No full-text available
To read the full-text of this research,
you can request a copy directly from the authors.
A Potential New Threat to Wild Life: Presence of UV Filters in Bird Eggs from a Preserved Area
Abstract
The present study uses bird eggs of 7 wild species as a biomonitoring tool for sunscreens occurrence. Seven UV filters (UV-Fs), including 3 hydroxy-metabolites of oxybenzone (benzophenone 3, BP3) were characterized in unhatched eggs from Doñana Natural Space (Southwestern, Spain). High frequency of detection was observed for all UV-Fs, ranging from 95% to 100%. The oxybenzone metabolite 4-hydroxybenzophenone (4HB) was ubiquitous at concentrations in the range 12.0-3,348ng g⁻¹ dry weight (dw). The parent compound, oxybenzone, was also present in all samples at lower concentrations (16.9-49.3 ng g⁻¹ dw). Due to the three BP3’s metabolites, benzophenone 1 (BP1), 4HB, and 4,4’-dihydroxybenzophenone (4DHB) presence in unhatched eggs, it can be inferred that parent compounds are absorbed into the bird through the upper gut and the OH-derivatives formed are transferred by the mother to the egg before the lying. White stork (Ciconia ciconia) and western marsh harrier (Circus aeruginosus) were the most contaminated species, with mean total UV-Fs concentrations of 834and 985ng g⁻¹ dw, respectively. Results evidenced that biomagnification process across the bird species studied cannot be ruled out.
... Most of the studies included were in vitro studies (although there are also some in vivo ones), from different parts of the world, and of moderate quality with a short duration. 11,15,33 The environmental impact of UV filters has been studied on different organisms, including microalgae (seawater and fresh water), 11,26,31,32,40,41 crustaceans, 26,31,34,38,41 molluscs, 26,31 corals, 23,24,27,28,30,36,37,39 fish, 22,25,29,35,42---44 and mammals. 25,33 Much of the impact occurs in embryos and larvae and in aquatic environments, particularly marine ones. ...
... However, there is also evidence of these products in land organisms (birds and rats). 15,33 Although a wide range of filters have been analyzed, BP-3 11,15,23,25,28---31,33---35,37---41 and OC 11,24---27,30,32,36---38 are the ones most widely studied. The duration of exposure to these UV filters was variable, from 24 h 23,34 to 42 days. ...
... Mitchelmore et al. 30 The presence of 8 UV filters in sea, marine sediments, and coral tissue. The most detected UV filter was BP-3 and its concentration was higher in areas where more people congregated Molins-Delgado et al. 15 The presence of UV filters in all samples of birds' eggs. The authors suggest that the mothers become contaminated on ingesting food, because of the limited capacity for urban wastewater treatment plants to remove UV filters. ...
Resumen
Los filtros ultravioleta (UV) se han convertido en compuestos de uso diario para millones de personas. Sin embargo, algunos de ellos no son biodegradables al 100% y las plantas de tratamiento de aguas residuales muchas veces no son capaces de filtrarlos correctamente. Todo ello está llevando a su diseminación ambiental y a la detección de distintos filtros UV en el suelo, las aguas continentales, los océanos y en múltiples organismos (algas, corales, peces, mamíferos, incluso aves terrestres). Además, algunos filtros UV, especialmente la benzofenona-3 y el octocrileno se han mostrado tóxicos en estos organismos. Entre sus efectos tóxicos destacamos el blanqueamiento de los corales y problemas metabólicos, enzimáticos y de capacidad reproductiva en prácticamente cualquier organismo. Existen datos preliminares sobre la posible bioacumulación de estos filtros UV en humanos, al detectarse en muestras de orina y leche materna. Sin embargo, el estudio del impacto medioambiental de los filtros UV presenta muchas limitaciones.
... Beyond their effects in adult phases, PPCPs might also affect subsequent generations, possibly due to maternal transfer of these compounds (Overturf et al., 2015;Zhou et al., 2020). Indeed, the maternal offloading of PPCPs has been observed among vertebrates (Alonso et al., 2015;Molins-Delgado et al., 2017;Peng et al., 2018;Zhou et al., 2019;Qiu et al., 2020). Exposure during embryonic development might have detrimental consequences (Birceanu et al., 2015;Peng et al., 2018) leading to decreased adult fitness and further populational effects (Nilsen et al., 2018). ...
... However, the lack of detection of octocrylene in uterine content samples suggested that this compound might not be transferred to the offspring. Contrarily, maternal transfer of octocrylene as well as other UV filter has been documented in other taxa (Alonso et al., 2015), including lecithotrophic species (Molins-Delgado et al., 2017). Based on previous estimates of sexual maturity for P. horkelii (Vooren et al., 2005;Martins et al., 2018), the individuals analyzed herein were not in their first reproductive cycle. ...
Maternal transfer is a notable contaminant source for elasmobranchs during the embryonic development. The maternal offloading of several compounds has been evaluated, especially concerning legacy contaminants. However, information on pharmaceuticals and personal care products (PPCPs) offload and, consequently, embryonic exposure is still unknown. Despite this, previous detection of PPCPs in pregnant females suggested the maternal offloading of these compounds in the Brazilian guitarfish Pseudobatos horkelii, yet progeny levels were not investigated. For this reason, our goal was to estimate and describe the maternal transfer of four PPCPs in P. horkelii. Diclofenac, methylparaben, octocrylene and triclosan were determined in liver and uterine content samples of five pregnant females using gas chromatography coupled to mass spectrometry. Diclofenac and methylparaben were detected in maternal and uterine content samples, whereas octocrylene and triclosan were only detected in maternal livers. This suggests that diclofenac and methylparaben are transferred to the offspring, at maximum transfer capacities of 27% and 6%, respectively. The lack of detection of other analytes in uterine content suggests that these contaminants might not be transferred. The concentrations observed for diclofenac and methylparaben are similar to those reported for adult elasmobranchs and teleosts, showing that embryos are exposed to considerable concentrations during their development. In addition, maternal diclofenac concentrations were not influenced by maternal size, suggesting that this species is continuously exposed in the studied area. These results are important for understanding the maternal offloading process and predicting PPCPs impacts throughout this species life cycle.
... However, it is noteworthy that BzP-1, 4-OH-BzP, BzP-2 and BzP-8 are documented metabolites of BzP-3 [30], and all of them were found in 17 out of 38 liver samples from Smøla. In a previous study, BzP-1, BzP-3, 4-OH-BzP, and 4,4 -dihydroxybenzophenone (4 DHB; which is an isomer of BzP-1) were reported in 39 unhatched raptor eggs (of 7 wild living species) from Doñana, southwestern Spain, where BzP-1 (range: 23.3−677 ng/g d.w.) and 4-OH-BzP (range: 12.0-3488 ng/g d.w.) were detected in the highest concentrations from all target analytes [50]. BzP-3 was also present in the raptor eggs, but in significantly lower concentrations (range: 18.2-49.3 ...
... BzP-3 was also present in the raptor eggs, but in significantly lower concentrations (range: 18.2-49.3 ng/g d.w.), while 4 DHB was found only in two samples (29.4 and 132 ng/g d.w.) [50]. ...
There is a growing concern about the occurrence of bisphenols and benzophenone UV filters in natural ecosystems, while data are limited regarding their actual occurrence in wildlife species, especially in raptors. In this study, concentrations of bisphenol and benzophenone UV filter analogues were determined in liver tissue samples (n = 38) from white-tailed eagles (Haliaeetus albicilla) that were found dead in Smøla (2006–2018), which is a Norwegian municipality that holds one of the densest breeding populations of white-tailed eagles in Europe. Bisphenol AF (BPAF; a fluorinated analogue) was the most ubiquitous contaminant since it was detected in 32 liver samples at concentrations ranging from 1.08 to 6.68 ng/g wet weight (w.w.), followed by bisphenol A (BPA, mean 10.4 ng/g w.w.), benzophenone-1 (BzP-1, mean 3.24 ng/g w.w.), and 4-hydroxybenzophenone (4-OH-BzP, mean 0.62 ng/g w.w.). The concentrations found in livers suggested that white-tailed eagles potentially accumulate bisphenols and benzophenone UV filters, which raises concern, as these plastic and personal care product-related emerging contaminants can show endocrine-disrupting properties. The high detection frequency of the fluorinated BPAF warrants further attention as other fluorinated compounds have proven to be extremely persistent and potentially harmful to wildlife.
... Regarding the analysis of the other miscellaneous CECs, only six studies were found in the literature with samples from different European countries: two on neonicotinoids in Finland (Byholm et al., 2018) and in Spain (Taliansky-Chamudis et al., 2017), one on UVfilters in Spain (Molins-Delgado et al., 2017), one on parabens in Germany and Polish coastal areas of the Baltic Sea (Xue and Kannan, 2016), one on paraffins in Sweden and Denmark (Yuan et al., 2019) and one on bisphenols and benzophenone-type UV-filters in Greenland and France (González-Rubio et al., 2020). ...
... However, studies on adverse effects and bioaccumulation of these compounds in wildlife are still scarce. The first study on UV-filters in European raptors was reported by Molins-Delgado et al. (2017). Seven UV-filters (Benzophenone-1 (BzP-1); BzP-3; 4-Hydroxybenzophenone (4-OH-BzP); 4,4′-dihydroxybenzophenone (4-DHB); octocrylene (OC); 2-ethylhexyl 4-(dimethylamino)benzoate (ODPABA); 2-(2Hbenzotriazole-2-yl)-4-methyl-6-(2-propyl)-phenol (AllylBZP)) were determined in unhatched eggs from Western marsh harriers (Circus aeruginosus) and common kestrels from a Spanish preserved area. ...
Raptors (birds of prey and owls) have been widely used as suitable bioindicators of environmental pollution. They occupy the highest trophic positions in their food chains and are documented to bioaccumulate high concentrations of persistent pollutants such as toxic metals and legacy persistent organic pollutants (POPs).Whereas raptors played a critical role in developing awareness of and policy for chemical pollution, they have thus far played a much smaller role in current research on contaminants of emerging concern (CECs). Given the critical knowledge obtained from monitoring 'legacy contaminants' in raptors, more information on the levels and effects of CECs on raptors is urgently needed. This study critically reviews studies on raptors from Europe reporting the occurrence of CECs with focus on the investigated species, the sampled matrices, and the bioanalytical methods applied. Based on this, we aimed to identify future needs for monitoring CECs in Europe. Perfluoroalkyl substances (PFASs), novel flame retardants (NFRs), and to a lesser extent UV-filters, neonicotinoids, chlorinated paraffins, parabens and bisphenols have been reported in European raptors. White-tailed Eagle (Haliaeetus albicilla), Peregrine falcon (Falco peregrinus) and Northern goshawk (Accipiter gentilis) were the most frequently studied raptor species. Among matrices, eggs, feathers and plasma were the most widely employed, although the potential role of the preen gland as an excretory organ for CECs has recently been proposed. This review highlights the following research priorities for pollution research on raptors in Europe: 1) studies covering all the main classes of CECs; 2) research in other European regions (mainly East Europe); 3) identification of the most suitable matrices and species for the analysis of different CECs; and 4) the application of alternative sample treatment strategies (e.g. QuEChERS or pressurized liquid extraction) is still limited and conventional solvent-extraction is the preferred choice.
