Impact of porous media grain size on the transport of multi-walled carbon nanotubes

Nanoparticles possess unique physical, electrical, and chemical properties which make them attractive for use in a wide range of consumer products. Through their manufacturing, usage, and eventual disposal, nanoparticles are expected to ultimately be released to the environment after which point they may pose environmental and human health risks. One critical component of understanding and modeling those potential risks is their transport in the subsurface environment. This study investigates the mobility of one important nanoparticle (multi-walled carbon nanotubes or MWCNTs) through porous media, and makes the first measurements on the impact of mean collector grain size (d(50)) on MWCNT retention. Results from one-dimensional column experiments conducted under various physical and chemical conditions coupled with results of numerical modeling assessed the suitability of traditional transport models to predict MWCNT mobility. Findings suggest that a dual deposition model coupled with site blocking greatly improves model fits compared to traditional colloid filtration theory. Of particular note is that the MWCNTs traveled through porous media ranging in size from fine sand to silt resulting in normalized concentrations of MWCNTs in the effluent in excess of 60% of the influent concentration.     

Excess colloid retention in porous media as a function of colloid size, fluid velocity, and grain angularity

The deposition and re-entrainment behaviors of five sizes of carboxylate-modified microspheres (ranging from 0.1 to 2.0 microm) were examined both in porous media and impinging jet systems under a variety of environmentally relevant pore fluid velocities (2-8 m day-'), and in both the absence and the presence of an energy barrier to deposition. The magnitudes of the deposition efficiencies were compared among the porous media and impinging jet systems under equivalent fluid velocities, solution chemistries, and surface chemistries. The observed deposition efficiencies were factors of about 5 to 50 greater in the porous media relative to the impinging jet across the entire size range of microspheres examined, demonstrating that this excess deposition in porous media is relevant to a wide range of colloid sizes. The magnitude of excess deposition increased with increasing fluid velocity, and was greatest for the smallest colloids (0.1 microm). A range between 15% and 40% of the excess retained colloids were released upon introduction of low ionic strength solution, indicating that they were retained via secondary energy minima without direct contact with the grain surfaces. The observations indicate that pore geometry is a critical governor of colloid deposition in the presence of an energy barrier, even in porous media composed of spherical collectors. A portion of this excess deposition results from retention in flow stagnation zones.     

Effects of natural organic matter and solution chemistry on the deposition and reentrainment of colloids in porous media

The role of humic acid in the transport of negatively charged colloids through porous media was examined. Adsorption of humic acid on latex colloids and silica collectors reduced the deposition of suspended particles and enhanced the reentrainment of deposited particles in porous media. These effects are considered to arise from additional electrostatic and steric contributions to the repulsive interaction energy due to the adsorption of negatively charged humic acid on both the suspended particles and the media collectors. At low ionic strength reversible deposition in shallow secondary minima is hypothesized to be the principal attachment mechanism, independent of the presence of humic acid. It is proposed that under these solution conditions, particle deposition and reentrainment are the result of a dynamic process, in which particles are continuously captured and released from secondary minima. At higher ionic strengths, deposition may be regarded as a combination of two mechanisms: capture in the primary well and capture in the secondary minimum. Theoretical calculations of the attachment efficiency were conducted using two existing mathematical models. The first model is based on deposition in the primary well (interaction force boundary layer, IFBL), and the second model is based on the Maxwell kinetic theory and deposition in the secondary minimum (Maxwell model). Simulations conducted with the Maxwell model provide significantly better fits of the experimental results than those conducted with the IFBL model.     

The effect of oxygen and carbon dioxide gradients on the vertical dispersion of grain insects in wheat

A study was made on the dispersion of 0–14 day old adult Oryzaephilus surinamensis (L.), Sitophilus oryzae (L.) and Rhyzopertha dominica (F.) at 25°C in vertical columns of wheat (m.c. 12.1%) 100 cm tall. When the columns contained ordinary air, O. surinamensis dispersed from top to bottom within 24 hr whereas S. oryzae and R. dominica penetrated to a depth of only 50 cm in 72 hr. When controlled gas gradients were imposed on the columns from the bottom, the concentration of O₂ in one series of experiments ranged from 0.9% at the bottom to 18.5% at the top whilst in another series that of CO₂ ranged from 70.5% to 3.3%. In both gas gradients the downward dispersion of O. surinamensis was restricted but the distribution of the other two insect species was unaffected because they did not penetrate deep enough to encounter unfavorable concentrations.     

