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Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g−1 dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.

Clear Creek in Golden, Colorado sees a large number of recreational users during summer, which is expected to result in release of sunscreen chemicals to the water. In this study, water samples were collected hourly for 72 hours over a busy holiday weekend, and were analyzed for the organic chemical – based (oxybenzone) and inorganic colloidal (titanium dioxide) active sunscreen constituents. An increase in oxybenzone concentration was observed daily during each day's peak recreational use, approximately 12:00 to 19:00 h. This corresponded with an increase in titanium concentration. Metals naturally co-occurring with titanium such as aluminum and iron also showed an increase of these elements during bathing periods as well, suggesting the titanium increase may also be partially the result of sediment resuspension, consistent with the shallow water depth. The ratio of titanium to both aluminum and iron increases relative to the background elemental ratios during peak recreational use. Estimates of titanium mass loading suggested that sunscreen use only could not explain the observed Ti : Al and Ti : Fe ratios and that resuspended sediments likely have an elevated titanium metal ratio compared to natural suspended sediments. Single particle ICP-MS (spICP-MS), used to analyze water samples for Ti-containing particles, did not show diurnal trends in total particle number. Overall, this is the first consecutive-multi-day monitoring study for compounds released from sunscreen to a natural water system, and it highlights the challenges in dealing with detection of NPs above a natural background.

Sunscreen products are mostly used to protect human skin from adverse effects of ultra-violet light like DNA damage, photo-aging and sunburns. Photo-stability is one of the critical requirements for an effective sunscreen. However, most commercially available sunscreen compounds exhibit photo-reactions leading to formation of harmful products. The objective of the current research was to investigate the photo-chemical and photo-physical properties of few selected sunscreens formulations and also to explore photo-stability and photo-sensitizing properties of few selected organic UV filters used in the sunscreens. Photo-degradation mechanisms of the selected sunscreens ingredients were analysed using time-resolved Laser Flash Photolysis and steady-state HPLC coupled with Mass Spectrometry. Oxybenzone (OXB) was revealed to be a sufficiently stable UV filter even after 24 h of radiation exposure, whereas, Avobenzone (AVOB) and Ecamsule (ECAM) were found to be a photo-unstable sunscreen.

There is a need to develop viable techniques for removal and/or recovery of organic and inorganic compounds from environmental matrices, due to their eco-toxicity, regulatory obligations or potential supplies as secondary materials. Simultaneous phosphorus (P) recovery and removal of emerging organic contaminants (caffeine, bisphenol A, 17α-ethinylestradiol and oxybenzone) from sewage sludge (SS) was assessed using the electrodialytic (ED) process. The SS samples were collected at the secondary settling tank between May and July, 2015. Different current intensities were tested continuously or sequentially (between 50, 75 and 100 mA), in a 2 compartment cell, placing the SS in the cathode end, separated from the anode end through an anion exchange membrane. After 24 h, between 45 and 55% of P electromigrated to the anode end in all experiments and the application of higher current intensities did not promote significant improvements in its recovery. After 72 h, the best results were obtained when 100 mA (0.21 mA/cm 2 ) were applied: 70% of P were recovered in the anolyte and between 79 and 96% of organic compounds were degraded. Still, the obtained anolyte enriched in P was not completely free of organic contaminants.

Sunscreen users may feel burned if they do and burned if they don’t: Concerns about the health and environmental effects of current sunscreens seem to be making consumers warier about using them and lawmakers more likely to restrict them. Some sunscreen compounds approved by the U.S. Food & Drug Administration, for instance, have recently fallen under scrutiny for their potential to disrupt hormone signaling, which is linked to increased cancer risk. And in July, the governor of Hawaii signed a bill to ban in-state sale of sunscreens containing either oxybenzone or octinoxate, suspected to harm coral reefs. Meanwhile, around the world skin cancer rates are on the rise: 132,000 cases of melanoma and 2 million to 3 million cases of other skin cancers occur each year. Inventing and approving new sunscreen compounds with fewer downsides could alleviate concerns and increase use, but cosmetic chemists working in this area have their

