The objective of this work is to formulate a novel and physics-based nanomechanics framework to connect geochemical reactions in host rock to the resulting morphological changes at the microscopic lengthscale and to the resulting geomechanical changes at the macroscopic lengthscale. The key idea is to monitor the fraction of minerals based on their mechanical signature. We illustrate this procedure on the Mt. Simon sandstone from the Illinois Basin. To this end, various acidic fluid systems were applied to Mt. Simon sandstone specimens. The chemistry, morphology, microstructure, and mechanical characteristics were investigated across multiple lengthscales. Grid indentation was carried out with a total of 6900 individual indentation tests performed on 24 specimens. A good agreement was observed between the composition computed using statistical nanoindentation and measurements employing independent methods such as scanning electron microscopy, electron-dispersive X-ray spectroscopy, X-ray diffraction analyses, mercury intrusion porosimetry, flow perporometry, and helium pycnometry. An increase in porosity and a decrease in K-feldspar content were observed following the incubation in CO2-saturated brine, suggesting dissolution reactions involving feldspar. Thus, a rigorous methodology is presented to connect geochemical reactions and related compositional changes at the nano- and microscopic scales to alterations of the constitutive behavior at the macroscopic level.
Mixing-driven reactions in porous media are ubiquitous and span natural and engineered environments, yet predicting where and how quickly reactions occur is immensely challenging due to the complex and nonuniform nature of porous media flows. In particular, in many instances, there is an enormous range of spatial and temporal scales over which reactants can mix. This paper aims to review factors that affect mixing-limited reactions in porous media, and approaches used to predict such processes across scales. We focus primarily on the challenges of mixing-driven reactions in porous media at pore scales to provide a concise, but comprehensive picture. We balance our discussion between state-of-the-art experiments, theory and numerical methods, introducing the reader to factors that affect mixing, focusing on the bracketing cases of transverse and longitudinal mixing. We introduce the governing equations for mixing-limited reactions and then summarize several upscaling methods that aim to account for complex pore-scale flow fields. We conclude with perspectives on where the field is going, along with other insights gleaned from this review.
Bench-scale experiments were performed on natural sediments to assess abiotic dechlorination of trichloroethene (TCE) under both aerobic and anaerobic conditions. In the absence of oxygen (<26 µM), TCE dechlorination proceeded via a reductive pathway generating acetylene and/or ethene. Reductive dechlorination rate constants up to 3.1 x 10-5 d-1 were measured, after scaling to in situ solid water ratios. In the presence of oxygen greater than 120 µM, TCE dechlorination proceeded via an oxidative pathway generating formic/glyoxylic and glycolic/acetic acids, and oxidative dechlorination rate constants (again scaled to in situ conditions) up to 7.4 x 10-3 d-1 were measured. These rates correspond to half-lives of 60 and 0.25 years for abiotic TCE dechlorination under anaerobic and aerobic conditions, respectively, indicating the potentially large impact of aerobic TCE oxidation in the field. For both reductive and oxidative TCE dechlorination pathways, measured first-order rate constants increased with increasing ferrous iron content, suggesting the role of iron oxidation. Hydroxyl radical formation was measured and increased with increasing oxygen and ferrous iron content. Rate constants associated with TCE oxidation products increased with increasing hydroxyl radical generation rates, and are zero in the presence of a hydroxyl radical scavenger, suggesting that oxidative TCE dechlorination is a hydroxyl radical driven process.
More than 10% of the global human population is now afflicted with kidney stones, which are commonly associated with other significant health problems including diabetes, hypertension and obesity. Nearly 70% of these stones are primarily composed of calcium oxalate, a mineral previously assumed to be effectively insoluble within the kidney. This has limited currently available treatment options to painful passage and/or invasive surgical procedures. We analyze kidney stone thin sections with a combination of optical techniques, which include bright field, polarization, confocal and super-resolution nanometer-scale auto-fluorescence microscopy. Here we demonstrate using interdisciplinary geology and biology (geobiology) approaches that calcium oxalate stones undergo multiple events of dissolution as they crystallize and grow within the kidney. These observations open a fundamentally new paradigm for clinical approaches that include in vivo stone dissolution and identify high-frequency layering of organic matter and minerals as a template for biomineralization in natural and engineered settings.
There is a growing need to monitor anthropogenic organic contaminants detected in water sources. DNA aptamers are synthetic single-stranded oligonucleotides, selected to bind to target contaminants with favorable selectivity and sensitivity. These aptamers can be functionalized and are used with a variety of sensing platforms to develop sensors, or aptasensors. In this critical review, we (1) identify the state-of-the-art in DNA aptamer selection, (2) evaluate target and aptamer properties that make for sensitive and selective binding and sensing, (3) determine strengths and weaknesses of alternative sensing platforms, and (4) assess the potential for aptasensors to quantify environmentally relevant concentrations of organic contaminants in water. Among a suite of target and aptamer properties, binding affinity is either directly (e.g., organic carbon partition coefficient) or inversely (e.g., polar surface area) correlated to properties that indicate greater target hydrophobicity results in the strongest binding aptamers, and binding affinity is correlated to aptasensor limits of detection. Electrochemical-based aptasensors show the greatest sensitivity, which is similar to ELISA-based methods. Only a handful of aptasensors can detect organic pollutants at environmentally relevant concentrations, and interference from structurally similar analogs commonly present in natural waters is a yet-to-be overcome challenge. These findings lead to recommendations to improve aptasensor performance.
The environmental impacts of a typical hydraulic fracturing operation for shale gas recovery were evaluated using life cycle assessment, with energy demands for well drilling and fracturing determined from GHGfrack model. Dominant environmental impacts stem from well construction, which are >63% in all categories (e.g., global warming and eutrophication), and mainly due to diesel fuel combustion and steel production. The relative impacts related to water use (i.e., fracturing fluid components, water/wastewater transportation, and wastewater disposal) are relatively small, ranging from 5 to 22% of total impacts in all categories; freshwater consumption for fracturing is also a small fraction of available water resources for the shale play considered. The impacts of replacing slickwater with CO2 or CH4-foam fracturing fluid (≤10 vol % water) were evaluated; total impacts decrease <12%, and relative impacts related to water use decrease to 2–9% of total impacts. Hence, switching to a foam-based fracturing fluid can substantially decrease water-related impacts (>60%) but has only marginal effects on total environmental impacts. Changes in lateral well length, produced to fresh-water ratios, fracturing fluid composition, and LCA control volume do not change these findings. More benefits could potentially be realized by considering water versus foam-related impacts of ecological health and energy production.