Semianalytical Solutions for Transport in Aquifer and Fractured Clay Matrix System

A three‐dimensional mathematical model that describes transport of contaminant in a horizontal aquifer with simultaneous diffusion into a fractured clay formation is proposed. A group of semianalytical solutions is derived based on specific initial and boundary conditions as well as various source functions. The analytical model solutions are evaluated by numerical Laplace inverse transformation and analytical Fourier inverse transformation. The model solutions can be used to study the fate and transport in a three‐dimensional spatial domain in which a nonaqueous phase liquid exists as a pool atop a fractured low‐permeability clay layer. The nonaqueous phase liquid gradually dissolves into the groundwater flowing past the pool, while simultaneously diffusing into the fractured clay formation below the aquifer. Mass transfer of the contaminant into the clay formation is demonstrated to be significantly enhanced by the existence of the fractures, even though the volume of fractures is relatively small compared to the volume of the clay matrix. The model solution is a useful tool in assessing contaminant attenuation processes in a confined aquifer underlain by a fractured clay formation.Abstract © AG

Ascorbate-Deficient vtc2 Mutants in Arabidopsis Do Not Exhibit Decreased Growth

This is the final version of the article. Available from Frontiers Media via the DOI in this record.In higher plants the L-galactose pathway represents the major route for ascorbate biosynthesis. The first committed step of this pathway is catalyzed by the enzyme GDP-L-galactose phosphorylase and is encoded by two paralogs in Arabidopsis – VITAMIN C2 (VTC2) and VTC5. The first mutant of this enzyme, vtc2-1, isolated via an EMS mutagenesis screen, has approximately 20–30% of wildtype ascorbate levels and has been reported to have decreased growth under standard laboratory conditions. Here, we show that a T-DNA insertion into the VTC2 causes a similar reduction in ascorbate levels, but does not greatly affect plant growth. Subsequent segregation analysis revealed the growth defects of vtc2-1 mutants segregate independently of the vtc2-1 mutation. These observations suggest that it is the presence of an independent cryptic mutation that affects growth of vtc2-1 mutants, and not the 70–80% decrease in ascorbate levels that has been assumed in past studies.This research is supported by a grant from the Australian Research Council (BL, CSC, JFG) and a Biotechnology and Biological Sciences Research Council grant (NS; BB/G021678/1)

Using Nanotechnology to Detect Nerve Agents

Nanotechnology has opened a wide range of opportunities having potential impacts in areas as diverse as medicine and consumer products. In collaboration with researchers at the University of Toledo UT, Air Force Institute of Technology AFIT scientists are exploring the possibility of using a nanoscale organic matrix to detect organophosphate OP nerve agents. Current techniques for detecting OP compounds are expensive and time consuming. Developing a nanoscale organic matrix sensor would allow for direct, real-time sensing under field conditions. This article describes the science behind such a sensor and its possible applications. High-performance sensors are needed to protect Soldiers and civilians from attack. At present, doctrine requires Air Force units to resume their primary mission within two hours of a chemical or biological strike.1 Meeting the two-hour operational goal may mean the difference between defeat and victory. However, OP detection capabilities now in place are limited in sensitivity, time required to operate, and ease of use, making the specified two-hour window difficult to meet

Analytical Solutions for Efficient Interpretation of Single-well Push-pull Tracer Tests

Single-well push-pull tracer tests have been used to characterize the extent, fate, and transport of subsurface contamination. Analytical solutions provide one alternative for interpreting test results. In this work, an exact analytical solution to two-dimensional equations describing the governing processes acting on a dissolved compound during a modified push-pull test (advection, longitudinal and transverse dispersion, first-order decay, and rate-limited sorption/partitioning in steady, divergent, and convergent flow fields) is developed. The coupling of this solution with inverse modeling to estimate aquifer parameters provides an efficient methodology for subsurface characterization. Synthetic data for single-well push-pull tests are employed to demonstrate the utility of the solution for determining (1) estimates of aquifer longitudinal and transverse dispersivities, (2) sorption distribution coefficients and rate constants, and (3) non-aqueous phase liquid (NAPL) saturations. Employment of the solution to estimate NAPL saturations based on partitioning and non-partitioning tracers is designed to overcome limitations of previous efforts by including rate-limited mass transfer. This solution provides a new tool for use by practitioners when interpreting single-well push-pull test results

