Alterations in the sterol signature of detritivorous fish along pollution gradients in the Río de la Plata basin (Argentina): From plant to sewage-based diet.

In order to assess the impact of sewage pollution on the diet of the strict detritivorous and migratory South American fish, Prochilodus lineatus, 16 sterol biomarkers were analyzed by gas chromatography-mass spectrometry from fish muscle (n: 144) collected along 1200 km in the Rio de la Plata basin. Sterol concentrations were fairly homogeneous (2.4 ± 1.3 mg g-1 dry weight), but their proportion in lipids was highly variable and inversely related to both body mass and lipid contents, reflecting the more conservative character of sterols compared to the rapid accumulation of fat as fish grows. As expected, the muscle sterol signature was widely dominated by cholesterol (92 ± 4.5% of total sterols), but it exhibited a remarkable diversity with variable proportions of fecal coprostanol (4.0 ± 4.4%) and plant sterols (3.1 ± 1.9%, e.g. sitosterol and campesterol). Muscle sterols exhibited contrasting geographical differences associated with dietary shifts from plant-derived detritus in the northern reaches of the basin (N: Paraná and Uruguay Rivers), to sewage dominated inputs at Buenos Aires (BA). Fish from BA are fattier (lipids: 35 ± 18 vs. 15 ± 9.0% at N), with higher total sterol contents (2.6 ± 1.3 vs. 1.9 ± 1.0 mg g-1), abundant coprostanol (5.3 ± 4.4 vs. 0.46 ± 1.1%) and lower plant sterols (2.6 ± 1.6 vs 4.6 ± 2.0%), reflecting a diet shifted to anthropogenic organic matter as opposed to vegetal detritus in the north. Accordingly, BA fish presented lower phyto/fecal sterol ratios (0.37 ± 0.21 vs. 0.91 ± 0.12 at N) and higher copro/epicoprostanol ratios (0.95 ± 0.082 vs 0.51 ± 0.25 at N), indicating fresh fecal inputs which provide a valuable supply of easily absorbed organic matter at this site. In addition, the sterol signature allowed to distinguish migratory fish from BA collected 900 km north (previously identified by their pollutant fingerprint and biochemical composition). In fact, coprostanol concentrations show a direct relationship with human populations along the basin, highlighting the usefulness of fecal sterol biomarkers as tracers of polluted fish stocks.

Long-Term (1970-2017) Temporal Trends of Polychlorinated Biphenyls in Fish, Settling Material, and Sediments from Populated and Remote Sites in Río de la Plata Estuary, Argentina.

Temporal trends of polychlorinated biphenyls (PCBs) were studied for detritivorous fish (1996-2017) and settling material (2002-2017) from polluted Buenos Aires coast and for a dated sediment core (1970-2013) from the outer Río de la Plata estuary. In spite of contrasting concentrations [5.3 ± 6.3 µg·g-1 dry weight (dw) for fish, 48 ± 26 ng·g-1 dw for settling material, and 1.5 ± 0.7 ng·g-1 dw for core], all three revealed exponentially decreasing trends over time (97%, 83%, and 83%, respectively). Time trends showed peak maxima coincident with Argentina's period of maximum PCB usage in 1973-1980 (80 cm depth in the core) and pulse discharges related to PCB banning in 2001-2002 (fish) with a lighter signature enriched in less persistent tri- and tetrachlorobiphenyls. The log-linear PCB time trends compare well with the predicted decrease for a high emission scenario from global emission data; the best fit was observed for the less impacted sediment core (-2%·year-1 versus -3%·year-1 for emission scenario). Steeper slopes are observed for the more polluted settling material (-5%·year-1) and especially for fish, in which the background decline trend tripled after the 2001 PCB pulse (from -7%·year-1 to -21%·year-1). These PCB time trends in related environmental compartments from contrasted sites provide rare evidence for evaluating the effectiveness of control measures in southern South America.