Kinetic gas-water transfer and gas accumulation in porous media during pulsed oxygen sparging

Gas-water mass transfer and the transport of dissolved gases in variably saturated porous media are key processes for in-situ remediation by pulsed gas sparging. In this context, gas dissolution tests were conducted during pulsed oxygen gas injection into sand columns. The columns were recharged with anoxic water, effluents were analyzed for dissolved O2, and tracer tests were performed to detect accumulation of trapped gas. In a second series oxygen gas was blended with sulfur hexafluoride (SF6), and O2 and SF6 breakthrough curves were recorded. To interpret experimental results, a numerical model was applied that simulates multi-species kinetic mass transfer during gas dissolution. The model predicted breakthrough curves of dissolved gas species and delivered spatially resolved values for gas phase accumulation and composition, which are not directly accessible experimentally. It was shown how dissolved nitrogen accumulates increasingly in trapped gas phase and inhibits its complete dissolution, in case the pulsed gas injections were operated based on O2 breakthrough only. Accumulation of nitrogen also retarded dissolved oxygen transport and thus oxygen breakthrough. Experiments plus modeling demonstrated that SF6 measurements are highly sensitive to the gas dissolution processes, and provide a more sensitive criterion for determining gas injection frequencies during pulsed biosparging.     

Effect of ferric oxyhydroxide grain coatings on the transport of bacteriophage PRD1 and Cryptosporidium parvum oocysts in saturated porous media

To test the effect of geochemical heterogeneity on microorganism transport in saturated porous media, we measured the removal of two microorganisms, the bacteriophage PRD1 and oocysts of the protozoan parasite Cryptosporidium parvum, in flow-through columns of quartz sand coated by different amounts of a ferric oxyhydroxide. The experiments were conducted over ranges of ferric oxyhydroxide coating fraction of lambda = 0-0.12 for PRD1 and from lambda = 0-0.32 for the oocysts at pH 5.6-5.8 and 10(-4) M ionic strength. To determine the effect of pH on the transport of the oocysts, experiments were also conducted over a pH range of 5.7-10.0 at a coating fraction of lambda = 0.04. Collision (attachment) efficiencies increased as the fraction of ferric oxyhydroxide coated quartz sand increased, from alpha = 0.0071 to 0.13 over lambda = 0-0.12 for PRD1 and from alpha = 0.059 to 0.75 over lambda = 0-0.32 for the oocysts. Increasing the pH from 5.7 to 10.0 resulted in a decrease in the oocyst collision efficiency as the pH exceeded the expected point of zero charge of the ferric oxyhydroxide coatings. The collision efficiencies correlated very well with the fraction of quartz sand coated by the ferric oxyhydroxide for PRD1 but not as well for the oocysts.     

Using elemental ratios to predict the density of organic material composed of carbon, hydrogen, and oxygen

A governing equation was developed to predict the density ρ(org) of organic material composed of carbon, oxygen, and hydrogen using the elemental ratios O:C and H:C as input parameters: ρ(org) = 1000 [(12 + 1(H:C) + 16(O:C)]/[7.0 + 5.0(H:C) + 4.15(O:C)] valid for 750 < ρ(org) < 1900 kg m(-3). Comparison of the actual to predicted ρ(org) values shows that the developed equation has an accuracy of 12% for more than 90% of the 31 atmospherically relevant compounds used in the training set. The equation was further validated for secondary organic material (SOM) produced by isoprene photo-oxidation and by α-pinene ozonolysis. Depending on the conditions of SOM production, ρ(org/SOM) ranged from 1230 to 1460 kg m(-3), O:C ranged from 0.38 to 0.72, and H:C ranged from 1.40 to 1.86. Atmospheric chemistry models that simulate particle production and growth can employ the developed equation to simulate particle physical properties. The equation can also extend atmospheric measurements presented as van Krevelen diagrams to include estimates of the material density of particles and their components. Use of the equation, however, is restricted to particle components having negligible quantities of additional elements, most notably nitrogen.     

