Chemical characterization of organic microcontaminant sources and biological effects in riverine sediments impacted by urban sewage and pulp mill discharges S. Chamorro a , V. Hernández a , V. Matamoros b,⇑ , C. Domínguez b , J. Becerra a , G. Vidal a , B. Piña b , J.M. Bayona b a Environmental Science Centre EULA-Chile, University of Concepción, P.O. Box 160-C, Concepción, Chile b Department of Environmental Chemistry, IDAEA-CSIC, Jordi Girona 18-26, E-08034 Barcelona, Spain highlights " Forty-five organic microcontaminants were identified in seven sediment samples from Biobío River. " A PCA study was conducted. " Domestic wastewater and Kraft pulp mills were the most important factors. " Domestic wastewater impact presents the highest estrogenic and dioxin-like activities. article info Article history: Received 16 May 2012 Received in revised form 21 August 2012 Accepted 27 August 2012 Available online 27 September 2012 Keywords: Biobío River Kraft pulp mill Microcontaminants Terpenes GCxGC ToF-MS abstract The Biobío River basin is highly impacted by a variety of anthropogenic activities such as pulp mills and urban wastewaters subjected to different treatment processes. This work assesses for the first time, the contamination source and biological effects (estrogenic and dioxin-like activities) in the river basin by the determination of 45 organic microcontaminants in seven sediment samples. Pressurized solvent extrac- tion combined with two-dimensional comprehensive gas chromatography coupled to time of flight mass spectrometry was employed for this purpose. The organic microcontaminants identified comprise mon- oterpenes, sesquiterpenes, diterpenes, ionones, lineal alkyl benzenes, polycyclic aromatic hydrocarbons, musk fragrances, sterols and phathalate esters. The presence of pine and eucalyptus pulp mill effluents increased the abundance of resin-derived neutral compounds and monoterpenes respectively. A principal component analysis showed that the Biobío River basin was impacted by domestic wastewater treatment plants (WWTPs), pine or eucalyptus Kraft pulp mills and pyrolytic and pyrogenic processes. Finally, the recombinant yeast assays showed that the presence of estrogenic and dioxin-like activity was mostly located in sediments impacted by domestic WWTP effluents. Ó 2012 Elsevier Ltd. All rights reserved. 1. Introduction Urban and industrial wastewater effluents subjected to differ- ent type of treatment processes are commonly discharged into riv- ers or lakes from inland cities (Laws, 2000). These waters contain a large variety of organic microcontaminants at trace or ultra-trace concentration levels (ng L À1 up to lgL À1 )(Hollender et al., 2008). Nevertheless, concern about the adverse effects related to the occurrence of some of these microcontaminants on the aquatic ecosystems has not arisen until the last decade (Schwarzenbach et al., 2006). For example, terpenoids, phytosterols and related compounds have been identified as a potential source of endocrine disruption effects caused by pulp and paper mill effluents (Hewitt et al., 2006; Orrego et al., 2009; Chamorro et al., 2010, 2013). On the other hand, estrogenic effects have also been identified in domestic wastewater treatment plant (WWTP) effluents due to the presence of steroid hormones and non-ionic surfactant degra- dation intermediates (Purdom et al., 1994; Tilton et al., 2002; Campbell et al., 2006; Silva et al., 2012). Little attention has been paid on the fate of these microcontaminants in sediments im- pacted by these sources of pollution. The accumulation of organic microcontaminants in sediments depends on their content and type of organic matter. Consequently, it is generally accepted that sediments constitute a sink for the most hydrophobic compounds that can, depending on the hydrographic conditions, be resus- pended on and reach the food chain (Bayona et al., 1991). Due to the high chemical complexity of the sediment extracts, the characterization of trace organic contaminants requires the use of high resolution and selectivity analytical techniques (Rich- ardson, 2012). In this regard, two-dimensional comprehensive 0045-6535/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.chemosphere.2012.08.053 ⇑ Corresponding author. E-mail address: victor.matamoros@idaea.csic.es (V. Matamoros). Chemosphere 90 (2013) 611–619 Contents lists available at SciVerse ScienceDirect Chemosphere journal homepage: www.elsevier.com/locate/chemosphere