Controls on the origin and cycling of riverine dissolved inorganic carbon in the Brazos River, Texas

Rivers draining watersheds that include carbonate bedrock or organic matter (OM)-rich sedimentary rocks frequently have ¹⁴C-depleted dissolved inorganic carbon (DIC) relative to rivers draining carbonate- and OM-free watersheds, due to dissolution of carbonate and/or decomposition of ancient OM. However, our results from a subtropical river, the Brazos River in Texas, USA, show that in this watershed human activities appear to dominate basin lithology in controlling the origin and metabolism of DIC. The middle Brazos flows through limestone and coal-bearing bedrock, but DIC isotope data suggest no limestone dissolution or respiration of ancient OM, and instead reflect efficient air?Cwater CO₂ exchange, degradation of relatively young OM and photosynthesis in the river as a result of river damming and urban treated wastewater input. The lower Brazos drains only small areas of carbonate and coal-bearing bedrock, but DIC isotope data suggest the strong influence of carbonate dissolution, with a potentially minor contribution from decomposition of old soil organic matter (SOM). Oyster shells and crushed carbonate minerals used in road construction are likely sources of carbonate in the lower Brazos, in addition to natural marl and pedogenic carbonate. Additionally, the generally low pCO₂ and high DIC concentration in the Brazos River lead to a low CO₂ outgassing:DIC export ratio, distinguishing the Brazos River from other rivers.