The influence of oxygen and organic hydrogen acceotors on glycolytic dioxide production in Brettanomyces anomalus

The yeast Brettanomyces anomalus showed the Custers effect in that under strictly anaerobic conditions, in the presence of glucose, CO₂ production was negligble. CO₂ production was stimulated by mixing anaerobic cell suspensions with an aerated glucose solution in astopped-flow cell. Glycolytic CO₂ production continued even after oxygen exhaustion. Studies using an open reaction vessel showed that the rate of glycolytic CO₂ production could be increased to a maximum level by exposing the anaerobic cell suspension to brief pulses of O₂. A cell suspension CO₂ at a maximal rate demonstrated the Pasteur effect on switching the mobile gas to a mixture conatining oxygen (5.05 KPa). In contrast to glycolytic CO₂ production in vivo nicotinamide pool responded rapidly to changes in oxygen concentration. The addition of acetaldehyde, acetone, or 3-hydroxy-butan-2-one led to a temprorary production of CO₂ at an initial rate depending on the concentration of substance added according to the Michaelis–Menten equation. The maximal rates were equal with all three substances, whereas tha apparent K_m values were different. The total amount of CO₂ produced was 22-fold greater than the amount of acetaldehyde added. Added organic hydrogen acceptors modulated the intracellular reedox balance of B. anomalus under conditions. These results are discussed in relation to the current hypothesis of the Custers effect.     

Pore-scale characterization of organic immiscible-liquid morphology in natural porous media using synchrotron X-ray microtomography

The objective of this study was to quantitatively characterize the pore-scale morphology of organic immiscible liquid residing within natural porous media. Synchrotron X-ray microtomography was used to obtain high-resolution, three-dimensional images of solid and liquid phases in packed columns. The image data were processed to generate quantitative measurements of organic-liquid blob morphology. Three porous media, comprising a range of particle-size distributions, were used to evaluate the impact of porous-medium texture on blob morphology. The sizes and shapes of the organic-liquid blobs varied greatly, ranging from small spherical singlets (> or = 0.03 mm in diameter) to large, amorphous ganglia with mean lengths of 4-5 mm. The smaller blobs were composed primarily of singlets, which comprised approximately half of all blobs for all three media. Conversely, large, complex blobs comprising four or more bodies composed 11-24% of the total number of blobs. However, the majority of the total organic-liquid surface area and volume was associated with the largest blobs. The ratio of median blob size to median grain size was close to unity for all three systems. The distribution of blob sizes was greatest for the porous medium with the broadest particle-size and pore-size distributions. These results illustrate the utility of synchrotron X-ray microtomography for characterizing fluid distributions at the pore scale in natural porous media.     

The influence of oxygen on ensilage. I. Laboratory studies

Grass was ensiled in laboratory silos in three separate experiments. In the first two of them, different oxygen treatment levels were achieved by ensiling different weights of herbage in the fixed volume of the laboratory silo. In the third experiment, the quantity of grass ensiled was kept constant, the oxygen level being varied by evacuation and injection of gas. Fermentation changes were followed during the period of ensilage. In all cases, when compared with the controls, oxygen treatments resulted in silages of lower lactate content, higher acetate content, higher pH and volatile N values. Butyrate was present in appreciable amounts in the high oxygen treated silages in Experiments 1 and 3. It was concluded that oxygen trapped in unconsolidated herbage had an adverse effect on fermentation resulting from not only oxidation of sugar but also from a direct effect on the activities of the microflora.     

Retention and transport of silica nanoparticles in saturated porous media: effect of concentration and particle size

Investigations on factors that affect the fate and transport of nanoparticles (NPs) remain incomplete to date. In the present study, we conducted column experiments using 8 and 52 nm silica NPs to examine the effects of NPs' concentration and size on their retention and transport in saturated porous media. Results showed that higher particle number concentration led to lower relative retention and greater surface coverage. Smaller NPs resulted in higher relative retention and lower surface coverage. Meanwhile, evaluation of size effect based on mass concentration (mg/L) vs particle number concentration (particles/mL) led to different conclusions. A set of equations for surface coverage calculation was developed and applied to explain the different results related to the size effects when a given mass concentration (mg/L) and a given particle number concentration were used. In addition, we found that the retained 8 nm NPs were released upon lowered solution ionic strength, contrary to the prediction by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The study herein highlights the importance of NPs' concentration and size on their behavior in porous media. To the best of our knowledge, it is the first report of an improved equation for surface coverage calculation using column breakthrough data.     