Similar to humans, pet animals are exposed to environmental contaminants through multiple sources and pathways. Although a few studies have demonstrated exposure of cats and dogs to environmental chemicals, little is known about exposure to bisphenols, benzophenone UV filters, and antibacterial agents. In this study, we measured three bisphenols, three benzophenone-type UV filters, triclosan (TCS), and triclocarban (TCC) in dog (n = 50) and cat urine (n = 50) collected from New York State, USA. Among bisphenols, BPS was found at the highest concentrations (mean ± SD: 3.2 ± 8.5 ng/mL in dogs and 8.85 ± 30.0 ng/mL in cats) with detection frequencies of 96% in dogs and 78% in cats. Among benzophenones, BP-3 (oxybenzone) was the dominant compound in pet urine, followed by BP-1 and BP-8. TCS was found at concentrations higher than those of TCC in both cat and dog urine. There were no significant differences in bisphenol concentrations between sexes or age groups, both in dogs and cats. The calculated hazard quotients (HQ) suggested that the current exposure levels of BPS and BP-3 in pets were 2–5 orders of magnitude below the tentative threshold values available for humans.

Systematic Review Protocol A Hypothesis-Driven Weight-of-Evidence Analysis to Evaluate Potential Endocrine Activity of Oxybenzone Following Exposure from UV Filters in Humans

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.

Christiano, R. S. C., Reilly, C. C., Miller, W. P., and Scherm, H. 2010. Oxytetracycline dynamics on peach leaves in relation to temperature, sunlight, and simulated rain. Plant Dis. 94:12131218. Oxytetracycline (OTC), a member of the tetracycline antibiotics, is used as a foliar spray to control Xanthomonas arboricola pv. pruni on stone fruits and Erwinia amylovora on pome fruits. We studied the dynamics of OTC residues on attached peach (Prunus persica) leaves treated with 300 ppm active ingredient of an agricultural OTC in relation to temperature, natural sunlight, and simulated rain. We further evaluated the potential of three ultraviolet (UV) protectants (lignin, titanium dioxide, and oxybenzone) and one sticker-extender (Nu Film-17) to prolong OTC longevity on the leaf surface. OTC residue was determined by high-pressure liquid chromatography (HPLC)-UV (C18 reversed-phase column). In controlled conditions in darkness, constant temperatures up to 40°C did not affect OTC degradation on leaves. In contrast, OTC residue decreased rapidly in natural sunlight in the absence of rain, declining, on average, by 43.8, 77.8, and 92.1% within 1, 2, and 4 days after application, respectively; 7 days after application, OTC levels were near the detection limit. Use of shade fabric with 10 and 40% sunlight transmittance, simulating overcast sky, reduced OTC degradation significantly but did not extend OTC persistence beyond 7 days. Areas under the OTC residue curve, summarizing OTC dynamics during the 7-day exposure period, were negatively and significantly correlated with solar radiation and UV radiation variables, but not with temperature. UV protectants and Nu Film-17 were ineffective in improving OTC persistence in outdoor conditions. Simulated rain at 44 mm h −1 drastically (by 67.2%) lowered OTC residue after 2 min, and levels were near the detection limit after 60 min of continuous rain, regardless of whether plants were exposed to rainfall 1 or 24 h after OTC application. In artificial inoculation experiments with X. arboricola pv. pruni on attached peach leaves, OTC concentrations ≥50 ppm active ingredient (corresponding to ≥0.06 µg OTC cm −2 leaf surface) were sufficient to suppress bacterial spot development. By extrapolation from our outdoor exposure experiments, similar OTC residues following application of labeled OTC rates would be reached after less than 2 days under full sunlight, after 4 days under overcast sky, or after 2 min of a heavy rainstorm.

Oxybenzone (benzophenone-3) is an ultraviolet radiation filter commonly used in personal care products including sunscreens, textiles and inks, and food and beverage containers, among others. Due to its widespread use, human exposures to oxybenzone are widespread. Oxybenzone is considered an endocrine disrupting chemical due to its antiestrogenic and antiandrogenic properties. We evaluated the effects of oral exposures to oxybenzone on the growth and morphology of the mammary gland, body weight and anogenital distance in BALB/c mice exposed to 30, 212 or 3000 μg/kg/day in utero and during lactation. Developmental exposures to oxybenzone reduced the size and growth of mammary gland in males prior to and during puberty. In exposed females, oxybenzone reduced mammary cell proliferation, decreased the number of cells expressing estrogen receptor α, and altered mammary gland morphology in adulthood. These results suggest that even low doses of oxybenzone can disrupt hormone sensitive organs during critical windows of development.