... OC is found in various environmental compartments including surface water, wastewater, living organisms, and sediment. Its concentration can reach 7 μg/L in the water column [2,[9][10][11]. In sediments, OC concentration can reach 400 ng/g dw [2,12]. ...
... The widespread occurrence of OC in the environment has led to its frequent detection in biota. Due to its lipophilic properties and stability, OC tend to accumulate in aquatic organism [5,10,[13][14][15][16][17][18]. The wide distribution of OC is all the more disturbing since it has recently been shown that it could be transformed and accumulated in forms that are more diffi cult to detect and quantify [19]. ...
... Concentrations of BzP-1, BzP-3, 4-OH-BzP, and 4,4′dihydroxybenzophenone (which is an isomer of BzP-1) were reported by Molins-Delgado et al. (2017) in 39 unhatched raptor eggs of 7 wild living species [western marsh harrier (Circus aeruginosus), common kestrel (Falco tinnunculus), white stork (Ciconia ciconia), slender-billed gull (Chroicocephalus genei), black headed gull (Chrococephalus ridibundus), gull-billed tern (Gelochelidon nilotica), and gadwall (Anas strepera)]. Mean concentrations of BP-3, BP-1, 4-OH-BzP and 4,4′dihydroxybenzophenone were ranging between species from 22.1 to 46.7 ng/g d.w., 38.1 to 433, 88.4 to 895, and 29.0 to 132, respectively, while the DRs in eggs ranged from 95 to 100% for all analogues indicating bioaccumulation. ...
... Mean concentrations of BP-3, BP-1, 4-OH-BzP and 4,4′dihydroxybenzophenone were ranging between species from 22.1 to 46.7 ng/g d.w., 38.1 to 433, 88.4 to 895, and 29.0 to 132, respectively, while the DRs in eggs ranged from 95 to 100% for all analogues indicating bioaccumulation. This was reflected in the egg concentrations, in which the rank order of mean BzPs concentrations found in those (for the majority of the assessed species) decreased as: 4-OH-BzP N BP1 N BP-3 (Molins- Delgado et al., 2017). This agreed to the rank order found in the raptor tissues in our study. ...
Environmental exposure to bisphenols and benzophenone UV filters has received considerable attention due to the ubiquitous occurrence of these contaminants in the environment and their potential adverse health effects. The occurrence of bisphenols and benzophenone UV filters is well established in human populations, but data is scarce for wildlife, and especially for raptors (birds of prey, falcons and owls). In this study, concentrations of eight bisphenols and five benzophenone UV filters were determined in six raptor tissues, including muscle, kidney, liver, brain, preen gland (uropygial gland) and adipose. The tissue samples (n = 44) were taken from dead raptor species (1997–2011), including Eurasian sparrowhawks (Accipiter nisus, n = 2) and long-eared owls (Asio otus, n = 2), both from France, and white-tailed eagles (Haliaeetus albicilla, n = 16) from Greenland. Overall, six bisphenols and four benzophenone UV filters were found in the samples. Bisphenol A (BPA), bisphenol F (BPF), benzophenone-8 (BzP-8) and 4-hydroxybenzophenone (4-OH-BzP) were the most abundant contaminants, accounting for median concentrations of 67.5, 3.01, 27.1 and 9.70 ng/g wet weight (w.w.), respectively. The potential role of the preen gland as a major excretory organ for bisphenols and benzophenone UV filters was suggested since the median sum concentration of the two contaminant classes in the white-tailed eagle tissues showed higher bioaccumulation potential in the preen gland (5.86 ng/g w.w.) than the liver (2.92) and kidney (0.71). The concentrations of these contaminants in the tissues of the three raptor species indicated a pattern of increasing detection rates and median concentrations with an increase of the species size and their expected trophic position. To the best of our knowledge, this is the first peer-reviewed study to document multiresidues of both contaminant classes in raptor tissues.
... This is especially true in areas, like the Mediterranean, that are highly impacted by tourism (Tovar-Sanches et al. 2019). Furthermore, because UV filters have been detected in various biological materials, such as fish (Balmer et al. 2005;Fent et al. 2010;Tsai et al. 2014;Langford et al. 2015;Gago-Ferrero et al. 2015;Emnet et al. 2015;Sang and Leung 2016), dolphins Alonso et al. 2015), and bird eggs (Molins-Delgado et al. 2017), biomagnification is a real concern (Fent et al. 2010;Sang and Leung 2016;Molins-Delgado et al. 2017). Many UV filters are thought to impact non-target organisms via endocrine disruption (Díaz-Cruz and Barceló 2009;Sánchez-Quiles and Tovar-Sánchez 2015). ...
... This is especially true in areas, like the Mediterranean, that are highly impacted by tourism (Tovar-Sanches et al. 2019). Furthermore, because UV filters have been detected in various biological materials, such as fish (Balmer et al. 2005;Fent et al. 2010;Tsai et al. 2014;Langford et al. 2015;Gago-Ferrero et al. 2015;Emnet et al. 2015;Sang and Leung 2016), dolphins Alonso et al. 2015), and bird eggs (Molins-Delgado et al. 2017), biomagnification is a real concern (Fent et al. 2010;Sang and Leung 2016;Molins-Delgado et al. 2017). Many UV filters are thought to impact non-target organisms via endocrine disruption (Díaz-Cruz and Barceló 2009;Sánchez-Quiles and Tovar-Sánchez 2015). ...
Organic UV filters are used worldwide in various personal care products as well as textiles, paints, plastic, food, and adhesives. They are main ingredients in sunscreen lotions that are used heavily by beachgoers in the summer season. There is thus an increasing concern regarding the fate of organic UV filters in the environment and their impact on living organisms. Many of the UV filters in use are hydrophobic and are expected to accumulate in the sediment phase in aquatic systems, but this has yet to be validated in situ. We targeted the UV filters benzophenone 3 (BP3), butyl methoxydibenzoylmethane (BMDBM), diethylhexyl butamido triazone (DBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), and methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT) in a freshwater lake and in a coastal bay in order to understand their distribution during summer 2016. Further, we examined their environmental partitioning by collecting samples from the surface water, the sediment phase, and water surface microlayer (SML). We show for the first time the presence of DBT, BEMT, and MBBT in environmental matrices (water, SML, and sediment). Notably, these UV filters were detected at low amounts in surface waters with maximum concentrations of 9.9 ng/L for DBT, 18.4 ng/L for BEMT, and below detection limits for MBBT and somewhat higher concentrations in the SML, with maximum concentrations of 43.3 ng/L for DBT, 5625.4 ng/L for BEMT, and 45.6 ng/L for MBBT. These filters were detected at even greater concentrations in the sediments, with maximum concentrations of 652.6 ng/g for DBT, 115.0 ng/g for BEMT, and 75.2 ng/g for MBBT (dry weight sediment). We also performed controlled laboratory experiments to determine their partitioning behavior, and we verified the actual solubility of many of the filters. This will help in determining the environmental fate and finally lead to a better risk assessment of these compounds. Together, these results corroborate the hypothesis that hydrophobic UV filters accumulate in the sediment phase and highlight the importance of discerning whether these UV filters impact the benthic community and their potential for bioaccumulation.
... Given the dearth of information on the toxicokinetics and toxicodynamics of these CECs in birds, we call for future research on this important topic. Another consideration is maternal transfer of CECs into eggs; the T1 sample was taken when the females had laid most or all of their eggs and may thus have excreted a notable amount of CECs into the eggs (Allen et al., 2021;Molins-Delgado et al., 2017). However, in our study there was no relationship between clutch size and concentration of ΣCECs at T1 (Fig. S1). ...
... Organic UV filters have been detected in the tissues of Eurasian sparrowhawks, French owls and Greenlandic eagles [111]. In a Spanish study retrieving the unhatched eggs of seven different bird species, including the white stork (Ciconia ciconia) and western marsh harrier (Circus aeruginosus), UV filters were present in the samples of all birds [112]. ...
Skin cancer is a global and increasingly prevalent issue, causing significant individual and economic damage. UV filters in sunscreens play a major role in mitigating the risks that solar ultraviolet ra-diation poses to the human organism. While empirically effective, multiple adverse effects of these compounds are discussed in the media and in scientific research. UV filters are blamed for the dis-ruption of endocrine processes and vitamin D synthesis, damaging effects on the environment, induction of acne and neurotoxic and carcinogenic effects. Some of these allegations are based on scientific facts while others are simply arbitrary. This is especially dangerous considering the risks of exposing unprotected skin to the sun. In summary, UV filters approved by the respective governing bodies are safe for human use and their proven skin cancer-preventing properties make them in-dispensable for sensible sun protection habits. Nonetheless, compounds like octocrylene and ben-zophenone-3 that are linked to the harming of marine ecosystems could be omitted from skin care regimens in favor of the myriad of non-toxic UV filters.
... Thus far the exposure to BPs have been described in wild marine mammals [49], turtles [50], fish [18, 51], mussels [52,53], free-living flatworms [54], prawns, and urchins [55]. In addition, BPs have also been found in the eggs and internal organs of wild marine and terrestrial birds [56][57][58]. ...
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.
... Nowadays, their accurate determination is a high topic concern along the Scientific Community. In fact, UVFs contamination may derive from different sources considering their wide use in personal 15 care products, plastics, paints and textile industries as well as preventing agents in many industrial, commercial and food products [75,76]. ...
Sunscreens are topical preparations containing one or more compounds that protect humans from ultraviolet (UV) light. This review focuses on analytical methods, particularly liquid chromatography, aimed at identifying and determining UV filters (UVFs) in environmental and marine biota matrices. A literature review was done using NIH (PubMed and Medline), FDA and EPA databases, Google Scholar, and Federal Regulations. This retrospective literature review is focused on the last five years. UVFs quantification in environmental and biological matrices showed a wide array of methods where liquid chromatography is predominant. The scientific literature identified a large variety of analytical methodologies that are compared in this review, to evaluate the better results in terms of limits of quantification and the possibility to identify as many analytes as possible simultaneously.
... Nowadays, their accurate determination is a high topic of concern in the Scientific Community. In fact, UVF contamination may derive from different sources, considering their wide use in personal care products, plastics, paints, and textile industries, as well as preventing agents in many industrial, commercial, and food products [74,75]. ...
Sunscreens are topical preparations containing one or more compounds that protect humans from ultraviolet (UV) light. This review focuses on analytical methods, particularly liquid chromatography, with the aim of identifying and determining UV filters (UVFs) in environmental and marine biota matrices. A literature review was conducted using NIH (PubMed and Medline), FDA and EPA databases, Google Scholar, and federal regulations. This retrospective literature review is focused on the last five years. UVF quantification in environmental and biological matrices showed a wide array of methods where liquid chromatography is predominant. The scientific literature identified a large variety of analytical methodologies that are compared in this review to evaluate the better results in terms of limits of quantification and the possibility to identify as many analytes as possible simultaneously.
