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The increasing use of UV filters, such as benzophenone-3 (BP-3) and titanium dioxide nanoparticles (TiO2 NPs), has raised concerns regarding their ecotoxicological effects on the aquatic environment. The aim of the present study was to examine the embryo-larval toxicity attributed to BP-3 or TiO2 NPs, either alone or in a mixture, utilizing zebrafish (Danio rerio) as a model after exposure to environmentally relevant concentrations of these compounds. Zebrafish embryos were exposed to BP-3 (10, 100, or 1000 ng/L) or TiO2 NPs (1000 ng/L) alone or in a mixture (BP-3 10, 100, or 1000 ng/L plus 1000 ng/L of TiO2 NPs) under static conditions for 144 hr. After exposure, BP-3 levels were determined by high-performance liquid chromatography (HPLC). BP-3 levels increased in the presence of TiO2 NPs, indicating that the BP-3 degradation decreased in the presence of the NPs. In addition, in the presence of zebrafish, BP-3 levels in water decreased, indicating that zebrafish embryos and larvae might absorb BP-3. Data demonstrated that, in general, environmentally relevant concentrations of BP-3 and TiO2 NPs, either alone or in a mixture, did not significantly induce changes in heart and spontaneous contractions frequencies, levels of reactive oxygen species (ROS), morphological and morphometric parameters as well as mortality rates during 144 hr exposure. However, the groups exposed to TiO2 NPs alone and in a mixture with BP-3 at 10 ng/L exhibited an earlier significant hatching rate than the controls. Altogether, the data indicates that a potential ecotoxicological impact on the aquatic environment exists. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Background: Photopatch testing represents the gold standard for the diagnosis of photoallergic contact dermatitis (PACD). We aimed to identify common photoallergens in our tertiary dermatological referral centre from 2012 to 2021, to compare this to the preceding period studied, and data from other communities. Methods: We conducted a retrospective review of all 90 patients who underwent photopatch testing at the National Skin Centre, Singapore, between 2012 and 2021. Results: Of 90 patients, 19 (21.1%) were male, and the mean age was 41.6 years. Eighty‐four (93.3%) underwent testing to our standard sunscreen series, 10 (11.1%) to our extended series, and 73 (81.1%) to their own items. Seventeen (18.9%) were diagnosed with PACD (i.e., photocontact allergy with present or past relevance), 12 (13.3%) with ACD, and 4 (4.4%) with photoaugmented ACD. Relevant reactions were commonest to oxybenzone (8, 9.5%) and mexenone (3, 3.6%). Eleven (15.1%) had PACD to their own items, with 3 of 4 (75%) tested to ketoprofen diagnosed with PACD and the remaining 1 (25%) with photoaugmented ACD. Age, race, sex, atopy, and site of involvement were not associated with photocontact allergy. Compared to the preceding time period, the overall frequency of photocontact allergy and PACD decreased, but rates of photoallergic reactions to individual photoallergens were not significantly different. Conclusion: Organic ultraviolet absorbers such as oxybenzone and mexenone remained the most relevant photoallergens. Personal item testing was valuable, and testing to ketoprofen should be considered. [ABSTRACT FROM AUTHOR]

Personal care products, such as UV filters, are frequently present in aquatic ecosystems, but studies on their impact on marine organisms are still scarce. Here we addressed the effects of benzophenone-3 (BP-3) on the antioxidant status of Perna perna mussels exposed to concentrations of 0.1 and 3 μg.L−1 for 72 h and 7 days. Glutathione peroxidase (GPx), glutathione reductase (GR), glutathione S-transferase (GST), glucose-6-phosphate dehydrogenase (G6PDH) activity and lipoperoxidation (MDA) were evaluated in the gills. A significant reduction (p < 0.05) in the activity of G6PDH and GPx was observed after exposure for 7 days to 0.1 µg.L−1. However, no significant differences were observed in GST activity and MDA levels, independently of the exposure time. Principal component analysis (PCA) showed an association of BP-3 highest concentration with GR and MDA at 72 h and only with GR at 7 days of exposure. Similarly, the integrated biomarker response (IBR) demonstrated GR and MDA alterations. In conclusion, environmentally relevant concentrations of BP-3 altered antioxidant and auxiliary enzymes, which could cause long-term damage to P.perna mussels. The need to implement more efficient techniques in wastewater treatment systems is pointed out, especially in summer, when UV filters are used more frequently and abundantly. [ABSTRACT FROM AUTHOR]

Purpose: Oxybenzone has received widespread attention owing to its extensive accumulation in the soil and adverse effects on plant growth. The aim of the study was to verify the potential of tobacco (Nicotiana tabacum) combined with the use of adenine and plant growth-promoting rhizobacteria (PGPR) (Methylophilus sp. strain FP-6) to enhance the efficiency of oxybenzone removal from the soil, and investigate the interaction between adenine and strain FP-6 that occurred during the phytoremediation process. Methods: First, we determined whether the presence of adenine stimulated the growth and plant growth-promoting (PGP) traits of strain FP-6, which was isolated in our previous study and demonstrated considerable potential for the degradation of oxybenzone. The combined effects of strain FP-6 and adenine on the growth of tobacco and the efficiency of oxybenzone removal from the soil were then investigated. Furthermore, we evaluated the soil enzyme activities and microbial community composition in tobacco-growing soil containing oxybenzone. Results: The adenine-FP6 amendment significantly improved photosynthetic efficiency and maintained the ion homeostasis of tobacco, which was destroyed by oxybenzone, thereby promoting the efficiency of phytoremediation of oxybenzone by tobacco (97.99%). Furthermore, a series of hydrolases involved in nutrient cycles and oxidoreductases with high reactivity to phenolic compounds in the soil were significantly up-regulated under this remediation strategy, which might be attributed to the increased relative abundance of some rhizosphere bacteria, such as Faecalibacterium, Agathobacter, and Sphingomonas. Conclusion: The findings of this study provide an economical and ecological phytoremediation strategy for the efficient remediation of oxybenzone -contaminated soils. [ABSTRACT FROM AUTHOR]

Benzophenone-3 (BP-3), utilized as a UV filter in cosmetic products, is an emerging contaminant that constitutes a threat to natural resources and environmental health. This study investigated the assimilation of the UV filter BP-3 in Crassostrea gigas oysters collected in Florianópolis, Santa Catarina, Brazil. Lyophilized oyster tissue extracts were prepared using the QuEChERS method, and LC-MS/MS was employed to determine the BP-3 concentration in the samples. The method was applied to specimens intentionally exposed to two concentrations of the contaminant, for different periods of exposure (1 and 7 days). Samples from treatment 1 (T1) were exposed to a concentration of 1 μg L−1 of the BP-3 standard, and samples from treatment 2 (T2) were exposed to a concentration of 100 μg L−1 of the BP-3 standard. The results revealed rapid absorption of BP-3, with an increase of 126% for lower concentrations, reaching 1.13 μg of BP-3 per gram of oyster tissue, and 17% for higher concentrations, reaching 34.6 μg of BP-3 per gram of oyster tissue after 7 days. The presence of BP-3 even in samples not directly exposed to the contaminant indicates its widespread environmental distribution. The rapid bioaccumulation suggests the need to consider seasonal variations, such as increased tourism in the summer. The validated analytical method demonstrated efficacy in quantifying BP-3, providing an integrated approach for long-term monitoring of pollution levels and their dynamic variations over time. In addition, variation in BP-3 levels in the samples may be related to transport patterns influenced by tides and discharges from septic system, highlighting the need to improve wastewater treatment. These findings underscore the necessity for continuous biomonitoring and effective environmental management to safeguard the health of marine ecosystems and humans. [Display omitted] • LC-MS/MS was optimized and validated for the extraction of analyte in oysters. • The recovery of the analyte was 89–101% confirming the accuracy of the method. • Benzophenone-3 was detected and quantified in the soft tissue of oysters. • Oysters are shown to be optimal biomonitors of benzophenone-3. [ABSTRACT FROM AUTHOR]

