Submarine groundwater discharge and associated nutrient fluxes in the Greater Bay Area, China revealed by radium and stable isotopes

The estuary-bay system is a common and complex coastal environment. However, quantifying submarine groundwater discharge (SGD) and associated nutrient fluxes in the complex coastal environment is challenging due to more dynamic and complicated riverine discharge, ocean processes and human activities. In this study, SGD and SFGD (submarine fresh groundwater discharge) fluxes were evaluated by combining stable and radium isotopes in the Guangdong-Hong Kong-Macau Greater Bay Area (GBA), a typical estuary-bay system. We first built a spatially distributed radium mass balance model to quantify SGD fluxes in coastal areas of GBA integrating the Pearl River Estuary (PRE), bays and shelf. We then used the stable water isotope (δH and δO) end-member mixing model to distinguish submarine fresh groundwater discharge (SFGD) from SGD. Based on the Ra mass balance, the estimated SGD fluxes in the PRE, adjacent bay, and shelf areas were (6.14 ± 2.74) × 10 m d, (3.00 ± 1.11) × 10 m d, and (5.00 ± 5.64) × 10 m d, respectively. Results showed that the largest area-averaged SGD was in the PRE, followed by that in the adjacent shelf and the bay. These differences may be mainly influenced by ocean forces, urbanization and benthic topographies controlling the variability of groundwater pathways. Further, the three end-member mixing model of Ra and salinity was developed to confirm the validity of the estimated SGD using the Ra mass balance model. In the two models, groundwater end-member and water apparent age estimation were the main sources of uncertainty in SGD. The estimated SFGD flux was (1.39 ± 0.76) × 10 m d, which accounted for approximately 12% of the total SGD. Combining stable and radium isotopes was a useful method to estimate groundwater discharge. Moreover, the estimated SGD associated dissolved inorganic nitrogen (DIN) flux was one order of magnitude higher than other DIN sources. SGD was considered to be a significant contributor to the DIN loading to the GBA. The findings of this study are expected to provide valuable information on coastal groundwater management and environmental protection of the GBA and similar coastal areas elsewhere.