Efficient identification of groundwater contamination is a major issue in the context of groundwater use and protection. This study used a new approach of multi-hydrochemical indicators, including the Cl-Br mass ratio, the hydrochemical facies, and the concentrations of nitrate, phosphate, organic contaminants, and Pb in groundwater to identify groundwater contamination in the Pearl River Delta (PRD) where there is large scale urbanization. In addition, the main factors resulting in groundwater contamination in the PRD were also discussed by using socioeconomic data and principal component analysis. Approximately 60% of groundwater sites in the PRD were identified to be contaminated according to the above six indicators. Contaminated groundwaters commonly occur in porous and fissured aquifers but rarely in karst aquifers. Groundwater contamination in porous aquifers is positively correlated with the urbanization level. Similarly, in fissured aquifers, the proportions of contaminated groundwater in urbanized and peri-urban areas were approximately two times that in non-urbanized areas. Groundwater contamination in the PRD was mainly attributed to the infiltration of wastewater from township-village enterprises on a regional scale. In addition, livestock waste was also an important source of groundwater contamination in the PRD. Therefore, in the future, the supervision of the wastewater discharge of township-village enterprises and the waste discharge of livestock should be strengthened to protect against groundwater contamination in the PRD.

Cadmium (Cd)-contaminated paddy soils are a big concern. However, the effect of irrigation with acid water on the migration and transformation of Cd and the effect of alternating redox conditions caused by intermittent irrigation on Cd aging processes in different depths of paddy soils are unclear. This study revealed Cd fractionation and aging in a Cd-contaminated paddy soil under four irrigation periods with acid water and four drainage periods, by applying a soil columns experiment and a sequential extraction procedure. The results showed that the dynamic changes of soil pH, oxidation reduction potential (ORP), iron (Fe) oxides and dissolved organic carbon (DOC) throughout the intermittent irrigation affected the transformation of Cd fractions. After 32 days, the proportion of exchangeable Cd (F1) to the total Cd decreased with a reduction of 24.4% and 20.1% at the topsoil and the subsoil, respectively. The labile fractions of Cd decreased, and the more immobilizable fractions of Cd increased in the different depths of soils due to the aging process. Additionally, the redistribution of the Fe and Mn oxide-bound Cd (F3) and organic matter and secondary-sulfide-bound Cd (F4) occurred at different depths of soils during the incubation time. Overall, the bioaccessibility of Cd in the subsoil was higher than that in the topsoil, which was likely due to the leaching and accumulation of soluble Cd in the deep soil. In addition, the aging processes in different depths of soils were divided into three stages, which can be mainly described as the transformation of F1 into F3 and F4.

Assessing natural background levels (NBLs) of chemical components in groundwater is useful for the evaluation of groundwater contamination in urbanized areas. The present study assessed the NBL of total dissolved solids (TDS) in various groundwater units in the Pearl River Delta (PRD) where urbanization is a large scale and discussed factors controlling groundwater salinity contamination in the PRD. Results showed that the NBL of TDS in groundwater in the coastal-alluvial plain was more than 1.5 times that in other groundwater units because of the seawater intrusion in this groundwater unit. By contrast, interactions of water and soils/rocks were the main factors controlling the NBLs of TDS in other groundwater units. Groundwater salinity contamination in the PRD was positively correlated with the urbanization level. Wastewater from township-village enterprises and industrial wastewater were likely to be the main sources for groundwater salinity contamination in the PRD. Moreover, the wastewater leakage from sewer systems was one of the main pathways for groundwater salinity contamination in urbanized areas, because the proportion of groundwater salinity contamination in urbanized areas formed in 1988–1998 was more than 1.5 times that in urbanized areas formed in 1998–2006 regardless of groundwater units. Besides, sewage irrigation and leakage of landfill leachate were also important sources for groundwater salinity contamination in the PRD.