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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]

[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]

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]

With increasing awareness regarding the risks of sunburn, photoaging, and skin cancer, the use of sunscreens has increased. Organic and inorganic filters are used in sunscreen products worldwide. Concerns have been raised regarding the environmental effects of commonly used organic ultraviolet (UV) filters, including oxybenzone (benzophenone-3), 4-methylbenzylidene camphor, octocrylene, and octinoxate (ethylhexyl methoxycinnamate). Studies have identified UV filters such as oxybenzone, octocrylene, octinoxate, and ethylhexyl salicylate in almost all water sources around the world and have commented that these filters are not easily removed by common wastewater treatment plant techniques. Additionally, in laboratory settings, oxybenzone has been implicated specifically as a possible contributor to coral reef bleaching. Furthermore, UV filters such as 4-methylbenzylidene camphor, oxybenzone, octocrylene, and octinoxate have been identified in various species of fish worldwide, which has possible consequences for the food chain. As dermatologists, it is important for us to continue to emphasize the public health impact of excessive sun exposure and advise our patients about proper photoprotection practice, which consists of seeking shade, wearing photoprotective clothing (including hats and sunglasses), and applying appropriate sunscreens. [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]

Abstract Although organic UV filters (OUVFs) benefit human health by preventing skin burns and cancer, several studies revealed that organic UV filters can induce developmental and reproductive toxicity to aquatic organisms. Discharge of OUVFs occurs predominantly at marine recreational hotspots, such as Lac Bay, Bonaire, and is predicted to increase significantly due to growing tourism worldwide. Unfortunately, there is no insight what the current and future discharge of OUVF at Lac Bay is. Therefore, this study aimed to 1) measure concentrations and estimate the risk of specific OUVFs to different nursery habitats at Lac Bay, and 2) compare measured and predicted concentration based risk assessment outcome. Results showed that at least one of the three nurseries at Lac Bay had a potential for adverse effects. Furthermore, predicted environmental concentrations of UV filter discharge can be applied to gain more insight in the order of extent of OUVF discharge by marine tourism. Highlights • UV filters oxybenzone and octocrylene are detected at Lac Bay Bonaire. • They are present at significant levels in both water column and surface microlayer. • Predicted concentrations of oxybenzone are in line with measured concentrations. • Risk assessment revealed environmental risk to Lac Bay's ecosystems. [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]

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]

Oxybenzone, a common ultraviolet (UV) filter, is a growing environmental concern due to its ecotoxicological effects. However, the responses of Symbiodiniaceae and their bacterial communities to oxybenzone are largely unknown. In this study, the effects of oxybenzone on Effrenium voratum and Cladocopium goreaui were investigated. The results revealed that sensitivity of Symbiodiniaceae to oxybenzone was species-dependent. 50 μg L−1 of oxybenzone significantly impacted the cell density of C. goreaui , causing a 36.73% decrease. When oxybenzone concentration increased to 500 μg L−1 and 5000 μg L−1, cell division was completely suppressed; meanwhile, chl- a content declined to zero. Compared to C. goreaui , E. voratum had higher resistance to oxybenzone. There was no significant difference in cell density between 50 μg L−1 group and control group. At higher dosage of oxybenzone (500 μg L−1 and 5000 μg L−1), the cell density declined 32.02% and 45.45% compared to the control group, respectively. Additionally, we revealed that the diversity and structure of bacterial community were affected by oxybenzone. Briefly, 500 μg L−1 and 5000 μg L−1 of oxybenzone altered the diversity of bacterial community in C. goreau. Furthermore, the relative abundances of Costertonia , Roseitalea , Rhodopirellula , and Roseobacter were negatively affected by oxybenzone ranging 50 μg L−1 to 5000 μg L−1. Compare to C. goreaui , the bacterial community composition associated with E. voratum was more stable. As revealed by KEGG pathway analysis, oxybenzone affected energy metabolism and inhibited the metabolism of cofactors and vitamins in C. goreaui , while 5000 μg L−1 of oxybenzone significantly altered the carbohydrate metabolism, membrane transport and amino acid metabolism in E. voratum. The changes of bacterial composition may contribute to the variation in algal growth. These results indicated that oxybenzone pollution could injury Symbiodiniaceae, even threaten coral reef ecosystems. [Display omitted] • E. voratum had a higher tolerance against oxybenzone than C. goreaui. • High level of oxybenzone decreased cell division and chl- a content. • Oxybenzone can damage algal cell structure. • Oxybenzone changed algal bacterial community composition and function. [ABSTRACT FROM AUTHOR]

