Transport of <i>Sporosarcina pasteurii</i> in sandstone and its significance for subsurface engineering technologies

The development of microbially mediated technologies for subsurface remediation and rock engineering is steadily increasing; however, we are lacking experimental data and models to predict bacterial movement through rock matrices. Here, breakthrough curves (BTCs) were obtained to quantify the transport of the ureolytic bacterium, Sporosarcina pasteurii, through sandstone cores, as a function of core length (1.8–7.5 cm), bacterial density (4 × 10&lt;sup&gt;6&lt;/sup&gt; to 9 × 10&lt;sup&gt;7&lt;/sup&gt; cells/ml) and flow rate (5.8–17.5 m/s). &lt;i&gt;S. pasteurii&lt;/i&gt; was easily immobilised within the homogeneous sandstone matrix (&gt;80%) in comparison to a packed sand column (&lt;20%; under similar experimental conditions), and percentage recovery decreased almost linearly with increasing rock core length. Moreover, a decrease in bacterial density or flow rate enhanced bacterial retention. A numerical model based on 1D advection dispersion models used for unconsolidated sand was fitted to the BTC data obtained here for sandstone. Good agreement between data and model was obtained at shorter rock core lengths (&lt;4 cm), suggesting that physicochemical filtration processes are similar in homogeneous packed sand and sandstones at these lengths. Discrepancies were, however observed at longer core lengths and with varying flow rates, indicating that the attributes of consolidated rock might impact bacterial transport progressively more with increasing core length. Implications of these results on microbial mineralisation technologies currently being developed for sealing fluid paths in subsurface environment is discussed

Microscale analysis of fractured rock sealed with microbially induced CaCO3 precipitation : influence on hydraulic and mechanical performance

Microbially induced CaCO3 precipitation (MICP) has shown great potential to reduce permeability in intact rocks as a means to seal fluid pathways in subsurface ground, for example to secure waste storage repositories. However, much less is known about how to apply MICP to seal fractured rock. Furthermore, there is limited information on the hydraulic and mechanical properties of MICP filled fractures, which are essential criteria to assess seal performance. Here, MICP injection strategies were tested on sandstone cores, aimed at obtaining a homogeneous porosity fill that reduced permeability by 3 orders of magnitude. The injection strategy resulting in the most homogenous calcite distribution was then applied to fractured granite cores, to yield transmissivity reduction of up to 4 orders of magnitude. Microscale analysis of these sealed granite cores using X‐ray computed tomography and electron microscopy showed that > 67% of the fracture aperture was filled with calcite, with crystals growing from both fracture planes, and bridging the fracture aperture in several places. Shear strength tests performed on these cores showed that the peak shear strength correlated well with the percentage of the fracture area where calcite bridged the aperture. Notably, brittle failure occurred within the MICP grout, showing that the calcite crystals were strongly attached to the granite surface. If MICP fracture sealing strategies can be designed such that the majority of CaCO3 crystals bridge across the fracture aperture, then MICP has the potential to provide significant mechanical stability to the rock mass as well as forming a hydraulic barrier

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 density functional theory study of Fe(II)/Fe(III) distribution in single layer green rust:a cluster approach

Green rust (GR) is a potentially important compound for the reduction of heavy metal and organic pollutants in subsurface environment because of its high Fe(II) content, but many details of the actual reaction mechanism are lacking. The reductive capacity distribution within GR is a key to understand how and where the redox reaction occurs and computational chemistry can provide more details about the electronic properties of green rust. We constructed three sizes of cluster models of single layer GR (i.e., without interlayer molecules or ions) and calculated the charge distribution of these structures using density functional theory. We found that the Fe(II) and Fe(III) are distributed unevenly in the single layer GR. Within a certain range of Fe(II)/Fe(III) ratios, the outer iron atoms behave more like Fe(III) and the inner iron atoms behave more like Fe(II). These findings indicate that the interior of GR is more reductive than the outer parts and will provide new information to understand the GR redox interactions. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1186/s12932-021-00076-0

Immobilization of Cr(VI) by sulphate green rust and sulphidized nanoscale zerovalent iron in sand media: batch and column studies

