Fragrances and PAHs in snow and seawater of Ny-Ålesund (Svalbard): Local and long-range contamination☆
Graphical abstract
Introduction
The Arctic environment is susceptible to increasing anthropogenic pressures (Barbante et al., 2017; Kallenborn et al., 2017) and the Svalbard Archipelago is a specifically vulnerable area of this region (Kozak et al., 2013): pollution may derive from long-range atmospheric transport (LRAT), mainly from Europe and Asia (Hermanson et al., 2010; Spolaor et al., 2017), characterized by particular episodes of Arctic haze with high levels of gaseous air pollutants (Stohl et al., 2007). Local sources include coal mines (Abramova et al., 2016; Kim et al., 2011), tourist shipping (Kozak et al., 2013) and local human settlements (Kallenborn et al., 2017). Also research stations may constitute sources of contamination in polar environments (Cabrerizo et al., 2016; Vecchiato et al., 2015a, 2015b). Comparing with other organic pollutants, little information is available about the presence of Personal Care Products (PCPs) in the Arctic region (Kallenborn et al., 2017), while the fate of next-generation contaminants was identified as a priority scientific question for the Antarctic ecosystem (Kennicutt et al., 2014). In the anthropized areas of the Arctic, pharmaceutical and PCP residues were reported in nearly all environmental compartments, being released mainly in the aquatic environment due to the lack of wastewater treatments (WWTPs), even in large settlements (Gunnarsdóttir et al., 2013; Kallenborn et al., 2017). Moreover low temperatures, low microbiological degradation and the light conditions strongly influence the transformation of PCPs in the polar environments (Kallenborn et al., 2017).
Amongst PCPs, long-lasting and stable Fragrance Materials (FMs) were recently detected in the coastal surface seawater of Terra Nova Bay in the Ross Sea, Antarctica (Vecchiato et al., 2017). The selected FMs were found in the treated discharges of the Italian research Mario Zucchelli Station (MZS), however in a nearby more undisturbed area, the seawater concentrations increased up to 100 ng L−1 during the seasonal melt of the sea ice and of its snow cover. The release throughout the melting of snow particle-bound contaminants was hypothesized, involving a contribution from atmospheric (long or short-range) transport of FMs. 17 semi-volatile fragrances were originally selected because of their stability. Few previous studies reported the occurrence of these compounds in the environment: FMs were found as pollutants in the Venice Lagoon, where sewages largely emit these contaminants into the surface seawater (Vecchiato et al., 2016). These compounds were also detected in open sea areas of the Mediterranean, highlighting the role of mesoscale hydrodynamics and LRAT as key factors (Vecchiato et al., 2018).
The common characteristics of 17 FMs are a long persistence as fragrances (ranging from a few weeks to months) and a chemical stability allowing their application in very different and aggressive commercial products, such as liquid bleach and acid cleaners (eindex.givaudan.com). Such features suggest their possible persistence in the environment (Vecchiato et al., 2016). In the works mentioned above Salicylate compounds generally resulted the most environmentally abundant and widely distributed FMs. The worldwide consumption of Benzyl, Hexyl and Amyl Salicylates has rapidly grown during the last years, making them High Production Volume (HPV) chemicals (>5000 tons/year), mainly because of their low production prices (under $5/kg) (Belsito et al., 2007; Gaudin, 2014). Benzyl Salicylate is included in the EU list of allergenic fragrances (Heisterberg et al., 2011) and is also employed as a UV-filter (Kameda et al., 2011). This compound was detected in U.S., European and Japanese wastewater treatment plants (WWTPs) (Godayol et al., 2015; Kameda et al., 2011; Negreira et al., 2010; Simonich et al., 2002, 2000), in river waters (Kameda et al., 2011; Negreira et al., 2010; Vila et al., 2016) and was also found in indoor air (Lamas et al., 2010), due to its large use as a fragrance. Moreover, Benzyl Salicylate shows an oestrogenic activity comparable to bisphenol A (BPA) (Zhang et al., 2012) and it gives oestrogenic responses in human breast cancer cells (Charles and Darbre, 2009).
The information gathered on the environmental occurrence of FMs in Antarctica leads to a series of open questions concerning their distribution in polar environments:
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previous works analyzed fragrances only in seawater, however their evolution in Antarctica seemed to be linked to inputs from snow. Are FMs more associated to seawater and possibly to sewage discharges, or to snow, therefore needing an atmospheric transport?
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Which is the role of the scientific stations as sources of PCPs in polar areas?
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Consequently, are FMs deriving from short or from long-range transport?