In this study, evaluated the combined effects of exposure to Benzophenone-3 (BP3), at an environmentally relevant concentration, with temperature increasing in the marine bivalve Amarilladesma mactroides. The BP3 (0.56 μg/L) at 20 °C increased reactive oxygen species (ROS) and antioxidants in the digestive glands of clams, without causing significant effect on lipid peroxidation (LPO). However, at high temperature (24 °C), BP3 suppressed antioxidant defenses, mainly glutathione peroxidase (GPx), lead to a rise in LPO in the digestive gland, however this condition increased hemocyte viability. The Integrated Biological Responses (IBR) approach shows that temperature influences BP3 effects, as the highest score was observed for animals exposed to 0.56 μg/L of BP3 at 20 °C (9.35), while the lowest was observed BP3 group at 24 °C (1.02). These results draw attention to the harmful effects of BP3 on bivalves, especially in a scenario of thermal stress. • BP3 activates biotransformation pathways in the digestive gland of the yellow clam. • The main biotransformation associated with BP3 detoxification is GSH and GST. • High temperature, predicted by IPCC, suppresses the biomarkers in Amarilladesma mactroides to BP3. • High temperature and BP3 in association cause oxidative stress. [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]

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]

Sunscreens generate a potentially important source of environmental contamination across marine and aquatic systems. Oxybenzone (benzophenone-3; BP-3) is one of the most common organic filters in chemical sunscreen and has been detected in seawater at high concentrations. In this study, we asked whether BP-3 contamination affected the photosynthesis, respiration, and photophysiology of rhodoliths collected offshore from popular Gulf of Mexico beaches in North Florida. We found no evidence for negative effects of the common organic UV filter BP-3 on Gulf of Mexico rhodoliths. This result is promising for the fate of these important algae who act as habitat builders and foundational components of global reef ecosystems. • Oxybenzone (benzophenone-3; BP-3) is one of the most common organic filters in chemical sunscreen. • Rhodoliths are calcifying red algae that are important habitat builders globally. • We found no negative effects of the common UV filter BP-3 on photosynthesis and respiration Gulf of Mexico rhodoliths. [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]

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]

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]

Abstract: Previous studies in extracts of sediments surrounding municipal outfalls off the coast of California, USA and effluents of New York City, NY, USA indicated the UV-filtering agent, oxybenzone (CAS# 131-57-7; benzophenone-3) as a potential estrogen. The effects of oxybenzone on estrogenic activity and reproduction were evaluated using a 14-day juvenile rainbow trout assay for plasma vitellogenin and a subsequent 21-day Japanese medaka reproduction assay. Significant induction of vitellogenin was observed in the rainbow trout at the 1000μg/L nominal concentration (749μg/L median measured value) of oxybenzone which was approximately 75 times greater than the concentrations observed in previous wastewater effluent. Vitellogenin induction was also observed in the 1000μg/L nominal concentration (620μg/L median measured) of oxybenzone in male Japanese medaka (Oryzias latipes) after 21 days of exposure. The number of eggs produced per female per day exposed to the same concentration (620μg/L) were significantly lower after 7 days, but returned to control values after 21 days. Fertilized eggs were then monitored for 20 days to assess hatching success. The overall percentage of fertilized eggs collected during the 21-day exposure that hatched was significantly lower in the 620μg/L oxybenzone concentration. There was also a temporal effect at this concentration as egg viability (percentage of fertilized eggs that hatched) was diminished 13–15 days after eggs were collected. All three oxybenzone concentrations (16, 132, and 620μg/L) and the 50ng/L estradiol positive control showed reduced hatching of eggs at day 15, and the 132 and 620μg/L oxybenzone concentrations diminished the percentage of eggs that hatched on days 13–15. These data indicate that the UV-filter oxybenzone alters endocrine or reproduction endpoints in two fish species, but at concentrations significantly higher than those measured in the environment. [Copyright &y& Elsevier]

