcripts on 5 & 10 dpf. Compared to the sham-exposed group, 4-MBC treated larvae exhibited changes in the expression of shha, ngn1, mbp, elavl3, α1-tubulin, syn2a, and gap43 genes. Since ngn1 induction is mediated by shh signaling during sensory neuron specification, the elevated protein expression of NGN1 indicates 4-MBC interference in the sonic hedgehog signaling pathway. This leads to sensory neuron impairment and function such as ‘sense’ as evident from reduced touch response. In addition, larval brain histology with a reduced number of cells in the Purkinje layer emblazing the defunct motor coordination. Predictive toxicity study also showed a higher affinity of 4-MBC to modeled Shh protein. Thus, the findings of the present work highlighted that 4-MBC is potential to induce developmental neurotoxicity at both behavioral and molecular functional perspectives, and developing D. rerio larvae could be considered as a suitable alternate animal model to assess the neurological dysfunction of organic UV filters.

Peracetic acid as an alternative disinfectant for micropollutants degradation and disinfection byproducts control in outdoor swimming pools

Peracetic acid (PAA) has garnered significant interest as a novel alternative to chlorine-based disinfectants for water treatment due to its broad-spectrum antimicrobial activity and its ability of reactive species generation when exposed to UV light. However, limited studies have investigated micropollutant degradation in the presence of PAA under solar irradiation. This is the first study to comprehensively investigate the photodegradation of caffeine (CAF) and 4-methylbenzylidene camphor (4-MBC) and the removal of disinfection byproducts (DBPs) in the presence of PAA under simulated solar light. The study revealed that the photodegradation of CAF and 4-MBC was significantly enhanced in the presence of PAA, following pseudo-first-order kinetics (R2 > 0.98) with reaction rates (kobs) of 0.220 and 0.111 h-1, respectively. In addition, substantial reduction of 21 DBPs, including trihalomethanes, haloacetic acids and haloacetonitriles, and no DBPs formation were observed in the presence of PAA and simulated solar irradiation. The proportion of coexisting H2O2 in the PAA solution considerably influenced target compounds degradation. CAF and 4-MBC were degraded faster under acidic conditions than under alkaline conditions. Hydroxyl radicals (·OH) dominated the degradation of CAF at different pH values, while direct photolysis and other reactive species played a major role in the degradation of 4-MBC.

Salting-out assisted liquid–liquid extraction combined with LC–MS/MS for the simultaneous determination of seven organic UV filters in environmental water samples: method development and application

Organic UV filters (OUVFs), the active ingredient in sunscreens, are of environmental concern due to reported ecotoxicological effects in aquatic biota. Determining the environmental concentrations of these chemicals is essential for understanding their fate and potential environmental risk. Salting‐out assisted liquid–liquid extraction (SALLE) coupled with liquid-chromatography tandem mass spectrometry (LC–MS/MS) was developed for simultaneous extraction, separation, and quantification of seven OUVFs (2,4-dihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 4-methylbenzylidene camphor, butyl-methoxy-dibenzoyl methane, octocrylene, octyl methoxycinnamate, and oxybenzone). Method detection limits (MDLs) ranged from 11 to 45 ng/L and practical quantification limits (PQLs) from 33 to 135 ng/L. Method trueness, evaluated in terms of recovery, was 69–127%. Inter-day and intra-day variability was < 6% RSD. The coefficients of determination were > 0.97. The method was applied to river and seawater samples collected at 19 sites in and near Port Phillip Bay, Australia, and temporal variation in OUVF concentrations was studied at two sites. Concentrations of OUVF were detected at 10 sites; concentrations of individual OUVFs were 51–7968 ng/L, and the maximum total OUVF concentration detected at a site was 8431 ng/L. Recreational activity and water residence time at the site contributed to OUVF’s environmental presence and persistence. The benefits of the SALLE-LC–MS/MS method include its simple operation, good selectivity, precision over a wide linear range, and that obtained extracts can be directly injected into the LC–MS/MS, overall making it an attractive method for the determination of these OUVFs in environmental water matrices. To our knowledge, this is the first report of the occurrence of OUVFs in Port Phillip Bay, Australia.

Exploring environmental obesogenous effects of organic ultraviolet filters on children from a case-control study

It has been globally recognized that obesity has become a major public health concern, especially childhood obesity. There is limited information, however, regarding the exposure risk of organic ultraviolet (UV) filters, a kind of emerging contaminant, on childhood obesity. This study would be made on 284 obese and 220 non-obese Chinese children with eight organic UV filters at urinary levels. The eight organic UV filters, including 2-Ethylhexyl 4-aminobenzoate (PABA-E), octisalate (EHS), homosalate (HMS), 2-Ethylhexyl-p-methoxycinnamate (EHMC), benzophenone-3 (BP-3), amiloxate (IAMC), octocrylene (OC) and 4-Methylbenzylidene camphor (4-MBC) were identified in urine samples with detection rates ranged from 35.32% to 100%, among which PABA-E, HMS, IAMC and OC were firstly detected in children’ s urine. And the urinary UV filters concentration was associated with genders, living sites, guardian education levels, household income, and dietary factors. Urinary EHMC concentrations and childhood obesity were positively associated for girls [Adjusted OR = 2.642 (95% CI: 1.019, 6.853)], while OC concentrations and childhood obesity were negatively associated for girls [Adjusted OR = 0.022 (95% CI: 0.001, 0.817)]. The results suggest that EHMC exposure may be an environmental obesogen for girls. Moreover, two statistical models were used separately to evaluate the impact of UV filter mixtures on childhood obesity, including the Bayesian kernel machine regression (BKMR) model and the quantile g-computation (qgcomp) model. The negative association between UV filter mixtures and childhood obesity was proposed from both BKMR and qgcomp models. Further experimental and epidemiological studies are called upon to discern the individual and mixture impacts of organic UV filters on childhood obesity.