Grain size and grain depth restrict oxygen movement in leaky hermetic containers and contribute to protective effect

Postharvest insect pests threaten the nutritional and financial security of smallholder farmers in the developing world. Hermetic storage, a technology that protects grain against insects by blocking their supply of oxygen, alleviates the problem of insect-caused losses. PICS (Purdue Improved Crop Storage) bags represent one hermetic technology that improves food availability and incomes of farmers. The polyethylene liners of PICS bags are sometime damaged during use, acquiring small holes or tears. Observations in the laboratory and field suggest that insect development remains localized around the point where the bag is damaged. We hypothesized that the grain within a hermetic container that has minimal localized damage (such as an insect hole), helps retard leakage of oxygen into the bag and contributes to limiting insect damage and to the overall protective effect. To test this hypothesis, we filled 4 cm dia. by 10 cm long PVC pipes with Callosobruchus maculatus (F.) infested cowpeas and sealed them with caps having a single, insect-sized hole in its center. A vertical tube positioned above the cowpea-filled PVC pipe was filled with one of three different grains (sesame, sorghum, and maize) to different depths (0, 5, 15, 30, 50 cm). Seed size and grain barrier depth significantly reduced the level of bruchid damage to the stored cowpea in the PVC container. Smaller sized grains used for the barriers retarded insect development more effectively than larger sized grains, while deeper grain depth was more effective than shallower barriers. The grain held in a hermetic container contributes in a small, but significant, way to the effectiveness of the containers.     

Characterizing pore-scale dissolution of organic immiscible liquid in natural porous media using synchrotron X-ray microtomography

The objective of this study was to characterize the pore-scale dissolution of organic immiscible-liquid blobs residing within natural porous media. Synchrotron X-ray microtomography was used to obtain high-resolution, three-dimensional images of the aqueous, organic-liquid, and solid phases residing in columns packed with one of two porous media. Images of the packed columns were obtained after a stable, discontinuous distribution (e.g., residual saturation) of the organic liquid (trichloroethene) had been established, and three subsequent times during column flushing. These data were used to characterize the morphology of the organic-liquid blobs as a function of dissolution, and to quantify changes in total organic-liquid volume, surface area, and water-organic liquid interfacial area. The dissolution dynamics of individual blobs appeared to be influenced by the local pore configuration. In addition to dissolution-induced shrinkage, some blobs were observed to separate into multiple distinct subunits. The median blob size decreased by approximately a factor of 2 at the point where approximately 90% of the initial organic-liquid volume had been removed. The ratio of capillary associated interfacial area to total water-organic liquid interfacial area increased by 50% at the point where approximately 95% of the initial mass had been removed. A nearly linear relationship was observed between both total and capillary associated interfacial area and organic liquid volumetric fraction. Changes in the measured aqueous-phase trichloroethene effluent concentrations were well correlated with changes in the volume, surface area, and number of blobs. The effluent concentration data were adequately described by a first-order mass transfer expression employing a constant value of the mass-transfer coefficient, with values for the water-organic liquid interfacial area obtained independently from the microtomography data.     

Transport and retention of colloidal aggregates of C60 in porous media: effects of organic macromolecules, ionic composition, and preparation method

The physical-chemical behavior of the fullerene C60 in environmental and physiological media is of interest for understanding the potential transport, exposure, and impacts of these materials on organisms and ecosystems. We considerthe role of electrolyte composition and concentration, the effect of organic macromolecules, and the mode of preparation of colloidal aggregates of C60 (nC60) on the deposition of these colloids in a porous medium such as a groundwater aquifer or a water treatment filter. Results for nC60 deposition are qualitatively consistent with trends anticipated by theory. Deposition was found to increase with increasing ionic strength, the presence of polysaccharide-type organic matter, and lower Darcy velocities. Factors that will tend to decrease the retention of these materials in porous media include a low ionic strength and the presence of humic-like substances, while the ionic strengths typical of many natural waters and the presence polysaccharide-based natural organic matter, as may be produced by algae or bacteria, will tend to favor deposition and reduced potential for exposure. Variability in the method of preparing colloidal aggregates of fullerenes was observed to yield significant differences in nC60 properties and transport behavior.     