Abstract: Warfarin is the most common agent used for control and prevention of venous as well as arterial thromboembolism. Although warfarin is administered as a racemic mixture of two stereoisomers (S and R), the S-form is mainly responsible for the anticoagulant effect. The anticoagulant effect of the drug is monitored by analysis of prothrombin complex (International Normalised Ratio,INR). In some cases, however, the measurements of plasma warfarin concentration are needed. Here, we present a new, rapid, sensitive and cost-effective HPLC-method for the determination of warfarin enantiomers in plasma. The chromatographic system consisted of Waters 616 gradient pump, Waters 996 photo diode array detector, Gilson 230 autoinjector and Pirkle (R,R) Whelk-O1 column (25cm×4.6mm I.D., 5μm). An isocratic mobile phase of methanol/acetonitrile/water (50/10/40, v/v) with 0.1% glacial acetic acid was used. The follow rate was 1mL/min. Data analysis was carried out with Waters Millennium32. The absorbance at 305nm was measured with a total run-time of 15min. Method linearity was studied by establishing regression data containing eight points over the range 0.08–10μg/mL. In this range, warfarin showed to be linear (r 2 =0.9997 for S-warfarin and r 2 =0.9998 for R-warfarin). The limit of detection in plasma was 16ng/mL for S-warfarin and 18ng/mL for R-warfarin. Limit of quatitation was defined as 10×LOD. The extraction recovery was approximately 80%. Also the relation between INR and warfarin concentration was investigated. As expected, there was a low correlation between these two variables (r =0.23, y =0.3044x +0.9712). This method offers a rapid and cost-effective determination of warfarin enantiomers in human plasma. [Copyright &y& Elsevier]

• Oxybenzone had a lower 96h-LC 50 value when compared to benzophenone. • UV light significantly decreased 96h-LC 50 value of both benzophenone and oxybenzone. • Co-exposure of UV light and oxybenzone significantly delayed hatching. • Oxybenzone induced catalase enzyme activity at a lower nominal concentration. • Oxybenzone had a higher ability to generate hydroxyl radicals. Benzophenones are widely used as organic UV filters in many personal care products, especially sunscreen, to protect humans from UV radiation. The increasing use of benzophenone class UV filters has raised concerns about the potential effects on the aquatic environment. These organic UV filters are designed to absorb UV light. However, to date, studies have not considered the potential of UV light to potentiate the toxicity of benzophenones in aquatic organisms. In this study using zebrafish embryos, we assessed the median lethal concentration (LC 50) and sub-lethal effects of benzophenone and oxybenzone either under natural levels of UV light or under laboratory light conditions. The LC 50 value in zebrafish embryos under both light conditions of oxybenzone was lower when compared to benzophenone. Interestingly, UV light significantly decreased the LC 50 values (increased toxicity) of both benzophenone and oxybenzone. The presence of UV light induced a significant increase in hydroxyl radical formation and this was reflected in both increased SOD activity and lipid peroxidation in oxybenzone treated groups. Exposure to either benzophenone or oxybenzone also delayed hatching between 60 and 96 hpf when comparing to the control group while UV exposure further delayed hatching only in oxybenzone-exposed embryos. The results demonstrate the importance of involving UV light in toxicity testing for UV filters and provide much-need information on the UV-induced toxicity of benzophenone and oxybenzone under ecologically realistic conditions. [ABSTRACT FROM AUTHOR]

Coral bleaching is a worldwide problem and more needs to be done to determine causes and potential solutions. A myopic focus on sunscreen ingredients as the proximate cause of coral bleaching provides consumers a false belief that enacted bans of these ingredients will erase decades of coral reef decline. Instead, these bans will likely only lead to decreased sunscreen use and exposure to potentially harmful UV radiation. A closer examination of all available evidence on the causes of coral reef bleaching needs to be undertaken, including a more thorough appraisal of studies conducted under artificial conditions using higher concentrations of sunscreen ingredients. Unlabelled Image • Coral bleaching resulting from climate change has occurred worldwide for decades. • Recent in vitro studies suggest sunscreen ingredients could cause coral to bleach. • Sunscreen ingredient bans are likely to be ineffective in restoring coral health. • Ingredient bans will likely result in decreased use and increased UV exposure. • All scientific evidence needs to be considered before banning sunscreen ingredients. [ABSTRACT FROM AUTHOR]

