Abstract

Concerns have been raised on the deterioration of groundwater quality associated with anthropogenic impacts such as oil extraction and overuse of fertilizers. However, it is still difficult to identify groundwater chemistry/pollution and driving forces in regional scale since both natural and anthropogenic factors are spatially complex. This study, combining self-organizing map (SOM, combined with K-means algorithm) and principal component analysis (PCA), attempted to characterize the spatial variability and driving factors of shallow groundwater hydrochemistry in Yan'an area of Northwest China where diverse land use types (e.g., various oil production sites and agriculture lands) coexist. Based on the major and trace elements (e.g., Ba, Sr, Br, Li) and total petroleum hydrocarbons (TPH), groundwater samples were classified into four clusters with obvious geographical and hydrochemical characteristics by using SOM - K-means clustering: heavily oil-contaminated groundwater (Cluster 1), slightly oil-contaminated groundwater (Cluster 2), least-polluted groundwater (Cluster 3) and NO3− contaminated groundwater (Cluster 4). Noteworthily, Cluster 1, located in a river valley with long-term oil exploitation, had the highest levels of TPH and potentially toxic elements (Ba, Sr). Multivariate analysis combined with ion ratios analysis were used to determine the causes of these clusters. The results revealed that the hydrochemical compositions in Cluster 1 were mainly caused by the oil-related produced water intrusion into the upper aquifer. The elevated NO3− concentrations in Cluster 4 were induced by agricultural activities. Water-rock interactions (e.g., carbonate as well as silicate dissolution and precipitation) also shaped the chemical constituents of groundwater in clusters 2, 3, and 4. In addition, SO42−-related processes (redox, precipitation of sulfate minerals) also affected groundwater chemical compositions in Cluster 1. This work provides the insight into the driving factors of groundwater chemistry and pollution which could contribute to groundwater sustainable management and protection in this area and other oil extraction areas.

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