Groundwater Discharge as a Source of Dissolved Carbon and Greenhouse Gases in a Subtropical Estuary

Groundwater may be highly enriched in dissolved carbon species, but its role as a source of carbon to coastal waters is still poorly constrained. Exports of deep and shallow groundwater-derived dissolved carbon species from a small subtropical estuary (Korogoro Creek, Australia, latitude ?31.0478°, longitude 153.0649°) were quantified using a radium isotope mass balance model (²³³Ra and ²²⁴Ra, natural groundwater tracers) under two hydrological conditions. In addition, air-water exchange of carbon dioxide and methane in the estuary was estimated. The highest carbon inputs to the estuary were from deep fresh groundwater in the wet season. Most of the dissolved carbon delivered by groundwater and exported from the estuary to the coastal ocean was in the form of dissolved inorganic carbon (DIC; 687 mmol m^?2 estuary day^?1; 20 mmol m^?2 catchment day^?1, respectively), with a large export of alkalinity (23 mmol m^?2 catchment day^?1). Average water to air flux of CO₂ (869 mmol m^?2 day^?1) and CH₄ (26 mmol m^?2 day^?1) were 5- and 43-fold higher, respectively, than the average global evasion in estuaries due to the large input of CO₂- and CH₄-enriched groundwater. The groundwater discharge contribution to carbon exports from the estuary for DIC, dissolved organic carbon (DOC), alkalinity, CO₂, and CH₄ was 22, 41, 3, 75, and 100 %, respectively. The results show that CO₂ and CH₄ evasion rates from small subtropical estuaries surrounded by wetlands can be extremely high and that groundwater discharge had a major role in carbon export and evasion from the estuary and therefore should be accounted for in coastal carbon budgets.