Isotopic insights into sources of acid driving weathering across a mountain-floodplain transition in the Amazon headwaters of Peru

The carbon budget associated with mineral weathering depends on the extent to which weathering is driven by strong acids (e.g., H2SO4, HNO3) as opposed to weak acids derived from atmospheric CO2 (e.g., H2CO3, organic acids). It has remained difficult to accurately partition acid sources associated with carbonate and silicate weathering, presenting an obstacle to quantifying weathering drawdown of CO2. Moreover, little is known about how acid sources change along material pathways from mountains, where rocks are eroded, producing reactive carbonate and silicate minerals, but also sulfides that generate H2SO4, and floodplains, where the resulting sediment is transported, deposited, and chemically reworked. Such mountain-floodplain transitions are increasingly recognized as important weathering reactors, making it important to quantify any associated variation in acid sources. In this study, these questions are addressed using the dissolved major element geochemistry, the carbon isotopic composition of dissolved inorganic carbon (δ13C DIC), and the sulfur isotopic composition of dissolved sulfate (δ34S) of rivers draining the Peruvian Andes and Madre de Dios floodplain. The dissolved major element geochemistry of the Andean headwater catchments suggests inputs of sulfuric acid (from the oxidation of sulfide minerals) but is also consistent with the weathering of sulfate minerals. The δ13C DIC values of river water samples from the Andean catchments provide key constraints and range from -18 to -5 ‰, which is consistent with the mixing of DIC derived from the weathering of silicates by respired CO2 and from the weathering of carbonates by either atmospheric CO2 or sulfuric acid. In order to distinguish between the two possible carbonate weathering agents, we calculated the fraction of carbonate-derived DIC both using an isotope mass balance model and a mineral mass balance model. These results were compared assuming either pure sulfuric acid or atmospheric CO2 weathering. The results of the two models match only if carbonate weathering is driven by sulfuric acid, and if a significant portion of silicate mineral weathering is also driven by sulfuric acid. In the floodplain, low δ13C DIC values in river waters indicate that respired CO2 is the dominant weathering agent of both carbonate and silicate minerals. This indicates that there is a major change in the sources of acidity between the Andes and the Madre de Dios floodplain, which suggests that not only do floodplains promote silicate mineral weathering, as recently identified elsewhere, but this floodplain weathering is also driven to a greater extent by acids derived from CO2, when compared to weathering in the Andes. To further constrain the importance of sulfuric acid weathering in this system, the δ34S of sulfate will be measured and used to determine the source of sulfate and its role in mineral dissolution independently of the major element and δ13C DIC data.