From March to June 2020, governments across the world imposed lockdowns in an attempt to reduce the transmission of COVID-19 during the early phase of the pandemic. This period of time in which human activity slowed worldwide has been coined the "Anthropause". The goal of this study was to determine if sunscreen pollution abated during the Anthropause and to identify the severity of the pollution when tourism/recreation recovered at two coastal units of the U.S. National Park System: Kaloko-Honokōhau National Historical Park in Hawaiʻi, U.S.A. and Cape Lookout National Seashore in North Carolina, U.S.A. Active ingredients of sunscreen products were measured in water and sand samples at both locations, including oxybenzone, octinoxate, octocrylene, octisalate, homosalate, and relevant breakdown products of some of these ingredients. A risk assessment was conducted on Anthropause and post-Anthropause contaminant levels for both locations to determine if there was a threat reduction during the Anthropause, and whether tourism recovery in the post-Anthropause period served as a threat to coastal wildlife. Both national park units exhibited an almost absolute reduction in the levels of sunscreen contamination during the Anthropause period, a striking commonality considering the geographic expanse separating the parks. Once travel restrictions were lifted, a large influx of tourists ensued at both locations, resulting in a relatively sudden and dangerous increase in the levels of sunscreen chemical pollution. This study supports the argument that unmanaged tourism is a source of coastal sunscreen pollution that poses a threat to the localized continuity of species populations and biodiversity, especially to coral reefs and fisheries. [Display omitted] • Sunscreen pollution in two U.S. National Park was abated during the 2020 COVID- Anthropause. • Post-Anthopause sunscreen levels at both National Parks were a hazard to wildlife. • Tourism and recreational-use were the primary sources of sunscreen pollution. • Mitigation includes education, accessibility of mineral sunscreens, and prohibitions. [ABSTRACT FROM AUTHOR]

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

Interactions between the popular sunscreen ingredients oxybenzone and homosalate and DNA bases have been studied using density functional theory and ab initio methods. Low-energy structures for each sunscreen ingredient interacting with each nucleotide base in either a pi-stacked or hydrogen-bonded fashion were found. The binding energies are comparable to those for the Watson–Crick–Franklin Ade-Thy and Cyt-Gua pairs. Pi-stacked and hydrogen-bonded structures are comparable in energy, with hydrogen-bonded structures having a more negative counterpoise-corrected binding energy, while the final pi-stacked structures are lower in energy. This is due to a geometrical rearrangement required to form the hydrogen bonds that raise the total energy of the complex. It was also found that when using the M06-2X density functional, the STO-3G basis set favors hydrogen bonding, but 6-31G(d) and 6–31 + G(s) basis sets predict similar binding geometries. [ABSTRACT FROM AUTHOR]

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

Ex vivo mammary explant systems are an excellent model to study interactions between epithelium and stromal cell types because they contain physiologically relevant heterotypic interactions in the background of genetically diverse patients. The intact human mammary tissue, termed patient‐derived explant (PDE), can be used to investigate cellular responses to a wide variety of external stimuli in situ. For this study, we examined the impact of cytokines or environmental chemicals on macrophage phenotypes. We demonstrate that we can polarize macrophages within human breast tissue PDEs toward M1 or M2 through the addition of interferon‐γ (IFNγ) + lipopolysaccharide (LPS) or interleukin (IL)‐4 + IL‐13, respectively. Elevated expression levels of M(IFNγ + LPS) markers (HLADRA and CXCL10) or M(IL‐4 + IL‐13) markers (CD209 and CCL18) were observed in cytokine‐treated tissues. We also examined the impact of the endocrine‐disrupting chemical, benzophenone‐3, on PDEs and measured significant, yet varying effects on macrophage polarization. Furthermore, a subset of the PDEs respond to IL‐4 + IL‐13 through downregulation of E‐cadherin and upregulation of vimentin which is reminiscent of epithelial‐to‐mesenchymal transition (EMT) changes. Finally, we were able to show immortalized nonmalignant breast epithelial cells can exhibit EMT characteristics when exposed to growth factors secreted by M(IL‐4 + IL‐13) macrophages. Taken together, the PDE model system is an outstanding preclinical model to study early tissue‐resident immune responses and effects on epithelial and stromal responses to stimuli found both endogenously in the breast and exogenously as a result of exposures. [ABSTRACT FROM AUTHOR]

A skin irritation test using in vitro reconstructed human epidermis (RhE) models was established for hazard identification of irritant chemicals in accordance with UN Globally Harmonized System of Classification and Labelling of Chemicals (GHS) category. In this study, EpiDerm™ was used to assess skin irritation by oxybenzone and N,N-diethyl-m-toluamide (DEET), which are widely used sunscreen and insect repellent components, respectively. EpiDerm™ was applied with oxybenzone and DEET, combined and sequentially with each single dose. Epidermal morphology and differentiation/proliferation were examined microscopically. Oxybenzone and sequential administration groups were determined as nonirritant with cell viability >50% and the morphology was comparable to the human epidermis. Contrastingly, the DEET and coadministration groups exhibited cell viability <50% and poor epidermal morphology. Interleukin (IL)-1α release from substance-treated EpiDerm™ increased inversely to cell viability, suggesting the pro-inflammatory reaction was initiated by DEET. CK-10, E-cadherin, Ki-67, laminin, and ceramide were identified as relevant markers to assess oxybenzone- or DEET-induced epidermal injury. In conclusion, these results may indicate to be aware of the possible skin irritation by indiscriminate use of oxybenzone and DEET without animal testing. [ABSTRACT FROM AUTHOR]

2-Hydroxy-4-methoxybenzophenone (HMB) is a common ingredient in personal care products and used as an UV stabilizer. In these studies, disposition and metabolism of [14C]HMB in rats and mice was assessed following single gavage administration (10, 100, or 500 mg/kg), single IV administration (10 mg/kg), or dermal application (0.1, 1, 10, or 15 mg/kg). Following gavage administration, [14C]HMB was well absorbed and excreted mainly in urine (39–57%) and feces (24–42%) with no apparent difference between doses, species or sexes. Distribution of HMB in tissues was minimal in rats (0.36%) and mice (<0.55%). Distribution of HMB following dermal application was comparable to that following gavage administration; no differences between doses, sexes, or species were observed but absorption varied between dose vehicles. Light paraffin oil had the highest absorption and excretion (98% of the HMB dose absorbed). In rats, HMB slowly appeared in the systemic circulation (Tmax ∼2–6 h) and had poor bioavailability (F%<1). Urine metabolites for both species and all routes included HMB, HMB-glucuronide, 2,4-dihydroxybenzophenone (DHB), DHB-glucuronide, and DHB-sulfates, and novel minor dihydroxy metabolites including 2,5-dihydroxy-4-methoxybenzophenone. In vitro hepatic metabolism in mice differed from human and in vivo metabolism especially for phase II conjugates. [ABSTRACT FROM AUTHOR]