[Display omitted] • Sensitive and simultaneous determination of sunscreen active ingredients avobenzone and oxybenzone in plasma. • First UHPLC-MS/MS report for the determination of avobenzone and oxybenzone in human plasma. • High-throughput sample preparation using Phree Phospholipid removal 96-well protein precipitation. • Application to a sunscreen clinical study. Application of sunscreen is one of many ways to protect skin from the harmful effects of UV radiation. Sunscreen products are widely used and regulated as over-the-counter drug products in the United States. The U.S. Food and Drug Administration recommends an assessment of human systemic absorption of sunscreen active ingredients with a Maximal Usage Trial. The FDA conducted a clinical study to determine the systemic exposure of sunscreen active ingredients present in 4 commercially available sunscreen products of different formulation types under maximal usage conditions. To support this clinical study, a sensitive and specific LC-MS/MS method for the simultaneous determination of the two sunscreens avobenzone and oxybenzone in human plasma was developed. Phospholipid removal 96-well protein precipitation plates were used for sample clean-up and the extracted samples were chromatographed on an Ethylene-Bridged Hybrid (BEH) C 18 column in isocratic flow using 10 mM ammonium formate in 0.1% formic acid and methanol (24:76, v/v) as a mobile phase. A triple quadrupole mass spectrometer in multiple reaction monitoring (MRM) mode was used to acquire data. The method was validated as per current FDA bioanalytical method validation guidance, in the ranges 0.20–12.00 ng/mL for avobenzone and 0.40–300.00 ng/mL for oxybenzone. The validated method was used to analyze these active ingredients in human clinical study samples. [ABSTRACT FROM AUTHOR]

• Degradation rate of BP3 was faster in the UV/persulfate (PS) than in the UV/H 2 O 2. • Degradation rate of BP3 by both processes was faster at in acidic pHs. • As pH increased, the contribution of •OH and •SO 4 – to BP3 degradation decreased. • BP3 degradation increased by NO 3 – ions, but decreased by HCO 3 –, Br– and humic acid. • Toxicity of V. fischeri for the BP3 byproducts decreased faster in the UV/PS reaction. The degradation of benzophenone-3 (BP3) in water via the UV/H 2 O 2 and UV/persulfate (UV/PS) reactions was investigated. The degradation of BP3 exhibited pseudo-first-order kinetics in both reactions. The degradation efficiency of BP3 was higher in the UV/PS reaction than in the UV/H 2 O 2 reaction. In both reactions, the observed rate constants (k obs) of BP3 degradation were highest at pH 6 and increased linearly with increasing dosage of H 2 O 2 and persulfate. The second-order rate constants of BP3 with •OH (k •OH_BP3) and •SO 4 – (k •SO4 − _BP3) were determined to be 1.09 (± 0.05) × 1010 and 1.67 (± 0.04) × 109 M-1 s-1, respectively. The k obs values of BP3 were affected by water components such as HCO 3 −, NO 3 −, Cl−, and Br− ions, as well as humic acid. Based on the identified transformation products (TPs), the degradation pathway of BP3 during both reactions was a hydroxylation reaction. The inhibition of bioluminescence in Vibrio fischeri due to BP3 and its TPs decreased more quickly in the UV/PS reaction than in the UV/H 2 O 2 reaction. The results suggest that the UV/PS process is a better alternative to the UV/H 2 O 2 process for removing BP3 and its toxicity in water. [ABSTRACT FROM AUTHOR]

Ultraviolet (UV) filters are compounds utilized in many manufacturing processes and personal care products such as sunscreen to protect against UV-radiation. These highly lipophilic compounds are emerging contaminants of concern in aquatic environments due to their previously observed potential to bioaccumulate and exert toxic effects in marine ecosystems. Currently, research into the toxic effects of UV filter contamination of freshwater ecosystems is lacking, thus the present study sought to model the effects of acute and chronic developmental exposures to UV filters avobenzone, oxybenzone and octocrylene as well as a mixture of these substances in the freshwater invertebrate, Daphnia magna , at environmentally realistic concentrations. Median 48-hour effect and lethal concentrations were determined to be in the low mg/L range, with the exception of octocrylene causing 50% immobilization near environmental concentrations. 48-hour acute developmental exposures proved to behaviourally impair daphnid phototactic response; however, recovery was observed following a 19-day post-exposure period. Although no physiological disruptions were detected in acutely exposed daphnids, delayed mortality was observed up to seven days post-exposure at 200 μg/L of avobenzone and octocrylene. 21-day chronic exposure to 7.5 μg/L octocrylene yielded complete mortality within 7 days, while sublethal chronic exposure to avobenzone increased Daphnia reproductive output and decreased metabolic rate. 2 μg/L oxybenzone induced a 25% increase in metabolic rate of adult daphnids, and otherwise caused no toxic effects at this dose. These data indicate that UV filters can exert toxic effects in freshwater invertebrates, therefore further study is required. It is clear that the most well-studied UV filter, oxybenzone, may not be the most toxic to Daphnia , as both avobenzone and octocrylene induced behavioural and physiological disruption at environmentally realistic concentrations. Unlabelled Image • D. magna neonates were exposed to ultraviolet filters (UVFs) for 2 or 21 days. • 48-hour UVF exposure reduced survivorship and behaviourally impaired daphnids. • Chronic exposure to 7.5 μg/L octocrylene resulted in complete 7-day mortality. • Chronic exposure to avobenzone or oxybenzone disrupted daphnid metabolic rate. • UVFs exhibit toxicity to Daphnia at environmentally realistic concentrations. [ABSTRACT FROM AUTHOR]

