This dissertation contributes to our understanding of the use of the Li-isotopic composition of seawater as a tracer of the earth system with a focus on the role of low-temperature hydrothermal systems within the lava section of the ocean crust. Experiments were conducted to study the exchange coefficient (D(Li/Ca)) and isotopic fractionation factor (α; 1000ln(α)=Δ) for lithium between inorganic calcite and an aqueous solution as a function of solution chemistry. These experiments show that, under the conditions used, D(Li/Ca) negatively correlates with solution H+/Ca2+ ratio (and the solution pH) and Δ positively correlates with solution pH. The change in D(Li/Ca) with solution chemistry is interpreted as indicating that Li is incorporated into calcite as LiHCO3, and hence depends on solution H+/Ca2+. A series of diffusion experiments were performed to test whether changes in pH led to changes in the aqueous Li speciation that would lead to changes in the relative diffusivity of the two Li-isotopes, but no such changes were observed. It is proposed that the change in Δ with changing solution pH may either reflect a kinetic or equilibrium isotope fractionation associated with changing solution chemistry. These results have important implications for interpreting the Li content of calcite that has undergone any diagenetic modification.
The Li-content and isotopic composition of rocks altered by low-temperature, off-axis hydrothermal systems in the upper oceanic crust were studied to better understand the role of these systems in controlling the Li-isotopic composition of seawater. Results of a detailed study of DSDP Holes 417A, 417D and 418A from 119 Myr Western North Atlantic Ocean basin show that the Li content of the lavas decreases with depth in the upper ~30 m below sediments while the Li-isotopic composition increases from a low value and then does not show systematic variation in deeper sections. No evidence was found to support a role for a change in mineralogy of alteration products to explain the observed variation in Li composition of lavas. There is also no evidence for the modification of the composition of hydrothermal fluid due to a mixture with sediment pore-fluid. Simple one-dimensional fluid flow and fluid-rock reaction models also cannot explain the observed variation. Instead, a model of free-circulation of seawater through the upper few tens of meters of the lavas, and leakage of modified fluid into the deeper portion of the lava pile seems to explain the observed variations best. To investigate the role of low-temperature off-axis hydrothermal systems on the Li content and isotopic composition of seawater from the Cretaceous to modern era, five DSDP/ODP holes with crustal age spanning from 13.6 to 95 Myr were studied in combination with results from previous studies. Results suggest that the average amount of Li added to the upper oceanic crust decreases, while its average Li-isotopic composition increases, from the Cretaceous to the modern. The simplest explanation for these variations may be a decrease in Li concentration and an increase in Li-isotopic composition, of seawater over this time interval. / Graduate
| Identifer | oai:union.ndltd.org:uvic.ca/oai:dspace.library.uvic.ca:1828/12262 |
| Date | 26 October 2020 |
| Creators | Seyedali, Minasadat |
| Contributors | Coogan, Laurence, Gillis, Kathryn M. |
| Source Sets | University of Victoria |
| Language | English, English |
| Detected Language | English |
| Type | Thesis |
| Format | application/pdf |
| Rights | Available to the World Wide Web |
Page generated in 0.0022 seconds