Ecotoxicological evaluation of four UV filters using marine organisms from different trophic levels Isochrysis galbana, Mytilus galloprovincialis, Paracentrotus lividus, and Siriella armata
Introduction
Emerging pollutants are chemical compounds not usually considered of interest in routine environmental analysis but that are becoming of environmental concern because of their increasingly common use and the potential risk to human and ecosystem health, including: pharmaceuticals and personal care products, endocrine disruptors, nanoparticles, industrial chemicals, biological metabolites and toxins among these substances (Richardson, 2010, Rosenfeld and Feng, 2011). Due to the increasing concern about the negative effects of extended exposure to sunlight, combinations of several chemicals – what we refer as UV filters – are being introduced not only into sunscreens but also into all kinds of cosmetic formulas (creams, shampoos). UV filters are aromatic compounds such as 4-Methylbenzylidene-camphor (4-MBC), Benzophenone-3 (BP-3), Benzophenone-4 (BP-4) and 2-Ethylhexyl-4-methoxycinnamate (EHMC) which are extensively used in common personal care products because they adsorb UV radiation. Composition of cosmetic products in Europe is regulated by Directive76/768/CEE (EC, 1976), and the maximum content of the above compounds in commercial products is by law 4% 4-MBC, 10% BP-3, 5% BP-4 and 10% EHMC. In USA the composition is regulated by US Food and Drug Administration (US Food 2013) and stipulates slightly different values for the maximum content of UV filters, namely: 6% BP-3, 10% BP-4 and 10% EHMC, the use of 4-MBC is not allowed as a sunscreen component in USA. Some UV filters are also considered chemicals of concern because they have shown estrogenic activity in in vitro laboratory tests on fish and other aquatic organisms (Balmer et al., 2005, Kunz and Fent, 2006, Kunz et al., 2006, Brausch and Rand, 2011).
To be effective, UV filters must be stable on exposure to UV radiation, but several studies have reported degradation by photolysis (Diaz-Cruz et al., 2008, Rodil et al., 2008, Richardson, 2010) and little is known about the toxicity of the degradation products. UV filters enter the marine environment from discharges of lakes and rivers (Balmer et al., 2005), from sewage sludge and from direct washing in recreational locations and beaches (Plagellat et al., 2006, Rodil et al., 2008, Fent et al., 2009). Their use is so widespread that they are commonly detected in wastewaters, swimming-pool waters, rivers, lakes and the oceanic superficial microlayer. However most information about the detection, concentration and effects on living organisms comes mainly from rivers and lakes where their high environmental concentration is increasingly worrying (Balmer et al., 2005, Buser et al., 2006, Fent et al., 2010). In contrast, data available from marine/coastal ecosystems are very scarce (Langford and Thomas, 2008, Rodil et al., 2012).
The aim of this study is to assess the behaviour in seawater and the toxicity to marine organisms of four of the most commonly used UV filters, 4-MBC, BP-3, BP-4 and EHMC. For the toxicity assessment four representative test organisms from three different trophic levels were used. These experiments provide a preliminary assessment of potential ecological risk of UV filters in coastal ecosystems, by following risk characterization procedures based on both the presence of these compounds in the marine environment and the inherent toxicity of these chemicals tested in laboratory bioassays. In our knowledge, this is the first risk assessment study of UV filters conducted in the marine environment.
Section snippets
Biological material and toxicity tests
All biological materials were provided by ECIMAT (Toralla Marine Station, University of Vigo), either cultured in the Marine Station or collected from the most oceanic part of Ria de Vigo (Galicia, NW Iberian Peninsula), and conditioned in running seawater facilities.
A non-axenic culture of Isochrysis galbana provided by ECIMAT was grown in a 10-fold diluted EDTA-free f/2 medium, and kept in an incubator at 20 °C with 24 h light cycle (salinity 34 ppt, ⩾8 mg L−1 dissolved oxygen, pH ∼ 8) until
Stability of the chemicals in solution
Concerning their stability in aqueous solution, the UV filters tested showed different behaviour depending on the substance and the experimental set-up (Table 1). In the testing conditions used for the Paracentotus lividus and M. galloprovincialis bioassays, BP-3 and 4-MBC showed remarkable stability, with an average drop of 23% for BP-3 and 27% for 4-MBC after 48 h. In contrast, EHMC was very instable and its measured concentration showed a 72% reduction after 48 h in solution. In the testing
Discussion
Based on the EC50 values, EHMC and 4-MBC are the most toxic UV filters for marine invertebrates, whereas BP-3 was selectively toxic for the microalgae I. galbana at concentrations as low as ng mL−1 units. Finally BP-4 was found to have the lowest toxicity for all test species. This ranking of toxicity is consistent with previous results on freshwater species, such as the crustacean D. magna (Fent et al., 2009) where EHMC was more toxic than 4-MBC, followed by BP-3 and finally BP-4. These
Acknowledgements
This research was funded by the Galician Government (Xunta de Galicia) through the Research Project Ref. 10MDS700006PR. One of us (E.P.) was granted with a FPU Fellowship from the Spanish Ministry of Education. R.R. and J.B.Q. were granted with Ramón y Cajal research program from the Spanish Ministry of Education. The authors acknowledge T. Tato, N. Trigo and the staff of ECIMAT for their helpful technical support.
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