Occurrence and Distribution of Three Low Molecular Weight PAHs in Caño La Malaria, Cucharillas Marsh (Cataño, Puerto Rico): Spatial and Seasonal Variability, Sources, and Ecological Risk

Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants with significant ecological and public health implications, particularly in urban wetlands exposed to chronic anthropogenic stress. This study evaluates the occurrence, spatial distribution, seasonal variability, and ecological risk of three low molecular weight PAHs-naphthalene (NAP), phenanthrene (PHEN), and anthracene (ANT)-in surface waters of Caño La Malaria, the main freshwater source of Cucharillas Marsh, Puerto Rico's largest urban wetland. Surface water samples were collected at four locations during both wet- and dry-season campaigns. Samples were extracted and quantified by GC-MS. NAP was the dominant compound, Σ3PAHs concentrations ranging from 7.4 to 2198.8 ng/L, with higher wet-season levels (mean = 745.79 ng/L) than dry-season levels (mean = 186.71 ng/L); most wet-season samples fell within the mild-to-moderate contamination category. Compositional shifts indicated increased levels of PHEN and ANT during the wet season. No significant spatial differences were found (<i>p</i> = 0.753), and high correlations between sites (r = 0.96) suggest uniform input sources. Diagnostic ratios, inter-species correlations, and principal component analysis (PCA) consistently indicated a predominant pyrogenic origin, with robust PHEN-ANT correlation (r = 0.824) confirming shared combustion-related sources. PCA revealed a clear separation between dry- and wet-season samples, with the latter showing greater variability and stronger associations with NAP and ANT. Ecological risk assessment using hazard quotients (HQ_water) indicated negligible acute toxicity risk across all sites and seasons (<0.01); the highest HQ_water (0.0095), observed upstream during the wet season, remained within this range. However, benchmark exceedances by PHEN and ANT suggest potential chronic risks not captured by the acute ERA framework. These findings support integrated watershed management practices to mitigate PAH pollution and strengthen long-term ecological health in tropical urban wetlands.