Oxybenzones like benzophenone-3 (BP3) are ultraviolet (UV) filters widely used in personal care products such as sunscreens. BP3 is currently receiving a great deal of attention because many of its properties, including high water solubility and potential to bioaccumulate, enable it to have damaging effects on aquatic ecosystems. One of these effects, the induction of coral bleaching, has led Hawaii to ban all sunscreens containing BP3. BP3 also appears to have endocrine-disrupting properties and has been found to affect animal physiology. However, behavioural consequences of BP3 exposure have yet to be thoroughly characterized. In the present study, we investigated the effects of BP3 on boldness, courtship and aggression in male Siamese fighting fish, Betta splendens , as little is known about the effects that BP3 has on fish social behaviour. To accomplish this, we assigned males to a treatment group (control, low, medium or high BP3 concentration) and completed individual (empty tank, novel environment and shoal) and social (courtship and aggression) behavioural assays before and after a 28-day exposure period. BP3 influenced the expression of social behaviours, with individual boldness generally unaffected. Changes in shoaling occurred regardless of BP3 concentration, while BP3-associated decreases in courtship and aggression were concentration dependent. Abnormal social behaviour may impede successful mating and alter territorial dynamics, with potentially heightened effects in species already experiencing other anthropogenic stressors. • UV filter BP3 changes social behaviour in male Siamese fighting fish. • Exposure to BP3 at any concentration led to more shoaling. • Dose-dependent effects of BP3 were found for courtship and aggression. • Distance displays were reduced by the two highest concentrations. • Contact behaviour decreased with low or high BP3 exposure but only for aggression. [ABSTRACT FROM AUTHOR]

Abstract The occurrence of UV-filters in the environment has raised concerns over potentially adverse impacts on corals. In this study, the concentrations of 13 UV-filters and 11 hormones were measured in surface seawater, sediment, and coral tissue from 19 sites in Oahu, Hawaii. At least eight UV-filters were detected in seawater, sediment, and coral tissue and total mass concentrations of all UV-filters were <750 ng L−1, <70 ng g−1 dry weight (dw), and <995 ng g−1 dw, respectively. Four UV-filters were detected in water, sediment, and coral tissue at detection frequencies of 63–100%, 56–91%, and 82–100%, respectively. These UV-filter concentrations generally varied as follows: water, homosalate (HMS) > octisalate (OS) > benzophenone-3 (BP-3, also known as oxybenzone) > octocrylene (OC); sediment, HMS > OS > OC > BP-3; coral, OS ≈ HMS > OC ≈ BP-3. BP-3 concentrations in surface seawater were <10 ng L−1 at 12 of 19 sites and highest at Waikiki beach (e.g. , 10.9–136 ng L−1). While BP-3 levels were minimal in sediment (e.g. , <1 ng g−1 dw at 18 of 19 sites), and ranged from 6.6 to 241 ng g−1 dw in coral tissue. No quantifiable levels of 2-ethylhexyl 4-methoxycinnamate (also known as octinoxate) were recorded in surface seawater or coral tissues, but 5–12.7 ng g−1 dw was measured for sediment at 5 of 19 sites. No hormones were detected in seawater or sediment, but 17α-ethinylestradiol was present in three corals from Kaneohe Bay. Surfactant degradation products were present in seawater, especially at Waikiki beach. These results demonstrate ubiquitous parts-per-trillion concentrations of UV-filters in surface seawater and is the first report of UV-filters in coral tissue from U.S.A. coastal waters. These data inform the range of environmentally-relevant concentrations for future risk assessments on the potential impacts of UV-filters on coral reefs in Oahu, Hawaii. Graphical abstract Unlabelled Image Highlights • First report of UV-filters in coral tissue from a USA coral reef. • At least 8 UV-filters 8detected in matched surface seawater, sediment and coral tissue from 19 sites in Oahu, Hawaii. • 8UV-filter concentrations in the parts per trillion (ng L-1) 8in surface seawater and in ng g-1 dw. in sediment and corals. • Octinoxate, 11 hormones and sucralose were not detected in surface seawater but surfactant degradation products were. • Overall highest UV-filter concentrations in all matrices were for homoslate and octisalate. [ABSTRACT FROM AUTHOR]

Abstract Oxybenzone (OBZ), an active ingredient in most sunscreens, was recently shown to be toxic to humans, corals and other animals. This study is the first to demonstrate that OBZ can significantly inhibit photosynthesis and respiration in the leaves of a higher plant, cucumber. An OBZ suspension content as low as 0.228 mg/L obviously inhibited the photosynthesis and respiration of cucumber. OBZ instantly inhibits the electron transport of chloroplasts and mitochondria in cucumber leaves. Probit analysis demonstrated that the effective content for 20% inhibition of photosynthetic electron transport was 11.7 mg/L (95% confidence level). The inhibition of photosynthesis and respiration restricts carbohydrate synthesis and ATP regeneration, respectively, limiting the energy available for metabolic processes including the synthesis of vital organic macromolecules such as proteins and nucleic acids in plant cells. The inhibition of photosynthesis also enhanced the excess excitation energy in chloroplasts, resulting in overproduction of reactive oxygen species (ROS), and the inhibition of respiration aggravated this process. ROS accumulation adversely affects the structure and function of proteins, DNA and membrane lipids in plant cells, interfering with normal metabolism and even leading to plant death. Therefore, reducing the use of OBZ is important for protecting global ecological security. Graphical abstract OBZ can enter cells to significantly inhibit photosynthesis and respiration in the leaves of a higher plant, cucumber. OBZ can instantly inhibit the electron transports of chloroplasts and mitochondria. The inhibition of photosynthesis and respiration would restrict the synthesis of carbohydrates and the regeneration of ATP, limiting the energy available for metabolic processes. The inhibition of photosynthesis increased the excess excitation energy in the plant cells, resulting in over-production of reactive oxygen species (ROS), the inhibition of respiration aggravated this process. The over-accumulation of ROS adversely affects the structure and function of proteins, DNA and membrane lipids in plant cells, interfering with normal metabolism and even leading to the death of plant. Image 103 Highlights • The OBZ suspension can instantly inhibit the electron transports of chloroplasts and mitochondria of cucumber. • An OBZ suspension content as low as 0.228 mg/L obviously inhibited the photosynthesis and respiration of cucumber. • The inhibition of photosynthesis and respiration cause the overproduction of reactive oxygen species (ROS). [ABSTRACT FROM AUTHOR]

Summary: What is known and objective: Hawaii will ban two major ingredients of sunscreens. This article reviews the reasons and future directions. Hawaii recently enacted legislation that will ban the use of two major ingredients of the majority of commonly used sunscreens. The reason for the ban is the ingredients' putative deleterious impact on marine ecosystems, particularly coral reefs. But sunscreens also save lives by decreasing the risk of UV‐induced skin cancers. We review both sides of the issue and potential implications for the healthcare system. Comment: Coral reefs consist of organisms in delicate equilibria that are susceptible to small changes in their surroundings. Recent natural and man‐made disruptions, direct or indirect, such as changes in ocean temperature and chemistry, ingress of invasive species, pathogens, pollution and deleterious fishing practices, have been blamed for the poor health, or even the outright destruction, of some coral reefs. The most popular sunscreen products contain two ingredients—oxybenzone and octinoxate—that have also been implicated in coral toxicity and will be banned. This creates a healthcare dilemma: Will the protection of coral reefs result in an increase in human skin cancers? What is new and conclusion: Concentration estimates and mechanism studies support an association—direct or indirect (via promotion of viral infection)—of sunscreens with bleaching of coral reefs. A ban on the two most common sunscreen ingredients goes into effect in Hawaii on January 1, 2021. Proponents suggest that this is a trend, just the first of many such bans worldwide; opponents warn of a dire increase in human skin cancers. As a result, alternative sunscreen compounds are being sought. Hawaii will ban two major ingredients of sunscreens. This article reviews the reasons and future directions. Hawaii recently enacted legislation that will ban the two major ingredients of the majority of commonly used sunscreens in order to protect marine ecosystems, particularly coral reefs. But sunscreens also save lives by decreasing the risk of UV‐induced skin cancers. This article reviews the issues and potential implications for healthcare providers. [ABSTRACT FROM AUTHOR]