Microplastics (MPs) lipophilic nature and widespread distribution raises concerns due to their increasing presence in the marine environment and their ability to adsorb organic contaminants, as being potential vehicles for transport and potential source of accumulation of organic contaminants by marine organisms. The organic UV-filter, oxybenzone (BP-3) is a constituent of sunscreens and personal care products, entering the marine environment either by direct contact with swimmers or by wastewater effluents. In this study the ecotoxicological effects of exposure to low-density polyethylene (LDPE) microplastics with and without adsorbed BP-3 were investigated in the peppery furrow shell clam, Scrobicularia plana. LDPE microplastics with a size range of 11–13 μm were previously contaminated with an environmentally relevant concentration of BP-3 (82 ng g−1). S. plana individuals were exposed to a concentration of 1 mg L−1 of microplastics with and without BP-3 adsorbed in a water-sediment exposure system for 14 days. Clams were sampled at the beginning of the experiment and after 3, 7, and 14 days of exposure. Multiple biomarkers were analysed to investigate the effect of exposure in different clam tissues, gills, digestive gland, and haemolymph. Antioxidant (superoxide dismutase, catalase, glutathione peroxidase) and biotransformation (glutathione-S-transferases) enzyme activities, oxidative damage (lipid peroxidation), genotoxicity (single and double strand DNA breaks), and neurotoxicity (acetylcholinesterase activity) were assessed along with two biomarker indexes to assess the overall health status. Results indicate that after 7 days of exposure MPs with adsorbed BP-3 induced oxidative stress and damage, when compared to exposure to virgin MPs and control treatments. Neurotoxic effects were also noted in MPs with adsorbed BP-3 after 14 days exposure, while some evidence points to increased genotoxicity with exposure time. Overall results indicate that gills were more affected by exposure to microplastics than digestive gland and that biomarkers alterations are apparently more related to the toxicity of BP-3 adsorbed than virgin MPs alone. Unlabelled Image • Virgin and BP-3 contaminated MPs induce oxidative stress in Scrobicularia plana as a tissue specific response with gills more adversely affected. • Virgin and BP3 contaminated MPs exposure induce oxidative damage in gills. • Only BP-3 contaminated MPs induces oxidative damage in the digestive gland. • Biomarkers alterations are more related to the toxicity of BP-3 than virgin MPs alone [ABSTRACT FROM AUTHOR]

Coral bleaching due to global warming currently is the largest threat to coral reefs, which may be exacerbated by altered water quality. Elevated levels of the UV filter oxybenzone in coastal waters as a result of sunscreen use have recently been demonstrated. We studied the effect of chronic oxybenzone exposure and elevated water temperature on coral health. Microcolonies of Stylophora pistillata and Acropora tenuis were cultured in 20 flow-through aquaria, of which 10 were exposed to oxybenzone at a field-relevant concentration of ~0.06 μg L−1 at 26 °C. After two weeks, half of the corals experienced a heat wave culminating at 33 °C. All S. pistillata colonies survived the heat wave, although heat reduced growth and zooxanthellae density, irrespective of oxybenzone. Acropora tenuis survival decreased to 0% at 32 °C, and oxybenzone accelerated mortality. Oxybenzone and heat significantly impacted photosynthetic yield in both species, causing a 5% and 22–33% decrease, respectively. In addition, combined oxybenzone and temperature stress altered the abundance of five bacterial families in the microbiome of S. pistillata. Our results suggest that oxybenzone adds insult to injury by further weakening corals in the face of global warming. Unlabelled Image • Chronic effect study on corals combining oxybenzone and elevated temperature. • Oxybenzone affected PS II of coral photosymbionts and altered coral microbiome. • Temperature effects were stronger than oxybenzone effects. • Sensitivities were species-dependent. • Oxybenzone adds insult to injury by weakening corals in the face of global warming. [ABSTRACT FROM AUTHOR]

