Vacuum‐enhanced recovery of water and NAPL: Concept and field test

Many hydrocarbon‐contaminated soils contain nonaqueous phase liquid (NAPL) following releases from facilities such as underground storage tanks and pipelines. The recovery of free product by pumping from extraction wells or trenches is often an essential prerequisite step prior to further remedial actions. Vacuum‐enhanced NAPL recovery (sometimes referred to as dual‐phase extraction or bioslurping) has attracted recent attention because it offers a means to increase NAPL recovery rates compared with conventional methods, and to accomplish dewatering, while also facilitating vapor‐based unsaturated zone cleanup. A conceptual model is presented that recognizes the effects that vacuum‐enhanced recovery has on soil water and NAPL, with a focus on liquid residing at negative gage pressures and therefore lacking sufficient potential energy to flow into a conventional recovery well or trench. The imposition during vacuum‐enhanced recovery of subatmospheric pressures within the subsurface can reduce the required potential energy (i.e., the entry suction), allowing liquid to be extracted that hitherto had not been able to flow into the well; moreover, it induces both pneumatic and hydraulic gradients toward the vacuum source that increase the rate of water and NAPL recovery. This conceptual model was tested during a 3‐week‐long pilot study at a South Carolina industrial site at which diesel fuel had been discovered in a saprolite formation. During Phase 1 of the pilot study, conventional recovery (liquid only) was carried out from a well screened at the water table, while during Phase 2 dual‐phase extraction was performed at the same well. The application of 27 kPa vacuum resulted in an increase in NAPL recovery from negligible (Phase 1) to approximately 6.6 l/d (Phase 2), with a concurrent increase in water recovery from approximately 190 to 760 l/ d. Neutron moisture probe observations revealed that vadose‐zone liquids underwent redistribution toward the extraction well in response to the onset of Phase 2, also in accordance with the conceptual model. An understanding of soil physical relationships is crucial to the successful application of these and other in situ soil remediation technologies.     

Comparison of Primary and Secondary Surfactant Flushing to Enhance LNAPL Recovery

Column experiments were conducted to compare the use of surfactants as a part of primary pumping to remove free phase NAPL to the use of surfactants to reduce or recover residual LNAPL in secondary treatment. Eight surfactant blends were tested, for a total of 48 column experiments. The column experiments show that the use of surfactants during primary pumping: (1) can potentially increase the amount of free product recovered; (2) can potentially reduce the amount of residual NAPL remaining after primary pumping; and (3) performs better than the use of surfactants to mobilize trapped residual NAPL.     

Effects of emulsion viscosity during surfactant‐enhanced soil flushing in porous media

Surfactants can potentially improve the efficiency of pump‐and‐treat technology for remediation of aquifers contaminated by nonaqueous phase liquids (NAPLs). However, the formation of emulsions during the removal process can Increase the viscosity in the system. This can result in pore clogging and reduction of flow, which inhibits the contaminant removal process. Formation of viscous emulsions has been identified in previous research as one of the probable causes for in situ field test failures using surfactant‐enhanced soil‐flushing technology. However, the effects of in situ emulsification and viscosity increases have not been quantified previously. The purpose of this article is to investigate effects of in situ emulsification on the remediation process. Laboratory column studies examined the mobilization of m‐xylene from porous media using a 1% alcohol ethoxylate surfactant solution (Witconol® SN90). Effects of in situ emulsification were determined. Glass columns (1.1 cm i.d. × 30 cm) were packed with 0.2‐mm glass beads to model soil media. Viscosities of emulsion solutions prepared with 1 % SN90 and various concentrations of m‐xylene were measured and compared with effluent collected during column‐flushing experiments. It was determined that as m‐xylene concentration in the emulsion solution Increases, viscosity increases. Viscosity increases caused a decrease in relative permeability within the soil column. As a result, the hydraulic gradient required to maintain a constant flowrate of 1.1 ml/min (using a syringe pump) through the soil column increased. Results show that a relatively small increase in viscosity could have a noticeable effect on the mobilization process. It is suggested that the surfactant/contaminant systems be screened to determine emulsion theology and the potential effects on the remediation process. The use of low‐concentration alcohol cosurfactants to reduce system viscosity was evaluated and was shown to be ineffective.     