... Additional potential effects are, among others, allergic reactions, cytotoxicity, and estrogenic effects (reviewed by Gilbert et al. (2013) and Egambaram et al. (2020)). With regard to ecotoxicological effects, some of the most problematic are the effects on corals (Downs et al. 2014;Fel et al. 2019;He et al. 2019) and other marine wildlife (recently reviewed by Lozano et al. (2020a), as well as the potential for bioaccumulation (Gago-Ferrero et al. 2015;Alonso et al. 2015;Molins-Delgado et al. 2017;Díaz-Cruz et al. 2019), due to the relative lipophilic nature of many of the organic UV filters. ...
Organic UV filters are important ingredients in many personal care products, including sunscreens. Evaluating the biodegradability of organic UV filters is key to estimate their recalcitrance and environmental fate and thus central to their overall environmental risk assessment. In order to further understand the degradation process, the aim was to investigate whether specific consortia could degrade certain UV filters. Several bacterial strains were isolated from enrichment cultures actively degrading octocrylene (OC), butyl methoxydibenzoylmethane (BM), homosalate (HS), and 2-ethylhexyl salicylate (ES) and were utilized to construct an in-house consortium. This synthetic consortium contained 27 bacterial strains and degraded OC, BM, HS, and ES 60–80% after 12 days, but not benzophenone-3 (BP3), methoxyphenyl triazine (BEMT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), diethylhexyl butamido triazone (DBT), ethylhexyl triazone (EHT), or diethylamino hydroxybenzoyl hexyl benzoate (DHHB). Furthermore, several commercial microbial mixtures from Greencell were tested to assess their degradation activity toward the same organic UV filters. ES and HS were degraded by some of the commercial consortia, but to a lesser extent. The rest of the tested UV filters were not degraded by any of the commercial bacterial mixes. These results confirm that some organic UV filters are recalcitrant to biodegradation, while others are degraded by a specific set of microorganisms.
Supplementary Information
The online version contains supplementary material available at 10.1007/s11356-023-31063-w.
... Oxybenzone is found to be environmentally harmful and is related to the bleaching and death of coral reefs. These UV filters can be estrogenic, developmentally toxic, or acutely toxic to aquatic organisms [23,24,25]. As such, the search for alternative naturally occurring plant-based compounds as active sunscreens becomes relevant [26,27,28,29,30]. ...
... Vila et al. (2016) recorded high concentration of BP-3 in Spain (692 mg.L À1 ), during summer in tourist areas. Studies have reported concentrations of UV filters, including BP-3, in aquatic organisms, such as bivalves (Groz et al. 2014;He et al. 2019), crustaceans (He et al. 2017), eels (Fent et al. 2010), freshwater (Zenker et al. 2008) and marine fish (Molins-Delgado et al. 2018), marine mammals (Gago-Ferrero et al. 2013a), seabirds (Molins-Delgado et al. 2017), and aquatic plants (Aznar et al. 2017). Due to their lipophilic properties (Log Kow ¼ 3.79) and relative stability to biotic degradation, UV filters tend to accumulate in biological tissues, such as muscle and adipose tissue (Gago-Ferrero et al. 2013b;Vione et al. 2013). ...
Personal care products, such as UV filters, are frequently present in aquatic ecosystems, but studies on their impact on marine organisms are still scarce. Here we addressed the effects of benzophenone-3 (BP-3) on the antioxidant status of Perna perna mussels exposed to concentrations of 0.1 and 3 μg.L-1 for 72 h and 7 days. Glutathione peroxidase (GPx), glutathione reductase (GR), glutathione S-transferase (GST), glucose-6-phosphate dehydrogenase (G6PDH) activity and lipoperoxidation (MDA) were evaluated in the gills. A significant reduction (p < 0.05) in the activity of G6PDH and GPx was observed after exposure for 7 days to 0.1 µg.L-1. However, no significant differences were observed in GST activity and MDA levels, independently of the exposure time. Principal component analysis (PCA) showed an association of BP-3 highest concentration with GR and MDA at 72 h and only with GR at 7 days of exposure. Similarly, the integrated biomarker response (IBR) demonstrated GR and MDA alterations. In conclusion, environmentally relevant concentrations of BP-3 altered antioxidant and auxiliary enzymes, which could cause long-term damage to P.perna mussels. The need to implement more efficient techniques in wastewater treatment systems is pointed out, especially in summer, when UV filters are used more frequently and abundantly.
... 24 In addition, BP3 was previously found in eggs of various bird species from Donãna National Park in Spain, with mean concentrations ranging from 22.1 to 46.7 ng/g (dry weight). 64 Due to the different units of concentration, it is difficult to compare the results from this previous study with the results of the present study, but assuming that avian eggs have a water content between 70 and 85%, 65 the concentrations of BP3 in Donãna National Park bird eggs were around 3.0 to 7.0 ng/g (ww), which were greater than those of fulmar and murre eggs from PLI, suggesting a potential geographic pattern for this contaminant in birds. The adverse effects of BP3 on birds are largely unknown, as with most chemicals of emerging concern, the potential effects associated with the observed wild levels cannot be determined at this time. ...
Ultraviolet (UV) absorbents and industrial antioxidants are contaminants of emerging concern (CECs), but little is known about their distribution in Arctic wildlife, as well as how these contaminants vary over time, across regions, and between species. We used archived egg samples to examine the temporal patterns of 26 UV absorbents and industrial antioxidants in three seabird species (black-legged kittiwakes Rissa tridactyla, thick-billed murres Uria lomvia, northern fulmars Fulmarus glacialis) sampled in Arctic Canada between 1975 and 2019. Various synthetic phenolic antioxidants, aromatic secondary amines, benzotriazole UV stabilizers, and organic UV filters were detected in the seabird eggs. Overall, kittiwakes had higher levels of several UV absorbents and industrial antioxidants. Most target contaminants reached their peak concentrations at different points during the 44-year study period or did not vary significantly over time. None of these contaminant concentrations have increased in recent years. The antioxidant 2-6-di-tert-butyl-4-methylphenol (BHT) was the most frequently detected contaminant in seabird eggs, and its level significantly declined over the course of the study period in kittiwake eggs but did not change in the eggs of murres and fulmars. Future research should examine the effects of these CECs on the health of avian species, the sources, and exposure pathways of these contaminants.
... Consequently, organic UV filters have been reported to bioaccumulate in various aquatic animals. However, these pollutants are not limited to marine environments only, since they have been detected in Swiss cormorants and bird eggs in Spain (Fent et al. 2010, Molins-Delgado et al. 2017. This fact illustrates the severity of biomagnification, a phenomenon which is very important in the ecosystem pollution analysis. ...
Sunscreen use has increased in recent years, as sunscreen products minimize the damaging effects of solar radiation. Active ingredients called ultraviolet (UV) filters or UV agents, either organic or inorganic, responsible for defending skin tissue against harmful UV rays, are incorporated in sunscreen formulations. UV agents have a serious impact on many members of bio communities, and they are transferred to the environment either directly or indirectly. Many organic UV filters are found to be accumulated in marine environments because of high values of the octanol/water partition coefficient. However, due to the fact that UV agents are not stable in water, unwanted by-products may be formed. Experimental studies or field observations have shown that organic UV filters tend to bioaccumulate in various aquatic animals, such as corals, algae, arthropods, mollusks, echinoderms, marine vertebrates. This review was conducted in order to understand the effects of UV agents on both the environment and marine biota. In vivo and in vitro studies of UV filters show a wide range of adverse effects on the environment and exposed organisms. Coral bleaching receives considerable attention, but the scientific data identify potential toxicities of endocrine, neurologic, neoplastic and developmental pathways. However, more controlled environmental studies and long-term human use data are limited. Several jurisdictions have prohibited specific UV filters, but this does not adequately address the dichotomy of the benefits of photoprotection vs lack of eco-friendly, safe, and approved alternatives.
... Among them, four UV filters commonly found in sunscreens and in environment were selected in this study: benzophenone-3 (BP3), butyl methoxydibenzoylmethane (BM), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), and methylene bisbenzotriazolyl tetramethylbutylphenol (MBBT). Environmental concentrations of these compounds are found in numerous reports, with recent reviews summarizing their concentrations in different matrices/compartments including rivers, lakes, coastal ocean, surface water, or sediments (Giokas et al. 2005;Ramos et al. 2015;Tsui et al. 2015;Molins-Delgado et al. 2017;Montes-Grajales et al. 2017). This study focused on sediment compartment. ...
UV filters are widely used in many pharmaceutical and personal care products such as sunscreen and cosmetics to protect from UV irradiation. Due to their hydrophobic properties and relative stability, they have a high capacity to accumulate in sediment. Little information is available on their ecotoxicity on fish. In aquatic ecosystems, fish eggs could be directly affected by UV filters through contact with contaminated sediment. The aim of this study was to investigate the individual toxicity of four UV filters: benzophenone-3 (BP3), butyl methoxydibenzoylmethane (BM), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), and methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), in embryo-larval stages of zebrafish Danio rerio. Fish eggs were exposed to single UV filters by contact with spiked sediment during 96 h at a concentration of 10 μg g⁻¹. Among the four UV filters tested, BP3 was the more toxic, reducing cardiac frequency and increasing standard metabolic rate of larvae.
... Most of the O-UVFs have log K O/W between 4 and 8, which means they are highly lipophilic and may accumulate in sediments and biota [62]. In fact O-UVFs have been found in highly impacted environments such as seawater, sand, and sediments from crowed beaches and densely populated coastal areas from the Mediterranean region, Asia, and North America [42,[63][64][65][66], sediments and waters from rivers and lakes from Europe and Asia [38,50,52,67,68], and in aquatic biota such as mussels, fish, dolphins, coral communities, bird eggs, and cormorants among others around the globe [43,[69][70][71][72]. They can also be found in remote places far from high human pressure such as the Tuamotu Archipelago (around 80 French Polynesian islands and atolls) in the middle of the Pacific Ocean, where Goksøyr et al. [73] detected in the sea surface microlayer (SML) concentrations of OMC, 4-MBC, BP-3, and 3-benzylidene camphor (3-BC) in the range of 5-55 ng/L [73]. ...
Since ancient times, humans have felt the need to protect their skin from the harmful effects of the sun: first with the use of vegetable oils or mud that were applied on the skin and then with the wearing of clothes, hats, or umbrellas. Today, the use of sunscreens around the world has become widespread. It has been shown that the use of these cosmetics can release large quantities of chemicals into coastal waters, either directly through bathing or indirectly through waste water treatment plants and atmospheric depositions. Due to the nature of the active ingredients of sunscreens, organic and inorganic UV filters, it has been proven that they can bioaccumulate and bioconcentrate in sediments and biota and can enter the food chain, being a problem whose true magnitude is still unknown.
