Transport of methane and noble gases during gas push-pull tests in dry porous media

A field method called the gas push-pull test (GPPT) was previously developed and tested for the in situ quantification of aerobic methane (CH4) oxidation by soil microorganisms. The GPPT consists of an injection followed by extraction of reactant and tracer gases into and out of the soil. Quantification of microbial activities from GPPTs requires insight in the transport of reactant and tracer gases under diverse field conditions. We investigated how the transport of differenttracer gases (He, Ne, and Ar) compares to that of the reactant gas CH4 during GPPTs conducted in a well-defined, dry porous media that mimicked an open system. Transport of gaseous components during GPPT is mainly driven by advection resulting from injection and extraction and diffusion driven by concentration gradients. Regardless of the advective component (selected injection/ extraction, flow rates 0.2-0.8 L min(-1)), diffusion was the dominant transport mechanism for gaseous components. This resulted in dissimilar transport of CH4 and the tracers He and Ne. Numerical simulations of GPPTs showed that similar transport of these components is only achieved at very high injection/extraction rates that, in practice, are not feasible since they would imply extremely short duration times of GPPTs to allow for consumption of a measurable amount of reactant(s) by soil microorganisms. However, Ar transport was similar to that of CH4. Hence, Ar may be a good tracer provided that it is injected at high concentrations (e.g., >25% [v/v]) to overcome its background concentration in soil air. Using moderate injection/ extraction rates (e.g., 0.6 L min(-1)) with injected volumes of 10-30 L will result in GPPT durations of 1-3 h, which would suffice to attain a measurable consumption of reactant(s) in soils having relatively high (e.g., first-order rate constants >0.3 h(-1)) microbial activities.     

Transport of methane and noble gases during gas push-pull tests in variably saturated porous media

The gas push-pull test (GPPT) is a single-well gas-tracer method to quantify in situ rates of CH4 oxidation in soils. To improve the design and interpretation of GPPT field experiments, gas component transport during GPPTs was examined in abiotic porous media over a range of water saturations (0.0 < or = Sw < or = 0.61). A series of GPPTs using He, Ne, and Ar as tracers for CH4 were performed at two injection/extraction gas flow rates (approximately 200 and approximately 700 mL min(-1)) in a laboratory tank. Extraction phase breakthrough curves and mass recovery curves of the gaseous components became more similar at higher Sw as water in the pore space restricted diffusive gas-phase transport. Diffusional fractionation of the stable carbon isotopes of CH4 during the extraction period of GPPTs also decreased with increasing Sw (particularly when Sw > 0.42). Gas-component transport during GPPTs was numerically simulated using estimated hydraulic parameters for the porous media and no fitting of data for the GPPTs. Numerical simulations accurately predicted the relative decline of the gaseous components in the breakthrough curves, but slightly overestimated recoveries at low Sw (< or = 0.35) and underestimated recoveries at high Sw (> or = 0.49). Comparison of numerical simulations considering and not considering air-water partitioning indicated that removal of gaseous components through dissolution in pore water was not significant during GPPTs, even at Sw = 0.61. These data indicate that Ar is a good tracer for CH4 physical transport over the full range of Sw studied, whereas, at Sw > 0.61, any of the tracers could be used. Greater mass recovery at higher Sw raises the possibility to reduce gas flow rates, thereby extending GPPT times in environments such as tundra soils where low activity due to low temperatures may require longer test times to establish a quantifiable difference between reactant and tracer breakthrough curves.     

Momentum-diffusive model for gas transfer in granular media

The development of controlled atmosphere storage technology for insect control requires an accurate prediction of the distribution of introduced gases in bulk grain. The published models are based on either diffusion theory or convective-diffusion theory. The momentum transport of gases, which is a key driving force for the gas mixture movements, has been neglected. In this paper, all the driving forces for gas transfer were investigated. A momentum-diffusive model is proposed. The model is based on the combined effects of concentration gradients, pressure gradients, and gravity on the transport of gases in the bulk grain. The experimental data for CO₂ transfer through connected columns of hot and cold wheat were used to validate the model. The equations were solved using the finite difference method, and the predictions from the proposed model were in good agreement with the experimental results.     

