Human exposure risk of organic UV filters: A comprehensive analysis based on primary exposure pathways.

The exposure of organic UV filters has been increasingly confirmed to induce adverse effects on humans. However, the critical exposure pathway and the vulnerable population of organic UV filters are not clearly identified. This paper attempts to evaluate the health risk of commonly used organic UV filters from various exposure routes based on comprehensive analysis strategy. The estimated daily intakes (EDI) and hazard quotient (HQ) values of organic UV filters through four pathways (dermal exposure, indoor dust, indoor air, and drinking water) for various age groups were determined. Although the total HQ values (0.01-0.4) from comprehensive exposure of organic UV filters were below risk threshold (1.0), infants were identified as the most vulnerable population, with EDI (75.71 ng/kg-bw/day) of 2-3 times higher than that of adults. Additionally, the total EDI values of individual exposure pathways were estimated and ranked as follows: indoor air (138.44 ng/kg-bw/day) > sunscreen application (37.2 ng/kg-bw/day) > drinking water (21.87 ng/kg-bw/day) > indoor dust (9.24 ng/kg-bw/day). Moreover, we successfully tailored the Sankey diagram to depict the EDI proportion of individual organic UV filters from four exposure pathways. It was noted that EHMC (ethylhexyl methoxycinnamate) and EHS (ethylhexyl salicylate) dominated the contribution of EDI (72 %) via indoor air exposure routes. This study serves as a crucial reference for enhancing public health risk awareness concerning organic UV filters, with a special focus on the vulnerable populations such as infants and children.

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

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

Determination and risk assessment of UV filters and benzotriazole UV stabilizers in wastewater from a wastewater treatment plant in Lüneburg, Germany.

UV filters and benzotriazole UV stabilizers are considered emerging contaminants in the environment. LC-MS/MS and GC-MS methods, involving a single solid phase extraction protocol, were developed and validated to determine eight UV filters and seven UV stabilizers, respectively in wastewater from a wastewater treatment plant (WWTP) in Lüneburg, Germany. The LC-MS/MS method exhibited extraction recoveries of ≥ 71% at six different fortification levels with limits of detection (LODs) range of 0.02 ng mL-1 - 0.09 ng mL-1. Extraction recoveries of 47 to 119% at six different fortification levels were obtained for the GC-MS method with LODs range of 0.01 - 0.09 ng mL-1. Among the UV filters, the highest mean concentration was determined for octocrylene (OCR) in influent (3.49 ng mL-1) while the highest mean concentration was measured for 2-hydroxy-4-octyloxybenzophenone (UV 531) in influent (0.44 ng mL-1) among the UV stabilizers. Potential risk to aquatic organisms was assessed by the risk quotient approach. Only OCR presented a high risk to aquatic invertebrates whereas 2-ethylhexyl 4-methoxycinnamate (EHMC) and 2-ethylhexyl salicylate (EHS) posed high risks to algae. Benzotriazole UV stabilizers presented negligible risks to aquatic invertebrates and fish. This work reports the detection of rarely studied 4-aminobenzoic acid (PABA) and UV 531 in WWTP influent and effluent. The occurrence and risk assessment of target benzotriazole UV stabilizers in wastewater from a German WWTP was demonstrated for the first time.

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

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

Distribution, sources, ecological and human health risks of organic ultraviolet filters in coastal waters and beach deposits in Hainan, China.

