A global assessment of arsenic (As), nickel (Ni), cobalt (Co) and chromium (Cr) was performed in environmental samples from an important industrial bay. Different fractions of water, sediments and tissues from four species of fish were analysed. Samples were collected from selected sampling sites during four consecutive samplings in spring and autumn seasons, in order to evaluate concentrations and their possible correlations among the aquatic compartments. While a higher availability of Cr and Ni was found in water, Co and As were the most available elements in sediments. In fish, the liver was the tissue with the highest proportion of As and Co, and gills showed the highest concentrations of Ni and Cr. Significance differences were observed among sites showing the pollution sources. In sediments, high correlations were found between total Co content and the most available fractions. Total Ni content highly correlated with the oxidisable fraction, while Cr total content tightly correlated with the least available fractions. Quality guideline values for sediments were frequently exceeded. In sediments and biota, concentrations were slightly higher than in other ecosystems, indicating that maritime, industrial and urban activities are affecting this type of ecosystem with great anthropogenic influence.