Effect of particle size on droplet infiltration into hydrophobic porous media as a model of water repellent soil

The wettability of soil is of great importance for plants and soil biota, and in determining the risk for preferential flow, surface runoff, flooding,and soil erosion. The molarity of ethanol droplet (MED) test is widely used for quantifying the severity of water repellency in soils that show reduced wettability and is assumed to be independent of soil particle size. The minimum ethanol concentration at which droplet penetration occurs within a short time (≤ 10 s) provides an estimate of the initial advancing contact angle at which spontaneous wetting is expected. In this study, we test the assumption of particle size independence using a simple model of soil, represented by layers of small (~0.2-2 mm) diameter beads that predict the effect of changing bead radius in the top layer on capillary driven imbibition. Experimental results using a three-layer bead system show broad agreement with the model and demonstrate a dependence of the MED test on particle size. The results show that the critical initial advancing contact angle for penetration can be considerably less than 90° and varies with particle size, demonstrating that a key assumption currently used in the MED testing of soil is not necessarily valid.     

谷物冷却机降温通风粮温变化规律实验研究

科学高效使用通风设备对粮仓通风,可有效控制粮堆温度,保障粮食储藏安全。为探究谷物冷却机通风过程中的粮堆温度变化规律,采用谷物冷却机先后对2个浅圆仓、3个超高大平房仓进行冷却通风对比实验。结果表明,浅圆仓通风效果良好,温度迁移速率约为1.7～1.9 m/d,通风11 d后会降低整仓粮温,无通风死角;平房仓通风过程中会形成风道,打乱粮堆原始冷心,有效降低平均粮温但无法实现整仓粮温均匀降低,存在通风死角。     

Effects of powdered activated carbon pore size distribution on the competitive adsorption of aqueous atrazine and natural organic matter

The pore size distribution (PSD) of adsorbents has been found to be an important factor that affects adsorption capacity for organic compounds; consequently, it should influence competitive adsorption in multisolute systems. This research was conducted to show howthe PSD of activated carbon affects the competition between natural organic matter (NOM) and the trace organic contaminant atrazine, with a primary emphasis on quantifying the pore blocking mechanism of NOM competition. Isotherm tests were performed for both atrazine and NOM from a groundwater on five powdered activated carbons (PACs) with widely different PSDs. The capacity for NOM correlated best with the surface area of pores in the diameter range of 15-50 A, although some NOM also adsorbed in the smaller pores as evidenced by a reduction in capacity for atrazine when NOM was present. Kinetic tests for atrazine on PACs with various levels of preadsorbed NOM showed that the magnitude of the pore blockage effect by NOM was lower for PACs with higher surface area of pores with diameter in the range of 15-50 A. Therefore increasing pores in the size range where NOM adsorb can reduce the extent of the pore blockage competitive effect on the target compound atrazine. The effect of PSD was further studied with a flow-through PAC-membrane hybrid watertreatment system, in which experimental results successfully verified model simulations by the COMPSORB model.     

The influence of relative humidity and thermal acclimation on the survival of adult grain beetles in cooled grain

The influence of humidity and thermal acclimation on the survival of Cryptolestes ferrugineus, Oryzaephilus surinamensis, Rhyzopertha dominica, Sitophilus granarius, S. oryzae and Tribolium castaneum in cooled wheat or flour at 45 and 70% relative humidity was studied in the laboratory. Young adults were held continuously at 30 or 32°C; cooled gradually to 13.5°C and held at that temperature; cooled gradually to 9°C and held at that temperature; or transferred directly to 9°C.

Survival at low temperatures differed, often considerably, between species, being generally shortest in T. castaneum (0.7–16 weeks) and longest in S. granarius (5–40 weeks). There was considerable interaction between the effects of temperature and humidity, with survival being, to varying degrees, shorter in 45% r.h. than in 70% r.h. At 45% r.h., an equilibrium relative humidity common in Australian storages, all species survived when the grain was cooled to 13.5°C but only S. granarius survived 26 weeks in grain cooled to 9°C.

Chill-coma temperature and acclimation temperature were linearly related in all species at each humidity. Neither the slopes nor intercepts of the relationships were influenced by humidity. There was generally an inverse relationship between survival and chill-coma temperature.

At 45% r.h., the increase in survival at 9°C attributable to acclimation ranged from 2-fold in S. oryzae (0.9 weeks) to 3.5-fold in C. ferrugineus (3.8 weeks). Corresponding values for beetles at 70% r.h. ranged from 2.3-fold in R. dominica (2.4 weeks) to 7.9-fold in C. ferrugineus (6.9 weeks).