... Although the real effect of these molecules in the human organism is still uncertain, it is well known that some commercialized chemical UV filters exhibit hormonal activity, negatively influencing on the reproduction cycle of organisms [7,14]. Additionally, in recent times, the maternal transfer of organic UV filters in humans [15], dolphins [16], and birds [17] has been proven. ...
The growing concern about the environmental impact and human health risk related to the excessive use of synthetic ingredients in cosmetics and topical formulations calls for the exploration of safe and sustainable natural alternatives. Lignin-rich lignocellulosic industrial wastes such as hazelnut and walnut shells were used as a lignin polymer source. Agro-derived lignins were evaluated as a potential natural active ingredient for health care products. Aside from the structural characteristics of isolated lignins, which were identified by GPC, Py-GC-MS, and 2D HSQC NMR techniques, functional properties such as antioxidant power and UV absorption ability were investigated. The SPF values found for creams containing 5% of hazelnut and walnut lignin content were 6.9 and 4.5, respectively. Additionally, both lignin types presented appropriate protection against UVA radiation, highly interesting property to block the full ultraviolet spectrum. The biological activity of isolated lignins assessed at different concentrations (0.01-1 mg/mL) and different times (24, 48, and 72 h) on murine fibroblast cell line 3T3 suggested their suitability for cosmetic applications.
... The laboratory-constructed aquatic food chain also indicated that no biomagnification of SER and ROX occurred along with the metabolite determination and multiple responses from the metabolic biomarkers (Boström et al., 2017;Ding et al., 2015b). Comparatively, the biomagnification potential of OC and BP3 were observed in marine mammals (Gago-Ferrero et al., 2013) and unhatched bird eggs (Molins-Delgado et al., 2017), respectively. Our previous study found parental transfer effects of EHMC in zebrafish (Danio rerio), causing severe oxidative stress and endocrine disruption effects in offspring . ...
... (Peng et al., 2017;Molins- Delgado et al., 2018); these chemicals have also been detected in the liver of dolphins from the coast of Brazil(Gago-Ferrero et al., 2013), in cormorants from Switzerland(Fent et al., 2010), and in unhatched eggs of birds species from the Natural Park of Doñana (SW of Spain), thus proving the biomagnification of these substances(Molins- Delgado et al., 2017). Moreover, these compounds cause a variety of different biological and toxicological responses, affecting survival, behavior, growth, development and reproduction, and these responses have been observed at various trophic levels: algae(Paredes et al., 2014;Giraldo et al., 2017;Mao et al., 2018), corals(Downs et al., 2014(Downs et al., , 2016, ...
... A large number of organic UV filters have entered into the natural environment due to their extensive use by people [2][3][4][5][6]. Studies have shown that most of the organic UV filters contain monocyclic or polycyclic aromatic structures, possess high hydrophobicity, easily accumulate in sediment as well as different tissues of organisms, and exhibit potential to bioaccumulate in living organisms and to biomagnify in the food web [7][8][9][10]. Considering the ubiquity of organic UV filters in the aquatic environment, increasing attention has been paid to their toxicological effects on aquatic organisms. ...
2-Ethylhexyl-4-dimethylaminobenzoate (EHDAB) is a commonly used organic ultraviolet filter. The bioaccumulation and biomagnification of EHDAB were investigated in two aquatic animals, the larvae of midge (Chironomus riparius) and crucian carp (Carassius carassius), and the metabolic enzyme responses in fish liver were determined. EHDAB in the larvae of midge reached a steady state within 10 days of sediment exposure. The biota-sediment accumulation factors ranged from 0.10 to 0.54, and were inversely proportional to the exposure concentrations. The EHDAB-contaminated larvae were used to feed the crucian carp. Within 28 days of feeding exposure, the EHDAB levels in fish tissues gradually increased with the increase of the exposure concentration, exhibiting an apparent concentration-dependence and time-dependence. The liver and kidneys were the main organs of accumulation, and the biomagnification factors of EHDAB ranged from 8.97 to 11.0 and 6.44 to 10.8, respectively. In addition, EHDAB significantly increased the activities of cytochrome P450 (CYP) 1A, CYP3A and glutathione S-transferase in the fish liver. Our results indicate that EHDAB may pose a risk of biomagnification in an aquatic environment and influence the biological processes of exposed organisms.
Numerous anthropogenic ultraviolet filters (UVF) have been detected in aquatic environments and concerns have arisen regarding their potential impacts on aquatic organisms. This manuscript reviews the environmental concentrations and potential toxicity of various UVF. The highest concentrations of UVF are typically observed near frequently visited recreational areas and during peak water-activity periods, which suggests that sunscreen application correlates with noticeable alterations in UVF concentrations. Aquatic concentrations of certain filters have sporadically exceeded 10 μg/L, although most measurements remain below 1 µg/L, which is below commonly reported toxicity levels. UVF have also been detected in aquatic organisms, typically ranging from nondetectable levels to a few hundred ng/g, depending on the species. The toxic effects from UVF, such as coral bleaching and diminished growth, have been observed in laboratory settings, however, toxicity tends to manifest only at significantly higher levels than what is typically detected in aquatic environments. Further research is imperative to provide consumers with improved guidance on selecting sunscreen containing UVF that poses the least environmental risk.
This paper provides insights into the occurrence of sunscreen products in the aquatic environment due to their excessive use and their potential damage to aquatic ecosystems. Sunscreens applied on human skin to eliminate the negative effects of ultraviolet (UV) light are mixtures containing not only UV filters, organic and inorganic compounds, but also emulsifiers, gelling agents, sensation enhancers, preservatives, antimicrobial agents, and antioxidants. The growing use of sunscreens, along with the boost of tourism, has led to the detection of these compounds in the environment. Ingredients of sunscreens often pose a threat to water quality, marine environment, aquatic life, even in agriculture, and therefore constitute an emerging risk to environmental and public health. The UV filters presented in water affect marine organisms and aquatic receptors, and can even end up in humans’ bodies via the food chain. Through a literature review, the occurrence of sunscreen ingredients in the aquatic environment was investigated, as well as the possible solutions for mitigation of sunscreen pollution. Mitigation of sunscreen pollution can be achieved through environmental education, the development of environmentally friendly products as well as with effective removal processes in wastewater treatment plants. Well-rounded campaigns can provide information and raise awareness, to motivate consumers to make proper use of products taking environmental concerns into account. The findings of this paper underline the extent and the severity of sunscreen pollution as well as the significance of education as a valuable tool for the mitigation of water pollution. In general, this review offers a comprehensive overview of the subject.
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.
Introduction
Benzophenones (BPs) are used in various branches of industry as ultraviolet radiation filters, but they pollute the natural environment, penetrate living organisms, and disrupt endocrine balance. Knowledge of the exposure of domestic animals to these substances is extremely scant. The aim of the study was to investigate long-term exposure of companion dogs to BPs and relate this to environmental factors.
Material and Methods
Hair samples taken from 50 dogs and 50 bitches from under 2 to over 10 years old were analysed for BP content with liquid chromatography–tandem mass spectrometry.
Results
The results revealed that dogs are most often exposed to 2-hydroxy-4-methoxybenzophenone (BP-3) and 4-dihydroxybenzophenone (BP-1). Concentration levels of BP-3 above the method quantification limit (MQL) were noted in 100% of the samples and fluctuated from 4.75 ng/g to 1,765 ng/g. In turn, concentration levels of BP-1 above the MQL were noted in 37% of the samples and ranged from <0.50 ng/g to 666 ng/g. Various factors (such as the use of hygiene and care products and the dog’s diet) were found to affect BP concentration levels. Higher levels of BP-3 were observed in castrated/spayed animals and in animals that required veterinary intervention more often.
Conclusion
The results obtained show that the analysis of hair samples may be a useful matrix for biomonitoring BPs in dogs, and that these substances may be toxic to them.
En el nivel de crecimiento de la población, se ha observado el aumento en la cantidad de productos, ya que son parte de nuestras vidas regularmente. Ya sea en casa, trabajando, en la calle o incluso en el patio, por lo que se observa cada vez más el uso de diferentes productos químicos. Algunas sustancias generan riesgo de salud pública. Los disruptores endocrinos son parte de estas sustancias, las cuales pueden alterar el sistema hormonal del organismo humano y generar su disfunción, lo que puede llegar a causar diferentes enfermedades relacionadas con la salud reproductiva de la mujer, además de trastornos en los hombres, trastornos metabólicos, enfermedades neurológicas, cáncer de tiroides o los trastornos cardiovasculares. Los efectos creados en el cuerpo son acumulados e irreversibles y pueden transferirse de generación a generación, sin probar la patología. En el presente artículo se indaga acerca de la contaminación en los medios acuáticos, haciendo hincapié en los productos de uso cotidiano con presencia de estos disruptores endocrinos en su contenido, como los distintos efectos causados a seres humanos y a la vida marina, por mencionar algunos: los bloqueadores solares en los cuales recientes estudios indican que podrían ser bioacumulativos, persistentes y tóxicos, también los fármacos, esto se debe a que en su mayoría presentan anillos aromáticos en su estructura. Por lo tanto, se cree que es importante tener una idea sobre estos disruptores endocrinos para buscar de esta forma la disminución de los contaminantes, así como su utilidad en productos de uso cotidiano.
Anthropogenic activities have caused a steady decline of common kestrel (Falco tinnunculus) since the 1980s. Effects, especially sublethal effects of contaminants, need to be investigated to ensure the conservation of this species. Data about countries, biological material, contaminants classes, and methodological approaches were collected from scientific publications to highlight gaps on common kestrel toxicology and ecotoxicology. We found that most studies have been conducted in Europe and in the field, underlining a lack of in vitro studies. The studies investigated manly contaminant levels, while sublethal effects, evaluation of emerging contaminants and use of non-invasive or low-invasive samples were scarce. This work shows important gaps on toxicological status of the common kestrel, highlighting the importance of developing a non-lethal approach that combines responses at different levels of biological organization, as well as data on chemical contamination and on the environment in which the different populations inhabit.
To carry out risk assessments of benzophenone-type UV filters (BPs), fast and accurate analytical methods are crucial to determine and monitor levels in the environment. This study presents an LC-MS/MS method that requires minimal sample preparation and yet can identify 10 different BPs in environmental samples such as surface or wastewater resulting in a LOQ range from 2 to 1060 ng/L. The method suitability was tested through environmental monitoring, which showed that, BP-4 is the most abundant derivative found in the surface waters of Germany, India, South Africa and Vietnam. BP-4 levels correlate with the WWTP effluent fraction of the respective river for selected samples in Germany. Peak values of 171 ng/L for 4-hydroxybenzophenone (4-OH-BP), as measured in Vietnamese surface water, already exceed the PNEC value of 80 ng/L, elevating 4-OH-BP to the status of a new pollutant that needs more frequent monitoring. Moreover, this study reveals that during biodegradation of benzophenone in river water, the transformation product 4-OH-BP is formed which contain structural alerts for estrogenic activity. By using yeast-based reporter gene assays, this study provides bio-equivalents of 9 BPs, 4-OH-BP, 2,3,4-tri-OH-BP, 4-cresol and benzoate and complements the existing structure-activities relationships of BPs and their degradation products.
