Dissolved metal(loid) concentrations and their relations with chromophoric and fluorescent dissolved organic matter in an urban river in Shenzhen, South China

Urbanization is often accompanied by aquatic metal(loid) pollution, which is regulated by dissolved organic matter (DOM). However, the relationships between dissolved metal(loid) concentration and the bulk, chromophoric, and fluorescent DOM in black and odorous urban rivers are still poorly understood. Here, we investigated the dissolved metal(loid) concentrations of Zn, Cu, Cr, As, Pb, and Cd and their correlations with DOM-related parameters in water samples from a polluted urbanized watershed in Shenzhen, China. The results showed that the Zn and Cu concentrations in the mainstream and tributary exceeded the national standards, and the wastewater treatment plant (WWTP) was an important source, as indicated by the abrupt concentration increases downstream of the WWTP. The dissolved metal(loid) concentrations were not always significantly correlated with the dissolved organic carbon (DOC) concentration or the ultraviolet absorbance at 254 nm (UV); however, they were more likely to be correlated with the maximum fluorescence intensity (Fmax) of protein-like fluorescent DOM components. A strong correlation between the Cu/DOC ratio and specific UV (SUVA) previously reported did not exist in the present study. Instead, the Cu/DOC ratio was positively correlated with the Fmax/DOC ratios for protein-like fluorescent DOM components. Our study highlights that protein-like fluorescent DOM may be more important than humic-like fluorescence DOM and chromophoric DOM in terms of interacting with dissolved metal(loid)s in black and odorous urban rivers.