Rare earth, major, and trace element composition of Monterey and DSDP chert and associated host sediment: Assessing the influence of chemical fractionation during diagenesis

Abstract

Chert and associated host sediments from Monterey Formation and Deep Sea Drilling Project (DSDP) sequences were analyzed in order to assess chemical behavior during diagenesis of biogenic sediments. The primary compositional contrast between chert and host sediment is a greater absolute SiO 2 concentration in chert, often with final SiO 2 ≥ 98 wt%. This contrast in SiO 2 (and Si Al ) potentially reflects precursor sediment heterogeneity, diagenetic chemical fractionation, or both. SiO 2 concentrations and Si Al ratios in chert are far greater than in modern siliceous oozes, however and often exceed values in acid-cleaned diatom tests. Compositional contrasts between chert and host sediment are also orders-of-magnitude greater than between multiple samples of the host sediment. Calculations based on the initial composition of adjacent host, observed porosity reductions from host to chert and a postulated influx of pure SiO 2, construct a chert composition which is essentially identical to observed SiO 2 values in chert. Thus, precursor heterogeneity does not seem to be the dominant factor influencing the current chert composition for the key elements of interest. In order to assess the extent of chemical fractionation during diagenesis, we approximate the precursor composition by analyzing host sediments adjacent to the chert. The SiO 2 concentration contrast seems caused by biogenic SiO 2 dissolution and transport from the local adjacent host sediment and subsequent SiO 2 reprecipitation in the chert. Along with SiO 2, other elements are often added (with respect to Al) to Monterey and DSDP chert during silicification, although absolute concentrations decrease. The two Monterey quartz chert nodules investigated, in contrast to the opal-CT and quartz chert lenses, formed primarily by extreme removal of carbonate and phosphate, thereby increasing relative SiO 2 concentrations. DSDP chert formed by both carbonate/phosphate dissolution and SiO 2 addition from the host. Manganese is fractionated during chert formation, resulting in MnO Al 2O 3 ratios that no longer record the depositional signal of the precursor sediment. REE data indicate only subtle diagenetic fractionation across the rare earth series. Ce Ce ∗ values do not change significantly during diagenesis of either Monterey or DSDP chert. Eu Eu ∗ decreases slightly during formation of DSDP chert. La n Yb n is affected only minimally as well. During formation of one Monterey opal-CT chert lens, REE Al ratios show subtle distribution changes at Gd and to a lesser extent near Nd and Ho. REE compositional contrasts between diagenetic states of siliceous sediment and chert are of a vastly smaller scale than has been noted between different depositional environments of marine sediment, indicating that the paleoenvironmental REE signature is not obscured by diagenetic overprinting.