Abstract

A comprehensive study is presented of the characteristics of calcareous concretions in the Connecticut Valley varved clay (CVVC), a glacial lake sediment, probed by an array of investigations, including compositional analyses via X-ray powder diffraction and energy-dispersive X-ray spectroscopy, mechanical property mapping by nanoindentation, selective dissolution, microstructure examination by optical and electron microscopy, and stable isotope analyses, with an objective to resolve some long-standing questions on their origin and growth mechanisms. Results show that these concretions are of a biogenic origin and consist of ~40 wt% primary host sediments and ~ 60 wt% secondary calcite post-depositionally precipitated as pore infills and inter-particle cement. The highly consistent layering and dry density between the carbonate-free host sediments in the concretions and in-situ varved sediments manifest that the precipitated calcite causes no disturbance to the original stratification and structure of the varved sediments. Moreover, both the mechanical properties (i.e., Young's modulus and hardness) and calcite concentration in concretions exhibit a radially decreasing pattern slightly disturbed by the sediments' layered textures. Further supported by the radial distribution patterns of stable carbon and oxygen isotopes, the CVVC concretions grow in a concentric pattern. A conceptual ion transport model is proposed to further interpret the growth mechanisms. These concretions grow radially in a nearly closed sediment system with diffusion-controlled transport of HCO3− from decaying organic matter and Ca2+ from porewater at direction-dependent rates dominated by the pore characteristics of the local host sediments. The diverse concretion morphologies are attributed to the different growth rates in different directions affected by the heterogeneous layering and pore sizes of the host sediments.

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