Tracing sewage contamination in a South Atlantic UNESCO Natural Heritage estuary using sedimentary linear alkylbenzenes and their diagnostic ratios

The Paranaguá Estuarine System (PES) is an extensive subtropical estuarine system on the Southern Brazilian coast. It encompasses one of the last preserved areas of the Atlantic Forest and is recognized by UNESCO as a Natural Heritage site. This study evaluates the human impact of rapid and unplanned urbanization, an inefficient sewage system, and two port complexes by using linear alkylbenzenes (LABs) as a molecular marker for sewage input. The LAB analyses included Soxhlet extraction, clean-up, and quantification, which was performed using a gas chromatograph coupled to a mass spectrometer. The concentrations of total LABs (∑LABs) in the dry-weight sediments of PES ranged from below detection limits to 42.7 ng g⁻¹, with an average of 6.5 ± 7.8 ng g⁻¹. The primary sources of LABs are rivers surrounding the city of Paranaguá, which receive sewage inputs. In contrast, the input of allochthonous organic carbon and fine sediments is primarily associated with discharges from the Antonina River watershed. The recent unplanned occupation of estuarine margins, with untreated or inadequately treated sewage discharged directly into the environment or cesspools, explains the low degradation levels of LABs found in some sectors of the PES. The current concentrations of LABs, lower than those along the Brazilian coast and in densely populated coastal countries, suggest good sediment quality. This study shows that LABs can serve as a geochemical tool for tracing sources and distinguishing impacts related to population density in one of the largest preserved subtropical estuarine areas in the Southern Hemisphere.