Modeling NAPL dissolution from pendular rings in idealized porous media

The dissolution rate of nonaqueous phase liquid (NAPL) often governs the remediation time frame at subsurface hazardous waste sites. Most formulations for estimating this rate are empirical and assume that the NAPL is the nonwetting fluid. However, field evidence suggests that some waste sites might be organic wet. Thus, formulations that assume the NAPL is nonwetting may be inappropriate for estimating the rates of NAPL dissolution. An exact solution to the Young‐Laplace equation, assuming NAPL resides as pendular rings around the contact points of porous media idealized as spherical particles in a hexagonal close packing arrangement, is presented in this work to provide a theoretical prediction for NAPL‐water interfacial area. This analytic expression for interfacial area is then coupled with an exact solution to the advection‐diffusion equation in a capillary tube assuming Hagen‐Poiseuille flow to provide a theoretical means of calculating the mass transfer rate coefficient for dissolution at the NAPL‐water interface in an organic‐wet system. A comparison of the predictions from this theoretical model with predictions from empirically derived formulations from the literature for water‐wet systems showed a consistent range of values for the mass transfer rate coefficient, despite the significant differences in model foundations (water wetting versus NAPL wetting, theoretical versus empirical). This finding implies that, under these system conditions, the important parameter is interfacial area, with a lesser role played by NAPL configuration.Key Points:Exact solution to the Young‐Laplace equation for pendular ringsTheoretical determination of the mass transfer rate coefficient under hydrophobic conditionsPredicts similar NAPL dissolution rates for oil‐wet and water‐wet conditionsPeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/145506/1/wrcr21729.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/145506/2/wrcr21729_am.pd

Modeling NAPL Dissolution from Pendular Rings in Idealized Porous Media

The dissolution rate of nonaqueous phase liquid (NAPL) often governs the remediation time frame at subsurface hazardous waste sites. Most formulations for estimating this rate are empirical and assume that the NAPL is the nonwetting fluid. However, field evidence suggests that some waste sites might be organic wet. Thus, formulations that assume the NAPL is nonwetting may be inappropriate for estimating the rates of NAPL dissolution. An exact solution to the Young‐Laplace equation, assuming NAPL resides as pendular rings around the contact points of porous media idealized as spherical particles in a hexagonal close packing arrangement, is presented in this work to provide a theoretical prediction for NAPL‐water interfacial area. This analytic expression for interfacial area is then coupled with an exact solution to the advection‐diffusion equation in a capillary tube assuming Hagen‐Poiseuille flow to provide a theoretical means of calculating the mass transfer rate coefficient for dissolution at the NAPL‐water interface in an organic‐wet system. A comparison of the predictions from this theoretical model with predictions from empirically derived formulations from the literature for water‐wet systems showed a consistent range of values for the mass transfer rate coefficient, despite the significant differences in model foundations (water wetting versus NAPL wetting, theoretical versus empirical). This finding implies that, under these system conditions, the important parameter is interfacial area, with a lesser role played by NAPL configuration. Abstract © AGU

Nano-Scale Hydroxyapatite: Synthesis, Two-Dimensional Transport Experiments, and Application for Uranium Remediation

Synthetic nano-scale hydroxyapatite (NHA) was prepared and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) methods. The XRD data confirmed that the crystalline structure and chemical composition of NHA correspond to Ca5OH(PO4)3. The SEM data confirmed the size of NHA to be less than 50 nm. A two-dimensional physical model packed with saturated porous media was used to study the transport characteristics of NHA under constant flow conditions. The data show that the transport patterns of NHA were almost identical to tracer transport patterns. This result indicates that the NHA material can move with water like a tracer, and its movement was neither retarded nor influenced by any physicochemical interactions and/or density effects. We have also tested the reactivity of NHA with 1 mg/L hexavalent uranium (U(VI)) and found that complete removal of U(VI) is possible using 0.5 g/L NHA at pH 5 to 6. Our results demonstrate that NHA has the potential to be injected as a dilute slurry for in situ treatment of U(VI)-contaminated groundwater systems

