Androgenic and antiandrogenic activities in water and sediment samples from the river Lambro, Italy, detected by yeast androgen screen and chemical analyses Ralph Urbatzka a , Anne van Cauwenberge b , Silvia Maggioni d , Luigi Vigano ` c , Alberta Mandich e , Emilio Benfenati d , Ilka Lutz a , Werner Kloas a,f, * a Department of Inland Fisheries, Leibniz-Institute of Freshwater Ecology and Inland Fisheries, Berlin, Germany b Institut Provincial d’Hygie `ne et de Bacte ´riologie, Mons, Belgium c Water Research Institute, National Council of Research (IRSA-CNR), Brugherio (Milan), Italy d Mario Negri Institute, Laboratory of Environmental Chemistry and Toxicology, Milan, Italy e Department of Environmental, Experimental and Applied Biology, University of Genoa, Italy f Department of Endocrinology, Institute of Biology, Humboldt-University, Berlin, Germany Received 5 July 2006; received in revised form 31 October 2006; accepted 24 November 2006 Available online 17 January 2007 Abstract The river Lambro is the most polluted tributary of the river Po in North Italy and was chosen as a representative water course dis- charging industrialized areas. Water and sediment samples of the river Lambro were investigated regarding the presence of endocrine disrupting compounds. A combined procedure was used consisting of solid-phase extraction and HPLC based fractionation of samples, of screening for (anti)androgenic activity using the yeast androgen screen (YAS) and of chemical analysis using HPLC–MS/MS and GC– MS. Androgenic and antiandrogenic activities were found in specific fractions of the water and sediment while the total extracts showed antiandrogenic activity only. The chemical analysis of the fractions and total extracts with antiandrogenic activities revealed the presence of compounds with suspected antiandrogenic potency such as bisphenol A, iprodione, nonylphenol, p,p 0 -DDE and tert-octylphenol but other unknown compounds contributed mainly to the observed antiandrogenic activities. The antiandrogenic load of the river Lambro ranged between 1.34 and 17.1 lM flutamide-equivalents and may pose a risk to aquatic environments. Future screenings for EDC in the environment that have the potential to interfere with reproduction of aquatic organisms should be extended to different modes of actions including (anti)androgenic ones. Ó 2006 Elsevier Ltd. All rights reserved. Keywords: Endocrine disruption; YAS; Environment; HPLC–MS/MS; GC–MS 1. Introduction Many chemicals released into the environment have been shown to interfere with the endocrine systems of dif- ferent organisms and are called endocrine disrupting com- pounds (EDC). Most attention in the field of endocrine disruption has been related to the estrogenic potential of chemicals. Several studies demonstrated estrogenic activity of single chemicals (Routledge and Sumpter, 1996; Folmar et al., 2002) and of environmental samples representing a mixture of synthetic and natural EDC (Cargouet et al., 2004; Pawlowski et al., 2004; Petrovic et al., 2004). In contrast, androgenic and antiandrogenic activities of chem- icals only recently came into focus. The interaction of (anti)androgenic chemicals with the androgen receptor may influence the normal sexual differentiation of males 0045-6535/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2006.11.041 * Corresponding author. Address: Department of Inland Fisheries, Leibniz-Institute of Freshwater Biology and Inland Fisheries, Mu ¨ ggelsee- damm 310, 12587 Berlin, Germany. Tel.: +49 30 64181630; fax: +49 30 64181799. E-mail address: werner.kloas@igb-berlin.de (W. Kloas). www.elsevier.com/locate/chemosphere Chemosphere 67 (2007) 1080–1087