Competitive Scavenging of Trace Metals by HFO and HMO during Redox-driven Early Diagenesis of Ferromanganese Nodules (11 pp)

-: Dedicated to Prof. Dr. Ulrich Förstner on his 65th birthday Background: Surface complexation models (SCM) alone have yet less successfully reproduced sorption isotherms of hydrous manganese oxides (HMO). This is in part due to the fact that the HMO structure may vary with pH, and also because microbially formed natural HMO has an oxidation number O/Mn 〈 2, i.e. is of non-stoichiometrical composition. The former effect has often led to severe artefacts, such as an under-prediction of metal sequestration at low pH, and non-comparable pK and pHZPC values in literature. The latter effect is of particular importance for environments of varying redox conditions like sediments. Objectives: We propose therefore a new sorption model comprising of amphoteric site SCM, ion exchange due to permanent charge compensation, and solid solution formation, in order to comply at least in part with the redox complexity of HMO phases of stable birnessite- and buserite-type structures. Methods: The model is run by a new Gibbs energy minimization code which is shown to be particularly suitable for such a sorption continuum approach. Results and Discussion: Initial calibration of the model was performed by experimental literature data on simple laboratory systems. Thus parameterised, we simulated on the basis of available field data the effect of redox-driven dissolution of a ferromanganese nodule on the partitioning of metals between the interacting HMO, HFO, and marine water phases. Our scenario model suggests that significant fraction of Mn and other metals, probably 50% or more, may be recycled to water column from the surface of the ferromanganese nodule upon gradual development of the bottom water stagnation, except of Zn for which a by far stronger net retention was found. Conclusion and Outlook: Our model, even if only a first approximation, clearly shows that stagnation in the marine bottom water, once occurring, can drastically change primary element proxy records in ferromanganese nodules, smoothing out any anomalous patterns in the most recent recor

GEM-Selektor geochemical modeling package: revised algorithm and GEMS3K numerical kernel for coupled simulation codes

Reactive mass transport (RMT) simulation is a powerful numerical tool to advance our understanding of complex geochemical processes and their feedbacks in relevant subsurface systems. Thermodynamic equilibrium defines the baseline for solubility, chemical kinetics, and RMT in general. Efficient RMT simulations can be based on the operator-splitting approach, where the solver of chemical equilibria is called by the mass transport part for each control volume whose composition, temperature, or pressure has changed. Modeling of complex natural systems requires consideration of multiphase-multicomponent geochemical models that include nonideal solutions (aqueous electrolytes, fluids, gases, solid solutions, and melts). Direct Gibbs energy minimization (GEM) methods have numerous advantages for the realistic geochemical modeling of such fluid-rock systems. Substantial improvements and extensions to the revised GEM interior point method algorithm based on Karpov's convex programming approach are described, as implemented in the GEMS3K C/C+ + code, which is also the numerical kernel of GEM-Selektor v.3 package ( http://gems.web.psi.ch ). GEMS3K is presented in the context of the essential criteria of chemical plausibility, robustness of results, mass balance accuracy, numerical stability, speed, and portability to high-performance computing systems. The stand-alone GEMS3K code can treat very complex chemical systems with many nonideal solution phases accurately. It is fast, delivering chemically plausible and accurate results with the same or better mass balance precision as that of conventional speciation codes. GEMS3K is already used in several coupled RMT codes (e.g., OpenGeoSys-GEMS) capable of high-performance computin

Competitive scavenging of trace metals by HFO and HMO during Redox-driven early diagenesis of ferromanganese nodules : dedicated to Prof. Dr. Ulrich Förstner on his 65th birthday

Background. Surface complexation models (SCM) alone have yet less successfully reproduced sorption isotherms of hydrous manganese oxides (HMO). This is in part due to the fact that the HMO structure may vary with pH, and also because microbially formed natural HMO has an oxidation number O/Mn < 2, i.e. is of non-stoichiometrical composition. The former effect has often led to severe artefacts, such as an underprediction of metal sequestration at low pH, and non-comparable pK and pH(ZPC) values in literature. The latter effect is of particular importance for environments of varying redox conditions like sediments. Objectives. We propose therefore a new sorption model comprising of amphoteric site SCM, ion exchange due to permanent charge compensation, and solid solution formation, in order to comply at least in part with the redox complexity of HMO phases of stable birnessite- and buserite-type structures. Methods. The model is run by a new Gibbs energy minimization code which is shown to be particularly suitable for such a sorption continuum approach. Results and Discussion. Initial calibration of the model was performed by experimental literature data on simple laboratory systems. Thus parameterised, we simulated on the basis of available field data the effect of redox-driven dissolution of a ferromanganese nodule on the partitioning of metals between the interacting HMO, HFO, and marine water phases. Our scenario model suggests that significant fraction of Mn and other metals, probably 50% or more, may be recycled to water column from the surface of the ferromanganese nodule upon gradual development of the bottom water stagnation, except of Zn for which a by far stronger net retention was found. Conclusion and Outlook. Our model, even if only a first approximation, clearly shows that stagnation in the marine bottom water, once occurring, can drastically change primary element proxy records in ferromanganese nodules, smoothing out any anomalous patterns in the most recent record

CemGEMS – an easy-to-use web application for thermodynamic modeling of cementitious materials

Thermodynamic equilibrium calculations for cementitious materials enable predictions of stable phases and solution composition. In the last two decades, thermodynamic modelling has been increasingly used to understand the impact of factors such as cement composition, hydration, leaching, or temperature on the phases and properties of a hydrated cementitious system. General thermodynamic modelling codes such as GEM-Selektor have versatile but complex user interfaces requiring a considerable learning and training time. Hence there is a need for a dedicated tool, easy to learn and to use, with little to no maintenance efforts. CemGEMS (https://cemgems.app) is a free-to-use web app developed to meet this need, i.e. to assist cement chemists, students and industrial engineers in easily performing and visualizing thermodynamic simulations of hydration of cementitious materials at temperatures 0-99 °C and pressures 1-100 bar. At the server side, CemGEMS runs the GEMS code (https://gems.web.psi.ch) using the PSI/Nagra and Cemdata18 chemical thermodynamic data-bases (https://www.empa.ch/cemdata). The present paper summarizes the concepts of CemGEMS and its template data, highlights unique features of value for cement chemists that are not available in other tools, presents several calculated examples related to hydration and durability of cementitious materials, and compares the results with thermodynamic modelling using the desktop GEM-Selektor code