The purpose of this article is to summarize biological monitoring information on UV-absorbing compounds, commonly referred as organic UV filters or sunscreen agents, in aquatic ecosystems. To date a limited range of species (macroinvertebrates, fish, and birds), habitats (lakes, rivers, and sea), and compounds (benzophenones and camphors) have been investigated. As a consequence there is not enough data enabling reliable understanding of the global distribution and effect of UV filters on ecosystems. Both liquid chromatography and gas chromatography coupled with mass spectrometry-based methods have been developed and applied to the trace analysis of these pollutants in biota, enabling the required selectivity and sensitivity. As expected, the most lipophilic compounds occur most frequently with concentrations up to 7112 ng g−1 lipids in mussels and 3100 ng g−1 lipids (homosalate) in fish. High concentrations have also been reported for 4-methylbenzilidenecamphor (up to 1800 ng g−1 lipids) and octocrylene (2400 ng g−1 lipids). Many fewer studies have evaluated the potential bioaccumulation and biomagnification of these compounds in both fresh and marine water and terrestrial food webs. Estimated biomagnification factors suggest biomagnification in predator–prey pairs, for example bird–fish and fish–invertebrates. Ecotoxicological data and preliminary environmental assessment of the risk of UV filters are also included and discussed.
Benzophenone (BP)-type UV filters are widely used in a variety of personal care products for the protection of skin and hair from UV irradiation. Despite the estrogenic potencies of BP derivatives, few studies have examined the occurrence of these compounds in human matrices. Furthermore, associations among exposure to these compounds and estrogen-dependent diseases (such as endometriosis) have not been examined previously. In this study, we determined the concentrations of five BP derivatives, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'OH-BP), and 4-hydroxybenzophenone (4OH-BP), in urine collected from 625 women in Utah and California, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS). The association of urinary concentrations of BP derivatives with an increase in the odds of a diagnosis of endometriosis was examined in 600 women who underwent laparoscopy/laparotomy (n = 473: operative cohort) or pelvic magnetic resonance imaging (n = 127: population cohort), during 2007-2009. 2OH-4MeO-BP, 2,4OH-BP, and 4OH-BP respectively were detected in 99.0%, 93.3%, and 83.8% of the urine samples analyzed, whereas the detection rates for 2,2',4,4'OH-BP and 2,2'OH-4MeO-BP were below 6.0%. Significant regional differences (higher concentrations in California) and monthly variations (higher concentrations in July and August) were found for urinary concentrations of 2OH-4MeO-BP and 2,4OH-BP. In addition, urinary concentrations of 2OH-4MeO-BP and 2,4OH-BP tended to be higher in more affluent, older, and leaner women. Adjusted odds ratios (ORs) and 95% confidence intervals (CIs) were estimated for the urinary concentrations of BP derivatives and the odds of an endometriosis diagnosis; ORs increased across quartiles of 2OH-4MeO-BP and 2,4OH-BP concentrations, but a significant trend was observed only between 2,4OH-BP and the odds of an endometriosis diagnosis in the operative cohort (OR = 1.19; 95% CI = 1.01, 1.41). When women in the highest quartile of 2,4OH-BP concentrations were compared with women in the first three quartiles, the OR increased considerably (OR = 1.65; 95% CI = 1.07, 2.53). Given that 2,4OH-BP possesses an estrogenic activity higher than that of 2OH-4MeO-BP, our results invite the speculation that exposure to elevated 2,4OH-BP levels may be associated with endometriosis.
Ultraviolet (UV) filters are vital constituents of sunscreens and other personal care products since they absorb, reflect and/or scatter UV radiation, therefore protecting us from the sun’s deleterious UV radiation and its effects. However, they suffer degradation, mainly through exposure towards sunlight and from reactions with disinfectant products such as chlorine. On the basis of their increasing production and use, UV filters and their degradation products have already been detected in the aquatic environment, especially in bathing waters. This paper presents a comprehensive review on the work done so far as to identify and determine the by-products of UV filter photodegradation in aqueous solutions and those subsequent to disinfection-induced degradation in chlorinated aqueous solutions, namely swimming pools. ► UV filters are present in swimming-pools water. ► UV filters generate chlorinated by-products in chlorine disinfected water. ► UV filters suffer photodegradation in aqueous solutions.
The present paper describes the development of a method for the simultaneous determination of five hormonally active UV filters namely benzophenone-3 (BP3), 3-(4-methylbenzylidene) camphor (4MBC), 2-ethylhexyl 4-(dimethylamino) benzoate (OD-PABA), 2-ethylhexyl 4-methoxycinnamate (EHMC) and octocrylene (OC) by means of solid-phase extraction and gas chromatography–electron impact ionization–mass spectrometry. Under optimized conditions, this methodology achieved low method limits of detection (needed for clean waters, especially drinking water analysis), between 0.02 and 8.42 ng/L, and quantitative recovery rates higher than 73% in all cases. Inter- and intraday precision for all compounds were lower than 7% and 11%, respectively. The optimized methodology was applied to perform the first survey of UV absorbing compounds in tap water from the metropolitan area and the city of Barcelona (Catalonia, Spain). In addition, other types of clean water matrices (mineral bottled water, well water and tap water treated with an ion-exchange resin) were investigated as well. Results evidenced that all the UV filters investigated were detected in the water samples analyzed. The compounds most frequently found were EHMC and OC. Maximum concentrations reached in tap water were 290 (BP3), 35 (4MBC), 110 (OD-PABA), 260 (EHMC), and 170 ng/L (OC). This study constitutes the first evidence of the presence of UV filter residues in tap water in Europe.
