Dominique J. Tobler

A field and modeling study of fractured rock permeability reduction using microbially induced calcite precipitation.

Microbially induced calcite precipitation (MICP) offers an attractive alternative to traditional grouting technologies for creating barriers to groundwater flow and containing subsurface contamination, but has only thus far been successfully demonstrated at the laboratory scale and predominantly in porous media. We present results of the first field experiments applying MICP to reduce fractured rock permeability in the subsurface. Initially, the ureolytic bacterium, Sporosarcina pasteurii, was fixed in the fractured rock. Subsequent injection of cementing fluid comprising calcium chloride and urea resulted in precipitation of large quantities (approximately 750 g) of calcite; significant reduction in the transmissivity of a single fracture over an area of several m(2) was achieved in around 17 h of treatment. A novel numerical model is also presented which simulates the field data well by coupling flow and bacterial and solute reactive transport processes including feedback due to aperture reduction via calcite precipitation. The results show that MICP can be successfully manipulated under field conditions to reduce the permeability of fractured rock and suggest that an MICP-based technique, informed by numerical models, may form the basis of viable solutions to aid pollution mitigation.

In-situ grown silica sinters in Icelandic geothermal areas

Field in-situ sinter growth studies have been carried out in five geochemically very different Icelandic geothermal areas with the aim to quantify the effects of water chemistry, (e.g. silica content (250 to 695 p.p.m. SiO(2)), salinity (meteoric to seawater), pH (7.5 to 10)), temperature (42-96 degrees C) and microbial abundance (prevalence, density) on the growth rates, textures and structures of sinters forming within and around geothermal waters. At each location, sinter growth was monitored over time periods between 30 min and 25 months using glass slides that acted as precipitation substrates from which sinter growth rates were derived. In geothermal areas like Svartsengi and Reykjanes, subaqueous sinters developed rapidly with growth rates of 10 and 304 kg year(-1 )m(-2), respectively, and this was attributed primarily to the near neutral pH, high salinity and medium to high silica content within these geothermal waters. The porous and homogeneous precipitates that formed at these sites were dominated by aggregates of amorphous silica and they contained few if any microorganisms. At Hveragerdi and Geysir, the geothermal waters were characterized by slightly alkaline pH, low salinity and moderate silica contents, resulting in substantially lower rates of sinter growth (0.2-1.4 kg year(-1 )m(-2)). At these sites sinter formation was restricted to the vicinity of the air-water interface (AWI) where evaporation and condensation processes predominated, with sinter textures being governed by the formation of dense and heterogeneous crusts with well-defined spicules and silica terraces. In contrast, the subaqueous sinters at these sites were characterized by extensive biofilms, which, with time, became fully silicified and thus well preserved within the sinter edifices. Finally, at Krafla, the geothermal waters exhibited high sinter growth rates (19.5 kg year(-1 )m(-2)) despite being considerably undersaturated with respect to amorphous silica. However, the bulk of the sinter textures and structure were made up of thick silicified biofilms and this indicated that silica precipitation, i.e. sinter growth, was aided by the surfaces provided by the thick biofilms. These results further suggest that the interplay between purely abiotic processes and the ubiquitous presence of mesophilic and thermophilic microorganisms in modern silica rich terrestrial hydrothermal settings provides an excellent analogue for processes in Earths and possibly Marss ancient past.

Controlled biomineralization of magnetite (Fe3O4) by Magnetospirillum gryphiswaldense

Abstract Results from a study of the chemical composition and micro-structural characteristics of bacterial magnetosomes extracted from the magnetotactic bacterial strain Magnetospirillum gryphiswaldense are presented here. Using high-resolution transmission electron microscopy combined with selected-area electron diffraction and energy dispersive X-ray microanalysis, biogenic magnetite particles isolated from mature cultures were analysed for variations in crystallinity and particle size, as well as chain character and length. The analysed crystals showed a narrow size range (∼14-67 nm) with an average diameter of 46±6.8 nm, cuboctahedral morphologies and typical Gamma type crystal size distributions. The magnetite particles exhibited a high chemical purity (exclusively Fe3O4) and the majority fall within the single-magnetic-domain range.

Monitoring bacterially induced calcite precipitation in porous media using magnetic resonance imaging and flow measurements

A range of nuclear magnetic resonance (NMR) techniques are employed to provide novel, non-invasive measurements of both the structure and transport properties of porous media following a biologically mediated calcite precipitation reaction. Both a model glass bead pack and a sandstone rock core were considered. Structure was probed using magnetic resonance imaging (MRI) via a combination of quantitative one-dimensional profiles and three-dimensional images, applied before and after the formation of calcite in order to characterise the spatial distribution of the precipitate. It was shown through modification and variations of the calcite precipitation treatment that differences in the calcite fill would occur but all methods were successful in partially blocking the different porous media. Precipitation was seen to occur predominantly at the inlet of the bead pack, whereas precipitation occurred almost uniformly along the sandstone core. Transport properties are quantified using pulse field gradient (PFG) NMR measurements which provide probability distributions of molecular displacement over a set observation time (propagators), supplementing conventional permeability measurements. Propagators quantify the local effect of calcite formation on system hydrodynamics and the extent of stagnant region formation. Collectively, the combination of NMR measurements utilised here provides a toolkit for determining the efficacy of a biological-precipitation reaction for partially blocking porous materials.