Organic ultraviolet filters (OUVFs) are extensively incorporated into both cosmetic items and industrial products and have been commonly found in water ecosystems. This study aims to examine the environmental levels, sources, ecological and human health risks of 14 commonly used OUVFs both in coastal water and beach deposit samples collected from the nearshore regions of Hainan Island and the South China Sea. This is first study highlighting the contamination of OUVFs in Hainan Island and utilizing economic and tourism data to confirm the potential source of OUVF pollution in costal aquatic and coastal ecosystem. Along the coastal tourist regions of Hainan Island, the median concentrations in coastal waters and beach deposits of these OUVFs fall within the range from 1.2 to 53.2 ng/L and 0.2-17.0 ng/g dw, respectively. In coastal water and beach deposit, the concentration of BP-3 was the highest, with median concentrations of 53.2 ng/L and 17.0 ng/g dw, respectively. Regarding human health risks, the daily intake of all 14 OUVFs through swimming was found to be 40-48 ng/kg/day. Ecological risk assessment indicates that BP-3 presents a medium risk for marine microalgae with a concurrent low risk for corals. The correlation analysis underscores a substantial interrelation of OUVFs in both coastal waters and beach deposits with various economic indicators, including annual rainfall, overnight tourists, total hotel rooms (unit), room occupancy rate, and sewage treatment capacity.

Analysis of the UV filter Benzophenone-3 assimilation in Crossostrea gigas oysters post-exposure in a controlled environment by LC-MS/MS.

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.

Prevalence of selected UV filter compounds in Biscayne National Park.

This research was carried out in order to assess a baseline occurrence in Biscayne National Park, Florida, of four organic contaminants: the UV filters oxybenzone, dioxybenzone, and benzophenone, as well as the topical pain reliever benzocaine. A total of 35 samples were taken from five locations within the park, four near barrier islands, and one at a coral reef. Analyses were carried out using liquid chromatography coupled to high-resolution mass spectrometry. Oxybenzone was detected in 26% of samples from the park at concentrations up to 31 ng/L. Benzophenone was detected in 49% of samples from the park at concentrations up to 131 ng/L. Benzocaine and dioxybenzone were not detected in any of the samples.

Concentrations, compositional profiles, and health risks of benzophenones among the Taiwanese population based on analysis of 23 daily consumed foods.

In this study, we analyzed the occurrence and distribution of 11 benzophenone-type ultraviolet filters (BPs) in 893 food samples spanning 7 food categories in Taiwan. We conducted a Monte Carlo simulation to determine the carcinogenic and noncarcinogenic risks of BPs. The results indicated that cornflakes had the highest mean level of BPs (103 ng/g), followed by bread (101 ng/g) and pastries (59 ng/g). BP was the most prevalent category, followed by 4-methylbenzophenone (4-MBP), 2-hydroxybenzophenone, and benzophenone-3. Estimation of the lifetime cancer risk (LTCR) of BP (average life expectancy of 80 years) placed them in the 50th and 97.5th percentiles [P50 (P97.5)] LTCR of 1.9 × 10-7 (5.7 × 10-6), indicating that BP in food poses a low renal hazard to the Taiwanese population. The noncarcinogenic risk of BPs was evaluated using a hazard quotient and combined margin of exposure (MOET), revealing a P50 (P97.5) hazard index of < 1 for BP, 4-MBP, and methyl-2-benzoylbenzoate. Although the P50 MOET values for all age groups were within the moderate range of concern, with a more conservative extreme (P2.5), the MOET values for the 0-3, 3-6, and 6-12 age groups fell below 100, indicating a high concern for renal degeneration and hyperplasia.

Biomonitoring of benzophenones in guano samples of wild bats in Poland.

Benzophenones (BPs) are substances used in the production of sunscreens, cosmetics, and personal care products. However, there is a lack of knowledge of BPs in wild animals. Therefore, the study aimed to assess the concentration of selected BPs commonly used in the cosmetic industry in guano samples collected from 4 colonies of greater mouse-eared bats (Myotis myotis). Liquid chromatography with tandem mass spectrometry (LC-MS/MS) was used to determine guano concentrations of benzophenone 1 (BP-1), benzophenone 2 (BP-2), benzophenone 3 (BP-3) and benzophenone 8 (BP-8). BP-1 levels above the method quantification limit (MQL) were noted in 97.5% of samples and fluctuated from <0.1 ng/g to 259 ng/g (mean 41.50 ng/g, median 34.8). The second most common was BP-3, which fluctuated from <0.1 ng/g to 19 ng/g (mean 6.67 ng/g, median 5.05), and its levels higher than MQL were observed in 40% of samples. BP-2 and BP-8 concentrations did not exceed the method detection limit (0.04 ng/g) in any analyzed sample. There were visible differences in the BP-1 and BP-3 levels among the studied bat colonies. Mean BP-1 concentration fluctuated from 11.23±13.13 ng/g to 76.71±65.51 ng/g and differed significantly between the colonies. Mean BP-3 concentration fluctuated from 5.03±6.03 ng/g to 9.18±7.65 mg/g, but it did not differ significantly between the colonies. The results show that guano is a suitable matrix for the assessment of wildlife exposure to BPs. This could be particularly advantageous in protected species, where not disturbing and stressing the animals are crucial.