A method was developed for the simultaneous determination of two groups of personal care products, namely UV filters (oxybenzone, 3-(4-methylbenzylidene)camphor, padimate-O, 2-ethylhexyl-4-methoxycinnamate, and octocrylene) and polycyclic aromatic musks (galaxolide and tonalide), in fish by in vivo solid-phase microextraction followed by gas chromatography–mass spectrometry. The in vivo method was validated by carrying out in vitro experiments; the method validation parameters were linearity (r2 > 0.98), interday precision (relative standard deviations

Sunscreens and other personal care products use organic ultraviolet (UV) filters such as oxybenzone, 4-methylbenzylidene camphor, Padimate-O, and octyl methoxycinnamate to prevent damage to human skin. While these compounds are effective at preventing sunburn, they have a demonstrated negative effect on cells and tissues across taxonomic levels. These compounds have a relatively short half-life in seawater but are continuously re-introduced via recreational activities and wastewater discharge, making them environmentally persistent. Because of this, testing seawater samples for the presence of these compounds may not be reflective of their abundance in the environment. Bioaccumulation of organic ultraviolet filters in a high-trophic level predator may provide greater insight to the presence and persistence of these compounds. To address this, the present study collected seawater samples as well as muscle and stomach content samples from the invasive Pacific lionfish (Pterois volitans) in the nearshore waters of Grenada, West Indies to examine the use of lionfish as potential bioindicator species. Seawater and lionfish samples were collected at four sites that are near point sources of wastewater discharge and that receive a high number of visitors each year. Samples were tested for the presence and concentrations of oxybenzone, 4-methylbenzylidene camphor (4-MBC), Padimate-O, and octyl methoxycinnamate (OMC) using liquid chromatography-mass spectrometry. Oxybenzone residues were detected in 60% of seawater samples and OMC residues were detected in 20% of seawater samples. Seawater samples collected in the surface waters near Grenada's main beach had oxybenzone concentrations more than ten times higher than seawater samples collected in less frequently visited areas and the highest prevalence of UV filters in lionfish. Residues of oxybenzone were detected in 35% of lionfish muscle and 4-MBC residues were detected in 12% of lionfish muscle. Padimate-O was not detected in either seawater or lionfish samples. No organic UV filters were detected in lionfish stomach contents. Histopathologic examination of lionfish demonstrated no significant findings attributed to UV filter toxicity. These findings report UV filter residue levels for the first time in inshore waters in Grenada. Results indicate that lionfish may be bioaccumulating residues and may be a useful sentinel model for monitoring organic ultraviolet filters in the Caribbean Sea.

The aim of this research was to investigate the influence of arbutin (3% w/w) and olive oil addition (3, 5, and 7% w/w) on characteristic and SPF values of sunscreen product containing oxybenzone and octyldimethyl PABA (3:7% w/w) in a carbomer 940 gel base. The characteristic test was conducted by observing the physical appearance, pH and spreading ability on the second day after the product was made; while the SPF values were measured through a spectrophotometric method. Based on the results of the characteristic test, it was evident that the addition of arbutin and olive oil affected the physical appearances i.e the organoleptic and consistency of sunscreen product as well as its spreading ability, but had no effect on its pH. However, the addition of arbutin and olive oil significantly improved the effectiveness of sunscreen product and increase in the concentration of olive oil resulted in a rise in the SPF values. Nonetheless, further study on the in vivo effectiveness using human subject is required to comprehend the SPF application.

