The purpose of this article is to summarize biological monitoring information on UV-absorbing compounds, commonly referred as organic UV filters or sunscreen agents, in aquatic ecosystems. To date a limited range of species (macroinvertebrates, fish, and birds), habitats (lakes, rivers, and sea), and compounds (benzophenones and camphors) have been investigated. As a consequence there is not enough data enabling reliable understanding of the global distribution and effect of UV filters on ecosystems. Both liquid chromatography and gas chromatography coupled with mass spectrometry-based methods have been developed and applied to the trace analysis of these pollutants in biota, enabling the required selectivity and sensitivity. As expected, the most lipophilic compounds occur most frequently with concentrations up to 7112 ng g−1 lipids in mussels and 3100 ng g−1 lipids (homosalate) in fish. High concentrations have also been reported for 4-methylbenzilidenecamphor (up to 1800 ng g−1 lipids) and octocrylene (2400 ng g−1 lipids). Many fewer studies have evaluated the potential bioaccumulation and biomagnification of these compounds in both fresh and marine water and terrestrial food webs. Estimated biomagnification factors suggest biomagnification in predator–prey pairs, for example bird–fish and fish–invertebrates. Ecotoxicological data and preliminary environmental assessment of the risk of UV filters are also included and discussed.
In this study the bioaccumulation kinetics of organic UV filters, such as 4-MBC, BP-3, BP-4, OC and OD-PABA in wild mussels was investigated. The uptake and accumulation of waterborne 4-MBC, BP-4 and OC was very rapid, and after only 24 h of exposure to 1 μg L , the tissular concentrations were 418, 263 and 327 μg kg d.w., respectively. The kinetics of bioaccumulation of BP-4 and OC significantly fitted to an asymptotic model with BCF values of 905 L kg and 2210 L kg , respectively. Measured bioaccumulation of the hydrophilic chemical BP-4 was much higher than predicted by K -based bioconcentration models, which would lead to a marked underestimation of actual risk. On the other hand, the patterns of uptake found for BP-3 and OD-PABA suggest biotransformation ability of mussels for these two chemicals.
This study examined the relationship between molecular properties and the fate of trace organic contaminants (TrOCs) in the aqueous and solid phases during wastewater treatment by MBR. A set of 29 TrOCs was selected to represent pharmaceuticals, steroid hormones, phytoestrogens, UV-filters and pesticides that occur ubiquitously in municipal wastewater. Both adsorption and biodegradation/transformation were found responsible for the removal of TrOCs by MBR treatment. A connection between biodegradation and molecular structure could be observed while adsorption was the dominant removal mechanism for the hydrophobic (log > 3.2) compounds. Highly hydrophobic (log > 3.2) but readily biodegradable compounds did not accumulate in sludge. In contrast, recalcitrant compounds with a moderate hydrophobicity, such as carbamazepine, accumulated significantly in the solid phase. The results provide a framework to predict the removal and fate of TrOCs by MBR treatment.
