The Carbon Budget of the Mekong River Basin: A Spatial and Temporal Study of Chemical Weathering

The chemical weathering of silicate rocks with carbonic acid is thought to play an important role in the consumption of atmospheric carbon dioxide (CO$_{2}$), which regulates global climate over million--year timescales. However, the climatic implications of chemical weathering of carbonate rocks with sulfuric acid, a process that can release geologically stored carbon to the atmosphere, are not thoroughly understood. Depending on the reaction environment the lithologically--sourced carbon released from the sulfuric acid weathering of carbonates can either degas as CO$_{2}$ instantaneously to the atmosphere, or can be transferred as bicarbonate (HCO$_{3}^{-}$) to the oceans to be precipitated as carbonate, releasing CO$_{2}$ on million--year timescales. It is important to consider the timescale of CO$_{2}$ release to assess whether a river basin is a transient, or long--term source of carbon to the atmosphere. Few studies have highlighted the importance of this weathering reaction and less have quantified the impact of CO$_{2}$ release from sulfuric acid weathering of carbonates in large scale catchments. Quantifying carbonate weathering with sulfuric acid requires the source of riverine sulfate (SO$_4^{2-}$) to be determined. This comes predominantly from two sources: sedimentary sulfate and sulfide. Sulfate released from the weathering of gypsum or anhydrite plays no role in the carbon cycle. Oxidative weathering of sedimentary sulfides, predominantly pyrite, produces sulfuric acid which can react with carbonates to release CO$_{2}$. Here, new coupled sulfur, $\delta^{34}S_{SO_4}$, and oxygen, $\delta^{18}O_{SO_4}$, isotope data on dissolved riverine sulfate and river water isotopes, $\delta^{18}$$O_{H_2O}$, from one of the world's largest rivers, the Mekong in Southeast Asia, are presented. A new two end member mixing model is used to partition sources of dissolved sulfate. Importantly, sulfate sources cannot be distinguished using $\delta^{34}S_{SO_4}$ alone, and hence $\delta^{18}O_{SO_4}$ must also be determined. The Mekong is the world's 10\textsuperscript{th} largest river in terms of discharge, yet is disproportionately understudied compared to many other large rivers where chemical weathering rates have been investigated. This study sampled 36 tributaries and 10 locations along the main channel to calculate the carbon budget of the Mekong River. Samples were collected over three field seasons, as well as a bi-monthly time--series from 2014-2017. HCO$_{3}^{-}$ and SO$_4^{2-}$ concentrations in the Mekong are up to 2709$\mu$mol/L and 720.3$\mu$mol/L respectively, and generally decrease downstream from the headwaters on the Tibetan Plateau. Samples display up to 20.7\permil difference in $\Delta^{18}$O$_{{SO_4}-{H_2O}}$, and $\delta^{34}S_{SO_4}$ ranges by $\sim$13.5\permil over the basin. The proportion of sulfate derived from the oxidative weathering of pyrite, $f_{pyr}$, calculated by the two end member mixing model varies between 0.18 and 0.83 in Mekong tributaries with a mean of 0.60 in the main channel. Sources of dissolved inorganic carbon (DIC) are partitioned using a forward model which incorporates the source of acidity in weathering reactions (carbonic or sulfuric) and the use of individual Ca/Na and Mg/K ratios in silicate end members of each tributary. Charge balance calculations with partitioned cations suggest the most likely reaction pathway of CO$_{2}$ release from sulfuric acid weathering of carbonates is instantaneous degassing. The weathering of carbonates by carbonic acid accounts for on average 81$\%$ of the total DIC flux for all tributaries, whilst carbonic acid weathering of silicates contributes on average 19$\%$ (ranging 7-60$\%$) of the total DIC flux in tributaries. Using a framework to track partitioned Ca$^{2+}$ ions, CO$_{2}$ consumption or release in the Mekong basin is shown graphically. On timescales shorter than carbonate precipitation, all Mekong tributaries are a sink of atmospheric CO$_{2}$. Annually, the instantaneous release of CO$_{2}$ from oxidative pyrite--driven weathering of carbonates is $\sim$16 times smaller than the drawdown of atmospheric carbon by carbonic acid weathering of both silicate and carbonate minerals. On million--year timescales, the headwater regions in China and one karst dominated tributary in the Middle Mekong release CO$_{2}$. The carbon budget of the Mekong varies throughout the year: during the monsoonal months the Mekong consumes atmospheric CO$_{2}$ but CO$_{2}$ is released during the dry season. Carbonic acid weathering of carbonates is carbon--neutral on million--year timescales, whereas the release of CO$_{2}$ from sulfuric acid weathering of carbonates is large enough to marginally offset the long--term sequestration of atmospheric CO$_{2}$ by carbonic acid weathering of silicates. Time--series samples and discharge measurements at Chroy Changvar, close to the mouth, are used to determine that the Mekong River basin is an annual net source of 0.01tC.km$^{-2}$.yr$^{-1}$ to the atmosphere. This differs to previous estimates, which indicate atmospheric CO$_{2}$ consumption by the Mekong. This thesis highlights the importance of determining the origin of sulfate in the world's largest rivers for the global carbon cycle, particularly in catchments with a high proportion of carbonate lithology.I was awarded a NERC DTP scholarship