The temperature dependence of shoot hydraulic resistance: implications for stomatal behaviour and hydraulic limitation

Recent soil pressurization experiments have shown that stomatal closure in response to high leaf–air humidity gradients can be explained by direct feedback from leaf water potential. The more complex temperature‐by‐humidity interactive effects on stomatal conductance have not yet been explained fully. Measurements of the change in shoot conductance with temperature were made on Phaseolus vulgaris (common bean) to test whether temperature‐induced changes in the liquid‐phase transport capacity could explain these temperature‐ by‐humidity effects. In addition, shoot hydraulic resistances were partitioned within the stem and leaves to determine whether or not leaves exhibit a greater resistance. Changes in hydraulic conductance were calculated based on an Ohm’s law analogy. Whole‐plant gas exchange was used to determine steady‐ state transpiration rates. A combination of in situ psychrometer measurements, Scholander pressure chamber measurements and psychrometric measurements of leaf punches was used to determine water potential differences within the shoot. Hydraulic conductance for each portion of the pathway was estimated as the total flow divided by the water potential difference. Temperature‐induced changes in stomatal conductance were correlated linearly with temperature‐induced changes in hydraulic conductance. The magnitude of the temperature‐induced changes in whole‐plant hydraulic conductance was sufficient to account for the interactive effects of temperature and humidity on stomatal conductance.     

Acknowledgment

In a water wet porous medium, the antecedent moisture content controls the entrapment of LNAPL at low capillary numbers. A two‐phase retention cell study of entrapment was conducted for LNAPL water systems in a carbonate sand. For two different LNAPL water systems, it was found that a linear expression related the residual LNAPL saturation to the antecedent water saturation. The prediction of trapped LNAPL saturation compares favorably to long‐column test data obtained for the same sand. A trapping model was developed, and its predictions were compared to field measurements of trapped LNAPL saturation. Deviations between predicted and measured LNAPL saturations arose when there was a change in the median pore size distribution. In addition, a series of three‐phase (air‐LNAPL‐water) retention cell tests measured the amount of LNAPL that became trapped when the water phase was maintained at a constant saturation during LNAPL withdrawal under a negative pressure head. Under these conditions, the amount of trapped LNAPL was higher than that measured by two‐phase tests at the same water saturation.     

Physical properties of oil-particle aggregate (OPA)-containing sediments

ABSTRACT

Sediments composed of oil-particle aggregates (OPAs) have unique physical characteristics. These in situ deposited sediments develop at locations where a continual or nearly continual discharge of non-aqueous phase liquids (NAPLs) have occurred, or are occurring through time. The NAPL discharged into the surface water body interacts with suspended particles in the water column. The particles adhere to the suspended NAPL, which generally is in the form of a bead, and produce a discrete aggregate. As the aggregate grows in response to additional particle adherence, the density of the unit increases and deposition occurs. The resulting sediment consists of a collection of discrete OPAs that form a network with small pores, where oil is tightly bound and/or contained. Porosity, water content, and dry bulk density measurements indicate the sediment formed by OPA deposition is physically unique. Although the sediment consists of a very open pore structure, the pore openings are relatively small, typically being less than 5 microns in diameter. These small pores inhibit fluid movement. Results of physical property testing suggest the OPA structure is retained upon deposition. Although the sediment contains NAPL, this original OPA structure inhibits the oil beads from coalescing, which would enable NAPL flow.     

NAPL mobility of OPA-containing sediments

ABSTRACT

In situ deposited non-aqueous phase liquid (IDN) sediments have unique characteristics that inherently mitigate the movement of separate phase liquids. IDN sediments are composed of oil-particle aggregates (OPAs). OPAs consist of an oil bead or globule with attached solid particles, such as clay platelets, silt and sand granules, and/or organic materials. IDN sediments develop at locations where a continual or near continual discharge of non-aqueous phase liquids (NAPLs) have occurred over a period of time. IDN sediments consist of an open network of small pores where fluids are retained. Although the pore structure is very open, the pore openings are relatively small, which appears to inhibit fluid movement. In particular, capillary pressure analyses indicate that NAPL was not generally released until pressures of at least 15 pounds per square inch (psi) were induced. In addition, centrifuge testing at 1,000 G shows that NAPL immobility is observed in samples at NAPL saturations as high a 12%. These data suggest that NAPL is retained within the smallest pores and is encapsulated within a network of larger pores filled with water. Although the sediment contains NAPL, this original OPA structure appears to inhibit the oil beads from coalescing, preventing NAPL flow.     

