Decision-tree-model identification of nitrate pollution activities in groundwater: A combination of a dual isotope approach and chemical ions.

To develop management practices for agricultural crops to protect against NO3(-) contamination in groundwater, dominant pollution activities require reliable classification. In this study, we (1) classified potential NO3(-) pollution activities via an unsupervised learning algorithm based on δ(15)N- and δ(18)O-NO3(-) and physico-chemical properties of groundwater at 55 sampling locations; and (2) determined which water quality parameters could be used to identify the sources of NO3(-) contamination via a decision tree model. When a combination of δ(15)N-, δ(18)O-NO3(-) and physico-chemical properties of groundwater was used as an input for the k-means clustering algorithm, it allowed for a reliable clustering of the 55 sampling locations into 4 corresponding agricultural activities: well irrigated agriculture (28 sampling locations), sewage irrigated agriculture (16 sampling locations), a combination of sewage irrigated agriculture, farm and industry (5 sampling locations) and a combination of well irrigated agriculture and farm (6 sampling locations). A decision tree model with 97.5% classification success was developed based on SO4(2-) and Cl(-) variables. The NO3(-) and the δ(15)N- and δ(18)O-NO3(-) variables demonstrated limitation in developing a decision tree model as multiple N sources and fractionation processes both resulted in difficulties of discriminating NO3(-) concentrations and isotopic values. Although only the SO4(2-) and Cl(-) were selected as important discriminating variables, concentration data alone could not identify the specific NO3(-) sources responsible for groundwater contamination. This is a result of comprehensive analysis. To further reduce NO3(-) contamination, an integrated approach should be set-up by combining N and O isotopes of NO3(-) with land-uses and physico-chemical properties, especially in areas with complex agricultural activities.

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