Field validation of a battery of biomarkers to assess sediment quality in Spanish ports M.L. Martı ´n-Dı ´az a,b, * , J. Blasco b , D. Sales c , T.A. DelValls a a Departamento de Quı ´mica Fı ´sica, Facultad de Ciencias del Mar y Ambientales, Polı ´gono Rı ´o San Pedro s/n, 11510 Puerto Real, Ca ´diz, Spain b Consejo Superior de Investigaciones Cientı ´ficas, Instituto de Ciencias Marinas de Andalucı ´a, Polı ´gono Rı ´o San Pedro s/n, 11510 Puerto Real, Ca ´diz, Spain c Departamento Ciencias Ambientales y Tecnologı ´a de los Alimentos, Facultad de Ciencias del Mar y Ambientales, Polı ´gono Rı ´o San Pedro s/n, 11510 Puerto Real, Ca ´diz, Spain Received 10 August 2006; received in revised form 13 March 2007; accepted 16 March 2007 A battery of biomarkers shows exposure to metals and organic compounds. Abstract Two marine invertebrates, the crab Carcinus maenas and the clam Ruditapes philippinarum, were used as bioindicator species to assess con- tamination when exposed in situ to sediment from different sites from four Spanish ports Cadiz (SW Spain), Huelva (SW Spain), Bilbao (NE Spain) and Pasajes (NE Spain). In an attempt to determine sediments toxicity, a combination of exposure biomarkers was analyzed in both species: metallothionein-like-proteins (MTLPs), ethoxyresorufin O-deethylase (EROD), glutathione S-transferase activity (GST), glutathi- one peroxidase (GPX) and glutathione reductase (GR). In parallel, physical and chemical characterization of the different sediments was per- formed and biological responses related to the contaminants. Significant induction of MTLPs was observed when organisms were exposed to metal contaminated sediments (port of Huelva), and EROD and GPX activities after exposure to sediments containing organic compounds (port of Bilbao and Pasajes). No significant interspecies differences were observed in biomarker responses except for the GST and GR. Ó 2007 Published by Elsevier Ltd. Keywords: Carcinus maenas; Ruditapes philippinarum; Dredged material; Oxidative stress; Metallothionein 1. Introduction Ecotoxicological data obtained in laboratory studies is often difficult to translate into accurate predictions of possible effects in the field. Since both overestimation and underesti- mation of effects may occur, laboratory biomarker results are best validated by field research. With respect to sediment, and especially dredged material, observations of a range of pa- rameters in individuals sampled from the field do not necessar- ily provide relevant information. The transplantation of caged organisms to evaluate dredged material toxicity avoids such drawbacks and allows field assessment to be integrated with laboratory assessment. Prior studies include the analysis of distinct biomarkers in caged mussels transplanted to NW Med- iterranean sediment (Munns et al., 2002) as well as in caged crabs and clams exposed to Spanish ports’ sediment (Martı ´n- Dı ´az et al., 2005). Dredged material has been found to have adverse environmental effects, resulting in international treaties and protocols for their proper environmental manage- ment. To this end, the OsloeParis Convention (OSPAR) and Helsinki Conventions (North Sea, North-East Atlantic, Baltic Sea) proposed guidelines to control the disposal of dredged material. Physical and chemical characteristics of the sediment are treated in these guidelines, together with biological effects. Nevertheless, biological effects are focused on the measure- ment of acute responses. The use of biomarkers for dredged material assessment is currently under review because of the * Corresponding author. Departamento de Quı ´mica Fı ´sica, Facultad de Cien- cias del Mar y Ambientales, Polı ´gono Rı ´o San Pedro s/n, 11510 Puerto Real, Ca ´diz, Spain. Tel.: þ34 956 016423; fax: þ34 956 016040. E-mail address: laura.martin@uca.es (M.L. Martı ´n-Dı ´az). 0269-7491/$ - see front matter Ó 2007 Published by Elsevier Ltd. doi:10.1016/j.envpol.2007.03.019 Available online at www.sciencedirect.com Environmental Pollution 151 (2008) 631e640 www.elsevier.com/locate/envpol