How Porosity and Permeability Vary Spatially With Grain Size, Sorting, Cement Volume, and Mineral Dissolution In Fluvial Triassic Sandstones: The Value of Geostatistics and Local Regression

Although it is well known that sandstone porosity and permeability are controlled by a range of parameters such as grain size and sorting, amount, type, and location of diagenetic cements, extent and type of compaction, and the generation of intergranular and intragranular secondary porosity, it is less constrained how these controlling parameters link up in rock volumes (within and between beds) and how they spatially interact to determine porosity and permeability. To address these unknowns, this study examined Triassic fluvial sandstone outcrops from the UK using field logging, probe permeametry of 200 points, and sampling at 100 points on a gridded rock surface. These field observations were supplemented by laser particle-size analysis, thin-section point-count analysis of primary and diagenetic mineralogy, quantitiative XRD mineral analysis, and SEM/EDAX analysis of all 100 samples. These data were analyzed using global regression, variography, kriging, conditional simulation, and geographically weighted regression to examine the spatial relationships between porosity and permeability and their potential controls. The results of bivariate analysis (global regression) of the entire outcrop dataset indicate only a weak correlation between both permeability porosity and their diagenetic and depositional controls and provide very limited information on the role of primary textural structures such as grain size and sorting. Subdividing the dataset further by bedding unit revealed details of more local controls on porosity and permeability. An alternative geostatistical approach combined with a local modelling technique (geographically weighted regression; GWR) subsequently was used to examine the spatial variability of porosity and permeability and their controls. The use of GWR does not require prior knowledge of divisions between bedding units, but the results from GWR broadly concur with results of regression analysis by bedding unit and provide much greater clarity of how porosity and permeability and their controls vary laterally and vertically. The close relationship between depositional lithofacies in each bed, diagenesis, and permeability, porosity demonstrates that each influences the other, and in turn how understanding of reservoir properties is enhanced by integration of paleoenvironmental reconstruction, stratigraphy, mineralogy, and geostatistics.

Modelling solute and microorganism transport through a peri-alpine gravel aquifer by considering the aquifer as a dual porosity fractured medium.

Approach:
In-situ passive gradient comparative artificial tracer testing, undertaken using solutes (Uranine and Iodide), Bacteria (E.coli and P.putida) and bacteriophage (H40/1), permitted comparison of the mobility of different sized microorganisms relative to solutes in the sand and gravel aquifer underlying Dornach, Germany.
Tracer breakthrough curves reveal that even though uranine initially arrived at observation wells at the same time as microbiological tracers, maximum relative concentrations were sometimes less than those of microbiological tracers, while solute breakthrough curves proved more disperse.
Monitoring uranine breakthrough with depth suggested tracers arrived in observation wells in discrete 0.5m-1m thick intervals, over the aquifer’s 12m saturated thickness. Nearby exposures of aquifer material suggested that the aquifer consisted of sandy gravels enveloping sequences of open framework (OW) gravel up to 1m thick. Detailed examination of OW units revealed that they contained lenses of silty sand up to 1m long x 30cm thick., while granulometric data suggested that the gravel was two to three orders of magnitude more permeable than the enveloping sandy gravel.
Solute and microorganism tracer responses could not be simulated using conventional advective-dispersive equation solutions employing the same velocity and dispersion terms. By contrast solute tracer responses, modelled using a dual porosity approach for fractured media (DP-1D) corresponded well to observed field data. Simulating microorganism responses using the same transport terms, but no dual porosity term, generated good model fits and explained the higher relative concentration of the bacteria, compared to the non-reactive solute, even with first order removal to account for lower RR. Geologically, model results indicate that the silty units within open framework gravels are accessible to solute tracers, but not to microorganisms.
Importance:
Results highlight the benefits of geological observations developing appropriate conceptual models of solute and micro organism transport and in developing suitable numerical approaches to quantifying microorganism mobility at scales appropriate for the development of groundwater supply (wellhead) protection zones.

Rapid, simple method for determining the porosity of mesoporous TiO2 films using a quartz crystal microbalance (QCM)

Two different mesoporous films of TiO2 were coated onto a QCM disc and fired at 450o C for 30 min. The first film was derived from a sol-gel paste that was popular in the early days of dye-sensitised solar cell, i.e. dssc, research, a TiO2(sg) film. The other was a commercial colloidal paste used to make examples of the current dssc cell; a TiO2(ds) film. A QCM was used to determine the mass of the TiO2 film deposited on each disc and the increase in the mass of the film when immersed in water/glycerol solutions with wt% values spanning the range 0-70%. The results of this work reveal that with both TiO2 mesoporous films the solution fills the film's pores and acts as a rigid mass, thereby allowing the porosity of each film to be calculated as: 59.1% and 71.6% for the TiO2(sg) and TiO2(ds) films, respectively. These results, coupled with surface area data, allowed the pore radii of the two films to be calculated as: 9.6 and 17.8 nm, respectively. This method is then simplified further, to just a few frequency measurements in water and only air to reveal the same porosity values. The value of the latter ‘one point’ method for making porosity measurements is discussed briefly.

Liquids with permanent porosity

Porous solids such as zeolites and metal-organic frameworks are useful in molecular separation and in catalysis, but their solid nature can impose limitations. For example, liquid solvents, rather than porous solids, are the most mature technology for post-combustion capture of carbon dioxide because liquid circulation systems are more easily retrofitted to existing plants. Solid porous adsorbents offer major benefits, such as lower energy penalties in adsorption-desorption cycles, but they are difficult to implement in conventional flow processes. Materials that combine the properties of fluidity and permanent porosity could therefore offer technological advantages, but permanent porosity is not associated with conventional liquids. Here we report free-flowing liquids whose bulk properties are determined by their permanent porosity. To achieve this, we designed cage molecules that provide a well-defined pore space and that are highly soluble in solvents whose molecules are too large to enter the pores. The concentration of unoccupied cages can thus be around 500 times greater than in other molecular solutions that contain cavities, resulting in a marked change in bulk properties, such as an eightfold increase in the solubility of methane gas. Our results provide the basis for development of a new class of functional porous materials for chemical processes, and we present a one-step, multigram scale-up route for highly soluble 'scrambled' porous cages prepared from a mixture of commercially available reagents. The unifying design principle for these materials is the avoidance of functional groups that can penetrate into the molecular cage cavities.