Distribution of fragrances and PAHs in the surface seawater of the Sicily Channel, Central Mediterranean
Graphical abstract
Introduction
The Mediterranean Sea is a semi-enclosed basin surrounded by highly populated regions (Berrojalbiz et al., 2011). Anthropic pressures largely influence the environment, deriving from industrialization, urbanization and agriculture, as well as fishing, maritime traffic, harbor activities and tourism (Castro-Jiménez et al., 2012; Er-Raioui et al., 2009). The rapid increase of the demographic pressure and of the economic evolution leads to a large number of organic pollutant sources constituting a threat to the environment and biodiversity of the area (Castro-Jiménez et al., 2012). The Mediterranean Sea is therefore a region of special interest to study the factors controlling distribution, transport and fate of pollutants in marine waters (Berrojalbiz et al., 2011). However there are major knowledge gaps, since, in comparison to offshore waters, most studies focus on sediments and on local coastal areas influenced by proximity to inputs and runoff from land-based sources (Berrojalbiz et al., 2011; Giuliani et al., 2015). In the open sea other key factors, such as atmospheric transport and deposition, become important drivers as significant diffuse sources (Tsapakis et al., 2006).
Among organic pollutants, very little is known about the presence of Personal Care Products (PCPs) in the Mediterranean: few studies report the presence of PCPs in surface waters, Wastewater Treatment Plants (WWTPs), sediments and organisms (Arpin-Pont et al., 2016) and this information is limited to coastal marine environments. Fragrance Materials (FMs) are widespread used ingredients of PCPs and previously synthetic musks represent a category of contaminants whose environmental fate was mainly investigated by the literature (Daughton and Ternes, 1999). However, little is known about other different FMs and this study is focused on 17 long-lasting and stable fragrances that are commercially available (Vecchiato et al., 2016). The trade names (Givaudan®) of the selected FMs are: Amberketal, Ambrofix, Amyl Salicylate, Benzyl Salicylate, Bourgeonal, Dupical, Hexyl Salicylate, Isobutavan, Lemonile, Mefranal, Myraldene, Okoumal, Oranger Crystals, Pelargene, Peonile, Tridecene-2-Nitrile, Ultravanil (Table SI1). The common features of these FMs are a long persistence as fragrances (tenacity on blotter) and a chemical stability that allows their application in very different commercial products (eindex.givaudan.com). Such characteristics are possible indications of their persistence in the environment. The selected FMs were recently found as contaminants in the Venice Lagoon, where sewage outlets largely emit these compounds into the surface seawater, with concentrations up to 10 μg L−1 in the innermost urban canals (Vecchiato et al., 2016). Traces were found also in the coastal surface seawater of Terra Nova Bay, Antarctica, where emissions from the nearby research station, as well as a contribution from atmospheric transport were hypothesized (Vecchiato et al., 2017). Among the 17 fragrances, Benzyl, Hexyl and Amyl Salicylates were investigated by a limited literature: because of their low prices (under $5/kg), these FMs are High Production Volume (HPV) chemicals with a worldwide annual consumption well over 5000 tons (Belsito et al., 2007; Gaudin, 2014). Benzyl Salicylate is also an allergenic UV-filter agent (Heisterberg et al., 2011; Kameda et al., 2011), with an oestrogenic activity comparable to bisphenol A (BPA) (Zhang et al., 2012) and giving oestrogenic responses in human breast cancer cells (Charles and Darbre, 2009). Benzyl and Hexyl Salicylates were detected in different WWTPs (Godayol et al., 2015; Kameda et al., 2011; Negreira et al., 2010; Simonich et al., 2000, Simonich et al., 2002), while fewer data are reported about Benzyl Salicylate in river waters (Kameda et al., 2011; Negreira et al., 2010; Vila et al., 2016).
More studies are available regarding Polycyclic Aromatic Hydrocarbons (PAHs) in the Mediterranean: the distribution of these compounds (deriving from incomplete combustions, direct dispersions of oil products and biogenic natural sources) was mainly investigated in coastal environments, while less studies considered the open sea areas (Berrojalbiz et al., 2011; Castro-Jiménez et al., 2012). The available information shows that the occurrence of PAHs in offshore waters is dependent from atmospheric transport and deposition, particle and plankton settling processes in the water column and the presence of mesoscale variability associated with gyres (Berrojalbiz et al., 2011; Castro-Jiménez et al., 2012; Parinos and Gogou, 2016).
The aim of this work is to study the distribution of fragrances and PAHs in the surface seawater of the Mediterranean: the coupling of a new class of pollutants with well-known tracers, as PAHs, could help the interpretation of the processes governing their environmental presence. In particular, the detection of the selected FMs in open sea areas far from direct sources would highlight the role of the long-range atmospheric or oceanic transport, involving the possible environmental persistence of these contaminants. The study area is located in the Sicily Channel, which is the central connection between the Eastern and Western Mediterranean and the samplings were aimed to distinguish contamination in offshore and coastal areas. To the best of our knowledge this is the first survey investigating PCPs in offshore Mediterranean surface seawater and the first study focused on PAHs in the Sicily Channel, where only previous scarce data were available.
Section snippets
Materials and methods
Seawater was sampled in July 2016 during the oceanographic cruise BANSIC 2016 (CNR R/V “Minerva Uno”) at the sites shown in Fig. 1 (Table SI2). Surface samples (0–1 m) were collected using a Niskin rosette, transferred in solvent-rinsed glass bottles and refrigerated at 4 °C until extraction, which was performed within 12 h from sampling.
In the Sicily Channel the surface Atlantic Water (AW) is advected by the Atlantic Ionian Stream (AIS) and the Atlantic Tunisian Current (ATC) (Fig. 1). In summer
Fragrances
Fragrances were detected in 27 out of 42 samples of surface seawater of the Sicily Channel, with the sum of the concentrations up to 112 ng L−1 (Table SI4). Focusing on the western transect towards Pantelleria Island, the coastal samples resulted with lower levels of FMs in comparison to offshore waters, where concentrations relatively peaked in the sample 772 (64 ng L−1; Fig. 2a) and in the near samples 605 and 939, resulting respectively 27 and 26 ng L−1. A similar pattern marks also the coastal
Conclusions
This study represents the first detection of the selected FMs in open sea environment. The distance from direct sources evidences the previously hypothesized persistence of these contaminants (Vecchiato et al., 2016, Vecchiato et al., 2017) involving processes of long-range transport. Both atmospheric and marine phenomena probably constitute key factors: on one hand the spatial distribution of the FMs, together with PAHs, can be explained considering the presence of hydrodynamic currents, as
Acknowledgments
This work was supported by the Italian Ministry for Education, University and Research's RITMARE flagship project. The authors gratefully acknowledge all the researchers, the crew of the r/v “Minerva 1” and his Captain Emanuele Gentile (Oceanographic Cruise BANSIC-2016). We also wish to thank Sara Padoan, Francesco Calore and Andrea Bertin from the chemical laboratory of S.E.S.A. SpA, who gave an invaluable technical support. Givaudan and the International Express Service (IES-Ingredients)
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