Several anthropogenic contaminants have been identified as competing with the thyroid hormone thyroxine (T4) for binding to transport proteins as transthyretin (TTR). This binding can potentially create toxicity mechanisms posing a threat to human health. Many organic UV filters (UVFs) and paraben preservatives (PBs), widely used in personal care products, are chemicals of emerging concern due to their adverse effects as potential thyroid-disrupting compounds. Recently, organic UVFs have been found in paired maternal and fetal samples and PBs have been detected in placenta, which opens the possibility of the involvement of TTR in the transfer of these chemicals across physiological barriers. We aimed to investigate a discrete set of organic UVFs and PBs to identify novel TTR binders. The binding affinities of target UVFs towards TTR were evaluated using in vitro T4 competitive binding assays. The ligand-TTR affinities were determined by isothermal titration calorimetry (ITC) and compared with known TTR ligands. In parallel, computational studies were used to predict the 3-D structures of the binding modes of these chemicals to TTR. Some organic UVFs, compounds 2,2′,4,4′-tetrahydroxybenzophenone (BP2, Kd = 0.43 μM); 2,4-dihydroxybenzophenone (BP1, Kd = 0.60 μM); 4,4′-dihydroxybenzophenone (4DHB, Kd = 0.83 μM), and 4-hydroxybenzophenone (4HB, Kd = 0.93 μM), were found to display a high affinity to TTR, being BP2 the strongest TTR binder (ΔH = −14.93 Kcal/mol). Finally, a correlation was found between the experimental ITC data and the TTR-ligand docking scores obtained by computational studies. The approach integrating in vitro assays and in silico methods constituted a useful tool to find TTR binders among common organic UVFs. Further studies on the involvement of the transporter protein TTR in assisting the transplacental transfer of these chemicals across physiological barriers and the long-term consequences of prenatal exposure to them should be pursued.
Organic ultraviolet absorbents (UVAs) have attracted increasing concern due to their ubiquity, bioaccumulation, and potential toxicity. However, available information on their occurrence and transfer in terrestrial environment is still extremely insufficient. In this study, we investigated twelve UVAs in the soils and five terrestrial plant species from a typical industrial area in South China, and found their total concentrations were 5.87–76.1 (median 13.1) and 17.9–269 (median 82.9) ng/g dry weight, respectively. Homosalate was dominant in soils while benzophenone and octrizole were predominant in plants, likely due to their complex sources and bioaccumulation preferences. The bioaccumulation factors (BAFs) were further evaluated based on the ratios of UVA concentrations in plants and soils. The observed BAFs of UVAs were compound and species-specific, and most of them were much >1.0, indicating the chemicals could be transferred from soils to plants. To the best of our knowledge, this is the first report of organic UVAs in field soil-plant systems, providing information that may improve our understanding of the bioaccumulability of these chemicals in terrestrial environment and the associated risks. More studies are needed to investigate the transfer and bioaccumulation of such chemicals in soils and terrestrial biota.
UV filters are used daily by millions of people. Not all of these filters, however, are 100% biodegradable, and many wastewater treatments plants are ill-equipped to filter them properly. As a result, UV filters are increasingly reaching the environment. Various types have been detected in soil, continental water, oceans, and numerous organisms, including algae, corals, fish, mammals, and even land birds. In addition, some filters, benzophenone-3 and octocrylene in particular, are toxic to these organisms. Toxic effects include coral bleaching and interference with metabolic, enzymatic, and reproductive activities in practically all organisms. Preliminary data suggest that UV filters may be bioaccumulating in humans, as they have been detected in urine and breast milk. It should be noted, however, that research into the environmental impact of UV filters holds challenges and limitations.
Sunscreens containing broad‐spectrum ultraviolet (UV) filters play an essential role in protecting the skin against the damage induced by sun overexposure. However, the widespread use of sunscreens and other personal care products containing these filters has led to these compounds being widely detected in the environment and being identified as emerging pollutants in marine waters. Concerns raised by laboratory studies investigating the potential impact of UV filters on coral communities have already led to bans on the use of some sunscreens in a few tourist hotspots. Although UV filter pollution may be just one of the many environmental factors impacting coral health worldwide, the media attention surrounding these studies and the legislative changes may lead patients to question dermatologists about the environmental safety of some sunscreen products. This review provides an overview of current knowledge on the impact of UV filters on marine ecosystems, concentrating on recent studies examining the effects of commonly used filters on organisms at low trophic levels and of how alternative approaches, such as metabolomics, can be used to further assess UV filter ecotoxicity. Current gaps in our knowledge are also discussed, most notably the need to increase our understanding of the longer‐term fate and behaviour of UV filters in the marine environment, develop more adapted standardized ecotoxicity tests for a wider range of marine species, and evaluate the impact of UV filters on the marine food web. We then discuss future perspectives for the development of new, more environmentally friendly, filters that may enable the use of the most toxic compounds to be reduced without compromising the effectiveness of sunscreen formulations. Finally, we consider how dermatologists play a key role in educating patients on the need for a balanced approach to sun exposure, sun protection, and conservation of the marine environment.
UV absorbing chemicals are used in numerous consumer products including over-the-counter sunscreens and other personal care products. Furthermore, UV stabilizing chemicals are now widely used in consumer goods including plastics, fabrics, paints, and building materials to protect the products from UV damage. The widespread use of UV absorbing and UV stabilizing chemicals in consumer goods has led to contamination of environmental matrices (including water, sewage, sediment, and dust), wildlife populations, and human bodies. In this chapter, we review the evidence for this widespread contamination, as well as what is known about the effects of some of these chemicals including the UV absorbing chemical oxybenzone (and its metabolites), and benzotriazole derivatives, a class of UV stabilizing chemicals.
Organic UV filters are continuously released in aquatic ecosystems due to their widespread use, especially in touristic coastal environments. Generally, organic UV filters are poorly soluble in water and tend to accumulate in the sediment compartment. This represents a conceivable risk for sediment-dwelling organisms and a potential for transfer of the UV filters up the food chain. This study aimed to assess the potential transfer of seven UV filters including benzophenone-3 (BP3), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), butyl methoxydibenzoylmethane (BM), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), 2-ethylhexyl salicylate (ES), diethylhexyl butamido triazone (DBT), and octocrylene (OC) from artificial spiked sediment (10 µg·g−1 dry weight) to sediment-dwelling worms. All UV filters were detected in the worms after 28 days of exposure, but only BP3 was apparently bioaccumulated, with a biota sediment accumulation factor (BSAF) of 12.38 ± 4.65. However, metabolomic profiling revealed that OC was metabolized by the worms into 11 fatty acid conjugates, demonstrating that OC did also accumulate in the worms in the form of OC–fatty acid conjugates. Here, the sole quantification of the parent organic UV filter underestimated the accumulation factor and the exposure of organisms. In general, it is therefore important to pair the conventional method (BSAF calculus) with other techniques, such as metabolomics, to assess the actual potential for bioaccumulation of xenobiotics including transformed xenobiotics.
Water quality is an issue of global concern intrinsically associated to the health and well-being of the society, and it essentially depends on the level of aquatic pollution. The problem of pollution by emerging contaminants (ECs) has gained special relevance in the twenty-first century. Emerging contaminants represent a wide variety of products with different properties that may persist in the environment and accumulate in animal and human tissues, with potential ability to produce toxic effects even at low doses. Some of these ECs are pharmaceuticals, personal care products (PCPs), plasticizers, pesticides, flame retardants, industrial additives, surfactants, nanomaterials, mycotoxins, and phytotoxins. Nowadays, wastewater treatment plants (WWTPs) are not efficiently removing some ECs, and they ultimately reach different water compartments (i.e. influent/effluent wastewaters, groundwater, rivers, lakes, marine environments, and sediments). These ECs and their metabolites may also suffer structural changes once in the environment, generating transformation products that may be more persistent or toxic than the parent compound. An increasing number of publications are detecting ECs in different water systems and organisms at a global scale. This raises concerns about the detrimental impacts on humans, animals, plants, and the environment. Although these contaminants generally produce few acute toxicity events as they are usually found at low concentrations in aquatic environments, they may produce adverse effects in a mid- and long-term basis. To date, information about the deleterious effects they may provoke is still limited, but some studies have reported different effects in organisms such as endocrine disruption, development of bacterial pathogen resistance and chronic toxicity. New advances in WWTP technologies are clearly needed to remove ECs more efficiently during the treatment processes, so that effluents discharged into water bodies may contain lower residue levels. In addition, further studies regarding the broad diversity of scientific and technological fields related to ECs and water quality are needed worldwide to improve water quality.
The ecological harm from methylsiloxanes has drawn worldwide attention. This study investigated three cyclic (D4–D6) and four linear siloxanes (L7–L10) in the eggs of free-range poultry collected near a rural industrial park in China and found total concentrations in the range of 19.2–1204 (median, 268) ng/g dry weight. Higher concentrations of methylsiloxanes were observed in chicken eggs than duck eggs. Cyclic siloxanes represented a median of 62.2% of the total methylsiloxane concentrations. A source assessment indicated that local soils and outdoor dust were more important sources of egg methylsiloxanes than poultry food. The partitioning of methylsiloxanes between egg yolk and egg albumen was investigated, and preferential distributions of the chemicals in the yolk were observed. This study confirmed that methylsiloxanes were highly prevalent in the study poultry eggs. The results suggested that the potential risks to some wild birds inhabiting this area should be of concern, as their physiologies and feeding ecologies are similar to those of the studied poultry, although available ecotoxicological data of the chemicals to birds remains scarce. Additional research is needed to characterize the accumulation of methylsiloxanes in different bird species and its associated adverse effects on their offspring.
Benzophenone-3 (BP3) is a widely used organic UV filter present in many environmental compartments. One way BP3 is released into the environment is through effluents from wastewater treatment plants (WWTPs). These plants are possible sources for degradation activity and WWTP sludge may potentially degrade BP3. Our goal was to identify any BP3 degrading microorganism(s) in WWTP sludge and to investigate whether the degradation was co-metabolic. Initial WWTP sludge microcosms spiked with BP3 showed 100% degradation after 20 days. Multiple transfers of these microcosms, while maintaining a strong selective pressure for BP3 degradation capabilities, resulted in the dominance of one bacterial strain. This strain was identified as Sphingomonas wittichii BP14P and was subsequently isolated. It was shown to degrade BP3 in a growth dependent manner. Strain BP14P utilized BP3 as the sole energy and carbon source and completely degraded BP3 after 7 days in minimal media. We tested the capability of BP14P to degrade nine other UV filters, but the degradation ability seemed to be restricted to BP3. However, whether this specificity is due to the lack of degradation genes, cellular transport or low bioavailability of the other UV filters remained unclear. The efficient degradation of BP3 by a group of bacteria well known for their potential for xenobiotic degradation is an important step forward for a complete risk assessment of the long-term environmental impact of BP3.