Abstract The extensive use of the organic UV filter oxybenzone has led to its ubiquitous occurrence in the aquatic environment, causing an ecotoxicological risk to biota. Although some studies reported adverse effects, such as reproductive toxicity, further research needs to be done in order to assess its molecular effects and mechanism of action. Therefore, in the present work, we investigated metabolic perturbations in juvenile gilt-head bream (Sparus aurata) exposed over 14 days via the water to oxybenzone (50 mg/L). The non-targeted analysis of brain, liver and plasma extracts was performed by means of UHPLC-qOrbitrap MS in positive and negative modes with both C18 and HILIC separation. Although there was no mortality or alterations in general physiological parameters during the experiment, and the metabolic profile of brain was not affected, the results of this study showed that oxybenzone could perturb both liver and plasma metabolome. The pathway enrichment suggested that different pathways in lipid metabolism (fatty acid elongation, α-linolenic acid metabolism, biosynthesis of unsaturated fatty acids and fatty acid metabolism) were significantly altered, as well as metabolites involved in phenylalanine and tyrosine metabolism. Overall, these changes are signs of possible oxidative stress and energy metabolism modification. Therefore, this research indicates that oxybenzone has adverse effects beyond the commonly studied hormonal activity, and demonstrates the sensitivity of metabolomics to assess molecular-level effects of emerging contaminants. Graphical abstract Image 1 Highlights • The first metabolomic study exposing fish to the UV filter oxybenzone. • Oxybenzone perturbed the liver and plasma metabolome, but not the brain metabolome. • Phenylalanine, tyrosine and lipid metabolisms altered based on pathway enrichment. • Signs of possible energy metabolism modification and oxidative stress were observed. • Metabolomics is sensitive to assess molecular-level adverse effects of xenobiotics. [ABSTRACT FROM AUTHOR]

The widespread occurrence of UV filters such as oxybenzone (OXY) in the aquatic ecosystems has raised social and scientific concern due to their high bioaccumulation potential and possible adverse effects in organisms. Within this context, the aim of the present work was to study the uptake, distribution, metabolization and elimination of OXY in different tissues (liver, gill and muscle) and biofluids (bile and plasma) of gilt-head bream ( Sparus aurata ) in a controlled seawater ecosystem (50 ng/mL OXY) within a 14-day exposure. The highest OXY concentrations in all the tissue/biofluids were found at the end of the experiment. The highest OXY levels were found in bile (1.8–17 μg/mL). In the case of liver, the concentrations found (9–160 ng/g) were lower than those expected for a lipidic matrix, which could be explained by a high OXY metabolization. Up to 20 Phase I and Phase II by-products of OXY were annotated by means of liquid chromatography–high resolution mass spectrometry, of which 12 were reported for the first time. In addition to OXY, its by-products might also cause adverse effects and their biomonitoring is advisable in order to fully characterize OXY exposure. [ABSTRACT FROM AUTHOR]

The efficient removal of Endocrine Disruptive Chemicals (EDCs) namely oxybenzone and atrazine using polysulfone (PSf) composite membranes is reported in this article. A negatively charged hydrophilic mixed matrix membrane was prepared by using Polyaniline modified halloysite nanotubes (PANi-HNT) and polysulfone. The X-ray diffraction (XRD) and attenuated total reflectance infrared (ATR-IR) technique confirm the conversion of Halloysite nanotubes to Polyaniline modified halloysite nanotubes and their presence in membrane matrix. The microvoids observable in the SEM images depict the internal structure of the membrane. Further, increasing in the water uptake and decreasing in the contact angle with respect to increasing the concentration of Polyaniline modified halloysite nanotubes confirm the enhancement of the membrane hydrophilicity. This hydrophilicity increases for higher concentrations of PANi-HNT leads to a significant improvement of the water flux. The removal efficiency of prepared mixed matrix membranes was found to be 98% for oxybenzone and 50% for atrazine. The separation process was discussed in terms of adsorption coefficient, membrane charge and mean pore size. Considering the performances highlighted in this study, the proposed membranes appear usable for the removal of EDCs from contaminated solutions. [ABSTRACT FROM AUTHOR]

UV-filters (UVFs) are active ingredients in personal care products that protect skin from exposure to UV light. Environmentally-relevant concentrations of UVFs have recently been linked to toxicity in aquatic organisms, necessitating research into improved UVF removal in water/wastewater treatment. Here, we investigated ozonation of the three most commonly employed UVFs: octinoxate (OMC), octocrylene (OC), and oxybenzone (OXY). Specific second-order rate constants for UVF reaction with ozone were identified as follows: OMC, 5.25 × 10 4 M −1 s −1 ; OC, 1.58 M −1 s −1 ; OXY (neutral), 3.80 × 10 2 M −1 s −1 ; and, OXY (anion), 1.51 × 10 6 M ‐1 s ‐1 . These kinetic parameters indicated that OMC and OXY undergo significant (2-log or greater) transformation for typical ozone exposures in disinfection processes; however, minimal oxidation is expected for OC. UV absorbance mapping was employed to characterize the loss of UVF activity ( i.e. , absorbance across the UV-A, UV-B, and UV-C ranges) during ozonation. These 4-dimensional maps also confirmed ozone attack mechanisms, namely reaction at phenolate (OXY) and olefin (OMC, OC) groups. Primary transformation products from these reactions were identified for all three UVFs of concern. For OC and OXY, the benzophenone structure is conserved, suggesting that transformation products retain toxicity concerns. [ABSTRACT FROM AUTHOR]

Oxybenzone (OBZ), a common ingredient in sunscreens and personal care products, has been frequently detected in effluents from municipal wastewater treatment plants and also in surface waters. OBZ is an emerging contaminant due to its adverse impacts on marine/aquatic ecosystems. To investigate the removal and degradation capacity of phytotreatment for OBZ, the common wetland plant species Cyperus alternifolius L. was exposed to this compound at 5, 25 and 50 μM for 120 h, respectively. Continuous uptake by roots and accumulation in plant tissues was observed over the exposure time, and depletion of spiked OBZ from the aqueous medium exceeded 73.9 ± 9.1% after 120 h. Similar to its fate in mammalian cells, OBZ is activated in a phase I reaction resulting in the hydroxylated metabolite 2,4-dihydroxybenzophenone (DHB). Independently, two phase II metabolites were identified as oxybenzone-glucoside (OBZ-Glu) and oxybenzone-(6- O -malonyl)-glucoside (OBZ-Mal-Glu) by LC–MS/MS. Formation of these metabolites increased over the experimental period. To our knowledge this is the first time that DHB, OBZ-Glu and OBZ-Mal-Glu are shown to be formed in higher plant tissues. Furthermore, plant defense systems-antioxidative enzymes (SOD, CAT, APOX and POX) were found to be elevated to counteract stress caused by exposure to OBZ. This study presents the huge potential of aquatic plants to cope with benzophenone type UV filters in contaminated water bodies. [ABSTRACT FROM AUTHOR]