Laboratory studies of steam stripping of LNAPL‐contaminated soils

Bench‐scale laboratory experiments were conducted to evaluate the effectiveness of steam injection for in situ remediation of soils contaminated by light nonaqueous‐phase liquids (LNAPLs). Several parametric studies were performed with various combinations of soils, LNAPLs, and steam injection conditions.

An increase in steam injection pressure produced a significant increase in LNAPL recovery efficiency. An increase in steam injection pressure from 12.4 to 44.8 kPa resulted in increased LNAPL recovery efficiency from 86 to 95% after one pore volume of steam injection. Higher steam injection pressure yielded maximum LNAPL recovery efficiency in significantly less time and required a smaller amount of steam than at low pressure.

An increase in soil grain size or an increase in grain‐size‐distribution slope resulted in increased LNAPL recovery efficiency. The final LNAPL residual saturation was approximately 0.5% for coarse‐grained soils and 1.8% for soils with finer grain sizes. Soils with finer grains required more time for treatment than soils with coarser grains.

Steam injection experiments with No. 2 heating oil and with jet fuel showed no significant variation in steam front propagation, temperature profile, and maximum LNAPL recovery efficiency. The LNAPL residual saturation after steam injection was essentially independent of the starting LNAPL saturation.     

Microemulsion‐mediated removal of residual gasoline from soil columns

In situ pumping of micellular solutions of surfactant (S) and cosurfactant (CoS) in water (W) through contaminated soils or aquifers offers potential for enhanced remediation of residual nonaqueous‐phase liquids (NAPLs). Extremely low interfacial tension generated between a W/S/CoS mixture and residual NAPL in soil pores may initially mobilize the NAPL, which is then transported temporarily as a separate phase by immiscible displacement. The NAPL is then solubilized by micro‐emulsification as the W/S/CoS mixture forms a stable W/S/CoS/NAPL micro‐emulsion that undergoes miscible displacement through the pore space. This remediation technique was tested under laboratory conditions by sequentially flushing a saline solution and a W/S/CoS mixture through columns of a sandy soil recently contaminated with residual leaded gasoline (LG). Prior to the flushings, the soil was initially contaminated by applying a W/S/CoS/LG microemulsion. A simple conceptual transport model with kinetic clogging of soil pores adequately described breakthrough curves for gasoline and organolead in the soil columns.     

The relationship between Chironomus plumosus burrows and the spatial distribution of pore-water phosphate, iron and ammonium in lake sediments

1. To study the influence of chironomids on the distribution of pore‐water concentrations of phosphate, iron and ammonium, we conducted a laboratory experiment using mesocosms equipped with two‐dimensional pore‐water samplers, filled with lake sediment and populated with different densities of Chironomus plumosus. 2. Specially designed mesocosms were used in the study. A 6‐mm deep space between the front plate and the pore‐water sampler at the back plate was just thick enough to allow the chironomids to live undisturbed, yet thin enough to force all the burrows into a two‐dimensional plane. 3. The courses of the burrows were observed during the experiment as oxidised zones surrounding them, as well as being identified with an X‐ray image taken at the end of the experiment. 4. We investigated the relationship between C. plumosus burrows and spatial patterns of pore‐water composition. Concentrations of the three ions were significantly less around ventilated burrows (54% to 24%), as bioirrigation caused a convective exchange of pore‐water enriched with dissolved species compared with the overlying water, and also because oxygen imported into the sediment resulting in nitrification of ammonium, oxidation of iron(II) and a co‐precipitation of phosphate with Fe(III) oxyhydroxides. 5. In mesocosms with chironomids, new (redox) interfaces occurred with diffusive pore‐water gradients perpendicular to the course of burrows and the site of major phosphate, ammonium and iron(II) release shifted from the sediment surface to the burrow walls.     

Influence of climate variability on plant production and N‐mineralization in Central US grasslands

Abstract. We assessed the influence of annual and seasonal climate variability over soil organic matter (SOM), above‐ground net primary production (ANPP) and in situ net nitrogen (N) mineralization in a regional field study across the International Geosphere Biosphere Programme (IGBP) North American mid‐latitude transect (Koch et al. 1995). We hypothesized that while trends in SOM are strongly correlated with mean climatic parameters, ANPP and net N‐mineralization are more strongly influenced by annual and seasonal climate because they are dynamic processes sensitive to short‐term variation in temperature and water availability. Seasonal and monthly deviations from long‐term climatic means, particularly precipitation, were greatest at the semi‐arid end of the transect. ANPP is sensitive to this climatic variability, but is also strongly correlated with mean annual climate parameters. In situ net N‐mineralization and nitrification were weakly influenced by soil water content and temperature during the incubation and were less sensitive to seasonal climatic variables than ANPP, probably because microbial transformations of N in the soil are mediated over even finer temporal scales. We found no relationship between ANPP and in situ net N‐mineralization. These results suggests that methods used to estimate in situ net N‐mineralization are inadequate to represent N‐availability across gradients where microbial biomass, N‐immobilization or competition among plants and microbes vary.     

