In the last few decades, the study of space-time distribution and variations of heavy metals in estuaries has been extensively studied as an environmental indicator. In the case described here, the combination of acid water from mines, industrial effluents and sea water plays a determining role in the evolutionary process of the chemical makeup of the water in the estuary of the Tinto and Odiel Rivers, located in the southwest of the Iberian Peninsula. Based on the statistical treatment of the data from the analysis of the water samples from this system, which has been affected by processes of industrial and mining pollution, the 16 variables analyzed can be grouped into two large families. Each family presents high, positive Pearson r values that suggest common origins (fluvial or sea) for the pollutants present in the water analyzed and allow their subsequent contrast through cluster analysis.