Multi-biomarker approach for the (eco)toxicity of UV-filter environmental pollution on the Mediterranean mussel Mytilus galloprovincialis in a multiple stressor context. The case of 4-MBC under salinity shifts.

Marine-coastal ecosystems are rapidly transforming because of climate change (CC). At the same time, the impacts of emerging organic contaminants (i.e., organic UV-filters) on these ecosystems are intensifying. In the Mediterranean, the consequences of these disturbances are occurring at a fast pace making this area a potential sentinel site to be investigated. While singular effects of organic UV-filters or CC-related factors on marine biota have been relatively described, their combined impact is still largely unknown. Thus, the objective of this study was to assess the long-term responses of the Mediterranean mussel Mytilus galloprovincialis towards anticipated salinity changes (decreases-S20 or increases-S40) when exposed to environmentally relevant concentrations of the UV-filter 4-methylbenzylidene camphor (4-MBC). An integrated multi-biomarker approach was applied, featuring general and oxidative stress, antioxidant and biotransformation enzyme capacity, energy metabolism, genotoxicity, and neurotoxicity biomarkers. Results showed that both projected salinities, considered separately, exerted non-negligible impacts on mussels' health status, with greater biological impairments found at S 40. Combining both stressors resulted in an evident increase in mussels' susceptibility to the UV-filter, which exacerbated the toxicity of 4-MBC. The dominant influence of salinity in the climate change-contaminant interaction played a crucial role in this outcome. The most severe scenario occurred when S 20 was combined with 4-MBC. In this situation, mussels exhibited a decrease in filtration rate, metabolic capacity and deployment of energy reserves increased, with an upregulation of biotransformation and inhibition of antioxidant enzyme activities. This exposure also led to the observation of cellular and DNA damage, as well as an increase in AChE activity. Furthermore, salinity-dependent bioaccumulation patterns were evaluated revealing that the lowest values in contaminated mussels are found at S 20. Overall, the present findings provide evidence that projected CC/pollutant scenarios may represent high risks for mussels’ populations, with global relevant implications for the ecosystem level.

Contaminants of emerging concern in urine: a review of analytical methods for determining diisocyanates, benzotriazoles, benzothiazoles, 4-methylbenzylidene camphor, isothiazolinones, fragrances, and non-phthalate plasticizers.

Human biomonitoring (HBM)frameworks assess human exposure to hazardous chemicals. In this review, we discuss and summarize sample preparation procedures and analytical methodology for six groups of chemicals of emerging concern (CECs), namely diisocyanates, benzotriazoles, benzothiazoles, 4-methylbenzylidene camphor, isothiazolinones, fragrances, and non-phthalate plasticizers, which are increasingly detected in urine, however, are not yet widely included in HBM schemes, despite posing a risk to human health. The sample preparation procedures depend largely on the chemical group; however, solid-phase extraction (SPE) is most often used due to the minimized sample handling, lower sample volume, and generally achieving lower limits of quantification (LOQs) compared to other extraction techniques. In terms of sample analysis, LC-based methods generally achieve lower limits of quantification (LOQs) compared to GC-based methods for the selected six groups of chemicals owing to their broader chemical coverage. In conclusion, since these chemicals are expected to be more frequently included in future HBM studies, it becomes evident that there is a pressing need for rigorous quality assurance programs to ensure better comparability of data. These programs should include the reporting of measurement uncertainty and facilitate inter-laboratory comparisons among the reporting laboratories. In addition, high-resolution mass spectrometry should be more commonly employed to enhance the specificity and selectivity of the applied analytical methodology since it is underrepresented in HBM. Furthermore, due to the scarcity of data on the levels of these CECs in urine, large population HBM studies are necessary to gain a deeper understanding of the associated risks.

ADME characterization and PBK model development of 3 highly protein-bound UV filters through topical application.

Estimating human exposure in the safety assessment of chemicals is crucial. Physiologically based kinetic (PBK) models which combine information on exposure, physiology, and chemical properties, describing the absorption, distribution, metabolism, and excretion (ADME) processes of a chemical, can be used to calculate internal exposure metrics such as maximum concentration and area under the concentration-time curve in plasma or tissues of a test chemical in next-generation risk assessment. This article demonstrates the development of PBK models for 3 UV filters, specifically octyl methoxycinnamate, octocrylene, and 4-methylbenzylidene camphor. The models were parameterized entirely based on data obtained from in vitro and/or in silico methods in a bottom-up modeling approach and then validated based on human dermal pharmacokinetic (PK) data. The 3 UV filters are "difficult to test" in in vitro test systems due to high lipophilicity, high binding affinity for proteins, and nonspecific binding, for example, toward plastic. This research work presents critical considerations in ADME data generation, interpretation, and parameterization to assure valid PBK model development to increase confidence in using PBK modeling to help make safety decisions in the absence of human PK data. The developed PBK models of the 3 chemicals successfully simulated the plasma concentration profiles of clinical PK data following dermal application, indicating the reliability of the ADME data generated and the parameters determined. The study also provides insights and lessons learned for characterizing ADME and developing PBK models for highly lipophilic and protein-bound chemicals in the future.