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

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

Assessing the Fate of Benzophenone-Type UV Filters and Transformation Products during Soil Aquifer Treatment: The Biofilm Compartment as Bioaccumulator and Biodegrader in Porous Media.

The fate of selected UV filters (UVFs) was investigated in two soil aquifer treatment (SAT) systems, one supplemented with a reactive barrier containing clay and vegetable compost and the other as a traditional SAT reference system. We monitored benzophenone-3 (BP-3) and its transformation products (TPs), including benzophenone-1 (BP-1), 4,4'-dihydroxybenzophenone (4DHB), 4-hydroxybenzophenone (4HB), and 2,2'-dihydroxy-4-methoxybenzophenone (DHMB), along with benzophenone-4 (BP-4) and avobenzone (AVO) in all involved compartments (water, aquifer sediments, and biofilm). The reactive barrier, which enhances biochemical activity and biofilm development, improved the removal of all detected UVFs in water samples. Among monitored UVFs, only 4HB, BP-4, and AVO were detected in sediment and biofilm samples. But the overall retained amounts were several orders of magnitude larger than those dissolved. These amounts were quantitatively reproduced with a specifically developed simple analytical model that consists of a mobile compartment and an immobile compartment. Retention and degradation are restricted to the immobile water compartment, where biofilm absorption was simulated with well-known compound-specific Kow values. The fact that the model reproduced observations, including metabolites detected in the biofilm but not in the (mobile) water samples, supports its validity. The results imply that accumulation ensures significant biodegradation even if the degradation rates are very low and suggest that our experimental findings for UVFs and TPs can be extended to other hydrophobic compounds. Biofilms act as accumulators and biodegraders of hydrophobic compounds.

Increasing exposure to the UV filters octocrylene and 2-ethylhexyl salicylate in Germany from 1996 to 2020: Human biomonitoring in 24-h urine samples of the German Environmental Specimen Bank (ESB).

The UV filters octocrylene (OC) and 2-ethylhexyl salicylate (EHS) are commonly used in sunscreens and frequently detected in environmental media. However, knowledge on human exposures is scarce. In this human biomonitoring (HBM) study, we analyzed concentrations of exposure biomarkers specific to OC (CPAA, DOCCA, 5OH-OC) and EHS (5OH-EHS, 5oxo-EHS, 5cx-EPS) in 24-h urine samples (n = 420) from the German Environmental Specimen Bank (ESB). These samples were collected from German students (20-29 years; 30 males/30 females per year) between 1996 and 2020 (4-year intervals; collection in winter). We found continuously increasing OC and EHS exposures (Jonckheere-Terpstra; p < 0.001) documented by very few to no samples with concentrations of the most sensitive biomarkers CPAA and 5cx-EPS above the limit of quantification (LOQ) in 1996 (5 % and 0 %, respectively) and reaching 100 % and 93 % above the LOQ in 2016, with median concentrations of 4.79 and 0.071 µg/L, respectively. In 2020, biomarker concentrations slightly decreased to 3.12 µg/L CPAA (97 %>LOQ) and 0.060 µg/L 5cx-EPS (88 %>LOQ). This general trend was confirmed by the other biomarkers, however at lower detection rates. Based on metabolite excretion in the 24-h urine samples and human toxicokinetic data, we calculated maximum daily intakes (DI) of 17 µg/(kg bw * d) OC and 59 µg/(kg bw * d) EHS. Based on a derived no-effect level (DNEL) of 0.8 mg/(kg bw * d), the OC exposures of individuals in our study did not indicate any health risk. Similarly, for EHS all biomarker concentrations were well below the HBM-I values of 12 µg/L 5OH-EHS and 11 µg/L 5cx-EPS. Our data proves the general applicability of specific OC and EHS metabolites for HBM in the general population and shows clearly increasing exposures. Higher (co-)exposures must be expected in populations with increased sunscreen use such as (summer) vacationers, children and outdoor workers.