Measured mass transfer coefficients in porous media using specific interfacial area

Bulk and intrinsic mass transfer processes across interfaces between nonaqueous phase liquids (NAPLs) and water were studied in water-saturated columns. Columns packed with different grain sizes of sand were used to create various NAPL-water interfacial areas along with different NAPL saturations. The intrinsic mass transfer coefficients were estimated from the bulk mass transfer coefficients, and the specific interfacial areas were measured using tracer studies. The bulk mass transfer coefficients increased with increasing NAPL-water specific interfacial area as well as NAPL saturation and pore velocity and with decreasing grain sizes. Moreover, the bulk mass transfer coefficients were correlated with NAPL-water specific interfacial area rather than NAPL saturation and were more sensitive at high NAPL-water interfacial areas than at low interfacial areas. In contrast, the intrinsic mass transfer coefficients were nearly independent of specific interfacial area and NAPL saturation but dependent on pore velocity. Reduction of NAPL saturation by dissolution caused a linear decrease in the bulk mass transfer coefficients.     

Mobilizing particles in a saturated zone during air sparging

The mobilization of soil particles changes the porosity of saturated zone during air sparging. Soil porosity is shown to be correlated with soil electrical resistivity. This study performs porosity-resistivity tests to establish the relationship between porosity and resistivity of quartz sand. Experiments, involving a large sandbox to simulate the saturated zone, are then performed to compare the resistivity of compacted sand before air injection with that after air injection. The relevant data enable the mobilization of quartz sand particles to be quantified. Results of the experiments indicate the mobilization of sand particles and an increase in porosity directly proportional to the rate at which air is injected. Besides, a layer of fine-grained particles covered the compacted sand at the upper boundary of sandbox after each air injection experiment. This is direct evidence that finer particles were transported upward during air sparging. Two methods were applied to verify the results of this study. The first verification method indicated that changes in porosity increased directly proportional to the air injection rate, which is consistent with shear theory. The other validation method indicated that the mass of sand in the tank did not change after air sparging, which indicates that the resistivity-porosity method is unbiased.     

Field study of pulsed air sparging for remediation of petroleum hydrocarbon contaminated soil and groundwater

Recent laboratory-scale studies strongly suggested an advantage to operating air-sparging systems in a pulsed mode; however, little definitive field data existed to support the laboratory-scale observations. This study aimed to evaluate the performance of a field-scale pulsed air-sparging system during a short-term pilot test and during long-term system operation. The air-sparging system consisted of 32 sparging points and had been previously operated in a continuous mode for two years before the field study was performed. The field study used instruments with continuous data logging capabilities to monitor the dynamic responses of groundwater and soil vapor parameters to air injection. The optimum pulsing frequency was based on the evidence that the hydrocarbon volatilization and oxygen dissolution rates dramatically dropped after the air-sparging system reached steady state. The short-term pilot test results indicated a substantial increase in hydrocarbon volatilization and biodegradation in pulsed operation. On the basis of the results of the pilottest, the air-sparging system was set to operate in a pulsed mode at an optimum pulsing frequency. Operation parameters were collected 2, 8, and 12 months after the start of the pulsed operation. The long-term monitoring results showed thatthe pulsed operation increased the average hydrocarbon removal rate (kg/day) by a factor of up to 3 as compared to the previous continuous operation. The pulsed air sparging has resulted in higher reduction rates of dissolved benzene, toluene, ethylbenzene, and xylenes (BTEX) than were observed during the continuous operation. Among BTEX, benzene's reduction rate was the highest during the pulsed air-sparging operation.     