This work aimed to investigate effects of the ocean contamination by the sunscreen Benzophenone-3 (BP3) and acidification, caused by CO 2 enrichment, to the yellow clam, Amarilladesma mactroides. Biochemical biomarkers were analyzed in tissues (gills, digestive gland, and mantle) of clams exposed to the environmental concentration of 1 μg/L BP3, at seawater natural pH (pH 8.1) and at lower pH (pH 7.6). The tissues responded in different ways considering their physiological roles. In general, BP3 altered activity of the enzymes, glutathione-S-transferase (GST) and glutathione cysteine ligase (GCL); but mostly increased the level of glutathione (GSH). These effects were enhanced by acidification, without augmenting lipid peroxidation (LPO). Carbonic anhydrase activity (CA) increased after BP3 exposure in the digestive gland and decreased in the gills at pH 7.6, while Ca2+-ATPase activity was affected by acidification only. Changing levels of these enzymes can alter shell formation and affect the bivalve maintenance in impacted environments. Unlabelled Image • Effects of Benzophenone-3 and low pH on the yellow clam, Amarilladesma mactroides • Benzophenone-3 affects antioxidant defenses in gills and digestive glands. • Water acidification affects Ca2+-ATPase activity. • Water acidification and Benzophenone-3 together inhibit carbonic anhydrase activity. • Acidification may enhance the toxicity of Benzophenone-3. [ABSTRACT FROM AUTHOR]

• The degradation of BP3 in chlorination and UV/chlorination were the faster at pH 8. • OH radical contribution in UV/chlorination to BP3 increased in acidic pH. • UV/chlorination of BP3 was promoted by HCO 3 − ions and was inhibited by humic acid. • Seven transformation products (TPs) of BP3 were identified during two reactions. • Toxicity with V. fischeri on TPs in UV/chlorination was lower than in chlorination. Benzophenone-3 (BP3) is a potential phenolic endocrine disrupter that is widely used as a sunscreen and ultraviolet (UV) stabilizer. The degradation of BP3 in water during chlorination and UV/chlorination reactions was investigated. The degradation of BP3 by both reactions followed pseudo-first-order kinetics. The pH profile of the observed pseudo-first-order rate constants (k obs) were bell shapes that depended on pH, and the highest k obs values were obtained at pH 8 for both reactions. The contribution of OH radicals (OH) on BP3 degradation under UV/chlorination conditions increased at acidic pH values, and the contribution of reactive chlorine species (RCS) such as Cl increased at neutral and basic pH values. The BP3 degradation rate was enhanced by the presence of HCO 3 − ions, but was inhibited by humic acid. A total of seven transformation products (TPs) of BP3 were identified during chlorination (TP-262, TP-296, TP-192, TP-226, and TP-118) and UV/chlorination (TP-244, TP-262, TP-278, and TP-296) reactions. Among the TPs, chloroform (TP-118) was only found in the chlorination reaction. The BP3 degradation pathways during both reactions were proposed based on these TPs. Degradation of BP3 was mainly associated with electrophilic aromatic halogenation in both reactions. Finally, the bioluminescence inhibition of Vibrio fischeri by the TPs produced from the BP3 during the UV/chlorination reaction was lower than that of the TPs obtained during chlorination, implying that the additional oxidation of BP3 occurs by the reactive radicals produced during the UV/chlorination reaction. [ABSTRACT FROM AUTHOR]