Magnetic graphene oxide carbon dot nanocomposites as an efficient quantification tool against parabens in water and cosmetic samples.

A new method is developed for the simultaneous detection and extraction of parabens, including methyl paraben (MP), ethyl paraben (EP), propyl paraben (PP), and butyl paraben (BP), based on magnetic graphene oxide carbon dot nanocomposites (Fe3O4@GO@CD). Fe3O4@GO@CD has been synthesized using one pot hydrothermal method by intercalating iron oxide and carbon dots between the layers of graphene oxide. Fe3O4@GO@CD was applied as the magnetic solid phase sorbent for the simultaneous extraction and detection of parabens from water (tap and river water) and cosmetic samples (hair serum and sunscreen cream). MP was measured at concentration of 0.25-0.26 ng/mL in hair serum, while PP at 0.32-0.33 ng/mL in sunscreen cream. Notably, good recoveries (88.74-98.03%; RSD = 2.31-6.88%) for river and tap water with detection limit of 0.039-0.046 ng/mL were attained. The method has good cyclability up to 16 cycles and was highly repeatable. All these findings suggest that the Fe3O4@GO@CD would be potential sorbent for the analysis of parabens.

Analysis of sunscreens and antibiotics in groundwater during the Covid-19 pandemic in the Riviera Maya, Mexico.

Tourism contributes to groundwater pollution, but quantifying its exact impact is challenging due to the presence of multiple pollution sources. However, the COVID-19 pandemic presented a unique opportunity to conduct a natural experiment and assess the influence of tourism on groundwater pollution. One such tourist destination is the Riviera Maya in Quintana Roo, Mexico (specifically Cancun). Here, water contamination occurs due to the addition of sunscreen and antibiotics during aquatic activities like swimming, as well as from sewage. In this study, water samples were collected during the pandemic and when tourists returned to the region. Samples were taken from sinkholes (cenotes), beaches, and wells then tested using liquid chromatography for antibiotics and active ingredients found in sunscreens. The data revealed that contamination levels from specific sunscreens and antibiotics persisted even when tourists were absent, indicating that local residents significantly contribute to groundwater pollution. However, upon the return of tourists, the diversity of sunscreen and antibiotics found increased, suggesting that tourists bring along various compounds from their home regions. During the initial stages of the pandemic, antibiotic concentrations were highest, primarily due to local residents incorrectly using antibiotics to combat COVID-19. Additionally, the research found that tourist sites had the greatest contribution to groundwater pollution, with sunscreen concentration increasing. Furthermore, installation of a wastewater treatment plant decreased overall groundwater pollution. These findings enhance our understanding of the pollution contributed by tourists in relation to other pollution sources.

Quantitation of Canadian organic ultraviolet filters using polarity switching and ultra-high performance liquid chromatography-tandem mass spectrometry.