Benzophenone (BP) is an ultraviolet filter (UVF) widely used in personal care products such as sunscreens and cosmetics. Excessive exposure to BP-type UVFs is a potential threat to human's health because of their endocrine-disrupting activity. Water stability of lanthanide compounds is crucial when they serve as luminescent sensors because of the practicality and recyclability. In this study, a water-stable luminescent Zn-Tb heterometallic coordination polymer was rationally designed and synthesized for rapid detection of BP. This material showed a high quenching effect, excellent selectivity, and fast response toward BP.
UV radiation is one of the critical environmental stress factors for human skin, which can trigger various problems such as pruritus, burning, erythema, premature skin aging, and skin cancer. Hence, UV‐protection has become an indispensable daily routine and the use of topical sunscreen products is rapidly increasing. However, there are emerging concerns over the efficiency and safety of existing chemical and physical UV filters used in consumer products. Furthermore, there is no universally approved method for assessing sun protection efficiency regardless of the immediate end user need to develop safer sunscreen products that afford broad‐spectrum photoprotection. It is evident that the current organic and inorganic UV filters have significant unfavorable impacts on human, environmental, and marine safety. Therefore, effective alternative UV filters should be established. This review article comprehensively describes the properties, safety, health, and ecological concerns of various UV filters including TiO2 and ZnO nanoparticles as well as the limitations of the testing protocols and guidelines provided by major regulatory bodies. The photoreactivity of UV filters used in sunscreen remains a major challenge and it is crucial to develop new sunscreen ingredients, which not only protect the consumer, but also the environment.
Exposure science, in its broadest sense, studies the interactions between stressors (chemical, biological, and physical agents) and receptors (e.g. humans and other living organisms, and non-living items like buildings), together with the associated pathways and processes potentially leading to negative effects on human health and the environment. The aquatic environment may contain thousands of compounds, many of them still unknown, that can pose a risk to ecosystems and human health. Due to the unquestionable importance of the aquatic environment, one of the main challenges in the field of exposure science is the comprehensive characterization and evaluation of complex environmental mixtures beyond the classical/priority contaminants to new emerging contaminants.
The role of advanced analytical chemistry to identify and quantify potential chemical risks, that might cause adverse effects to the aquatic environment, is essential. In this paper, we present the strategies and tools that analytical chemistry has nowadays, focused on chromatography hyphenated to (high-resolution) mass spectrometry because of its relevance in this field. Key issues, such as the application of effect direct analysis to reduce the complexity of the sample, the investigation of the huge number of transformation/degradation products that may be present in the aquatic environment, the analysis of urban wastewater as a source of valuable information on our lifestyle and substances we consumed and/or are exposed to, or the monitoring of drinking water, are discussed in this article. The trends and perspectives for the next few years are also highlighted, when it is expected that new developments and tools will allow a better knowledge of chemical composition in the aquatic environment. This will help regulatory authorities to protect water bodies and to advance towards improved regulations that enable practical and efficient abatements for environmental and public health protection.
The occurrence of eight organic UV filters (UV-Fs) was assessed in fish from four Iberian river basins. This group of compounds is extensively used in cosmetic products and other industrial goods to avoid the damaging effects of UV radiation, and has been found to be ubiquitous contaminants in the aquatic ecosystem. In particular, fish are considered by the scientific community to be the most feasible organism for contamination monitoring in aquatic ecosystems. Despite that, studies on the bioaccumulation of UV-F are scarce. In this study fish samples from four Iberian river basins under high anthropogenic pressure were analysed by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Benzophenone-3 (BP3), ethylhexyl methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4MBC) and octocrylene (OC) were the predominant pollutants in the fish samples, with concentrations in the range of ng/gdryweight (d.w.). The results indicated that most polluted area corresponded to Guadalquivir River basin, where maximum concentrations were found for EHMC (241.7ng/gd.w.). Sediments from this river basin were also analysed. Lower values were observed in relation to fish for OC and EHMC, ranging from below the limits of detection to 23ng/gd.w. Accumulation levels of UV-F in the fish were used to calculate biota-sediment accumulation factors (BSAFs). These values were always below 1, in the range of 0.04-0.3, indicating that the target UV-Fs are excreted by fish only to some extent. The fact that the highest concentrations were determined in predators suggests that biomagnification of UV-F may take place along the freshwater food web.
Copyright © 2015. Published by Elsevier B.V.
Reactions of sunscreen agents, octyl dimethyl-p-aminobenzoate (ODPABA) and octyl-p-methoxycinnamate (OMC), with hypochlorite in aqueous solution were investigated under the conditions that simulate swimming pool disinfection sites. Chlorination byproducts were determined by GC-MS. At a concentration of 9µM, ODPABA reacted rapidly with free chlorine in the buffered solution at pH 7.0, OMC reacted with hypochlorite reasonably slowly under the same condition. ODPABA and OMC produced chlorine-substituted compounds as intermediates, whic hw ere decomposed to cleavaged products of ester-bond during the aqueous chlorination process. The chlori- nation intermediates of OMC exhibited weak mutagenic on Salmonella typhimurium TA100 strain without the S9 mix. The extent of the reactions depended on the chlorine dose, solution pH, and compound structures.
Most current bioexposure assessments for UV filters focus on contaminants concentrations in fish from river and lake. To date there is not information available on the occurrence of UV filters in marine mammals. This is the first study to investigate the presence of sunscreen agents in tissue liver of Franciscana dolphin (Pontoporia blainvillei), a species under special measures for conservation. Fifty six liver tissue samples were taken from dead individuals accidentally caught or found stranded along the Brazilian coastal area (six States). The extensively used octocrylene (2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate, OCT) was frequently found in the samples investigated (21 out of 56) at concentrations in the range 89-782 ng.g-1 lipid weight. São Paulo was found to be the most polluted area (70% frequency of detection). Nevertheless, the highest concentration was observed in the dolphins from Rio Grande do Sul (42% frequency of detection within that area). These findings constitute the first data reported on the occurrence of UV filters in marine mammals worldwide.
Zur Erfassung der UV-Filtersubstanzen wird eine Methode vorgestellt, die die simultane Bestimmung dieser Verbindungen und von Organochlorverbindungen wie PCB und DDT in unterschiedlichen Fischkompartimenten bis in den ng/kg-Bereich ermöglicht. Die Nachweisgrenzen liegen zwischen 40 und 90 ng/kg Filet und die Wiederfindungsraten bewegen sich zwischen 78 und 104%. Die Belastung von Wasser und Fischen des Meerfelder Maares, Eifel, mit UV-Filtersubstanzen wurde 1991 und 1993 exemplarisch untersucht. Insgesamt konnten in den Fischen des Meerfelder Maares 6 UV-Filtersubstanzen identifiziert und quantifiziert werden. Die im Sommer 1991 gefangenen Barsche waren mit 2,0 mg/kg Fett (Summe nachgewiesener UV-Filtersubstanzen) und die Rotaugen von 1993 mit 0,50 mg/kg Fett belastet. In beiden Fischarten lag die Belastung in der gleichen Größenordnung wie die der Organochlorverbindungen PCB und DDT. In den Rotaugen aus drei weiteren deutschen Seen konnte im Filet Methylbenzylidencampher, eine lipophile UV-Filtersubstanz, nachgewiesen werden. Diese Befunde zeigen, daß UV-Filtersubstanzen in deutschen Seen weir verbreitet und vermutlich als relevante Umweltchemikalien zu betrachten sind. Da im Wasser der Seen die Konzentrationen der UV-Filter substanzen meistens unter der Bestimmungsgrenze lagen, können Fische für diese lipophilen Verbindungen als Expositionsmonitor verwendet werden. Eine ökotoxikologische Bewertung ist zum jetzigen Zeitpunkt nicht möglich, da die Datenlage völlig unzureichend ist.
We report for the first time levels of persistent organic pollutants in marine bird eggs from an oceanic island in the Indian Ocean, the world's third largest ocean. Ten eggs each of the Common Noddy, also known as the Brown Noddy (Anous stolidus), and Sooty Tern (Sterna fuscata) were collected from Ile Cocos off the coast of the island of Rodrigues, located 560km east of the island of Mauritius. ΣPCBs had the highest levels (2.2 and 2.6ng/gwm, wet mass; 20 and 19ng/glm, lipid mass) for common Noddy and Sooty Tern, respectively (and following), then ΣDDT (1.9 and 3.1ng/gwm; 17 and 23ng/glm), and mirex (0.96 and 0.69 ng/g wm; 8.7 and 5.0ng/glm). ΣChlordanes (0.094 and 0.15ng/gwm; 0.48 and 0.73ng/glm) and Σtoxaphenes (0.26 and 0.61ng/gwm; 2.4 and 5.9ng/glm) are rare data for these compounds from this ocean. Brominated flame retardants were low (0.08 and 0.07ng/gwm; 0.7 and 0.7ng/glm). Multivariate analyses indicated different contamination patterns in the prey items as Sooty Terns had significantly higher levels of mean Σchlordanes and Σtoxaphenes, as well as CB105, -108 and -157. p,p'-DDE had an association with thinner eggshells in the Sooty Tern. Although the contaminant levels were in all respects low, industrialisation, development on the periphery, commercial exploitation of the marine environment, and pollutants transferred over long distances by marine debris is likely to add to chemical pressure in this region. Monitoring changes in background levels of pollutants in remote regions will indicate such trends, and marine bird eggs from Rodrigues would be an excellent site.
Organic ultraviolet (UV) filters are compounds used to absorb UV radiation and are increasingly being used as a result of growing concern about UV radiation and skin cancer. Their growing use may increase environmental contamination and exposure through the food chain. There is therefore major concern about the environmental fate and potential effect of organic UV filters used in beauty creams, hair sprays, shampoos, and other personal-care products, as well as those added to plastics and other materials to prevent degradation of polymers and pigments.This review describes the processes undergone by these compounds once released into the environment and the instrumental methods based on chromatography and mass spectrometry reported in the literature for their determination in environmental samples. We include concentrations found in the environment (e.g., water, soil, sediments, sludge and biota). The main focus is on metabolites, photodegradates and by-products of wastewater treatment.
Benzotriazoles are a group of UV absorbing compounds considered emerging contaminants that are used in different personal care products, and therefore, it is of high interest to develop sensitive and fast methods for investigating their presence in the environment. In this work, we present the development and application of a novel method based on on-line solid-phase extraction coupled to ultra-performance liquid chromatography with tandem mass spectrometry detection (SPE-UPLC-MS/MS) for the determination of seven benzotriazole UV stabilizers (BUVSs) in coastal marine and wastewater samples. This process is compared with a conventional off-line SPE procedure followed by UPLC-MS/MS. The parameters affecting the performance of the sample preparation and determination processes were evaluated. The results indicate that the on-line procedure provides for better sensitivity and reproducibility and is faster and easier than the off-line procedure. The detection limits and quantification limits achieved were in the range of 0.6-4.1 ng∙L(-1) and 2.1-14 ng∙L(-1) and relative standard deviation between 6.2 and 10%. The developed method was applied to coastal marine and wastewater samples from Gran Canaria Island (Spain). All of the BUVSs studied were detected in the samples from wastewater treatment plants and two were found in the seawater samples (UV P in the range of 2.8-4.4 ng∙L(-1) and UV 360 between 3.6 and 5.2 ng∙L(-1)).