Chemoeffectors decrease the deposition of chemotactic bacteria during transport in porous media

Bacterial chemotaxis enables motile cells to move along chemical gradients and to swim toward optimal places for biodegradation. However, its potentially positive effects on subsurface remediation rely on the efficiency of bacterial movement in porous media, which is often restricted by high deposition rates and adhesion to soil surfaces. In well-controlled column systems, we assessed the influence of the chemo-effectors naphthalene, salicylate, fumarate, and acetate on deposition of chemotactic, naphthalene-degrading Pseudomonas putida G7 in selected porous environments (sand, forest soil, and clay aggregates). Our data showed that the presence of naphthalene in the pore water decreased deposition of strain 67 (but not of a derivative strain, P. putida 67.C1 (pHG100), nonchemotactic to naphthalene) by 50% in sand-filled columns, as calculated by the relative adhesion efficiency (at). Similar effects were observed with P. putida G7 strain for the other chemoeffectors. Deposition, however, depended on the chemoeffector's chemical structure, its interaction with the column packing material, and concomitantly its pore-water concentration. As the presence of the chemoeffectors had no influence on the physicochemical surface properties of the bacteria, we suggest that chemotactic sensing, combined with changed swimming modes, is likely to influence the deposition of bacteria in the subsurface, provided that the chemoeffector is dissolved at sufficient concentration in the pore water.     

苦荞发芽过程中不同部位的黄酮合成动态研究

以苦荞种子为原料,研究其在发芽过程中胚根、胚轴和子叶中总黄酮以及芦丁、槲皮素的合成动态。结果表明:苦荞发芽过程中,其胚根、子叶中总黄酮含量在3～9d范围内增加幅度较大,增加至第9d时达到最大值,然后处于相对稳定水平;胚轴中的总黄酮含量逐渐降低。芦丁含量变化趋势和总黄酮含量变化趋势基本一致。胚根、子叶中的槲皮素含量在3～9d范围内逐渐降低,第9d后处于相对稳定水平;胚轴中的槲皮素含量逐渐升高。在同一发芽时间,总黄酮含量子叶中最高,其次是胚轴,胚根中含量最低。      

Heavy metal capture and accumulation in bioretention media

Heavy metal capture and accumulation in bioretention media were investigated through the use of a one-dimensional filtration equation for particulate metals, advection/dispersion/adsorption transport equations for dissolved metals, and sequential extractions. Predicted spatial profiles and partitioning patterns of captured metals were compared to data derived from a bioretention cell in the District of Columbia. Zinc, lead, and copper profiles showed a high surface accumulation, significantly decreasing with the media depth. Surface street particle-enriched areas had the highest heavy metal levels, demonstrating a close relationship between capture of metals and runoff particles. Sequential extractions suggested that most captured metals were of anthropogenic origin. Soluble-exchangeable bound metals from the sequential extraction correlated well with predicted aqueous dissolved metals; the more strongly associated metal fractions correlated with modeled runoff and media particulate metals. A simple risk evaluation indicated thatlead isthe limiting metal in bioretention accumulation. On the basis of information collected in this study, a shallow bioretention cell design is suggested for systems with a focus on metal capture.     

Experimental studies of the influence of grain size, oxygen availability and organic carbon availability on bioclogging in porous media

Changes in the hydraulic properties of porous material due to bioclogging have been observed in many laboratory simulations and field studies. Because such changes in hydraulic properties influence the movement of fluids and contaminants, microbial ecology data are required for improved transport modeling. Here we investigate the effects of environmental variables previously shown to influence bioclogging, specifically oxygen availability, sediment grain size, and organic carbon (nutrient) concentration on the hydraulic properties of simulated subsurface environments. Our study provides evidence of a different clogging mechanism for aerobic and anaerobic microbial communities under high organic carbon concentrations (400 mg L(-1)). This work also suggests that the clogging mechanism operating in anaerobic microbial communities is more sensitive to carbon availability than that in the aerobic microbial communities. We found that grain size does have an effect on clogging, but it appears that there is a threshold carbon concentration, and therefore biomass, below which these effects are insignificant. Differences between the microbial communities that developed under different oxygenation conditions were detected using 16s rRNA analysis.     