Ultraviolet filters (UVFs) absorb UV light and are comprised of numerous classes of compounds including inorganic and organic. They have been used for decades in protecting humans from skin damage and cancer. Recent studies have shown that UVFs are found in many phases of abiotic and biotic systems with their physical-chemical characteristics determining environmental fate and potential biological impacts such as bioaccumulation. This study developed a unified method to quantify eight UVFs (avobenzone, dioxybenzone, homosalate, octinoxate, octisalate, octocrylene, oxybenzone, and sulisobenzone) by solid phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry using polarity switching. The validated method resulted in accuracies ranging from 75 to 112%, MLD/MLQs of 0.00015/ 0.00049 to 0.0020/ 0.0067 ng mL-1, and precisions of 1.8 to 22.6% (intraday) and 1.3 to 17.2% (interday). The method was applied to chlorinated outdoor pool waters in the City of Winnipeg, Manitoba, Canada. This method could be adapted for a variety of chlorinated and unchlorinated waters such as drinking water, wastewater, and surface waters.

Dispersive liquid-liquid microextraction and Monte Carlo simulation of margin of safety for octocrylene, EHMC, 2ES, and homosalate in sunscreens.

Dispersive liquid-liquid microextraction (DLLME) using a floating organic drop has been optimized and used for the sample preparation of four commonly used ultraviolet filter (UVF) substances in sunscreens. Plackett-Burman experimental design was used to screen 10 variables in DLLME. The most significant variables were then optimized by using a response surface method with a Box-Behnken design. DLLME followed by an optimized HPLC identified octocrylene, 2-ethylhexyl-4-methoxycinnamate, ethylhexyl salicylate, and homosalate as the frequently found UVFs in commercial sunscreens. The systemic exposure dosage and margin of safety (MoS) for the identified UVFs were estimated using in-use concentrations and application patterns. The average systemic exposure dosage values for octocrylene, 2-ethylhexyl-4-methoxycinnamate, ethylhexyl salicylate, and homosalate were 0.52, 0.61, 0.020, and 0.079 mg/kg body weight per day, respectively. Whereas the average MoS values for individual UVFs ranging from 296 to 3160 were all significantly higher than the limit value of 100, the combined exposure risks were slightly above the limit. The probabilistic health risk assessment using Monte Carlo simulation revealed that the combined MoS values were (mean, 10‰, 90‰) 342, 119, and 441, respectively. Regarding the usage of sunscreen cosmetics containing the UVFs studied, these results indicate a safety concern for those who apply multiple UVF products.

Evaluation of antioxidant, photoprotective and antinociceptive activities of Marcetia macrophylla extract: potential for formulation of sunscreens / Avaliação da atividade antioxidante, photoprotetora e antinociceptiva de Marcetia macrophylla: potencial formulação fotoprotetora

The antioxidant, photoprotective and antinociceptive Marcetia macrophylla active extract was investigated as an active ingredient in a sunscreen cream formulation. Thus, the M. macrophylla extract showed IC50 of 3.43 mg/ml of the antioxidant (DPPH∙ scavenging test) and Sun Protection Factor of 20.25 (SPF/UV-B, at 250 µg/ml) and UV-A of 78.09% (photobleaching trans-resveratrol test). The antinociceptive activity was superior to all standards tested using the in vivo acetic acid-induced writhing test (99.14% at the dose of 200 mg/kg) and the high-performance liquid chromatography coupled with diode array detector and mass spectroscopy multi-stage (HPLC-DAD-MS/MS) enabled the structural characterization of the quercetin-3-O-hexoside, quercetin-3-O-pentoside and quercetin-3-O-desoxihexoside. The pharmaceutical formulation containing the Marcetia macrophylla crude active extract was prepared and the physicochemical tests (organoleptic characteristics, pH analysis and centrifugation), the in vitro UVB (sun protection factor, SPF) and UVA (β-carotene) using the spectroscopic method were investigated. The formulation showed satisfactory results concerning the physicochemical parameters evaluated and active against the UV test. Thus, M. macrophylla showed biological activities with potential use in pharmaceutical preparations.

