As an alternative procedure to conventional water quality assessment, the presence and combined toxicity of dissolved organic contaminants in water at five sites in the Forth estuary and the Firth of Forth, Scotland, United Kingdom was investigated using silicone rubber passive sampling devices (SR-PSDs) and an algal growth inhibition bioassay. SR-PSDs were deployed in water at the five sites for ~2 months. Following retrieval, extracts from the deployed SR-PSDs were assessed for both algal growth inhibition and the occurrence of a wide range of organic contaminants, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and a variety of plant protection products (PPPs; commonly referred to collectively as 'pesticides'). The 72 h algal growth inhibition test was performed using a native marine phytoplankton (Diacronema lutheri) in 24 well microplates. Freely dissolved (e.g. bioavailable) concentrations of PAHs and PCBs were determined using performance reference compounds (PRCs). The algal toxicity tests exhibited varied effects at the five sites indicating the presence of, and exposure to, phytotoxic compounds and their potential toxicity in the Forth. The individual and total dissolved concentrations of 40 PAHs and 32 PCBs measured in the study were relatively low and showed input of petrogenic, atmospheric and sewage related sources. Several pesticides of diverse polarities were identified in the water suggesting sources from both riverine input and direct discharges. The study thus illustrates the value of combining bioassays and chemical analysis (with effective sampling technique) for a realistic and rapid assessment of organic contaminants in the aquatic environment.