Chemical Controls on the Dissolution Kinetics of Calcite in Seawater

Citation

Subhas, Adam Vinay (2017) Chemical Controls on the Dissolution Kinetics of Calcite in Seawater. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z93X84P3. https://resolver.caltech.edu/CaltechTHESIS:06092017-091849904

Abstract

Calcium carbonate minerals are abundant on the earth’s surface. Delivery of alkalinity to the oceans is balanced by the production and burial of calcium carbonate in marine sediments, which results in a large reservoir of sedimentary calcium carbonate both in the ocean and in terrestrial rocks. Alkalinity also provides oceanic buffering capacity, which today results in about 60 times more dissolved carbon dioxide in the world oceans than is present as carbon dioxide gas in the atmosphere. Because calcium carbonate formation removes alkalinity from the oceans, calcium carbonate precipitation leads to the outgassing of carbon dioxide from the ocean into the atmosphere. Likewise, the dissolution of calcium carbonate adds alkalinity to the oceans, leading to an increased buffering capacity and a drawdown of atmospheric carbon dioxide concentration.

Calcium carbonate precipitation in the form of calcite and aragonite is almost exclusively mediated by biological organisms such as corals, coccoliths, and foraminifera, which use these minerals as components in their shells. calcium carbonate is overproduced by organisms in the ocean relative to the flux of alkalinity delivered to the oceans by rivers. Thus, a significant portion of calcium carbonate must be dissolved back into seawater for the ocean alkalinity cycle to come into steady state. Because of the link between alkalinity and carbon dioxide, the ocean alkalinity cycle has a direct effect on atmospheric carbon dioxide concentration especially on timescales less than 100,000 years.

How fast calcium carbonate dissolves back into seawater is thus a crucial rate in determining the response of the oceanic system to perturbations in either alkalinity or carbon dioxide input to the ocean-atmosphere system. We are testing the kinetics of this system with the large amount of carbon dioxide emitted from fossil fuel burning, about one third of which has dissolved into the surface ocean. This process is known as ocean acidification, as carbon dioxide is an acid, soaking up buffering capacity and dropping ocean pH. This carbon dioxide will eventually be neutralized through the dissolution of carbonate rich deep-sea sediments, but the process will take a long time. This thesis makes new measurements calcite dissolution in seawater, in an attempt to build an understanding of the chemical processes responsible for dissolution kinetics.

I first introduce the new method, in which carbon-13 labeled calcium carbonate is dissolved in undersaturated seawater. Mass loss is directly traced by measuring the appearance of carbon-13 in seawater over time. The dissolution rate of calcite is a highly nonlinear function of calcite saturation state.

Next, I show that this tracer can tell us about the balance of precipitation and dissolution at the mineral surface. I use this balance to constrain mass fluxes due to precipitation and dissolution as a function of saturation state. I also show that the enzyme Carbonic Anhydrase (CA), which rapidly equilibrates carbon dioxide and carbonic acid, greatly enhances the rate of calcite dissolution especially near equilibrium. A model of dissolution is presented in which CA is most effective in the region where dissolution proceeds via etch pit nucleation at surface defects.

The dissolution behavior of biogenic carbonates is also investigated using the carbon-13 method. I cultured coccoliths, foraminifera, and soft corals in carbon-13-labeled seawater so that their skeletons incorporated the carbon-13 tracer. These skeletons were then used in dissolution experiments. I show that both magnesium and organic matter contained within the calcite lattice have large effects on the dissolution behavior of biogenic carbonates. Magnesium content generally increases dissolution rate, and it is hypothesized that highly soluble magnesium-rich phases are preferentially removed from dissolving carbonates. Organic content generally decreases dissolution rate. It is hypothesized that organic matrices within the calcite lattice promote re-precipitation reactions, due to the balance of dissolution and precipitation rates in our data, and their promotion of precipitation during biomineralization.

I then analyze in 2- and 3-dimensions dissolved foraminiferal tests to locate where and how mass is being lost. It is shown that dissolution proceeds along specific layers, that are consistent with the size and location of Mg-rich carbonate spherules that are initially deposited during chamber formation. Surface topography generation of foraminiferal tests shows that sub-micron features are formed rapidly and then quickly eroded into larger pits and channels. These larger channels then propagate and cover the test surface at higher amounts of mass loss.

Finally, the involvement of CA in carbonate dissolution necessitates the measurement of CA activity in the environment, especially in carbonate-rich ecosystems such as reefs, carbonate-rich sediments, and carbonate-rich marine particles. To this end, I survey a number of available techniques for measuring CA activity. In the end, it is shown that the most effective method is based on measuring the depletion of oxygen-18 from carbon-13- and oxygen-18-labeled DIC, as measured by membrane inlet mass spectrometry (MIMS). This method is promising and shows about 0.1 nM CA present in unfiltered surface seawater collected from San Pedro Basin.

Thesis Files