Rapid changes in diatom silica surface charge density, silanol abundance, and oxygen isotope values elucidate silica maturation processes in biogenic silica

Abstract:

Oxygen isotope values of biogenic silica are increasingly used as proxies of paleoenvironmental conditions. Numerous studies have demonstrated a strong relationship between the diatom silica and the temperature/oxygen isotope value of the formation water; however, some studies have indicated that early diagenesis of biogenic silica may alter the oxygen isotope values by several permil. Quantification of the maturation process has proven difficult since the mechanisms that drive post-mortem changes in the silica oxygen isotope values have not been well characterized. New silica maturation data from marine diatoms, Stephanopyxis turris, cultured in a controlled laboratory experiment demonstrate rapid post-mortem decline in silica reactivity. A decrease in relative abundance of surface silanol groups coincides with a decrease in the surface charge density (excess proton concentration) of freshly harvested frustules. Over a maturation period of 20 days at 85ºC, S. turris samples in a 0.7 M NaCl solution at a pH of 8.0 demonstrate a rapid decrease in the surface charge density from -380 µmoles/g to -16 µmoles/g (Figure 1). FTIR analyses reveal a decrease in the abundance of silanol groups (Si-OH) in the diatom frustules occurs over the same time period. It is important to note that the surface charge density and silanol relative abundance appear to have an asymptotic change through time, indicating that further alteration/reactivity is greatly reduced. Preliminary data indicate that post-mortem increases in the oxygen isotope values of diatom silica observed here and in other studies are coincident with a reduction in the surface charge density and silanol abundance. These experiments demonstrate that rapid post-mortem alteration of biogenic silica is occurring and provide a possible mechanism for alteration of oxygen isotope values in biogenic silica.