A Microkinetic Model of Calcite Step Growth

In spite of decades of research, mineral growth models based on ion attachment and detachment rates fail to predict behavior beyond a narrow range of conditions. Here we present a microkinetic model that accurately reproduces calcite growth over a very wide range of published experimental data for solution composition, saturation index, pH and impurities. We demonstrate that polynuclear complexes play a central role in mineral growth at high supersaturation and that a classical complexation model is sufficient to reproduce measured rates. Dehydration of the attaching species, not the mineral surface, is rate limiting. Density functional theory supports our conclusions. The model provides new insights into the molecular mechanisms of mineral growth that control biomineralization, mineral scaling and industrial material synthesis.

Silica and Alumina Nanophases: Natural Processes and Industrial Applications

Silica (SiO2) and alumina (Al2O3) nanophases control several important global element cycles. They play a crucial role in rock weathering and thus affect and are affected by Earth’s response to global climate change. The phases that form through various precipitation and crystallisation reactions, often adjacent to each other, are also important in a plethora of industrial applications. During the formation of both silica and alumina phases, multiple reaction stages controlled by changes in physicochemical parameters govern solid-liquid interface reactions and phase inter-transformations; these stages invariably include hydrolysis and condensation reactions, followed by nucleation and growth of poorly ordered solid nanoparticles, which ultimately dehydrate and crystallise to various polymorphs that in turn can inter-transform through subsequent reactions. In this chapter, we summarise the state of knowledge on reactions that lead to the formation and transformations of silica and alumina colloids in view of experimental evidence in pure and amended systems, compare these with field observations and contrast and compare these with principal processes relevant in industrial applications.

The metagenomics of biosilicification: causes and effects

Abstract In order to determine the links between geochemical parameters controlling the formation of silica sinter in hot springs and their associated microbial diversity, a detailed characterisation of the waters and of in situ-grown silica sinters was combined with molecular phylogenetic analyses of the bacterial communities in Icelandic geothermal environments. At all but one site, the microorganisms clearly affected, and in part controlled, the formation of the macroscopic textures and structures of silica sinter edifices. In addition, the class and genera level phylogenetic diversity and distribution appeared to be closely linked to variations in temperature, salinity and pH regimes.

Formation of Silica-Lysozyme Composites Through Co-Precipitation and Adsorption

Interactions between silica and proteins are crucial for the formation of biosilica and the production of novel functional hybrid materials for a range of industrial applications. The proteins control both precipitation pathway and the properties of the resulting silica-organic composites. Here we present data on the formation of silica-lysozyme composites through two different synthesis approaches (co-precipitation vs. adsorption) and show that the chemical and structural properties of these composites, when analyzed using a combination of synchrotron-based scattering (total scattering and SAXS), spectroscopic, electron microscopy and potentiometric methods vary dramatically. We document that while lysozyme was not incorporated into nor did its presence alter the molecular structure of silica, it strongly enhanced the aggregation of silica particles due to electrostatic and potentially hydrophobic interactions, leading to the formation of composites with characteristics differing from pure silica. The differences increased with increasing lysozyme content for both synthesis approaches. Yet, the absolute changes differ substantially between the two sets of composites, as lysozyme did not just affect aggregation during co-precipitation but also particle growth and likely polymerization during co-precipitation. Our results improve the fundamental understanding of how organic macromolecules interact with dissolved and nanoparticulate silica and how these interactions control the formation pathway of silica-organic composites from sodium silicate solutions, a widely available and cheap starting material.

A Silicate/Glycine Switch To Control the Reactivity of Layered Iron(II)–Iron(III) Hydroxides for Dechlorination of Carbon Tetrachloride

Layered FeII-FeIII hydroxide chloride (chloride green rust, GRCl) has high reactivity toward reducible pollutants such as chlorinated solvents. However, this reactive solid is prone to dissolution, and hence loss of reactivity, during storage and handling. In this study, adsorption of silicate (Si) to GRCl was tested for its ability to minimize GRCl dissolution and to inhibit reduction of carbon tetrachloride (CT). Silicate adsorbed with high affinity to GRCl yielding a sorption maximum of 0.026 g of Si/g of GRCl. In the absence of Si, the pseudo-first-order rate constant for CT dehalogenation by GRCl was 2.1 h-1, demonstrating very high reactivity of GRCl but with substantial FeII dissolution up to 2.5 mM. When Si was adsorbed to GRCl, CT dehalogenation was blocked and FeII dissolution extent was reduced by a factor of 28. The addition of glycine (Gly) was tested for reactivation of the Si-blocked GRCl for CT dehalogenation. At 30 mM Gly, partial reactivation of the GRCl was observed with pseudo-first-order rate constant for CT reduction of 0.075 h-1. This blockage and reactivation of GRCl reactivity demonstrates that it is possible to design a switch for GRCl to control its stability and reactivity under anoxic conditions.

The size and polydispersity of silica nanoparticles under simulated hot spring conditions

Abstract The nucleation and growth of silica nanoparticles in supersaturated geothermal waters was simulated using a flow-through geothermal simulator system. The effect of silica concentration ([SiO2]), ionic strength (IS), temperature (T) and organic additives on the size and polydispersity of the forming silica nanoparticles was quantified. A decrease in temperature (58 to 33°C) and the addition of glucose restricted particle growth to sizes <20 nm, while varying [SiO2] or IS did not affect the size (30-35 nm) and polydispersity (±9 nm) observed at 58°C. Conversely, the addition of xanthan gum induced the development of thin films that enhanced silica aggregation.