Global silicate weathering flux over-estimated because of sediment-water cation exchange

Rivers carry the dissolved and solid products of silicate mineral weathering, a process that removes CO2 from the atmosphere and provides a key negative climate feedback over geological timescales. Here we show that in some river systems, a reactive exchange pool on river suspended particulate matter, bonded weakly to mineral surfaces, increases the mobile cation flux by 50%. The chemistry of both river waters and the exchange pool demonstrate exchange equilibrium, confirmed by Sr isotopes. Global silicate weathering fluxes are calculated based on riverine dissolved sodium (Na+) from silicate minerals. The large exchange pool supplies Na+ of non- silicate origin to the dissolved load, especially in catchments with widespread marine sediments, or where rocks have equilibrated with saline basement fluids. We quantify this by comparing the riverine sediment exchange pool and river water chemistry. In some basins, cation exchange could account for the majority of sodium in the river water, significantly reducing estimates of silicate weathering. At a global scale, we demonstrate that silicate weathering fluxes are over-estimated by 12-28%. This over-estimation is greatest in regions of high erosion and high sediment loads where the negative climate feedback has a maximum sensitivity to chemical weathering reactions. In the context of other recent findings that reduce the net CO2 consumption through chemical weathering, the magnitude of the continental silicate weathering fluxes and its implications for solid Earth CO2 degassing fluxes needs to be further investigated.NER

Global silicate weathering flux overestimated because of sediment–water cation exchange

Rivers carry the dissolved and solid products of silicate mineral weathering, a process that removes CO2 from the atmosphere and provides a key negative climate feedback over geological timescales. Here we show that in some river systems, a reactive exchange pool on river suspended particulate matter, bonded weakly to mineral surfaces, increases the mobile cation flux by 50%. The chemistry of both river waters and the exchange pool demonstrate exchange equilibrium, confirmed by Sr isotopes. Global silicate weathering fluxes are calculated based on riverine dissolved sodium (Na+) from silicate minerals. The large exchange pool supplies Na+ of non- silicate origin to the dissolved load, especially in catchments with widespread marine sediments, or where rocks have equilibrated with saline basement fluids. We quantify this by comparing the riverine sediment exchange pool and river water chemistry. In some basins, cation exchange could account for the majority of sodium in the river water, significantly reducing estimates of silicate weathering. At a global scale, we demonstrate that silicate weathering fluxes are over-estimated by 12-28%. This over-estimation is greatest in regions of high erosion and high sediment loads where the negative climate feedback has a maximum sensitivity to chemical weathering reactions. In the context of other recent findings that reduce the net CO2 consumption through chemical weathering, the magnitude of the continental silicate weathering fluxes and its implications for solid Earth CO2 degassing fluxes needs to be further investigated

Global silicate weathering flux overestimated because of sediment–water cation exchange

Rivers carry the dissolved and solid products of silicate mineral weathering, a process that removes CO2 from the atmosphere and provides a key negative climate feedback over geological timescales. Here we show that, in some river systems, a reactive exchange pool on river suspended particulate matter, bonded weakly to mineral surfaces, increases the mobile cation flux by 50%. The chemistry of both river waters and the exchange pool demonstrates exchange equilibrium, confirmed by Sr isotopes. Global silicate weathering fluxes are calculated based on riverine dissolved sodium (Na+) from silicate minerals. The large exchange pool supplies Na+ of nonsilicate origin to the dissolved load, especially in catchments with widespread marine sediments, or where rocks have equilibrated with saline basement fluids. We quantify this by comparing the riverine sediment exchange pool and river water chemistry. In some basins, cation exchange could account for the majority of sodium in the river water, significantly reducing estimates of silicate weathering. At a global scale, we demonstrate that silicate weathering fluxes are overestimated by 12 to 28%. This overestimation is greatest in regions of high erosion and high sediment loads where the negative climate feedback has a maximum sensitivity to chemical weathering reactions. In the context of other recent findings that reduce the net CO2 consumption through chemical weathering, the magnitude of the continental silicate weathering fluxes and its implications for solid Earth CO2 degassing fluxes need to be further investigated