Hydrodynamic aspects of particle clogging in porous media

Data from 6 filtration studies, representing 43 experiments, are analyzed with a simplified version of the single-parameter O'Melia and Ali clogging model. The model parameter displays a systematic dependence on fluid velocity, which was an independent variable in each study. A cake filtration model also explains the data from one filtration study by varying a single, velocity-dependent parameter, highlighting that clogging models, because they are empirical, are not unique. Limited experimental data indicate exponential depth dependence of particle accumulation, whose impact on clogging is quantified with an extended O'Melia and Ali model. The resulting two-parameter model successfully describes the increased clogging that is always observed in the top segment of a filter. However, even after accounting for particle penetration, the two-parameter model suggests that a velocity-dependent parameter representing deposit morphology must also be included to explain the data. Most of the experimental data are described by the single-parameter O'Melia and Ali model, and the model parameter is correlated to the collector Peclet number.     

Straining of nonspherical colloids in saturated porous media

We explore the effects of colloid shape on straining kinetics by measuring the filtration of spherical and nonspherical colloids within saturated columns packed with quartz sand. Our observations demonstrate that the transport of peanut-shaped colloids matches the transport of spherical colloids with diameters equal to the minor-axis length of the peanut-shaped colloids. The straining rates of the spherical colloids vary linearly with the ratio of colloid diameter (d(p)) to sand-grain diameter (d(g)) for 0.0083 < d(p)/d(g) < 0.06. This linear relationship also quantifies the straining rates of the peanut-shaped particles provided that the particle's minor axis length is used for d(p). Results of pore-scale simulations reveal that a peanut-shaped particle adopts a preferred orientation as it approaches a pore-space constriction such that its major axis tends to align with the local flow direction. The extent of this reorientation increases with the particle's aspect ratio. Findings from this research suggest that straining is sensitive to changes in colloid shape and thatthe kinetics of this process can be approximated on the basis of measurable properties of the nonspherical colloids and porous media.     

Adsorption of natural organic matter to air-water interfaces during transport through unsaturated porous media

To better understand how interactions with the air phase influence the movement of natural organic matter (NOM) through the vadose zone, we measured the transport of soil-humic acid (SHA) through laboratory columns packed with partially saturated sand. Our results demonstrate that sorptive reactions at air-water interfaces reduce SHA mobility and that the affinity of SHA for the air phase increases as the porewater pH declines from 8 to 3.9. SHA desorption from air-water interfaces is negligible for conditions of constant pH, but release of bound SHA occurs in response to perturbations in porewater pH. We analyzed the effluent samples collected from our laboratory columns using high-performance size-exclusion chromatography. The results of this analysis demonstrate that the SHA did not fractionate appreciably during transport through the columns, suggesting that the various components of the SHA pool (as distinguished on the basis of molecular weight) express an equal affinity for the air-water interfaces over the range of pH conditions tested. A mathematical model incorporating irreversible, second-order rate laws to simulate adsorption at air-water and solid-water interfaces closely describes the SHA breakthrough data. The mass-transfer parameters that govern this model vary in a discernible fashion with changes in porewater pH, and the parameter trends are consistent with published theories for SHA adsorption.     

Effects of pulsed electric field pretreatment on mass transfer and quality of beef during marination process

This study aimed to evaluate the effects of pulsed electric field (PEF) pretreatment on mass transfer, microstructure and eating quality of beef during marination process. Results showed that PEF could achieve a good effect of promoting marination with a small energy input (0.78–12.50 kJ/kg). Under the best condition (2.0 kV/cm, 125 pulses, 12.50 kJ/kg), the marination time was reduced by almost 33%, whereas the diffusion coefficient values increased up to 51.8% and 69.0% for NaCl and water, respectively. The marination process was modeled with Fick's second law and the model showed good fit. Furthermore, the cell disintegration results and the microstructure analysis showed that the main reason for PEF accelerating marination might be due to the expansion of gaps between muscle bundles with its membrane permeabilization potential. For quality properties, tenderness was enhanced up to 22.9% (2.0 kV/cm, 125 pulses, 12.50 kJ/kg), but all conditions did not significantly (P > 0.05) influence their color, purge loss and cooking loss.Industrial relevanceIn our research, the PEF-assisted marination process could significantly (P < 0.05) enhance the NaCl uptake of beef and reduce the marination time with the potential to improve meat tenderness. These results indicated that PEF could be a promising and effective pretreatment for the marination process of meat products.     