Background: To explain observed differences during SPF determination using either an in vivo or in vitro method, we hypothesized on the presence of ingredients having anti-inflammatory properties. Methodology/Principal Findings: To research our hypothesis, we studied the 21 UV filters both available on the market and authorized by European regulations and subjected these filters to the phorbol-myristate-acetate test using mice. We then catalogued the 13 filters demonstrating a significant anti-inflammatory effect with edema inhibition percentages of more than 70%. The filters are: diethylhexyl butamido triazone (92%), benzophenone-5 and titanium dioxide (90%), benzophenone-3 (83%), octocrylene and isoamyl p-methoxycinnamate (82%), PEG-25 PABA and homosalate (80%), octyl triazone and phenylbenzimidazole sulfonic acid (78%), octyl dimethyl PABA (75%), bis-ethylhexyloxyphenol methoxyphenyl triazine and diethylamino hydroxybenzoyl hexylbenzoate (70%). These filters were tested at various concentrations, including their maximum authorized dose. We detected a dose-response relationship. Conclusions/Significance: The anti-inflammatory effect of a sunscreen ingredient may affect the in vivo SPF value. Citation: Couteau C, Chauvet C, Paparis E, Coiffard L (2012) UV Filters, Ingredients with a Recognized Anti-Inflammatory Effect. PLoS ONE 7(12): e46187. doi:10.1371/journal.pone.0046187
Organic UV filters including benzophenone-3 (BP-3) are widely used to protect humans and materials from damage by UV irradiation. Despite the environmental occurrence of BP-3 in the aquatic environment, little is known about its effects and modes of action. In the present study we assess molecular and physiological effects of BP-3 in adult male zebrafish ( ) and in eleuthero-embryos by a targeted gene expression approach focusing on the sex hormone system. Fish and embryos are exposed for 14 days and 120 hours post fertilization, respectively, to 2.4–312 μg/L and 8.2–438 μg/L BP-3. Chemical analysis of water and fish demonstrates that BP-3 is partly transformed to benzophenone-1 (BP-1) and both compounds are accumulated in adult fish. Biotransformation to BP-1 is absent in eleuthero-embryos. BP-3 exposure leads to similar alterations of gene expression in both adult fish and eleuthero-embryos. In the brain of adult males , and are down-regulated at 84 μg/L BP-3. There is no induction of vitellogenin expression by BP-3, both at the transcriptional and protein level. An overall down-regulation of the , , and transcripts is observed in the testes, suggesting an antiandrogenic activity. No histological changes were observed in the testes after BP-3 treatment. The study leads to the conclusion that low concentrations of BP-3 exhibit similar multiple hormonal activities at the transcription level in two different life stages of zebrafish. Forthcoming studies should show whether this translates to additional physiological effects. ► Activity of UV filter benzophenone-3 (BP-3) is assessed in zebrafish. ► BP-3 is partly metabolized to benzophenone-1 by adult fish but not embryos. ► Alterations of gene expression are similar in adult males and embryos. ► Gene expression alterations point to multiple hormonal activity of BP-3.
The accumulation of EHMC, OCT and OD-PABA, three common UV filter compounds, was investigated in marine mussels. Wild and were sampled in ten sites along the French Atlantic and Mediterranean coasts from June to November. In mussel tissues, 100% of the samples had quantifiable EHMC concentrations ranging from 3 to 256 ng g dry weight, while 55% of the samples had detectable OCT concentrations ranging from under 2 to 7 112 ng g dry weight. These concentrations significantly increased with the rising air temperature in summer, the recreational pressure and the geomorphological structure of the sampling sites (its lack of openness to the wide). This is the first study to report bioaccumulation of UV filters in marine mussels, thus highlighting the need for further monitoring and assessment. ► UV filters were detected in wild mussels collected along the French coast. ► EHMC and OCT were detected while OD-PABA was never detected. ► The concentration of UV filters increased with air temperature and recreational pressure. ► Bioaccumulation of EHMC in coastal wild mussels is dependent on recreational activities.
► Sludge from a WWTP was treated in a fungal slurry reactor with . ► Twenty-four pharmaceuticals were removed at important extents. ► UV-filters and brominated flame retardants were also degraded. ► Overall toxicity of sludge increased despite the pollutant removal. Conventional wastewater treatments are inefficient in the removal of many organic pollutants. The presence of these contaminants in the final sludge represents a source of environmental pollution due to the increasing use of biosolids in land application. A biotechnological approach which employed the fungus in a sludge-bioslurry reactor was assessed in order to remove several groups of emerging pollutants. Biological fungal activity was monitored by means of ergosterol and laccase determinations. Fifteen out of 24 detected pharmaceuticals were removed at efficiencies over 50% after the treatment, including eight completely degraded. Removal ranged between 16–53% and 22–100% for the brominated flame retardants and the UV-filters, respectively. Only two of all the detected compounds remained unchanged after the treatment. Although elimination results are promising, the toxicity of the final sludge increased after the treatment. This finding is contrary to the toxicity results obtained in similar treatments of sludge with in solid-phase.