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

A new voltammetric methodology is proposed for the simultaneous determination of the organic UV filters oxybenzone (benzophenone 3, BP3) and octocrylene (OC) in personal care products and in wastewater extracts. It is based on previous adsorptive stripping voltammetric (AdSV) methods developed for hanging mercury drop electrodes, adapted to the special characteristics of carbon-based screen-printed electrodes. Among the carbon substrates tested, regular carbon screen-printed devices exhibited the best performance, with detection limits of 4.8 and 6.6 μmol L−1 and linearity ranges of 16–400 and 22–400 μmol L−1 for BP3 and OC, respectively, and, as compared to mercury electrodes, with the advantages of environmental safety, easy of use, low cost and compatibility with automation and flow measurements. The methodology has been successfully tested in real samples and compared to the standard methodology by liquid chromatography – tandem mass spectrometry (LC-MS/MS). © 2019 Elsevier B.V., The authors acknowledge the support of Generalitat de Catalunya, Spain (Project 2017SGR311), the Water Research Institute of the Universitat de Barcelona (IdRA) and the Spanish Ministry of Science, Innovation and Universities through the Project ROUSSEAU (CTM2017-89767-C3-1-R).

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) C18 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.

(SOE2/P5/F0505) UIDB/04085/2020 UIDB/04612/2020 UIDP/04612/2020 SFRH/BPD/114660/2016 CEECIND/04210/2017) This study analyses the electrokinetic (EK) contribution to the removal from a clay soil of a mixture of 10 different contaminants of emerging concern (CECs; 17β-estradiol, E2; sulfamethoxazole, SMX; bisphenol A, BPA; ibuprofen, IBU; 17α-ethinylestradiol, EE2; oxybenzone, OXY; diclofenac, DCF; triclosan, TCS; caffeine, CAF; carbamazepine, CBZ). After 4 days, the CECs natural attenuation was between 0% (CBZ) and 90% (E2) yet increasing with the application of EK (20 mA, 12 h ON/OFF) to 14% (CBZ) and 100% (E2). When EK was applied, the CECs more recalcitrant to biodegradation (i.e. ≤ 13% biotic decay) mostly underwent electro-chemical induced degradation (OXY, DCF, TCS, CAF, CBZ). Daily irrigation enhanced the rates of the electro-oxidation -osmosis and -migration, increasing the CECs decay. After 8 days of EK treatment, the CECs decay increased, surpassing the decay lag phase of some compounds (OXY, TCS, and CBZ). Yet after 16 days, most CECs showed similar removals with and without EK, with EK only acting positively on SMX, OXY, TCS and CBZ (ca. +10%). Our results support that EK application can improve the removal of CECs from soil, however, under the conditions tested, 16-day treatment lead to pH alterations that decreased the bioremediation efficiency and inhibited electro-degradation near the cathode. proof epub_ahead_of_print

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.

Nowadays, the industry is quite commonly using nanoparticles of titanium dioxide (nTiO2) especially in sunscreens, due to its higher reflective index in comparison to micron size TiO2. Its high demand causes its widespread environmental occurrence, thus damaging the environment. The aquatic ecosystems are the most vulnerable to contamination by nTiO2. Like other engineered nanoparticles, nTiO2 has demonstrated generation of reactive oxygen species (ROS) and reactive halogen species (RHS) in the aquatic environment under UV radiation. This study investigated the toxicity of nTiO2 towards two aquatic indicator organisms, one from freshwater (Daphnia magna) and the other from seawater (Artemia sp.), under simulated solar radiation (SSR). Daphnia magna and Artemia sp. were co-exposed in 16 h SSR and 8 h darkness cycles to different concentrations of nTiO2. The estimated EC50 at 48 h for D. magna was 3.16 mg nTiO2/L, whereas for A. sp. no toxic effects were observed. When we exposed these two organisms simultaneously to 48 h of prolonged SSR using higher nTiO2 concentrations, EC50 values of 7.60 mg/L and 5.59 mg/L nTiO2 for D. magna and A. sp., respectively, were obtained. A complementary bioassay was carried out with A. sp., by exposing this organism to a mixture of nTiO2 and organic UV filters (benzophenone 3 (oxybenzone, BP3), octocrylene (OC), and ethyl 4-aminobenzoate (EtPABA)), and then exposed to SSR. The results suggested that nTiO2 could potentially have negative impacts on these organisms, also this work outlines the different characteristics and interactions that may contribute to the mechanisms of environmental (in salted and freshwater) phototoxicity of nTiO2 and UV radiation, besides their interaction with organic compounds., Authors acknowledge the financial support of the Spanish Ministry of Science and Innovation, for projects ROUSSEAU (CTM2017-89767-C3-1-R), CEX2018-000794-S, and CTQ2017-86466-R., and AGAUR-Gencat project 2017SGR131. A.C. Soler acknowledges Mexican CONACyT for her doctoral grant (Ref. 409154).