Nano-Scale Hydroxyapatite: Synthesis, Two-Dimensional Transport Experiments, and Application for Uranium Remediation

Synthetic nano-scale hydroxyapatite (NHA) was prepared and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) methods. The XRD data confirmed that the crystalline structure and chemical composition of NHA correspond to Ca5OH(PO4)3. The SEM data confirmed the size of NHA to be less than 50 nm. A two-dimensional physical model packed with saturated porous media was used to study the transport characteristics of NHA under constant flow conditions. The data show that the transport patterns of NHA were almost identical to tracer transport patterns. This result indicates that the NHA material can move with water like a tracer, and its movement was neither retarded nor influenced by any physicochemical interactions and/or density effects. We have also tested the reactivity of NHA with 1 mg/L hexavalent uranium (U(VI)) and found that complete removal of U(VI) is possible using 0.5 g/L NHA at pH 5 to 6. Our results demonstrate that NHA has the potential to be injected as a dilute slurry for in situ treatment of U(VI)-contaminated groundwater systems

Peptide Nanotube Encapsulated Enzyme Biosensor for Vapor Phase Detection of Malathion, an Organophosphorus Compound

This study explores the use of a butyrylcholinesterase (BChE)-based, reversible reaction biosensor using screen-printed electrodes (SPEs) having a smaller working surface area than the single-use electrodes previously studied. Previous research demonstrated the prospective application of a single-use biosensor fabricated with an acetylcholinesterase (AChE) enzyme encapsulated in peptide nanotubes (PNTs) and enhanced with horseradish peroxidase (HRP) to detect organophosphorus compounds (OPCs) in aqueous and gas phases. In the current study, potential improvements to the biosensor are investigated. BChE-based biosensors were fabricated using PNTs, HRP, and Nafion in combination to increase the reactive surface area, enhance sensitivity, and maintain enzyme stability. Cyclic voltammetry (CV) was used along with the new modified sensor to measure malathion concentration in the gas phase. The results show that a BChE-based biosensor could reliably measure gas phase malathion concentrations between 6–25 ppbv by CV with the extent of inhibition linearly proportional to the malathion concentration (R2 = 0.941). This research demonstrated that fabricated BChE-based biosensors could be stored without cold storage requirement for up to six weeks with minimal performance degradation. Moreover, the sensor electrodes were each reused several times, and were still useable at the conclusion of the research. This research demonstrates the potential of fabricating a reusable, inexpensive biosensor that is capable of OPC detection with high sensitivity and a low detection limit without a long-term cold storage requirement

Unintended Consequences: Potential Downsides of the Air Force\u27s Conversion to Biofuels

The desire to reduce US dependence on foreign energy, ongoing environmental concerns, and the rising cost of petroleum have sparked significant development of greener alternative and renewable energy sources such as alcohol-based biofuels. To address these issues, the Department of Defense DOD has moved to diminish its reliance on petroleum for fueling aircraft and ground equipment. The US Air Force, in alignment with DOD objectives, has initiated several goals for reducing its use of energy: (1) decrease the use of petroleum-based fuel by 2 percent annually for the vehicle fleet, (2) increase the use of alternative fuel in motor vehicles annually by 10 percent, (3) certify all aircraft and weapon systems for a 5050 alternative fuel blend by 2011, and (4) have Air Force aircraft flying on 50 percent alternative fuel blends by 2016.1 This aggressive timetable moves the world s single largest petroleum consumer, the DOD, squarely into the alternative energies market. As the world s most prodigious fuel consumer, the DOD would likely drive segments of the aviation and motor fuels markets around the world to meet the demand for newly formulated alternative fuels and to convert existing fuel delivery systems to support the new market. Although conversion to alternative fuels can clearly lower the production of carbon dioxide, the risks that potential fuel spills pose to soil and groundwater are only now becoming clear