A rapid, simple and economic High Performance Thin Layer Chromatography (HPTLC) method for the simultaneous quantification of Oxybenzone and Avobenzone in various personal care products available in local markets in and around Chennai is developed and validated. Central Composite design (CCD) with three factors and one response was employed to study the robustness of the developed method. The best chromatographic separation was achieved employing Toluene: Acetonitrile: Ethyl acetate (4: 5: 1 v/v/v) as solvent system. Densitometric analysis was carried out at 332 nm. The developed method is examined for validation parameters like linearity, specificity, precision, accuracy and robustness. The method was found linear over a wide range of 2.5 - 200 ng/band with a regression coefficient of 0.9998 and 0.9991 for Oxybenzone and Avobenzone respectively. All the validation parameters were found to be within the acceptance limit. The proposed and developed HPTLC method can be applied for routine analysis of Oxybenzone and Avobenzone, in the presence of other excipients in cosmetic products and can also be extended to analysis in pharmaceuticals and food products. [ABSTRACT FROM AUTHOR]

Benzophenone-3 (BP-3) and its major metabolite benzophenone-1 (BP-1) are widely used as UV filters in sunscreens and cosmetics to prevent sunburn and skin damage, or as stabilizers to prevent photodegradation in many commercial products. As a result, their presence is ubiquitous in the environment, wildlife and humans. Based on endocrine disruption concerns, international regulatory agencies are performing a closer evaluation. This work aimed to comprehensively review the available human relevant evidence for safety issues in MEDLINE/PubMed in order to create a structured database of studies, as well as to conduct an integrative analysis as part of the Human Biomonitoring for Europe (HBM4EU) Initiative. A total of 1,635 titles and abstracts were screened and 254 references were evaluated and tabulated in detail, and classified in different categories: i) exposure sources and predictors; ii) human biomonitoring (HBM) exposure levels to perform a meta-analysis; iii) toxicokinetic data in both experimental animals and humans; iv) in vitro and in vivo rodent toxicity studies; and v) human data on effect biomarkers and health outcomes. Our integrative analysis showed that internal peak BP-3 concentrations achieved after a single whole-body application of a commercially available sunscreen (4% w/w) may overlap with concentrations eliciting endocrine disrupting effects in vitro , and with internal concentrations causing in vivo adverse female reproductive effects in rodents that were supported by still limited human data. The adverse effects in rodents included prolonged estrous cycle, altered uterine estrogen receptor gene expression, endometrium hyperplasia and altered proliferation and histology of the mammary gland, while human data indicated menstrual cycle hormonal alterations and increased risk of uterine fibroids and endometriosis. Among the modes of action reported (estrogenic, anti-androgenic, thyroid, etc.), BP-3 and especially BP-1 showed estrogenic activity at human-relevant concentrations, in agreement with the observed alterations in female reproductive endpoints. The meta-analysis of HBM studies identified a higher concern for North Americans, showing urinary BP-3 concentrations on average 10 and 20 times higher than European and Asian populations, respectively. Our work supports that these benzophenones present endocrine disrupting properties, endorsing recent European regulatory efforts to limit human exposure. The reproducible and comprehensive database generated may constitute a point of departure in future risk assessments to support regulatory initiatives. Meanwhile, individuals should not refrain from sunscreen use. Commercially available formulations using inorganic UV filters that are practically not absorbed into systemic circulation may be recommended to susceptible populations. [ABSTRACT FROM AUTHOR]

Recent studies of the sunscreen constituent oxybenzone have suggested that the dominant mechanism underlying the efficient photoprotection it offers relies on an initial ultrafast enol → keto tautomerisation, followed by nonadiabatic transfer to the ground electronic state. Subsequent collisions with the solvent bath then reform the original enol -tautomer. Utilising femtosecond transient electronic absorption spectroscopy we explore the dissipation of electronic excitation energy in oxybenzone in the presence of titanium dioxide, a widely used, and complementary sunscreen component. We find the relaxation dynamics of this popular organic filter are unaltered by the presence of this favoured inorganic scatterer and the overall dynamics can be described by the additive contribution of the individual constituents. The combination of the two components provides broadband photoprotective properties justifying the widely used organic filter and inorganic scatterer mixtures in commercial sunscreen products. [ABSTRACT FROM AUTHOR]

• Women with medium to high levels of oxybenzone in their urine was associated with giving birth to neonates with Hirschsprung's Disease (HSCR). • Exposure to oxybenzone from sunscreen use demonstrates that enough chemical<>crosses into the mother's blood making it available to the fetus. • Levels found in fetuses are indeed high enough to inhibit migration of neural crest cells during critical embryonic development. Oxybenzone is a ultraviolet (UV) absorber used in 70% of sunscreen products, is a recognized endocrine disrupting chemical (EDC) and is small enough to pass through skin and placenta barriers. Numerous studies have identified this chemical in the urine/blood of pregnant women as well as in fetal and umbilical cord blood. A recent study demonstrated that women with medium to high levels of oxybenzone in their urine was associated with giving birth to neonates with Hirschsprung's Disease (HSCR). Testing in human cell lines confirmed that low levels of oxybenzone has the potential to disrupt cell migration and function in a manner similar to what is associated with HSCR. Analysis of human exposure levels to oxybenzone from sunscreen use, under normal conditions, demonstrates that enough chemical can cross into the mother's blood making it available to the fetus at high enough levels that can indeed inhibit migration of neural crest cells during critical embryonic development. [ABSTRACT FROM AUTHOR]

The article focuses on the study conducted by the authors to assess patient beliefs and informational sources regarding the safety and use of sunscreen. Topics discussed include safety and efficacy of sunscreens, demonstration of lack of knowledge among public about sunscreen ingredients and their effects and prevention of squamous cell carcinoma by regular use of Sunscreen.

In this review, we discuss the importance of biological and artificial photoprotection against overexposure to harmful ultraviolet radiation. Transient electronic and transient vibrational absorption spectroscopies are highlighted as important tools in understanding the energy transfer in small molecules, with a focus on the application to commercial sunscreens with representative examples given. Oxybenzone, a common ingredient in commercial sunscreens and sinapoyl malate, a biological sunscreen in plant leaves are presented as case studies. [ABSTRACT FROM AUTHOR]

UV filters are a kind of emerging contaminant, and their transformation behavior in water treatment processes has aroused great concern. In particular, toxic products might be produced during reaction with disinfectants during the disinfection process. As one of the most widely used UV filters, oxybenzone has received significant attention, because its transformation and toxicity changes during chlorine oxidation are a concern. In our study, the reaction between oxybenzone and chlorine followed pseudo-first-order and second-order kinetics. Three transformation products were detected by LC-MS/MS, and the stability of products followed the order of tri-chloro-methoxyphenoyl > di-chlorinated oxybenzone > mono-chlorinated oxybenzone. Disinfection byproducts (DBPs) including chloroform, trichloroacetic acid, dichloroacetic acid and chloral hydrate were quickly formed, and increased at a slower rate until their concentrations remained constant. The maximum DBP/oxybenzone molar yields for the four compounds were 12.02%, 6.28%, 0.90% and 0.23%, respectively. SOS/umu genotoxicity test indicated that genotoxicity was highly elevated after chlorination, and genotoxicity showed a significantly positive correlation with the response of tri-chloro-methoxyphenoyl. Our results indicated that more genotoxic transformation products were produced in spite of the elimination of oxybenzone, posing potential threats to drinking water safety. This study shed light on the formation of DBPs and toxicity changes during the chlorination process of oxybenzone. [ABSTRACT FROM AUTHOR]