A low saline backwater canal, mainly utilized for domestic and agricultural purposes, has been analyzed for the possible presence of organic micropollutants (OMP) and their potential removal was explored by multilayered microfiltration membranes. The qualitative as well as quantitative analysis were carried out for a span of one year using the technique of liquid chromatography connected with high resolution mass spectrometry (LC-Q-TOF-MS). The identification of the formally unknown compounds was initially done using non-target analysis based on the mass accuracy, isotopic pattern and MS/MS spectral interpretation. Results of the non target screening revealed the presence of 11 OMPs. Five of these OMPs were confirmed using standards; these include chlorophene (CHP), oxybenzone (OXY), N, N-diethyl-meta-toluamide (DEET), N, N-diethyl-benzamide (DEB) and dibutyl phthalate (DBP). Among the confirmed OMPs, the highest concentration was observed for DBP (244.61 ng l−1). The most frequently observed OMP in the study area was DBP while the least was DEB which is an insect repellent as well as a degradation product of DEET. The ecological risk associated with the target compounds has also been analyzed by calculating the risk quotient (RQ) and the results revealed that at the detected levels, these compounds are capable of causing low to medium risk. Low pressure (

Detection of metal nanoparticles (NPs) in the environment is an analytical challenge of interest due to increasing use of nanomaterials in consumer and industrial products. Detecting NPs associated with human activities is affected by both the magnitude and variation in background concentrations of natural NPs. In this work, we investigated the potential release of titanium dioxide (TiO2) NPs from sunscreen in three recreational rivers, with a time-intensive sampling regime on one river, in order to determine the range and variability of natural, background titania (Ti). Conventional ICP analysis for total metal concentrations, single particle ICP-MS for NP concentrations, and electron microscopy aided in assessing mineralogical morphology and composition. Oxybenzone, a widely-used organic sunscreen, was measured and used as a surrogate for the intensity of recreational activity in the water. Statistically significant increases in Ti concentrations were observed in Clear Creek, CO during one recreation period, but the significance of other instances of recreation-associated Ti increases was unclear, in part due to storm impacts on the natural suspended sediment load of the stream. A comparison of three recreational rivers showed increases in both Ti mass concentrations and NP sizes occur during recreation in both Clear Creek, CO and the Salt River, AZ, but no detectable changes in the Truckee River, NV. However, size distributions were variable in background samples, which make the significance of differences observed during recreation unclear. These results underline that the release of engineered nanoparticles to a natural system cannot be detected without a well-defined background, including measures of its variability during the study period.

A series of undergraduate laboratory experiments that utilize reversed-phase HPLC separation, inductively coupled plasma spectroscopy (ICP), and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) are described for the analysis of commercial sunscreens. The active ingredients of many sunscreen brands include zinc or titanium oxide in addition to organic acids. Students determine the zinc content using ICP, and the chemical composition as well as particle sizes using SEM-EDS. The organic UV absorbers octocrylene and oxybenzone are quantified using HPLC. With the incorporation of these interesting characterization techniques in second or fourth-year chemistry courses, and by having students analyze sunscreen samples that are medically relevant in terms of health effects, students engage in timely research and at the same time gain exposure to a variety of instruments in the analysis of a familiar household product.

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 (100μM) was eliminated from the medium by hairy roots after 3h 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.

