Assessing natural background levels of geogenic contaminants in groundwater of an urbanized delta through removal of groundwaters impacted by anthropogenic inputs: New insights into driving factors

Knowledge on driving forces controlling natural background levels (NBLs) of geogenic contaminants (GCs) in groundwater of coastal urbanized areas are still limited because of complex hydrogeological conditions and anthropogenic activities. This study assesses NBLs of two GCs including arsenic (As) and manganese (Mn) in four groundwater units of the Pearl River Delta (PRD) with large scale urbanization by using a preselection method composed of the chloride/bromide mass ratio versus chloride concentration and the oxidation capacity with the combination of Grubbs' test. More importantly, driving factors controlling NBLs of As/Mn in groundwater of the PRD are discussed. Results showed that groundwater As/Mn concentrations in residual datasets were independent of land-use types, while those in original datasets in different land-use types were distinct because of various human activities, indicating that the used preselection method in this study is valid for NBLs-As/Mn assessment in groundwater of the PRD. NBL-As in coastal-alluvial aquifers was >6 times that in other groundwater units. NBL-Mn in coastal-alluvial aquifers was 1.4 times that in alluvial-proluvial aquifers, and both were >4 times that in other two groundwater units. High NBLs-As/Mn in coastal-alluvial aquifers is mainly attributed to reduction of FeMn oxyhydr(oxides) induced by mineralization of organic matter in Quaternary sediments. Elevated pH also contributes higher NBL-As in coastal-alluvial aquifers. By contrast, higher NBL-Mn in alluvial-proluvial aquifers than in other two groundwater units mainly ascribes to reduction of FeMn oxyhydr(oxides) in Quaternary sediments triggered by irrigation of reducing river waters. In addition, more occurrence of As/Mn-rich sediments and the infiltration of As/Mn-rich river water are also important factors for high NBLs-As/Mn in coastal-alluvial aquifers. This study shows that revealing natural driving factors of GCs-rich groundwater in coastal urbanized areas on the basis of identification of contaminated groundwaters via the used preselection methods is acceptable.