Minerals such as titanium dioxide, TiO2, and zinc oxide, ZnO, are well known active semiconductor photocatalysts used extensively in heterogeneous photocatalysis to destroy environmental pollutants that are organic in nature, They are also extensively used in sunscreen lotions as active broadband sunscreens that screen both UVB (290-320 nm) and UVA (320-400 nm) sunlight radiation and as high SPF makers. When so photoactivated by UV light, however, these two particular metal oxides are known to generate highly oxidizing radicals (-OH and O-2(-.)) and other reactive oxygen species (ROS) such as H2O2 and singlet oxygen, O-1(2), which are known to be cytotoxic and/or genotoxic. Hydroxyl ((OH)-O-.) radicals photogenerated from photoactive TiO2 specimens extracted from commercial sunscreen lotions [R. Dunford, A. Salinaro, L. Cai, N. Serpone, S. Horikoshi, H. Hidaka, J. Knowland, FEBS Lett. 418 (1997) 87] induce damage to DNA plasmids in vitro and to whole human skin cells in cultures. Accordingly, the titanium dioxide particle surface was modified to produce TiO2 specimens of considerably reduced photoactivity. Deactivation of TiO2 diminishes considerably, in some cases completely suppresses damage caused to DNA plasmids, to human cells, and to yeast cells compared to non-modified specimens exposed to UVB/ UVA simulated solar radiation. The photostabilities of sunscreen organic active agents in neat polar and apolar solvents and in actual commercial formulations have been examined [N. Serpone, A. Salinaro, A.V. Emeline, S. Horikoshi, H. Hidaka, J. Zhao, Photochem. Photobiol. Sci. 1 (2002) 9701. With rare exceptions, the active ingredients undergo photochemical changes (in some cases form free radicals) and the sunscreen lotions lose considerable Sun protection efficacy only after a relatively short time when exposed to simulated sunlight UVB/UVA radiation, confirming the recent findings by Sayre et al. [R.M. Sayre, J.C. Dowdy, A.J. Gerwig, W.J. Shields, RN. Lloyd, Photochem. Photobiol. 81 (2005) 4521. (c) 2006 Elsevier B.V. All rights reserved.
Recognition of the harmful effects of ultraviolet (UV) radiation on the skin has triggered development of organic chemicals (commonly referred as UV filters) that can absorb UV radiation and attenuate the negative effects of sunlight exposure. Depending on the properties and the intended degree of protection, a wide array of combinations is being marketed as delivering protection against most kinds of UV-induced skin damage. However, some UV filters have dermatological implications, so maximum applicable concentrations have been established. To monitor to what extent commercial products comply with the mandatory limits, several analytical methods have been used for their determination in cosmetics and related products. Further research on the efficacy of UV filters applied on the skin surface has brought to light a gradual attenuation of their UV-protective capacity that cannot solely be attributed to photo-induced decomposition. Investigations carried out to elucidate the reasons underlying this behaviour concluded that UV filters may be systematically absorbed through the skin surface or even released during bathing and washing activities. These observations gave rise to numerous studies aiming to investigate the magnitude and effects of skin penetration as well as accumulation in the water environment. Because of the need for more in-depth investigation into the behavior of UV filters, the initial demand for product certification has been extended to include reliable analytical methods to determine these substances at low concentration levels and in complex matrices (e.g., biological and environmental samples). Until now, most of the available methods, although designed to cover a large variety of substances, quantify them at only high-mg/L levels; however, recently, researchers have paid special attention to developing more sensitive procedures able to determine these substances in biological tissues and fluids or environmental samples at ng/L levels without matrix interferences. This article gives a comprehensive outline of the accumulated knowledge on UV-filter determination in biological and environmental samples and encourages further research in this new, challenging field of analytical, health and environmental science.
► Lichen extracts and compounds are evaluated for their photoprotective activities. ► extract and gyrophoric acid are valuable UV filters candidates. ► Salazinic acid presents characteristics of a UVA booster. Three lichen extracts and ten lichenic compounds have been screened for their photoprotective activities. The determination of their Sun Protection Factor (SPF) and Protection Factor-UVA (PF-UVA) values was done . Among them, a extract and gyrophoric acid exhibited SPF values over 5, which is better than Homosalate (SPF ≈ 4). Their photoprotective properties are only slightly modified after a 2-hours period of irradiation. Salazinic acid and presented characteristics of a UVA booster like the butyl-methoxydibenzoylmethane (Avobenzone) (PF-UVA ≈ 2 vs. 2.8 for Avobenzone). Salazinic acid was a better anion superoxide scavenger than ascorbic acid and none of them exhibited a photosensitizing cytotoxicity by exposing them on HaCaT cells to UVA radiations (photo-irritancy factor PIF < 5).