Our recent investigations into the 3D printing of poly(propylene fumarate) (PPF), a linear polyester, using a DMD-based system brought us to a resin that used titanium dioxide (TiO2) as an ultraviolet (UV) filter for controlling cure depth. However, this material hindered the 3D printing process due to undesirable lateral or "dark" curing (i.e., in areas not exposed to light from the DMD chip). Well known from its use in sunscreen, another UV filter, oxybenzone, has previously been used in conjunction with TiO2. In this study we hypothesize that combining these two UV filters will result in a synergistic effect that controls cure depth and avoids dark cure. A resin mixture (i.e., polymer, initiator, UV filters) was identified that worked well. The resin was then further characterized through mechanical testing, cure testing, and cytotoxicity testing to investigate its use as a material for bone tissue engineering scaffolds. Results show that the final resin eliminated dark cure as shown through image analysis. Mechanically the new scaffolds proved to be far weaker than those printed from previous resins, with compressive strengths of 7.8 ± 0.5 MPa vs. 36.5 ± 1.6 MPa, respectively. The new scaffolds showed a 90% reduction in elastic modulus and a 74% increase in max strain. These properties may be useful in tissue engineering applications where resorption is required. Initial cytotoxicity evaluation was negative. As hypothesized, the use of TiO2 and oxybenzone showed synergistic effects in the 3D printing of PPF tissue engineering scaffolds.

The carbonylative Suzuki–Miyaura reaction between aryl tosylates/triflates with arylboronic acid is herein reported, using base-free conditions and a balloon pressure of carbon monoxide. Under these conditions, unsymmetrical biaryl ketones were obtained in modest to excellent yields. This method was adapted to the synthesis of oxybenzone and ketoprofen in good yields under mild conditions.

Organic ultraviolet filters (UV-F) are increasingly being used in personal care products to protect skin and other products from the damaging effects of UV radiation. In this study, marine water was collected monthly for approximately one year from six coastal South Carolina, USA sites and analyzed for the occurrence of seven organic chemicals used as UV filters (avobenzone, dioxybenzone, octocrylene, octinoxate, oxybenzone, padimate-o and sulisobenzone). The results were used to examine the relationship between beach use and the distribution of UV-F compounds along coastal South Carolina, USA. Five of the seven target analytes were detected in seawater along coastal South Carolina during this study. Dioxybenzone and sulisobenzone were not detected. The highest concentrations measured were >3700 ng octocrylene/L and ~2200 ng oxybenzone/L and beach use was greatest at this site; a local beach front park. Patterns in concentrations were assessed based on season and a measure of beach use.

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.

Little information is available on the bioaccumulation and trophic transfer of pharmaceuticals and personal care products (PPCPs) in urban rivers system, particularly for those affected by water transfer. Herein, a comprehensive study was conducted to investigate the biological residues, bioaccumulation and trophic transfer of 45 PPCPs in the Nanjing Qinhuai River system under the background of water diversion projects. A total of 30 compounds were detected with a descending order of overall concentration as plankton > benthic mollusc > fish (except grass carp). Higher biological residues were observed in the downstream than those in the upstream, with the largest increase for fish (136.4 %) and the lowest increase for phytoplankton (5.4 %). However, the bioaccumulation classifications of most PPCPs were unchanged among the three different water-diversion regions. Trophic magnification factors (TMFs) of organic UV filters (homosalate, oxybenzone, ethylhexyl methoxycinnamate and octocrylene) ranged from 1.23 to 2.04, suggesting trophic magnification potential, while trophic dilution for pharmaceuticals (sertraline, citalopram, caffeine and roxithromycin) with TMFs of 0.42 to 0.50 were observed. A notable positive correlation was observed between the pH-dependent distribution coefficient (logDow) and the TMFs of the PPCPs (P