Oxybenzone (OBZ), known as Benzophenone-3, is a commonly used UV filter in sun tans and skin protectants, entering aquatic systems either directly during recreational activities or indirectly through wastewater treatment plants discharge. To study the potential degradation capacity of plants for OBZ in phytotreatment, a well-established hairy root culture ( Armoracia rusticana ) was treated with OBZ. More than 20% of spiked OBZ (100 μM) was eliminated from the medium by hairy roots after 3 h of exposure. Two metabolites were identified as oxybenzone-glucoside (OBZ-Glu) and oxybenzone-(6- O -malonyl)-glucoside (OBZ-Mal-Glu) by LC–MS/MS and TOF–MS. Formation of these metabolites was confirmed by enzymatic synthesis, as well as enzymatic and alkaline hydrolysis. Incubation with O -glucosyltransferase ( O -GT) extracted from roots formed OBZ-Glu; whereas β- d -Glucosidase hydrolyzed OBZ-Glu. However, alkaline hydrolysis led to cleavage of OBZ-Mal-Glu and yielded OBZ-Glu. In the hairy root culture, an excretion of OBZ-Glu into the growth medium was observed while the corresponding OBZ-Mal-Glu remained stored in root cells over the incubation time. We propose that metabolism of oxybenzone in plants involves initial conjugation with glucose to form OBZ-Glu followed by malonylation to yield OBZ-Mal-Glu. To our best knowledge this first finding presenting the potential of plants to degrade benzophenone type UV filters by phytoremediation. [ABSTRACT FROM AUTHOR]

• Magnetic BiOI-based microrobots modificated with tailored Fe 3 O 4 NPs are presented. • Achieving magnetic navigation while preserving an enhanced photoresponse is discussed. • An effective on-the-fly photocatalytic removal of UV-pollutants is proved. • Pioneering use of microrobots against sunscreens residues. Growing awareness of the harmful effects derived from sunlight overexposure has led to a regular use of sunscreens. Nonetheless, major environmental side-effects have been concurrently originated due to the increasing concentration of related pollutants. Considering the advantages that microrobots offer for water remediation tasks, magnetically-driven photoactive microrobots (i.e., MG-µROSES) are here developed as a pioneering response from the field to face this global threat. Particularly, photoactive bismuth oxyiodide (i.e., BiOI) flower-like microparticles (i.e., µROSES) have been prepared and modified with tailored Fe 3 O 4 nanoparticles through a mild surface functionalization. Therefore, static µROSES acquired an appealing magnetic steering motion and an easy retrieval without sacrificing large BiOI surface areas. The performance of MG-µROSES against the main organic UV-filter in suntan lotions (i.e., oxybenzone, BP-3) has been analyzed. An effective photocatalytic degradation —in pure water and under visible light— has been observed and attributed to the synergistic combination of adsorption and photocatalytic activity provided by this appropriate design. Moreover, the noticeable enhancement of the photocatalytic degradation of BP-3 by MG-µROSES has been linked to their magnetically-driven navigation, favoring an on-the-fly : (i) adsorption of BP-3; and (ii) distribution of the photogenerated reactive oxygen species, in particular hydroxyl radicals (OH·)). All in all, an efficient strategy based on photoresponsive magnetic microrobots against sunscreens residues is presented. Hence, a potential contender to beat alternative traditional methodologies is offered. [ABSTRACT FROM AUTHOR]

A preponderance of recent evidence indicates that oxybenzone and other personal-care product chemicals threaten the biota inhabiting various ecological niches. What is understudied is the ecotoxicological impact of oxybenzone, a UV filter in sunscreens and anti-aging products, to terrestrial/soil organisms that are keystone species in these habitats. In the present study, acute exposure (14-day) to oxybenzone resulted in earthworm mortality (LC 50 of 364 mg/kg) and growth rate inhibition. Environmentally relevant concentration of oxybenzone (3.64, 7.28 and 36.4 mg/kg) at exposures of 7-day, 14-day, 28-day induced oxidative stress and neurotoxicity followed by perturbations in reproduction processes and changes in vital organs. Decreased levels of superoxide dismutase (SOD) and catalase (CAT) activity were statistically lower than controls (p < 0.05) on day 14 for all three concentrations, while glutathione-s-transferase (GST) activity was significantly elevated from controls on days 7 and 14. On day 28, SOD and CAT activities were either not significantly different from the control or were higher, demonstrating a temporal multiphasic response of anti-oxidant enzymes. GST activity on day 28 was significantly reduced compared to controls. Acetylcholinesterase levels across the three-time points exhibited a complicated behaviour, with every exposure concentration being significantly different from the control. Chronic exposure negatively influences earthworm health status with elevated biomarker values analysed using IBRv2 index. This, in turn, impacted higher levels of hierarchical organization, significantly impairing reproduction and organismal homeostasis at the histological level and manifesting as decreasing cocoon formation and successful hatching events. Thus, the overall findings demonstrate that oxybenzone is toxic to Eisenia fetida at low-level, long-term exposure. Based on the concentration verification analysis and application of the EPA PestDF tool, oxybenzone undergoes single first-order kinetics degradation in OECD soil with DT50 and DT90 as 8.7–28.9 days, respectively. [Display omitted] • Oxybenzone (BP-3) exposure poses a very high-risk quotient of 7.78 to earthworms. • BP-3 DT50 and DT90 ranged 8.7–13.5 and 24.3–38.6 days in OECD soil. • BP-3 triggers oxidative stress and acetylcholinesterase levels. • BP-3 impairs reproduction and organismal homeostasis at histological level. • BP-3 is toxic to E. fetida at environmentally relevant concentrations. [ABSTRACT FROM AUTHOR]

In 2019, sands in nearby runoff streams from public beach showers were sampled on three islands in the State of Hawaii and tested for over 18 different petrochemical UV filters. Beach sands that are directly in the plume discharge of beach showers on three of the islands of Hawaii (Maui, Oahu, Hawai'i) were found to be contaminated with a wide array of petrochemical-based UV-filters that are found in sunscreens. Sands from beach showers across all three islands had a mean concentration of 5619 ng/g of oxybenzone with the highest concentration of 34,518 ng/g of oxybenzone at a beach shower in the Waikiki area of Honolulu. Octocrylene was detected at a majority of the beach shower locations, with a mean concentration of 296.3 ng/g across 13 sampling sites with the highest concentration of 1075 ng/g at the beach shower in Waikiki. Avobenzone, octinoxate, 4-methylbenzylidene camphor and benzophenone-2 were detected, as well as breakdown products of oxybenzone, including benzophenone-1, 2,2'-dihydroxy-4-methoxybenzophenone, and 4-hydroxybenzophenone. Dioxybenzone (DHMB) presented the highest concentration in water (75.4 ng/mL), whereas octocrylene was detected in all water samples. Some of these same target analytes were detected in water samples on coral reefs that are adjacent to the beach showers. Risk assessments for both sand and water samples at a majority of the sampling sites had a Risk Quotient > 1, indicating that these chemicals could pose a serious threat to beach zones and coral reef habitats. There are almost a dozen mitigation options that could be employed to quickly reduce contaminant loads associated with discharges from these beach showers, like those currently being employed (post-study sampling and analysis) in the State of Hawaii, including banning the use of sunscreens using petrochemical-based UV filters or educating tourists before they arrive on the beach. [Display omitted] • Beach showers are a point-source of contamination to coastal surface waters. • Sunscreen contamination was highest at beaches with the highest visitation rates. • Concentrations of UV sunscreens pose a threat to terrestrial and aquatic receptors. • Apply mitigation options to reduce sunscreen pollution from beach showers. [ABSTRACT FROM AUTHOR]