To answer these questions and to expand the study to the Arctic we focused on the area of Ny-Ålesund, Svalbard, sampling seawater and snow at increasing distances from the village. Ny-Ålesund is one of the northernmost permanent settlement and is situated in the northwestern part of Spitsbergen, Svalbard. This research facility was previously a coal-mining town and faces the open fjord of Kongsfjorden (20 km long and 4–10 km wide) (Kim et al., 2011; Pouch et al., 2017; Spolaor et al., 2017). Due to the remoteness of the archipelago, different organic compounds were analyzed in the Svalbard snow to study the atmospheric transport of both natural tracers (Barbaro et al., 2017; Scalabrin et al., 2012; Turetta et al., 2016) and anthropogenic pollutants (Garmash et al., 2013; Hermanson et al., 2010; Zangrando et al., 2013).
In order to enhance the interpretation of the processes and sources of the fragrances, the analyses of FMs were coupled to the determinations of a class well-known tracers, as Polycyclic Aromatic Hydrocarbons (PAHs). Several studies determined PAHs in different compartments of the Svalbard environment, such as aerosol (Cecinato et al., 2000), snow (Abramova et al., 2016; Kozioł et al., 2017; Vehviläinen et al., 2002), rainfall (Krawczyk and Skręt, 2005), surface water (Kosek et al., 2018; Polkowska et al., 2011), soil (Marquès et al., 2017), sediment (Jiao et al., 2009; Kim et al., 2011; Pouch et al., 2017) and biota (Szczybelski et al., 2016). PAHs were found to derive mainly from local combustions (Cecinato et al., 2000), long-range transport (Kosek et al., 2018; Vehviläinen et al., 2002) or from a combination of both processes (Abramova et al., 2016; Jiao et al., 2009; Kozioł et al., 2017; Polkowska et al., 2011). Also the presence of (previously) operating coal mines represents a source of PAHs (Jiao et al., 2009; Kim et al., 2011; Pouch et al., 2017). Recently cold-adapted PAH-degrading bacterial strains were isolated in the Kongsfjorden and in the Ny-Ålesund harbor (Crisafi et al., 2016). Air concentrations of PAHs and persistent organic pollutants (POPs) are weekly monitored at the Zeppelin mountain station (ebas.nilu.no).
Less information is available about PCPs and emerging pollutants in Svalbard: the presence of bisphenol S and surfactants was detected in the sediments of Kongsfjorden (Nejumal et al., 2018) and a possible contribution from the Ny-Ålesund settlement was hypothesized for the accumulation of volatile siloxanes in marine biota (Warner et al., 2010). The long-range transport of polyfluoroalkyl substances (PFASs) was monitored at the Zeppelin station (Wong et al., 2018), while deposition fluxes dominated the air-sea gas exchange of the polycyclic musk fragrances Galaxolide (HHCB) and Tonalide (AHTN) (Xie et al., 2007). A general overview reviewing the distribution of pharmaceuticals and PCPs in the Arctic was recently published (Kallenborn et al., 2017).
The aim of this study was to investigate the local and long-range pollution of FMs and PAHs in the Arctic environment, identifying the major transport patterns, in order to achieve a proper management and protection of the polar ecosystems.
Section snippets
Materials and methods
Surface seawater and snow samples were collected in April 2017 (Table SI1) in solvent-rinsed glass bottles at the sites shown in Fig. 1. Samplings were performed before the seasonal melting of the snow, in order to describe in detail the spatial distribution of the analytes in the surface snow and to assay their occurrence in seawater independently from possible inputs from snowmelt. Seawater was collected from the shore at the sites W1 and W2 and the samplings were repeated after 1 and 2
Fragrances in seawater and snow
Fragrances were detected at different levels in the samples, with the sum of the concentrations resulting below 5.8 ng L−1 in the seawater and up to 72 ng L−1 in the surface snow (Fig. 2). Those FMs resulting below method detection limits (MDL) in any sample (Amberketal, Dupical, Isobutavan, Lemonile, Mefranal, Myraldene, Okoumal, Pelargene, Tridecene-2-Nitrile, Ultravanil) were excluded from the following discussion.
Focusing on seawater, the occurrence of FMs resulted rather occasional and
Conclusions
The results show that contamination of the Arctic environment with fragrances occurs through both local and long-range pollution. Confirming previous findings, scientific stations may constitute a source of FMs to the nearby area and the snow would probably constitute the decisive key for their deposition: the relatively low levels of FMs in seawater of the Kongsfjorden, sampled before the seasonal melting, are similar to those found in Antarctica in comparable conditions (Vecchiato et al., 2017
Acknowledgments
The authors gratefully acknowledge Francesco Calore for his help during analyses. Marion Maturilli (Meteorological Observatory of the AWIPEV research base) kindly provided us the wind data from Ny-Ålesund. Givaudan and the International Express Service (IES-Ingredients) provided the commercial standards of FMs free of charge. Elga Lab water, High Wycombe UK, supplied the pure water system used in this study.
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This paper has been recommended for acceptance by Klaus Kummerer.