Importance A prior pilot study demonstrated the systemic absorption of 4 sunscreen active ingredients; additional studies are needed to determine the systemic absorption of additional active ingredients and how quickly systemic exposure exceeds 0.5 ng/mL as recommended by the US Food and Drug Administration (FDA). Objective To assess the systemic absorption and pharmacokinetics of the 6 active ingredients (avobenzone, oxybenzone, octocrylene, homosalate, octisalate, and octinoxate) in 4 sunscreen products under single- and maximal-use conditions. Design, Setting, and Participants Randomized clinical trial at a clinical pharmacology unit (West Bend, Wisconsin) was conducted in 48 healthy participants. The study was conducted between January and February 2019. Interventions Participants were randomized to 1 of 4 sunscreen products, formulated as lotion (n = 12), aerosol spray (n = 12), nonaerosol spray (n = 12), and pump spray (n = 12). Sunscreen product was applied at 2 mg/cm2to 75% of body surface area at 0 hours on day 1 and 4 times on day 2 through day 4 at 2-hour intervals, and 34 blood samples were collected over 21 days from each participant. Main Outcomes and Measures The primary outcome was the maximum plasma concentration of avobenzone over days 1 through 21. Secondary outcomes were the maximum plasma concentrations of oxybenzone, octocrylene, homosalate, octisalate, and octinoxate over days 1 through 21. Results Among 48 randomized participants (mean [SD] age, 38.7 [13.2] years; 24 women [50%]; 23 white [48%], 23 African American [48%], 1 Asian [2%], and 1 of unknown race/ethnicity [2%]), 44 (92%) completed the trial. Geometric mean maximum plasma concentrations of all 6 active ingredients were greater than 0.5 ng/mL, and this threshold was surpassed on day 1 after a single application for all active ingredients. For avobenzone, the overall maximum plasma concentrations were 7.1 ng/mL (coefficient of variation [CV], 73.9%) for lotion, 3.5 ng/mL (CV, 70.9%) for aerosol spray, 3.5 ng/mL (CV, 73.0%) for nonaerosol spray, and 3.3 ng/mL (CV, 47.8%) for pump spray. For oxybenzone, the concentrations were 258.1 ng/mL (CV, 53.0%) for lotion and 180.1 ng/mL (CV, 57.3%) for aerosol spray. For octocrylene, the concentrations were 7.8 ng/mL (CV, 87.1%) for lotion, 6.6 ng/mL (CV, 78.1%) for aerosol spray, and 6.6 ng/mL (CV, 103.9%) for nonaerosol spray. For homosalate, concentrations were 23.1 ng/mL (CV, 68.0%) for aerosol spray, 17.9 ng/mL (CV, 61.7%) for nonaerosol spray, and 13.9 ng/mL (CV, 70.2%) for pump spray. For octisalate, concentrations were 5.1 ng/mL (CV, 81.6%) for aerosol spray, 5.8 ng/mL (CV, 77.4%) for nonaerosol spray, and 4.6 ng/mL (CV, 97.6%) for pump spray. For octinoxate, concentrations were 7.9 ng/mL (CV, 86.5%) for nonaerosol spray and 5.2 ng/mL (CV, 68.2%) for pump spray. The most common adverse event was rash, which developed in 14 participants. Conclusions and Relevance In this study conducted in a clinical pharmacology unit and examining sunscreen application among healthy participants, all 6 of the tested active ingredients administered in 4 different sunscreen formulations were systemically absorbed and had plasma concentrations that surpassed the FDA threshold for potentially waiving some of the additional safety studies for sunscreens. These findings do not indicate that individuals should refrain from the use of sunscreen. Trial Registration ClinicalTrials.gov Identifier:NCT03582215

There has been recent extensive controversy concerning potential environmental and health hazards of oxybenzone (also known as benzophenone-3 and Eusolex 4360). Although there has been widespread related media attention, there is little definitive scientific research supporting the associated concerns. Given these controversies, it is critical that dermatologists have a clear understanding of the underlying issues related to oxybenzone in order to effectively counsel their patients. The purpose of this article is to provide dermatologists with a framework for presenting this issue to patients. Within, we address questions such as: 1) Is oxybenzone the reason for coral bleaching? 2) Is there data to suggest that oxybenzone is harmful to humans? 3) Why is oxybenzone used in the majority of US sunscreens? and 4) Are there other potential problems with oxybenzone restrictions that could lead to more skin cancer in the future? After a careful review of the evidence, we conclude that, in our opinion, there is little definitive scientific research supporting the associated concerns and that before this evidence exists, given the benefits of oxybenzone-containing sunscreens in skin cancer prevention, this ban is premature. Banning an ingredient commonly used in most sunscreens may lead to confusion among consumers and have the untoward outcome of less sunscreen being used overall.

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.

A practical and highly para-selective C-H difluoromethylation of aromatic ketones has been developed by employing tetrakis(triphenylphosphine)palladium(0) as the catalyst and triphenylphosphine as the ligand. In addition to general aromatic ketones, this transformation was compatible with bioactive compounds and well-known drugs, such as oxybenzone, ketoprofen, zaltoprofen, and propafenone. Moreover, a mechanistic study revealed that a palladium intermediate coordinated by a carbonyl group promotes highly para-selective difluoromethylation.

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 CO2 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.