The effect of pH, grain size, and organic ligands on biotite weathering rates

Biotite dissolution rates were determined at 25 °C, at pH 2–6, and as a function of mineral composition, grain size, and aqueous organic ligand concentration. Rates were measured using both open- and closed-system reactors in fluids of constant ionic strength. Element release was non-stoichiometric and followed the general trend of Fe, Mg > Al > Si. Biotite surface area normalised dissolution rates (ri) in the acidic range, generated from Si release, are consistent with the empirical rate law: ri=kH,iaxiH+ where kH,i refers to an apparent rate constant, aH+ designates the activity of protons, and xi stands for a reaction order with respect to protons. Rate constants range from 2.15 × 10−10 to 30.6 × 10−10 (molesbiotite m−2 s−1) with reaction orders ranging from 0.31 to 0.58. At near-neutral pH in the closed-system experiments, the release of Al was stoichiometric compared to Si, but Fe was preferentially retained in the solid phase, possibly as a secondary phase. Biotite dissolution was highly spatially anisotropic with its edges being ∼120 times more reactive than its basal planes. Low organic ligand concentrations slightly enhanced biotite dissolution rates. These measured rates illuminate mineral–fluid–organism chemical interactions, which occur in the natural environment, and how organic exudates enhance nutrient mobilisation for microorganism acquisition

Understanding watershed hydrogeochemistry: 2. Synchronized hydrological and geochemical processes drive stream chemostatic behavior

This article is a companion to Bao et al. [2017], doi: 10.1002/2016WR018934.Why do solute concentrations in streams remain largely constant while discharge varies by orders of magnitude? We used a new hydrological land surface and reactive transport code, RT‐Flux‐PIHM, to understand this long‐standing puzzle. We focus on the nonreactive chloride (Cl) and reactive magnesium (Mg) in the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO). Simulation results show that stream discharge comes from surface runoff (Qs), soil lateral flow (QL), and deeper groundwater (QG), with QL contributing >70%. In the summer, when high evapotranspiration dries up and disconnects most of the watershed from the stream, Cl is trapped along planar hillslopes. Successive rainfalls connect the watershed and mobilize trapped Cl, which counteracts dilution effects brought about by high water storage (Vw) and maintains chemostasis. Similarly, the synchronous response of clay dissolution rates (Mg source) to hydrological conditions, maintained largely by a relatively constant ratio between “wetted” mineral surface area Aw and Vw, controls Mg chemostatic behavior. Sensitivity analysis indicates that cation exchange plays a secondary role in determining chemostasis compared to clay dissolution, although it does store an order‐of‐magnitude more Mg on exchange sites than soil water. Model simulations indicate that dilution (concentration decrease with increasing discharge) occurs only when mass influxes from soil lateral flow are negligible (e.g., via having low clay surface area) so that stream discharge is dominated by relatively constant mass fluxes from deep groundwater that are unresponsive to surface hydrological conditions.EAR 07‐25019EAR 12‐39285EAR 13‐3172

An experimental study of dolomite dissolution rates at 80°C as a function of chemical affinity and solution composition

International audienc

Reaction of citric acid with calcite

Copyright © 2007 Elsevier Ltd All rights reserved.M.H. Al-Khaldi, H.A. Nasr-El-Din, S. Mehta and A.D. Al-Aamrihttp://www.elsevier.com/wps/find/journaldescription.cws_home/215/description#descriptio