基于多孔介质热/质传递理论的流体—颗粒食品热处理数值模拟研究进展

概述了基于多孔介质热/质传递理论构建数学模型的原理与发展,从蒸发描述、参数测定及定解条件设定等方面分析了多孔介质数学模型开发与应用的关键问题及其研究进展,总结了多孔介质数学模型应用于流体—颗粒食品热处理的优势、挑战与发展前景。     

Hydrodynamic and chemical factors in clogging by montmorillonite in porous media

Clogging by colloid deposits is important in water treatment filters, groundwater aquifers, and petroleum reservoirs. The complexity of colloid deposition and deposit morphology preclude models based on first principles, so this study extends an empirical approach to quantify clogging using a simple, one-parameter model. Experiments were conducted with destabilized suspensions of sodium- and calcium-montmorillonite to quantify the hydrodynamic and chemical factors important in clogging. Greater clogging is observed at slower fluid velocity, consistent with previous investigations. However, calcium-montmorillonite causes 1 order of magnitude less clogging per mass of deposited particles compared to sodium-montmorillonite or a previously published summary of clogging in model granular media. Steady-state conditions, in which the permeability and the quantity of deposited material are both constant, were not observed, even though the experimental conditions were optimized for that purpose. These results indicate that hydrodynamic aspects of clogging by these natural materials are consistent with those of simplified model systems, and they demonstrate significant chemical effects on clogging for fully destabilized montmorillonite clay.     

Determination of NAPL-water interfacial areas in well-characterized porous media

The nonaqueous-phase liquid (NAPL)-water interfacial area is an important parameter which influences the rate of NAPL dissolution in porous media. The aim of this study was to generate a set of baseline data for specific interfacial area for a two-phase-entrapped NAPL-water system in well-characterized porous media and subsequently use these data to evaluate two current theoretical models. The first model tested distributes entrapped NAPL over the pore classes based on Land's algorithm and assumes the resulting blobs to be spherical. The other model is thermodynamically based, assuming that reversible work done on the system results in an increase in interfacial area, such that the area between drainage and imbibition retention curves can be related to the interfacial area. Interfacial tracer tests (IFTT) were used to measure specific entrapped NAPL (hexadecane)-water interfacial areas in columns packed with four grades (12/20, 20/30, 30/40, 40/50) of silica sand. By use of the anionic surfactant dihexylsulfosuccinate (Aerosol MA80), IFTT gave specific interfacial areas between 58 cm(-1) for the finest sand and 16 cm(-1) for the coarsest, compared to values of between 33 and 7 cm(-1) for the first model and between 19 and 5 cm(-1) for the thermodynamic model. Results from the literature suggest that nonspherical blobs shapes occur relatively frequently; hence it is reasonable to suggest that the assumption of spherical NAPL blobs may explain the underprediction by the first model. The thermodynamic model underestimates the interfacial area because it assumes that entrapment occurs only within the largest pores. A modified version of the latter model, allowing entrapment across all pore classes, yielded values between 58 and 13 cm(-1). Of the models tested the modified thermodynamic model best predicts the interfacial area.     

Pore-scale quantification of colloid transport in saturated porous media

It is currently not clear how to quantifiably relate pore-scale observations of colloid transportto larger scales, so,we proposed a geometric theory showing that pore-scale-derived rate constants may be appropriate to model a larger scale system. This study considered three different types of colloids: latex microspheres, Escherichia coli, and microspheres made of poly lactic acid (PLA). Colloid attachment and detachment rate constants were calculated using digital microscope images, taken in rapid (1 s) sequences, from which rates of attaching and detaching colloids were readily observed. Average rate constants from >1000 images per colloid-type were used to model Darcy-scale colloid transport breakthrough curves. The modeled and observed breakthrough curves agreed well for all three types of colloids. However, for latex and PLA microspheres, the model systematically under predicted the breakthrough curves' rising limb, which may indicate that the rate "constants" are actually dependent on the amount of attached colloids. Insights into these sorts of complexities are best addressed by research that considers both pore-scale phenomena and larger-scale transport responses.