An environmental friendly and fully automated method using in-syringe magnetic stirring assisted dispersive liquid–liquid microextraction coupled with high-performance liquid chromatography has been developed for the determination of UV filters in environmental water samples. The main “green” features on this method are the use of an ionic liquid as extracting solvent, avoiding the use of chlorinated solvents, and the on-line microextraction, preconcentration, separation and detection minimizing the use of reagents and so the waste generation. After sample treatment, 20 µL of the organic droplet was injected onto the HPLC-UV system. Various parameters affecting the extraction efficiency were studied using multivariate optimization approach, including the quantity of extraction and dispersive solvents, extraction and sedimentation time, ionic strength and pH. Under optimized conditions, limits of detection were within the range of 0.08–12 µg/L, for 3.5 mL sample volume. Linearity ranges were up to 500 µg/L for the UV-filters studied. Furthermore, enrichment factors ranging from 11 to 23 folds were obtained. Intra- and inter-assay precisions were 6% and 8%, respectively. Finally, the proposed method was successfully applied to determine UV filters in surface seawater and swimming pool samples attaining satisfactory recoveries over the range of 89–114% and 86–107%, respectively.
UV absorbing compounds are of emerging concern due to their large production volumes, their persistence or pseudo-persistence, and their potential adverse effects. This is the first study investigating the environmental occurrence and potential hazard of organic UV stabilizers and UV filters in the North and Baltic Sea surface sediments, including the connecting Skagerrak and Kattegat straits. In total, nineteen substances were identified over the entire study area, including the rarely studied compounds ethylhexyl triazone (EHT) and bisoctrizole (UV-360). Octocrylene (OC) was the predominant compound in this study with regard to detection frequency (79%) and concentrations (up to 9.7 ng/g dw). OC accounted for more than 65% of UV stabilizer contamination in the German Bight. The triazine derivative EHT was quantified in the Rhine-Meuse-Delta and the German Bight in concentrations up to 2.0 ng/g dw. In the Baltic Sea, benzotriazole UV stabilizers accounted for 60% of the contamination, with UV-360 as the main substance. The estimated environmental hazard quotients indicated a negligible impact on benthic and sediment-dwelling organisms in the North and Baltic Seas. Region-specific contamination pattern and riverine influences were revealed. The results suggest that both direct and indirect sources contribute to the UV stabilizer and UV filter contamination in the study area.
A Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) methodology followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis was developed to extract thirteen synthetic musk compounds (SMCs: cashmeran, celestolide, phantolide, traseolide, galaxolide, tonalide, musk ambrette, musk xylene, musk ketone, musk tibetene, musk moskene, ethylene brassylate and exaltolide) and six ultraviolet-filters (UVFs: 2-ethylhexyl 4-dimethylaminobenzoate, 3-(4′-methylbenzylidene) camphor, 2-ethylhexyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, benzophenone and drometrizole trisiloxane) from tomatoes. The proposed methodology was optimized: 2 g of freeze-dried tomato was extracted with 4 mL of water and 10 mL of ethyl acetate, adding 6 g of MgSO and 1.5 g of NaCl, then a dispersive solid-phase extraction was performed using 3 g of MgSO , 300 mg of primary-secondary amino adsorbent (PSA) and 300 mg of octadecyl-silica (C18). Validation delivered recoveries between 81 (celestolide) and 119% (musk tibetene), with relative standard deviations <10%. The instrumental limit of detection varied from 0.02 (2-ethylhexyl 4-methoxycinnamate) to 3.00 pg (exaltolide and musk xylene). Regarding the method quantification limits, it ranged between 0.4 (celestolide) and 47.9 ng g dw (exaltolide). The method was applied to different varieties of tomatoes ( ), revealing UVFs and SMCs between 1 and 210 ng g dw. Higher concentrations were found for benzophenone (29–210 ng g dw) and galaxolide (9–53 ng g dw). The risk associated to the ingestion of contaminated tomatoes has also been estimated, showing that a potential health risk is unlikely.