The pollution of the surface waters by pharmaceuticals and personal care products (PPCPs) has attracted worldwide attention, but data regarding their occurrence and potential risks for the aquatic biota on tropical coastal rivers of South America are still scarce. In this context, the occurrence and the preliminary ecological risk assessment of eleven pharmaceuticals of various therapeutic classes (including cocaine and its primary metabolite, benzoylecgonine) were investigated, for the first time, in five rivers of São Paulo, southeast Brazil, covering a coastline of about 140 km, namely Perequê River, Itinga River, Mongaguá River, Itanhaém River and Guaraú River. Although these five rivers are born in well-preserved areas of the Atlantic rainforest biome, on its way to sea and when they cross the urban perimeter, they receive untreated sewage discharges containing a complex mixture of contaminants. In addition, a “persistence, bioaccumulation and toxicity” (PBT) approach allowed to pre-select the priority PPCPs to be monitored in this coastline. Identification of several PPCPs in the samples was done using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Ten PPCPs were successfully quantified in all five rivers, namely caffeine (9.00–560.00 ng/L), acetaminophen (<LOQ–22.24 ng/L), benzoylecgonine (0.30–14.93 ng/L), atenolol (0.12–13.22 ng/L), losartan (0.10–8.42 ng/L), diclofenac (0.76–3.93 ng/L), cocaine (0.05–3.22 ng/L), furosemide (<LOQ–3.16), carbamazepine (0.04–0.50 ng/L) and orphenadrine (<LOQ–0.14 ng/L). From an ecological risk perspective, caffeine, acetaminophen and losartan can be considered as priority PPCPs because they showed low to moderate risks to algae, crustacean and fishes. However, using the PBT approach, carbamazepine and orphenadrine were also classified as priority compounds, followed by furosemide, acetaminophen, cocaine and losartan (all in second position) and caffeine, atenolol, diclofenac and benzoylecgonine (all in third position). This study provides valuable information to reinforce the importance of continuous monitoring of the coastal rivers of South America (containing PPCPs and illicit drugs) whose diffuse loads flow continuously into the marine ecosystems. Furthermore, ecotoxicological studies (especially with tropical marine organisms) to assess the long-term toxicity of these bioactive compounds are urgent.