By switching great skuas Catharacta skua from one isotopically distinct diet to another, we measured diet-tissue discrimination factors and tested the assumption that dietary nitrogen and carbon isotope signatures are incorporated into blood and feathers at similar rates. We also examined the effects of metabolic rate and looked for evidence of isotopic routing. We found that blood delta(15)N and delta(13)C signatures altered after the diet switch at similar rates (14.4 d and 15.7 d, respectively). Qualitative analyses imply that the same was true with feathers. Mass balance calculations suggest that only a small amount of lipid is likely to be involved in the synthesis of blood and feathers. Differences in diet-tissue discrimination factors before and after the diet switch may mean that toward the end of the experiment, some of the nutrients for blood synthesis had been coming from stores. Repeated measures mixed models provided evidence that increases in metabolic rate might accelerate fractional turnover rates in blood. There is a need for more laboratory-based experimental isotope studies in order to address further questions that this study has raised.
In this work, we evaluate whether in vitro systems are good predictors for in vivo estrogenic activity in fish. We focus on UV filters being used in sunscreens and in UV stabilization of materials. First, we determined the estrogenic activity of 23 UV filters and one UV filter metabolite employing a recombinant yeast carrying the estrogen receptor of rainbow trout (rtERalpha) and made comparisons with yeast carrying the human hERalpha for receptor specificity. Benzophenone-1 (BP1), benzophenone-2 (BP2), 4,4-dihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4-trihydroxy-benzophenone, and phenylsalicylate showed full dose-response curves with maximal responses of 81-115%, whereas 3-benzylidene camphor (3BC), octylsalicylate, benzylsalicylate, benzophenone-3, and benzophenone-4 displayed lower maximal responses of 15-74%. Whereas the activity of 17beta-estradiol was lower in the rtERalpha than the hERalpha assay, the activities of UV filters were similar or relatively higher in rtERalpha, indicating different relative binding activities of both ER. Subsequently, we analyzed whether the in vitro estrogenicity of eight UV filters is also displayed in vivo in fathead minnows by the induction potential of vitellogenin after 14 days of aqueous exposure. Of the three active compounds in vivo, 3BC induced vitellogenin at lower concentrations (435 microg/l) than BP1 (4919 microg/l) and BP2 (8783 microg/l). The study shows, for the first time, estrogenic activities of UV filters in fish both in vitro and in vivo. Thus we propose that receptor-based assays should be used for in vitro screening prior to in vivo testing, leading to environmental risk assessments based on combined, complementary, and appropriate species-related assays for hormonal activity.
UV filters as emerging contaminants are of great concern and their wide detection in aquatic environments indicates their chemical stability and persistence. This review summarized the photolytic and photocatalytic degradation of UV filters in contaminated water. The findings indicated that limited research has been conducted on the photolysis and photocatalysis of UV filters. Photolysis of UV filters through UV irradiation in natural water was a slow process, which was accelerated by the presence of photosensitisers e.g. triplet state of chromaphoric dissolved organic matter (³CDOM*) and nutrients but reduced by salinity, dissolved organic matter (DOM) and divalent cations. UV Photocatalysis of 4-methylbenzylidene camphor and 2-phenylbenzimidazole-5-sulfonic acid was very effective with 100% removal within 30 min and 90 min using medicated TiO2/H2O2 and TiO2, respectively. The radiation source, type of catalyst and oxygen content were key factors. Future research should focus on improved understanding of photodegradation pathways and by-products of UV filters.
Recent studies demonstrated that the common pyrethroid insecticides are present in aquatic biota tissues. In this study, 123 samples of unhatched eggs of 16 wild bird species collected from 2010 to 2012 in Doñana National and Natural Park were analysed to determine 13 pyrethroids. This study represents the first time that pyrethroids are detected in tissues of terrestrial biota, 93% of these samples being positive to those pollutants. Levels of total pyrethroids ranged from not detected to 324 ng g⁻¹ lw. The samples were characterized by stable isotope analysis. Species with diets based on anthropogenic food showed higher levels of pyrethroids and lower values of δ¹⁵N. Finally, we characterized the isomers of pyrethroids and discerned some isomeric- and enantiomeric-specific accumulations. In particular, tetramethrin and cyhalothrin showed an enantiomeric-selective accumulation of one enantiomer, highlighting the need to assess toxicological effects of each enantiomer separately to be able to make a correct risk assessment of pyrethroids in birds.
Eggs of Purple Heron (Ardea purpurea) were collected from three sampled sites inside the Ebro River basin in years 2006 and 2007. These sites were located besides (Flix), upstream (Aiguabarreig) and downstream (Delta) a chlor-alkali plant. Organochlorine compounds (OCs) such as dichlorodiphenyltrichloroethanes (DDTs), polychlorobiphenyls (PCBs), polychlorostyrenes (PCSs), hexachlorobenzene (HCB), pentachlorobenzene (PeCB) and hexachlorocyclohexanes (HCHs) were analysed to assess what are the accumulation patterns of these compounds in aquatic migratory birds breeding in the area of influence of the emissions from this industrial installation. Comparison of the egg concentrations between the three sites show higher concentrations of compounds manufactured in the past in the factory (PCBs, p,p'-DDT) or by-products of OC synthesis (HCB, PeCB and PCSs) in Flix than in Aiguabarreig reflecting a clear influence from the emissions of the chlor-alkali plant. The eggs collected in the Ebro Delta showed higher concentrations of total DDTs (mainly p,p'-DDE) than in the reference site (Aiguabarreig) which could reflect past applications of this insecticide in the area for agriculture. In contrast, HCHs were found in higher concentrations in the Delta and Aiguabarreig than in the Flix Reservoir. These compounds have been used as insecticides in agriculture and were not manufactured in the chlor-alkali plant. The present results show that despite Purple Herons are migratory birds, the food web transfer of OCs during the breeding season is sufficient for the accumulation of these compounds in the eggs, leading to statistically significant concentration differences between sites. These differences are consistent with the emissions of these pollutants from industrial or agricultural sources to the aquatic environments. Some of the p,p'-DDE concentrations observed in the area nearby the chlor-alkali plant are above the threshold effects for reproductive impairment.
In the framework of the study of emerging pollutants in the aquatic environment, personal care products (PCPs) play a relevant role as they are used in everyday life. They are continuously introduced into the natural water compartment, mainly through treated and untreated sewage but also via different pathways. This chapter describes the “state of the art” of the distribution and impact of PCPs on European natural waters (rivers, lakes, groundwater, drinking water, etc.). An extensive review of the recent literature has been carried out, gathering together the most relevant studies and presenting the results in five sections: fragrances, UV filters, detergents, preservatives, and repellents. In each section, data on the main molecules employed in PCP formulations are reported and compared. The physicochemical properties of many PCP compounds are summarized in the respective tables along with an additional table listing the measured concentrations of all PCPs detected in waters all over Europe.
The present study describes the development, validation and application of a fully automated analytical method based on on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry (on line SPE-HPLC-MS/MS) to assess the removal efficiency in water works and the ecotoxicological implications derived of the two most used benzotriazole-class UV stabilizers (BZTs), namely 1H-benzotriazole (BZT) and 5-methyl-1H-benzotriazole (MeBZT). Influent and effluent wastewater samples from 20 wastewater treatment plants (WWTPs) were analyzed. Removal rates (RE%) and half-lives (t1/2) for each BZTs were calculated and correlated to the hydraulic retention time (HRT) of each plant. Both BZTs were detected in all influent and effluent samples (concentrations in the range 26.7ngL(-1)-42.9μgL(-1)), with the highest concentrations corresponding to MeBZT. Results indicated that both compounds were recalcitrant (RE% in the range 11.8-94.7%) and that no clear influence of HRT on removals could be drawn. Finally, the potential environmental risk posed by the levels of BZTs detected was evaluated calculating the hazard quotients (HQs) MeBZT was the only BZTs posing a risk to Vibrio fischeri, Daphnia galeata and Pimephales promelas.
The occurrence of classical (polybrominated diphenyl ethers, PBDEs) and emerging FRs (dechloranes, hexabromobenzene (HBB), pentabromoethyl benzene (PBEB) and decabromodiphenyl ethane (DBDPE)) in unborn eggs of 14 different species from Doñana Natural Space and surrounding areas was studied. PBDEs, Dec-602, Dec-603 and DP were detected in all the species, whereas HBB, PBEB, DBDPE and Dec-604 were not detected in any sample. ΣPBDE and ΣDechlorane levels ranged from 1.40 to 90.7, and from 0.77 to 260 ng/g lw, respectively. BDE-209 was the most abundant BDE congener in almost all the species, whereas Dec-602 was the predominant among dechloranes. In general, levels of PBDEs and dechloranes were similar and even higher for dechloranes, probably indicating the increasing use of dechloranes as a result of legal restrictions on PBDEs. In both cases, the most contaminated specie was the white stork. Using stable isotope characterization, differences among species and possible biomagnification processes were also evaluated. PBDE levels increased as the trophic position increased, showing biomagnification capacity. The same behavior was observed for Dec-602 and Dec-603; however, DP levels were not linearly correlated with trophic level. These results show that more attention should be given to emerging FRs such as dechloranes since they show similar environmental behavior as PBDEs.
The photochemical behavior of the sunscreen agent octyl-dimethyl-p-aminobenzoic acid (ODPABA) was studied in different aqueous solutions and under different conditions. ODPABA photolysis was performed under laboratory conditions using a xenon light source and under natural sunlight conditions in sea, swimming pool as well as in distilled water. The influence of dissolved organic matter (DOM) on the degradation kinetics was also studied in the presence of various concentrations of humic acids (HA). The phototransformation was shown to proceed via pseudo-first-order reaction in all cases and the reaction rates followed the order: distilled water > swimming pool water > seawater, depending mainly on the presence of dissolved organic matter that retarded the photolysis reaction. Kinetic experiments were monitored with HPLC/UV–DAD and the half-lives (t1/2) varied between 1.6 and 39h in simulated solar irradiation and between 27 and 39h in natural sunlight conditions. The product distribution during illumination was strongly dependent on the constitution of the irradiated media. Irradiation of the aqueous ODPABA solutions gave rise to several transformation products that were isolated by means of solid-phase extraction (SPE) and identified using GC–MS techniques. These were formed mainly through dealkylation and hydroxylation reactions and were detected in all aqueous solutions investigated. In the case of swimming pool water some additional byproducts were isolated and were tentatively identified as chlorinated intermediates, formed by the subsequent chlorination of the parent molecule as well as other intermediates.