The state of Hawaii recently passed legislation banning the sale of sunscreens containing oxybenzone and octinoxate, two chemicals that have been documented to be harmful to coral reef ecosystems, beginning in 2021. However, little is currently known about the sunscreen use patterns of beach-goers in Hawaii. To gain more information about the potential effectiveness of the ban, we surveyed beach-goers to better understand: the prevalence of oxybenzone and octinoxate in sunscreens, the proportion of sunscreens that are purchased in Hawaii and out of state, what factors go into people's selection of sunscreens, awareness of the harmful effects these chemicals, and willingness to switch to "reef-safe" sunscreen alternatives. Slightly over half of sunscreens were purchased in the state of Hawaii, meaning that almost half of sunscreens being used will not be subject to the chemical ban. Approximately 75% of beach goers stated that they were aware of the harmful effects of some sunscreen chemicals, but nearly one-third still used sunscreens containing oxybenzone or octinoxate. While this study only documented the presence or absence of the two banned chemicals, the majority of sunscreens still contained other UV blocking chemicals or nano-sized mineral particles that are potentially detrimental to coral health. The majority of respondents stated that they would be willing to switch to reef safe sun protection alternatives, but this is hindered by respondents' lack of knowledge about which chemicals they should avoid. Clear and consistent "reef safe" labeling standards would enable individuals to make more informed sunscreen purchasing decisions. • Awareness of sunscreen chemical impacts on coral is high amongst Hawaii beach goers. • Hawaii's upcoming chemical ban will affect approximately half of sunscreens in use. • Oxybenzone and/or octinoxate was present in thirty-two percent of sunscreens used. • Awareness reduced but did not eliminate banned chemicals in beach goer's sunscreens. • Clear labelling standards could help enable more reef safe sunscreen choices. [ABSTRACT FROM AUTHOR]

The efficiency of the analytical methods based on vibrational spectroscopy has been widely verified in a high number of publications. In addition, it has been recognized that the pretreatment of the original signals is absolutely necessary to obtain enough quality in the subsequent classification and/or regression models. In fact, an inappropriate pretreatment makes the results worse. It is also impossible to give "a priori" rules that guarantee the adequacy of a pretreatment for specific data. The effect of the pretreatments is evaluated through their impact on the quality of the classification and/or regression models built from them due to the double dependence (on the data and on the purpose of the analysis). The effect of the pretreatment has been evaluated using partial least squares regression (PLSR) in some works and the root mean squares in prediction or in cross-validation has been always used as a criterion to evaluate the regression in all these cases. However, it seems appropriate to use quality criteria of the calibration of the analytical method through the figures of merit: the significance of the regression, the absence of constant or proportional bias, the residual standard deviation, the mean of the absolute values of the relative errors and the capability of detection. In this work, the use of these analytical criteria in a desirability function is proposed for the first time with calibration data of oxybenzone obtained by ATR-FTIR and PLSR. This desirability function enables to choose the best pretreatment among the 39 possibilities studied. In addition, it is shown that the same optimum is not obtained if the minimum of RMSEC_CV is considered as a criterion. • Signal pretreatment mostly influences the vibrational spectroscopy methods. • A procedure to obtain the best pretreatment is developed for PLSR calibration. • The procedure is a multicriteria strategy that models the accuracy line quality. • The performance of the procedure has been proved for calibration of BP3 by ATR-FTIR. [ABSTRACT FROM AUTHOR]

• OBZ directly inhibited PET and RET of algae, suppressing photosynthesis and respiration, causing excess excitation energy. • The OBZ inhibition of photosynthesis and respiration lead to lack of energy supply to various metabolisms in the cell. • The over accumulated ROS caused by OBZ further impacted on photosynthesis, respiration, growth and bleaching of pigments. • The damage to algae through accumulated ROS and lack of energy supply represents secondary OBZ-induced algal damages. Oxybenzone (OBZ; benzophenone-3, CAS# 131-57-7) is a known pollutant of aquatic and marine ecosystems, and is an ingredient in over 3000 personal care products, as well as many types of plastics. The aim of this study is to explore the different toxicities of OBZ on an eukaryotic (Chlorella sp.) and a prokaryotic algae (Arthrospira sp.). OBZ is a photo-toxicant, with all observed toxicities more sever in the light than in the dark. Cell growth and chlorophyll inhibition were positively correlated with increasing OBZ concentrations over time. Twenty days treatment with OBZ, as low as 22.8 ng L−1, significantly inhibited the growth and chlorophyll synthesis of both algae. Both algae were noticeably photo-bleached after 7 days of exposure to OBZ concentrations higher than 2.28 mg L−1. Relatively low OBZ concentrations (0.228 mg L−1) statistically constrained photosynthetic and respiratory rates via directly inhibiting photosynthetic electron transport (PET) and respiration electron transport (RET) mechanisms, resulting in over production of reactive oxygen species (ROS). Transmission and scanning electron microscopy showed that the photosynthetic and respiratory membrane structures were damaged by OBZ exposure in both algae. Additionally, PET inhibition suppressed ATP production for CO 2 assimilation via the Calvin-Benson cycle, further limiting synthesis of other biomacromolecules. RET restriction limited ATP generation, restricting the energy supply used for various life activities in the cell. These processes further impacted on photosynthesis, respiration and algal growth, representing secondary OBZ-induced algal damages. The data contained herein, as well as other studies, supports the argument that global pelagic and aquatic phytoplankton could be negatively influenced by OBZ pollution. [ABSTRACT FROM AUTHOR]