Chromate, Cr(VI), contamination in soil and groundwater poses serious threat to living organisms and environmental health worldwide. Sulphate green rust (GR$_{SO4}$), a naturally occurring mixed-valent iron layered double hydroxide has shown to be highly effective in the reduction of Cr(VI) to poorly soluble Cr(III), giving promise for its use as reactant for in situ remedial applications. However, little is known about its immobilization efficiency inside porous geological media, such as soils and sediments, where this reactant would ultimately be applied. In this study, we tested the removal of Cr(VI) by GR$_{SO4}$ in quartz sand fixed-bed column systems (diameter × length = 1.4 cm × 11 cm), under anoxic conditions. Cr(VI) removal efficiency (relative to the available reducing equivalents in the added GR$_{SO4}$) was determined by evaluating breakthrough curves performed at different inlet Cr(VI) concentrations (0.125–1 mM) which are representative of Cr(VI) concentrations found at contaminated sites, different flow rates (0.25–3 ml/min) and solution pH (4.5, 7 and 9.5). Results showed that (i) increasing Cr(VI) inlet concentration substantially decreased Cr(VI) removal efficiency of GR$_{SO4}$, (ii) flow rates had a lower impact on removal efficiencies, although values tended to be lower at higher flow rates, and (iii) Cr(VI) removal was enhanced at acidic pH conditions compared to neutral and alkaline conditions. For comparison, Cr(VI) removal by sulphidized nanoscale zerovalent iron (S-nZVI) in identical column experiments was substantially lower, indicating that S-nZVI reactivity with Cr(VI) is much slower compared to GR$_{SO4}$. Overall, GR$_{SO4}$ performed reasonably well, even at the highest tested flow rate, showing its versatility and suitability for Cr(VI) remediation applications in high flow environments

Siderite nucleation pathways as a function of aqueous solution saturation state at 25 °C

The mechanisms of siderite (FeCO3) nucleation from aqueous solution depend on the fluid saturation state. In this study we investigate the effect of aqueous fluid saturation on the nucleation pathway of siderite. Thereof, we performed a series of turbidity and batch experiments. Turbidity measurements indicate that at low saturation indices (SI < 3.69), siderite nucleation proceeds via the direct nucleation of crystalline siderite from the aqueous fluid. The direct precipitation of crystalline siderite is confirmed by X-Ray diffraction (XRD) analysis. This is the first study to report the direct nucleation of siderite at near-equilibrium conditions. At higher saturation indices (SI ≥ 3.69), nucleation proceeds via the initial precipitation of amorphous ferrous carbonate (AFC) followed by the nucleation and growth of crystalline siderite. XRD spectra confirm the initial precipitation of AFC and its transformation to crystalline siderite. Such differences in the nucleation mechanism likely affect both the reactivity of the resulting siderite and its isotopic composition. Insight into the aqueous fluid saturation state during siderite nucleation could thus be crucial for the accurate interpretation of the isotopic signature in natural systems

The Structure of Sulfidized Zero-Valent Iron by One-Pot Synthesis: Impact on Contaminant Selectivity and Long-Term Performance

Sulfidized zerovalent iron (sZVI) is widely studied because of its remarkable reactivity with a number of groundwater contaminants. Nonetheless, its nanoscale structure is not well understood. As such, there is an uncertainty on how sZVI structure controls its reactivity and fate in the subsurface environment. Using pair distribution function analyses, we show that sZVI made from one-pot synthesis using dithionite as sulfur precursor consists of an Fe0 core with a shell composed dominantly of short-range ordered Fe­(OH)2 and FeS having coherent scattering domains of less than 8 Å. Reactivity experiments show that increasing shell material significantly decreases rate for cis-dichloroethene (cis-DCE) reduction, whereas the opposite is observed for trichloroethene (TCE). The results are consistent with a conceptual model wherein cis-DCE reduction requires active Fe0 sites, which become largely inaccessible when shell material is abundant. Conversely, an increase in FeS shell volume led to faster TCE reduction via direct electron transfer. Aging experiments showed that sZVI retained >50% of its TCE removal efficiency after 30-day exposure to artificial groundwaters. The decline in sZVI reactivity due to long-term exposure to groundwater, is attributed to Fe0 oxidation from water reduction coupled by reorganization and recrystallization of the poorly ordered shell material, which in turn reduced access to reactive FeS sites