A fast gas chromatography/mass spectrometry method was developed and validated for the analysis of the potential endocrine disrupters octinoxate and oxybenzone in swimming pool water samples based on the solvent-free solid-phase microextraction technique. The low-pressure gas chromatography/mass spectrometry method used for the fast identification of UV filter substances was compared to a conventional method in terms of sensitivity and speed. The fast method proposed resulted in 2 min runs, leading to an eightfold decrease in the total analysis time and a sevenfold improvement in detection limits. The main parameters affecting the solid-phase microextraction process were also studied in detail and the optimized conditions were as follows: fiber coating, polyacrylate; extraction mode, direct immersion; extraction temperature, 25°C; sample volume, 5 mL; extraction time 45 min; pH 6.5. Under the optimized conditions, a linear response was obtained in the concentration range of 0.5-25 μg/L with correlation coefficients in the range 0.990-0.999. The limits of detection were 0.17-0.29 μg/L, and the recoveries were 80-83%. Combined method uncertainty was assessed and found to be less than 7% for both analytes for concentrations equal to or higher than 5 μg/L. Pool water samples were analyzed to demonstrate the applicability of the proposed method. Neither octinoxate nor oxybenzone were detected in the swimming pool water samples at concentrations above the respective limits of detection. [ABSTRACT FROM AUTHOR]

Oxybenzone is one type of ultraviolet (UV) filters that have been widely used as active ingredients in sunscreen and personal care products. The input of oxybenzone in the ocean through wastewater and swimmers has been a serious environmental pollution issue. Although oxybenzone has been reported as a toxicant to some marine animals and microalgae, its toxicity effect on macroalgae is still unknown. This study investigates the physiological responses of an aquaculture red macroalga, Gracilaria vermiculophylla , after twenty-days exposure to three different concentrations (0.1, 0.001 and 0.00001 mM) of oxybenzone. At the concentration of 0.1 mM, oxybenzone significantly decreased the growth rate, pigment content and photosynthetic rate, suggesting a high toxicity to G. vermiculophylla. At other two lower concentrations, oxybenzone induced no significant changes on physiological responses besides a decrease of pigment content at 0.001 mM. Our results revealed the toxicity and tolerance of oxybenzone on G. vermiculophylla. • Gracilariopsis vermiculophylla has a high tolerance against BP-3. • The significant reduction of growth was observed at 0.1 mM BP-3, much higher than the concentration reported in nature. • Irreversible loss of pigments was observed at 0.1 mM BP-3. • The BP-3 absorbed by G. vermiculophylla can be accumulated within the thalli. [ABSTRACT FROM AUTHOR]

Hanauma Bay is a 101-acre bay created by the partial collapse of a volcanic cone and once supported a vibrant coral reef system. It is the most popular swimming area in the Hawaiian Islands and has been reported to have averaged between 2.8 and 3.5 million visitors a year between the 1980s and the 2010s, with visitors averaging between 3000–4000 a day and peaking around 10,000–13,000 per day. Concentrations of oxybenzone and other common UV filters were measured in subsurface water samples and in sands from the beach-shower areas in Hanauma Bay. Results demonstrate that beach showers also can be a source of sunscreen environmental contamination. Hydrodynamic modeling indicates that oxybenzone contamination within Hanauma Bay's waters could be retained between 14 and 50 h from a single release event period. Focusing on only oxybenzone, two different Hazard and Risk Assessment analyses were conducted to determine the danger of oxybenzone to Hanauma Bay's coral reef system. Results indicate that oxybenzone contamination poses a significant threat to the wildlife of Hanauma Bay. To recover Hanauma Bay's natural resources to a healthy condition and to satisfactorily conserve its coral reef and sea grass habitats, effective tourism management policies need to be implemented that mitigate the threat of sunscreen pollution. [Display omitted] • Oxybenzone ranged from 30 ng/L to 27,880 ng/L in near-shore waters in Hanauma Bay. • Beach showers are a point-source of contamination. • Retention time of oxybenzone within Hanauma Bay was as long as 50 h. • Oxybenzone in Hanauma Bay is a threat to the ecological integrity of Hanauma Bay. [ABSTRACT FROM AUTHOR]

Hanauma Bay is a 101-acre bay created by the partial collapse of a volcanic cone and once supported a vibrant coral reef system. It is the most popular swimming area in the Hawaiian Islands and has been reported to have averaged between 2.8 and 3.5 million visitors a year between the 1980s and the 2010s, with visitors averaging between 3000–4000 a day and peaking around 10,000–13,000 per day. Concentrations of oxybenzone and other common UV filters were measured in subsurface water samples and in sands from the beach-shower areas in Hanauma Bay. Results demonstrate that beach showers also can be a source of sunscreen environmental contamination. Hydrodynamic modeling indicates that oxybenzone contamination within Hanauma Bay's waters could be retained between 14 and 50 h from a single release event period. Focusing on only oxybenzone, two different Hazard and Risk Assessment analyses were conducted to determine the danger of oxybenzone to Hanauma Bay's coral reef system. Results indicate that oxybenzone contamination poses a significant threat to the wildlife of Hanauma Bay. To recover Hanauma Bay's natural resources to a healthy condition and to satisfactorily conserve its coral reef and sea grass habitats, effective tourism management policies need to be implemented that mitigate the threat of sunscreen pollution. [Display omitted] • Oxybenzone ranged from 30 ng/L to 27,880 ng/L in near-shore waters in Hanauma Bay. • Beach showers are a point-source of contamination. • Retention time of oxybenzone within Hanauma Bay was as long as 50 h. • Oxybenzone in Hanauma Bay is a threat to the ecological integrity of Hanauma Bay. [ABSTRACT FROM AUTHOR]

Abstract: The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6–11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k obs) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 μM. The k obs were used to determine the apparent second-order rate coefficient (k app) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k int) from the k app as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k 1,OxY = 306 ± 81 M−1s−1 and k 1,DiOxY = 154 ± 76 M−1s−1, respectively. The kint for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k 2,OxY = 1.03(±0.52) × 106 M−1s−1 and k 2_1,DiOxY = 4.14(±0.68) × 105 M−1s−1. Also, k int for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k 2_2,DiOxY = 2.17(±0.30) × 103 M−1s−1. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6–10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent; however, chloroform to UV filter molar yields at pH 8 were 0.221 CHCl3/OXY and 0.212 CHCl3/DiOXY. [Copyright &y& Elsevier]