O extrato bruto de Marcetia macrophylla mostrou atividade antioxidante, fotoprotetora e antinociceptiva, sendo em seguida investigado como ingrediente ativo em uma formulação fotoprotetora. Assim, o extrato de M. macrophylla apresentou atividade antioxidante com IC50 de 3,43 mg/mL (teste de sequestro do DPPH∙) e Fator de Proteção Solar de 20,25 (FPS/UV-B, 250 µg/mL) e UV-A de 78,09% (teste de fotobranqueamento do trans-resveratrol). A atividade antinociceptiva usando o teste in vivo de contorções abdominais induzidas por ácido acético foi superior a todos os padrões testados (99,14% na dose de 200 mg/Kg). A análise por cromatografia líquida de alta eficiência acoplada a detector de fotodiodos e espectroscopia de massas multi-estágio (CLAE-DAD-EM/EM) possibilitou a caracterização dos flavonoides quercetina-3-O-hexosídeo, quercetina-3-O-pentosídeo e quercetina-3-O-desoxihexosídeo. A formulação farmacêutica contendo o extrato ativo bruto de Marcetia macrophylla foi preparada e os testes físico-químicos (características organolépticas, análise de pH e centrifugação), o UVB in vitro (fator de proteção solar, FPS) e UVA (β-caroteno) foram investigados. A formulação apresentou resultados satisfatórios frente aos parâmetros físico-químicos avaliados e ativos contra UV. Assim, M. macrophylla apresentou atividades biológicas com potencial uso em preparações fitofarmacêuticas.

In vitro approaches to antioxidant screening for the development of a sunscreen formulation

Abstract The incorporation of antioxidants into sunscreens may provide additional skin photoprotection against the harmful photobiological effects of ultraviolet radiation. The present study evaluated the applicability of a screening approach to the assessment of the antioxidant and photoprotective properties of vitamin C, vitamin E, and coenzyme Q10 and then determined the performance of the most effective antioxidant in a sunscreen formulation. Antioxidant activity was assessed by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, 2,2`-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) assay, and oxygen radical absorbance capacity (ORAC) assay, and the photoprotective potential was investigated by the yeast photoprotection assay. The antioxidant with the best effect was incorporated into sunscreen formulations which were evaluated for 120 days regarding their in vitro photoprotective parameters. Vitamin C showed high antioxidant capacity as well as a photoprotective potential against simulated solar irradiation applied for times longer than 1 h. Although the Sun Protection Factor, UVA/UVB ratio and critical wavelength did not differed significantly (p<0.05) between the formulation blank and the formulations containing 0.5% or 1% vitamin C, formulations with vitamin C kept their photostability for 6 months. Consequently, the proposed screening approach seems to be promising for the development of an antisolar photostable formulation containing vitamin C as an antioxidant.

Concentrations, Compound Profiles, and Possible Sources of Organic UV Filters in Human Milk in China.

Ultraviolet (UV) filters are of great concern due to their wide occurrence, bioaccumulation, and toxicity. Little is known about human exposure to UV filters. A total of 3467 individual human milk samples from 24 Chinese provinces were collected during 2017-2019. The concentrations of 12 UV filters in 100 pooled milk samples were determined. The total UV filter concentration was 78-846 (mean 235 ± 120) ng/g lipid weight. The highest and lowest total mean concentrations were for samples from Qinghai and Sichuan provinces, respectively. A significant positive correlation was found between UV radiation levels and UV concentrations in the samples. The dominant UV filters were 2-(2-hydroxy-5-methylphenyl) benzotriazole (UV-P) and ethylhexyl methoxycinnamate (EHMC), which contributed means of 32 and 22%, respectively, to the total concentrations. Plastic products and sunscreens were probably the sources of UV-P and EHMC in the human milk from China, respectively. The mean 2-(3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole (UV-328) concentration was 2.6 ± 2.6 ng/g lipid weight. The UV filter profiles were similar to profiles for samples from Japan, the Philippines, and Switzerland but not for samples from Korea and Vietnam. The estimated daily UV filter intake for breastfed infants was below the corresponding reference dose. This was the first large-scale study of UV filters in human milk and will help assess the risks posed.

Beach showers as sources of contamination for sunscreen pollution in marine protected areas and areas of intensive beach tourism in Hawaii, USA.

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.