Large scale occurrence of aluminium-rich shallow groundwater in the Pearl River Delta after the rapid urbanization: Co-effects of anthropogenic and geogenic factors.

Aluminium(Al)-rich (> 0.2 mg/L) groundwater has received more concerns because of its harmful to human beings. Origins of large-scale occurrence on Al-rich groundwater in urbanized areas such as the Pearl River Delta (PRD) are still little known. The current work was conducted to investigate spatial distribution of Al-rich groundwater in the PRD, and to discuss its origins in various aquifers. For that, 265 groundwater samples and 15 river water samples were collected, and 21 hydrochemical parameters including Al were analyzed by using conventional analytical procedures. The results showed that groundwater Al concentrations were up to 22.64 mg/L, and Al-rich groundwater occurred in 15% of the area occupied by the PRD. Al-rich groundwater in the coastal-alluvial aquifer was about 2 times those in alluvial-proluvial and fissured aquifers, whereas the karst aquifer was absent. In the coastal-alluvial aquifer, Al-rich groundwater in the peri-urban area was 2 or more times those in urbanized and agricultural areas, whereas the remaining area was absent. By contrast, in the alluvial-proluvial aquifer, Al-rich groundwater in the remaining area was 1.5-3.5 times that in other areas; in the fissured aquifer, the distribution of Al-rich groundwater was independent of land-use types. The infiltration of wastewater from township enterprises was main anthropogenic source for Al-rich groundwater in urbanized and peri-urban areas, whereas irrigation of Al-rich river water was the main one in the agricultural area. Naturally dissolution of Al-rich minerals in soils/rocks, triggered by both of pH decrease resulted from nitrification of contaminated ammonium (e.g., sewage leakage, the use of nitrogen fertilizer) and acid deposition, was the main geogenic source for Al-rich groundwater in the PRD. The contribution of anthropogenic sources to Al-rich groundwater in the coastal-alluvial aquifer was more than that in alluvial-proluvial and fissured aquifers, whereas the contribution of geogenic sources was opposite. In conclusion, the discharge of township enterprises wastewater and ammonium-rich sewage, the emission of nitrogen-containing gas, and the use of nitrogen fertilizer should be preferentially limited to decrease the occurrence of Al-rich groundwater in urbanized areas such as the PRD.