Source apportionment of river water pollution is critical in water resource management and aquatic conservation. Comprehensive application of various GIS-based multivariate statistical methods was performed to analyze datasets (2009–2011) on water quality in the Liao River system (China). Cluster analysis (CA) classified the 12 months of the year into three groups (May–October, February–April and November–January) and the 66 sampling sites into three groups (groups A, B and C) based on similarities in water quality characteristics. Discriminant analysis (DA) determined that temperature, dissolved oxygen (DO), pH, chemical oxygen demand (CODMn), 5-day biochemical oxygen demand (BOD5), NH4+–N, total phosphorus (TP) and volatile phenols were significant variables affecting temporal variations, with 81.2% correct assignments. Principal component analysis (PCA) and positive matrix factorization (PMF) identified eight potential pollution factors for each part of the data structure, explaining more than 61% of the total variance. Oxygen-consuming organics from cropland and woodland runoff were the main latent pollution factor for group A. For group B, the main pollutants were oxygen-consuming organics, oil, nutrients and fecal matter. For group C, the evaluated pollutants primarily included oxygen-consuming organics, oil and toxic organics.
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