Perfluorinated compounds: Levels, trophic web enrichments and human dietary intakes in transitional water ecosystems Monia Renzi a,⇑ , Cristiana Guerranti b,c , Andrea Giovani b , Guido Perra b , Silvano E. Focardi b a Department of Biological and Environmental Sciences and Technologies, University of the Salento, SP Lecce-Monteroni, 73100 Lecce, Italy b Department of Physical, Earth and Environmental Sciences, University of Siena, Via Mattioli 4, 53100 Siena, Italy c Institute of Clinical Physiology, National Research Council (CNR), Via Moruzzi, 1, 56100 Pisa, Italy article info Keywords: Perfluorooctane sulfonate (PFOS) Perfluorooctanoic acid (PFOA) Transitional water ecosystems Daily dietary intakes Trophic web enrichments abstract The results of a study on levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), analyzed in terms of HPLC-ESI-MS in water, sediment, macrophyte, bivalve, crustacean and fish samples, are reported here. The aim of the research is to define, for the first time, PFOA/S levels in a heavily human- stressed transitional water ecosystem (Orbetello lagoon, Italy) and evaluate trophic web enrichments and human dietary intakes. The results obtained show that: (i) levels significantly higher than those reported in the literature were found in mussels, clams and crabs; (ii) the river is a significant pollution source; (iii) although absolute levels are relatively low, macroalgae proliferation contributes to redistribute pollutants from river-affected areas throughout the entire lagoon basin; (iv) to the best of our current knowledge, water-filtering species considered in this study are the most exposed to PFOA/S pollution; (v) human daily dietary intakes of PFOA/S through Slow Food-endorsed product consumption are below maximum tolerable levels suggested by the EFSA. Ó 2013 Elsevier Ltd. All rights reserved. 1. Introduction Perfluorinated organic compounds (PFCs) are emergent persis- tent organic pollutants widely used for industrial and commercial applications including adhesives, agrochemicals, fire-fighting retardants, foams propellants, food packaging, lubricants, medi- cines, paints, polishes, refrigerants, and surfactant production (Renner, 2001). In particular, fire-fighting use for accident preven- tion during high-risk military procedures, routine fire-fighting training exercises and airport activities are the main direct sources of pollution of soil, fresh water and groundwater (Moody and Field, 2000), but leaching from discarded food packaging and runoff from discarded painted objects also produce significant indirect emis- sions (Renzi, 2012 and citations therein). These emission sources release significant quantities of PFCs into the aquatic environment. In Europe for the year 2007, PFOS and PFOA discharges along the entire European river network to coastal areas have been estimated to be around 20 and 30 tons/ year, respectively (Pistocchi and Loos, 2009). Although in widespread use for a variety of purposes, these chemicals are hazardous substances which could affect the health of ecosystems and organisms due to their endocrine-disrupting activity, of which relatively little is described in the literature (Richardson and Ternes, 2005; Renzi, 2012 and citations therein). Recently, some studies documented PFCs in wildlife tissues (Kannan et al., 2002; Olivero-Verbel et al., 2006; Perra et al., 2010) and human body fluid samples (Yeung et al., 2006; Guerranti et al., 2013), suggesting a significant wide-ranging diffusion in the environment and a concrete exposure risk for human populations (Midasch et al., 2006). A general lack of knowledge on environmental levels and bio- enrichment dynamics is reported for transitional water ecosystems as well as river effluents or lagoons. This study, carried out in the Orbetello lagoon (Italy), aims to: (i) provide data on PFC levels in a large number of different envi- ronmental and biological matrices; (ii) compare observed levels with values reported in the literature for other aquatic ecosystems both in Europe and worldwide; (iii) evaluate the occurrence of enrichments throughout the lagoon trophic web; (iv) evaluate dai- ly dietary intakes for humans related to the consumption of Slow Food-endorsed products from the lagoon. 2. Materials and methods 2.1. PFC physical–chemical features PFCs are anionic fluorine-containing surfactants soluble in both water and oil and characterized by a half-life of more than two months in water and more than six months in sediments/soils 0025-326X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.marpolbul.2013.09.014 ⇑ Corresponding author. Tel.: +39 0832298604; fax: +39 0832298722. E-mail address: monia.renzi@unisalento.it (M. Renzi). Marine Pollution Bulletin 76 (2013) 146–157 Contents lists available at ScienceDirect Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul