Long-Term Statistical Assessment of the Water Quality of Tundja River
Two major environmetric methods (Cluster analysis (CA) and Principal components analysis (PCA)) were applied for statistical assessment of the water quality of trans-border river Tundja. The study used long-term monitoring data from 26 sampling sites characterized by 12 physicochemical parameters. Clustering of chemical indicators results in 3 major clusters: the first one shows the impact of anthropogenic sources, the second - the impact of agriculture and farming activities and the last one describes the role of the physical parameters on the water quality and also the impact of urban wastes. For better assessment of the monitoring data, PCA was implemented, which identified four latent factors. Two of them - "urban wastes" factor and "agriculture" factor correspond almost entirely to clusters 3 and 2 from the previous statistical analysis. The third one, named "industrial wastes" factor, reveals a specific seasonal behavior of the river system. The last latent factor describes the active reaction of the water body and is determined as "acidity" factor. The linkage of the sampling sites along the river flow by CA formed two clusters with the spatial "upstream-downstream" separation. The apportionment model of the pollution determined the contribution of each one of identified pollution factors to the total concentration of each one of the water quality parameters.
Statistical Calibration of Model Solution of Analytes
A new method based on spectrophotometric-partial least-squares procedure was proposed for simultaneously determination of thorium and zirconium using SPADNS (4,5-Dihydroxy-3-(p-sulfophenylazo)-2,7-naphthalene disulfonic acid, trisodium salt) as a color reagent. Absorbance measurements were made in the range of γ = 541÷620 nm with 1.0 nm steps in buffered solutions at pH 3.5. The linear ranges were obtained for 0.5÷11.5 and 1.5÷14.5 μg cm-3 for Th4+ and Zr4+ ions, respectively. The limits of detection were determined 0.4 and 1.2 μg cm-3 for thorium and zirconium, respectively. The standard deviation (n = 3) and recovery percent of 10 samples in the prediction set were obtained in the amplitude 0.22÷0.38 μg cm-3 and 91.3÷109.2, respectively. The proposed method was used for simultaneously determination of mentioned ions in spiked real water samples and wastewater. The results show that the method is applicable for the analysis of samples with similar matrix.