Insect repellent N,N-diethyl-m-toluamide (DEET) and sunscreen oxybenzone have shown a synergistic percutaneous enhancement when applied concurrently. Both compounds are extensively metabolized in vivo into a series of potentially toxic metabolites: 2 metabolites of DEET, N,N-diethyl-m-hydroxymethylbenzamide (DHMB) and N-ethyl-m-toluamide (ET), and 3 metabolites of oxybenzone, 2,4-dihydroxybenzophenone (DHB), 2,2-dihydroxy-4-methoxybenzophenone (DMB), and 2,3,4-trihydroxybenzophenone (THB). In this study, the metabolites were extensively distributed following intravenous and topical skin administration of DEET and oxybenzone in rats. Combined application enhanced the disposition of all DEET metabolites in the liver but did not consistently affect the distribution of oxybenzone metabolites. The DHMB appeared to be the major metabolite for DEET, while THB and its precursor DHB were the main metabolites for oxybenzone. Repeated once-daily topical application for 30 days led to higher concentrations of DEET metabolites in the liver. Hepatoma cell studies revealed a decrease in cellular proliferation from all metabolites as single and combined treatments, most notably at 72 hours. Increased accumulation of DHMB and ET in the liver together with an ability to reduce cellular proliferation at achievable plasma concentrations indicated that simultaneous exposure to DEET and oxybenzone might have the potential to precipitate adverse effects in a rat animal model. [ABSTRACT FROM AUTHOR]

The separation of oxybenzone, octocrylene, octinoxate and avobenzone were carried out on waters C18, 5 µ (250 X 4.6 mm) column. The compounds were eluted using a mobile phase of MeOH : H2O (90:10 % v/v) at a flow rate of 1.0 mL/min and were monitored using UV detector at 330 nm. The retention times were 4.5, 7.6, 11.2 and 12.4 for octocrylene, octinoxate and avobenzone respectively. The reliability and analytical performance of the proposed RP-HPLC procedure were statistically validated with respect to linearity, ranges, system suitability, precision, accuracy, robustness, ruggedness, detection and quantification limits. The linear correlation coefficient at range of 12-28 µg/mL of assay concentration levels was found to be 0.999 for all drugs. Repeatability, inter day precision, intraday precision, ruggedness and robustness expressed as the percentage relative standard deviation (% RSD) were less than 2, accuracy by recovery study of were found to be between 99.0 % and 101.0 %. LOD values were found to be 0.07, 0.28, 2.12 and 2.54 µg/mL for octocrylene, octinoxate and avobenzone respectively. LOQ values were found to be 0.00, 0.00, 0.03 and 0.04 µg/mL for oxybenzone, octocrylene, octinoxate and avobenzone respectively. [ABSTRACT FROM AUTHOR]

Sunscreens are believed to be a valuable tool in providing photoprotection against the detrimental effects of UV radiation, a known carcinogen. However, a number of controversies have developed regarding their safety and efficacy. This review summarizes the relevant studies surrounding these controversies. Evidence of the prevention of skin cancer, an oft-cited reason for sunscreen use, was examined as it pertains to squamous cell carcinoma, basal cell carcinoma and melanoma. We also reviewed studies examining the effects of sunscreen on the synthesis of vitamin D, an essential nutrient whose role in health and disease continues to grow. Lastly, we analyzed studies surrounding the safety and toxicity of oxybenzone, retinyl palmitate and nanoparticles of zinc oxide (ZnO) and titanium dioxide (TiO). The overwhelming majority of available data is drawn from studies conducted using antiquated sunscreen formulations. Nonetheless, our research revealed that topical use of sunscreen protects against squamous cell carcinoma, does not cause vitamin D deficiency/insufficiency in practice and has not been demonstrated to adversely affect the health of humans. Given the established benefits of UV protection, the use of sunscreens remains an important part of an overall photoprotective strategy. Future sunscreens with improved formulation should ideally offer superior protection. With increased usage of sunscreen by the public, continuous and vigilant monitoring of the overall safety of future products is also needed. [ABSTRACT FROM AUTHOR]

Abstract: Pharmaceuticals and personal care products (PPCPs) are now routinely detected in raw and treated municipal wastewater. Since conventional wastewater treatment processes are not particularly effective for PPCP removal, treated wastewater discharges are the main entry points for PPCPs into the environment, and eventually into our drinking water. This study investigates the use of laccase-catalyzed oxidation for removing low concentrations of PPCPs from municipal wastewater primary effluent. Oxybenzone was selected as a representative PPCP. Like many other PPCPs, it is not recognized directly by the laccase enzyme. Therefore, mediators were used to expand the oxidative range of laccase, and the efficacy of this laccase–mediator system in primary effluent was evaluated. Eight potential mediators were investigated, and 2,2′-Azino-bis(3-ethylbenzthiazoline-6sulphonic acid) diammonium salt (ABTS), a synthetic mediator, and acetosyringone (ACE), a natural mediator, provided the greatest oxybenzone removal efficiencies. An environmentally relevant concentration of oxybenzone (43.8nM, 10μg/L) in primary effluent was completely removed (below the detection limit) after two hours of treatment with ABTS, and 95% was removed after two hours of treatment with ACE. Several mediator/oxybenzone molar ratios were investigated at two different initial oxybenzone concentrations. Higher mediator/oxybenzone molar ratios were required at the lower (environmentally relevant) oxybenzone concentration, and ACE required higher molar ratios than ABTS to achieve comparable oxybenzone removal. Oxybenzone oxidation byproducts generated by the laccase–mediator system were characterized and compared to those generated during ozonation. Enzymatic treatment generated byproducts with higher mass to charge (m/z) ratios, likely due to oxidative coupling reactions. The results of this study suggest that, with further development, the laccase–mediator system has the potential to extend the treatment range of laccase to PPCPs not directly recognized by the enzyme, even in a primary effluent matrix. [Copyright &y& Elsevier]

The objective of the current study was to formulate solid lipid nanoparticles of oxybenzone to enhance its sunscreening efficacy while reducing its side effects. Solid lipid nanoparticles (SLNs) of oxybenzone were prepared by the solvent diffusion method. A complete 24 factorial design was used to optimize preparations. The study design involves the investigation of four independent variables, namely lipid type (Glyceryl monostearate, GMS; and Witepsol E85, WE85), lipid concentration (5 and 10%), polyvinyl alcohol (PVA) concentration (1 and 2%), and ethanol/acetone ratios (1:1 and 3:1, v/v), in terms of their effect on the particle size and entrapment efficiency. GMS was found of significantly increase the p.s. and EE%. SLNs prepared using 10% lipid had slower drug release compared to those prepared using 5%. The candidate oxybenzone-loaded SLN formula (SLN2) consisting of 0.5% oxybenzone, 10% GMS, 1% PVA, and ethanol/acetone (1:1, v/v) was then formulated into a gel and compared to the corresponding free oxybenzone nanosuspension and placebo SLN. The formulations were evaluated for skin irritation, in vitro sun protection factor, and ultraviolet A protection factors. The incorporation of oxybenzone into solid lipid nanoparticles greatly increased the SPF and UVA protection factor of oxybenzone more than five-fold while providing the advantage of overcoming skin irritancy problems. [ABSTRACT FROM AUTHOR]

Oxybenzone wax microparticles (MPs) were prepared by the hydrophobic congealable disperse phase method. The formulation of oxybenzone-loaded MPs was optimized using a 24 experimental design. Factorial analysis indicated that the main MP characteristics were influenced by initial drug loading, emulsification speed, emulsifier concentration and hydrophilic-lipophilic balance. MPs were spherical with 50.5-88.1 µm size range, 17.8-38.9 drug content in mg/100 mg MPs and 33.1-87.2% oxybenzone release in 1 h. A wide range of sunscreen delivery systems suitable for different formulation purposes were generated which may contribute to the advanced formulation of sunscreen products with improved performance. [ABSTRACT FROM AUTHOR]