So far, the very few studies addressing the occurrence of UV filters (UV F) in biota showed important limitations in the analysis of the so complex biological matrices. In order to improve the knowledge on the bioaccumulation of UV F by fish, a simple and highly sensitive method was successfully developed and validated for the simultaneous determination of eight extensively used UV F and transformation products with a wide range of physicochemical properties. The present study demonstrated that liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) using a QqLIT mass analyser was applicable to the simultaneous analysis of UV F in fish. Pressurized liquid extraction (PLE) was chosen for the sample pretreatment due to the good extraction efficiency provided. An additional SPE clean-up step was added in order to minimize matrix effects and to improve the sensitivity. The method allowed recovery efficiencies in the range 70-112% for most compounds at the three spike levels. The low limits of detection (MLOD) achieved (0.1-6.0ng/g dw) allowed the reliable quantification of UV F residues in fish samples. The developed methodology was applied to assess the occurrence of UV F in different fish species from the Guadalquivir river basin (Spain). Results confirmed the bioaccumulation of benzophenone-3 (BP3), ethylhexyl methoxycinnamate (EHMC) and octocrylene (OC) in the fish samples. The maximum concentration of 240ng/g dw corresponded to EHMC, which was also the most ubiquitous compound. The reported concentrations constitute the first occurrence data of UV F residues in fish from Iberian rivers.
Reactions of sunscreen agents, octyl dimethyl-p-aminobenzoate (ODPABA) and octyl-p-methoxycinnamate (OMC), with hypochlorite in aqueous solution were investigated under the conditions that simulate swimming pool disinfection sites. Chlorination byproducts were determined by GC-MS. At a concentration of 9 µM, ODPABA reacted rapidly with free chlorine in the buffered solution at pH 7.0, OMC reacted with hypochlorite reasonably slowly under the same condition. ODPABA and OMC produced chlorine-substituted compounds as intermediates, which were decomposed to cleavaged products of ester-bond during the aqueous chlorination process. The chlori-nation intermediates of OMC exhibited weak mutagenic on Salmonella typhimurium TA100 strain without the S9 mix. The extent of the reactions depended on the chlorine dose, solution pH, and compound structures.
Anthropogenic organic contaminants have been found in even the most remote locations. To assess the global distribution and possible effects of such contaminants, we examined the tissues of two species of albatross collected from Midway Atoll in the central North Pacific Ocean. These birds have an extensive feeding range covering much of the subtropical and northern Pacific Ocean. Anthropogenic contaminants were found at relatively great concentrations in these birds. The sum of 19 polychlorinated biphenyl (PCB) congeners ranged from 177 ng/g wet weight in eggs to 2,750 ng/g wet weight in adult fat. Total toxic equivalents (TEQs) derived from polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) ranged from 17.2 to 297 pg/g wet weight in the same tissues, while the inclusion of TEQs from PCBs increased these values to 48.4 and 769 pg/g wet weight, respectively. While contaminant concentrations varied between species and tissues, the contaminant profile was relatively uniform. The profile of contaminants detected was unusual in that much of the TEQs was contributed by two pentachlorinated congeners (2,3,4,7,8-pentachlorinated dibenzofuran and 1,2,3,7,8-pentachlorinated dibenzo-p-dioxin), and the profiles of PCB congeners did not match known sources. When compared to other studies the concentrations detected in the Midway Atoll samples were near or above the thresholds known to cause adverse effects in other fish-eating bird species.
The extraction of fifteen polymer additives which are used as antioxidants, uv stabilizers, process lubes, flame retardants,
and antistats from eight formulations of polystyrene is demonstrated with supercritical carbon dioxide and compared to traditional
dissolution/precipitation extractions. The purpose of the study was two fold: 1) the development of a high performance liquid
chromatography method(s) for the additives and 2) the determination of the viability of supercritical fluids for extraction
of the additives from polystyrene. Nine of the additives were assayed via reversed phase liquid chromatography while, the
remaining six additives could not be assayed in this manner. In order to develop an extraction method for the additives, the
effects of static extraction time, CO2 density, and temperature were first investigated. These preliminary extractions revealed that a static period which afforded
an opportunity for the polymer to swell combined with a high CO2 density and temperature above the polymer glass transition yielded quantitative recoveries of the additives. Triplicate extractions
of the various polystyrene formulations matched additive recoveries obtained by the traditional dissolution/precipitation
method but the former method was faster and used less organic solvent.
Methyl sulfone (MeSO2-) and hydroxylated (OH-) metabolites of polychlorinated biphenyls (PCBs) have emerged as important classes of environmental
contaminants in wildlife and humans. The detection of persistent MeSO2-PCBs was first shown in tissues of Baltic grey seal in the mid-1970s. In the last decade the detection and quantification
of these metabolites in biota has gained momentum. MeSO2-PCBs are one of the major classes of organochlorine contaminants in humans and several marine and a few terrestrial mammal
species. A number of studies have demonstrated the toxicological potential of MeSO2-PCBs including tissue selective retention via non-covalent protein binding, induction of cytochrome P450 enzymes, and endocrine-related
effects. More recently OH-PCBs have gained greater scientific notoriety in environmental toxicology as a consequence of the
capability of certain OH-PCB congeners to bind with the thyroxine transport protein, transthyretin, and their interaction
with thyroid and estrogen hormone receptors. Research on environmentally persistent MeSO2-PCBs and OH-PCB metabolites reported in the last two decades is presented, discussed and summarized. Topics include the relative
importance and mechanisms of biochemical formation in the context of PCB biotransformation, physico-chemical properties, and
chemical synthesis, nomenclature and analysis. The chemical analysis summary encompasses tissue extraction, compound separation
and methods of detection. MeSO2-PCB and OH-PCB toxicokinetics are addressed such as species- and congener-specific formation and clearance, persistence in
biota and tissue specific retention. The known biological and toxicological activities of these PCB metabolites are also summarized.
Levels and trends of persistent organic pollutants and trace elements in seabirds breeding in the vast Canadian Arctic have been monitored since 1975. Data from this monitoring have indicated both spatial and temporal variation across the region, attributable in part to differences in species' diets, differences in regional deposition patterns, and unidirectional trends in contaminants reaching this area from emissions in temperate and tropical areas to the south. Seabird tissues have served as effective biomonitors to examine this variation, and national and international collaboration in this monitoring effort has promoted valuable synthetic assessments of spatial and temporal patterns in Arctic contaminants. Here we review the history of the monitoring program, the critical role played by Environment Canada's National Wildlife Specimen Bank, and we summarize important spatial and temporal trends in various contaminants in Canadian Arctic seabirds.
In this paper, a novel technique has been developed for the determination of benzophenone-3 and its metabolites in urine using solid-phase microextraction (SPME) combined with gas chromatography–quadrupole ion trap mass spectrometry (GC–MS). Benzophenone-3 is a common ingredient found in sunscreens and other products. Because benzophenone-3 and other sunscreening compounds may be absorbed into the body, methods for monitoring the accumulation, metabolism, and excretion of these compounds need to be developed. Three kinds of SPME fibers were used and compared for this study. Parameters for the detection were examined in an aqueous medium and are listed as follows: equilibrium time, multiple extractions from the same vial vs. different vials, the maximum desorption temperature and time, and the effects of both salt and solvent on the extraction efficiency. Human urine samples were then spiked with standard benzophenone solutions and analyzed with the SPME method to determine linear range, limit of detection, and precision. Linear range determinations fell within 10–1000 ng/ml with precisions averaging 7% RSD. Ultimately a urine specimen taken after a human subject had applied a commercially available sunscreen product was tested for benzophenone and its metabolites. Benzophenone-3 and 2,4-dihydroxybenzophenone were detected and the former was subjected to both SPME and SPE quantitation methods with comparable results of 260 and 200 ng/ml, respectively.
Concentrations of PCDD/Fs, PCBs and PBDEs were measured in 56 egg samples collected from waterbirds of different species (Great Egret, Little Egret, Night Heron and Chinese Pond Heron) from different regions of Hong Kong (Ho Sheung Heung, Mai Po Village and Mai Po Lung Village) during 2000 and 2006. Dominance of 2,3,4,7,8-PeCDF indicates a signature associated with commercial usage of PCBs. Although no significant variations were observed within- and between-site in the levels of PCDD/Fs, coplanar PCBs and PBDEs, the concentrations of coplanar PCBs were much higher than PCDD/Fs. Similarity in composition profiles of PCDD/F and coplanar PCBs from different egretries is possibly associated with non-point sources of these contaminants to Hong Kong. Predominant accumulation of BDE-47, BDE-99 and BDE-100 suggested the penta-BDE technical mixtures usage in Hong Kong and its vicinity. Toxic equivalency and Monte Carlo simulation technique showed potential risks on waterbirds due to their exposure to PCDD/Fs.
A new sensitive method has been successfully developed and validated for the simultaneous determination and quantification of nine estrogenic UV filters (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-4, 4,4-dihydroxybenzophenone, ethyl-4-aminobenzoate, 2-ethyl-hexyl-4-trimethoxycinnamate, 3-(4-methylbenzylidene)-camphor, 3-benzylidene-camphor) in different environmental matrices. After optimisation of extraction conditions for the best recovery of polar to lipophilic compounds from fish tissue and a subsequent lipid clean-up in HPLC, fish extraction recoveries exceeded 72% for all nine UV filters. Identification and quantification of compounds was performed for lipophilic UV filters with gas chromatography-electroionisation-mass spectrometry and for polar and mid-polar compounds with liquid chromatography coupled to electrospray ionisation mass spectrometry. Instrumental detection limits (IDL) varied between 5 and 260 pg injected and method detection limits (MDL) were in the low ng/g lipids range for all test compounds. The described analytical methods are shown to be useful to screen for estrogenic UV filters in environmental samples such as fish and polar organic chemical integrative samplers.
Sun-blocking agents including eight UV filters (UVF) and 10 UV light stabilizers (UVLS) were measured in water and sediment collected from 22 rivers, four sewage treatment plant effluents (STPE) and three lakes in Japan. Total sun blocking agents levels ranged from N.D. to 4928 ng/L and from 2.0 to 3422 μg/kg dry wt in surface water and in sediment, respectively. Benzyl salicylate, benzophenone-3, 2-ethyl hexyl-4-methoxycinnamte (EHMC) and octyl salicylate were dominant in surface water receiving wastewater effluents and STPE, although UV-328, benzophenone and EHMC were dominant in other surface water except background sites. Three UVF and nine UVLS were observed from all sediment and their compositions showed similar patterns with UV-328 and UV-234 as the most prevalent compounds. Homosalate, octocrylene, UV-326, UV-327, UV-328 and UV-234 were significantly correlated with Galaxolide® in sediments. Concentrations of UV-327 and UV-328 also had strong correlation between those of UV-326 in sediment.