Topical sunscreen products are universally applied by numerous individuals to protect their skin from the detrimental effects of UV radiation. However, lately, studies have revealed the risks associated with percutaneous absorption of UV filters leading to undesirable systemic side effects such as hormonal disturbances and allergies. In this study, an innovative sunscreen formulation was developed based on starch microsponges as a key carrier encapsulating an organic sunscreen benzophenone‑3. The developed starch microsponges were characterized by scanning electron microscopy and nitrogen adsorption/desorption analysis. The results showed that starch microsponges possessed a high BET surface area (85.45 m2/g) with spherical porous morphology with pore size <200 nm. Benzophenone‑3 was loaded into the starch microsponges by immersion/solvent evaporation and benzophenone‑3 loaded starch microsponges were characterized by scanning electron microscopy, differential scanning calorimetry, powder X-ray diffraction, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption measurements. Results corroborated that benzophenone‑3 was successfully entrapped within the nanopores of starch microsponges. A starch microsponge based sunscreen cream was formulated, characterized and clinically tested. Rheological, texture and sensorial assessment showed that starch microsponges based sunscreen product showed good spreadability, non-sticky, rich texture favorable for consumer usage. In vitro and ex-vivo studies demonstrated benzophenone‑3 loaded starch microsponges gave improved photoprotection, higher SPF and reduced cutaneous penetration compared to raw benzophenone‑3 cream. Clinically, patch study confirmed that the developed starch microsponges based sunscreen cream was skin safe and biocompatible. Thus, the amalgamation of sunscreen molecule benzophenone‑3 into starch microsponges produced a safe, effective innovative sunscreen product. Unlabelled Image • Starch microsponges (SM) were fabricated, characterized and used as a key carrier to adsorb BNZ into its nanopores. • A starch microsponge based novel sunscreen cream was formulated and clinically proven safe for consumer usage. • UV protective efficacy, SPF and sensory profile of sunscreen cream was improved owing to encapsulation of BNZ into SM. • SM based sunscreen cream gave enhanced stratum corneum deposition and minimal skin permeation compared to raw BNZ cream. [ABSTRACT FROM AUTHOR]

Avobenzone (AVO), oxybenzone (OXY), and octyl methoxycinnamate (OMC), are widely used UV filters. The aim of this study was to investigate the effect of incorporation in mesoporous silica (SBA-15) on their cutaneous deposition and permeation. Stick formulations containing "free" and "incorporated" UV filters (SF1 and SF2, respectively) were prepared and characterized with respect to their physicochemical, thermal, and functional properties. Cutaneous delivery experiments using porcine skin with quantification by UHPLC-MS/MS, demonstrated that skin deposition of AVO and OXY after application of SF2 for 6 and 12 h was significantly lower than that from SF1 at each time-point (Student t -test, p < 0.05): e.g. OXY permeation across the skin was 30-, 12- and 1.5-fold lower after 6, 12 and 24 h, respectively, following application of SF2. Cutaneous biodistribution profiles of AVO and OXY to 800 µm evidenced a significant decrease in the amounts in the viable epidermis and dermis. In contrast, deposition of the more lipophilic OMC was not significantly different (p ˃ 0.05). In vitro photoprotective efficacy results demonstrated that adsorption/entrapment of UV filters enhanced the sun protection factor by 94%. In conclusion, SBA-15, an innovative mesoporous material, increased photoprotection by UV filters while reducing their cutaneous penetration and transdermal permeation. [ABSTRACT FROM AUTHOR]

Electromagnetic radiation in the ultraviolet, visible, and infrared ranges all produce biologic effects. Ultraviolet filters are the most well-studied photoprotective measure for the adverse effects of ultraviolet radiation. Because of the reported endocrinologic effects of oxybenzone in animal studies, its effects on coral reefs, and its photocontact allergy potential, its use has been minimized in many countries worldwide. New developments in topical antioxidants and oral and subcutaneous agents (eg, Polypodium leucotomos extract, afamelanotide, nicotinamide) with photoprotective and antiphotocarcinogenic properties could potentially provide addition modalities for protection against the effects of visible light and infrared radiation. [ABSTRACT FROM AUTHOR]