An ignored anatomical variable: pore shape shows a nonrandom variation pattern in xylem cross sections

Anatomical characteristics of vessels have a profound impact on the hydraulic conductivity of the xylem. However, pore shape, the cross‐section shape of a vessel, has been ignored in previous hydraulic architecture studies. In this study, we examined whether pore shape tended to be circular, and whether variation in pore shape may be affected by water flow path‐length and cambial age. The circularity of pores in Betula platyphylla Roth and Quercus mongolica (only earlywood) were analyzed from the pith to the bark along the water flow path. It was found that although there were very few pores with perfectly circular shape, solitary pores did tend to be regularly circular. The pore shape of sequentially formed vessels in the xylem was influenced by cambial age and flow path‐length. Pore shape tended to be more circular as flow path‐length increased or cambial age decreased. Circular pore shape appears to be an important morphogenetic mechanism for hydraulic architecture development, and studies of it expand our understanding of the structure–function relationships of the xylem.     

Stomatal dynamics are limited by leaf hydraulics in ferns and conifers: results from simultaneous measurements of liquid and vapour fluxes in leaves

Stomatal responsiveness to vapour pressure deficit (VPD) results in continuous regulation of daytime gas‐exchange directly influencing leaf water status and carbon gain. Current models can reasonably predict steady‐state stomatal conductance (g_s) to changes in VPD but the g_s dynamics between steady‐states are poorly known. Here, we used a diverse sample of conifers and ferns to show that leaf hydraulic architecture, in particular leaf capacitance, has a major role in determining the g_s response time to perturbations in VPD. By using simultaneous measurements of liquid and vapour fluxes into and out of leaves, the in situ fluctuations in leaf water balance were calculated and appeared to be closely tracked by changes in g_s thus supporting a passive model of stomatal control. Indeed, good agreement was found between observed and predicted g_s when using a hydropassive model based on hydraulic traits. We contend that a simple passive hydraulic control of stomata in response to changes in leaf water status provides for efficient stomatal responses to VPD in ferns and conifers, leading to closure rates as fast or faster than those seen in most angiosperms.     

The effect of soil‐particle size on hydrocarbon entrapment near a dynamic water table

The entrapment of residual hydrocarbon globules by water table fluctuations can produce a long‐term contamination threat to groundwater supplies that is difficult to remove. The mobilization of entrapped hydrocarbon globules depends on the balance between capillary and gravitational forces represented by the Bond number. It is important to estimate the potential for hydrocarbon entrapment at a spill site due to its influence on the effectiveness of remediation efforts. The present work focuses on the influence of particle diameter on hydrocarbon entrapment for a typical LNAPL (light nonaqueous‐phase liquid). Laboratory column tests have been conducted using a dual‐beam gamma densitometer to measure saturations of the three phases (water, air, and hydrocarbon). Soltrol 170^®, a solvent manufactured by Phillips 66 Co., is used as the hydrocarbon. Residual saturation of the Soltrol is measured after fluctuations in water table level to establish the distribution and consistency of hydrocarbon entrapment below the water table. Glass particles of nearly uniform size were used to represent a sandy soil. In the experiments, average particle sizes ranged from 210 to 6000 μm. Data were also taken using the synthetic soil matrix approved by the U.S. Environmental Protection Agency (EPA) for contamination studies. Results show that the distribution of trapped LNAPL is quite uniform and that the average residual saturation is about 13% up to a particle diameter of 710 μm. Above this diameter, residual saturation decreases with particle size. The corresponding critical Bond number, determined experimentally, agrees well with the predicted value of 1.6.     

Regulation of ephrin‐A expression in compressed retinocollicular maps

Retinotopic maps can undergo compression and expansion in response to changes in target size, but the mechanism underlying this compensatory process has remained a mystery. The discovery of ephrins as molecular mediators of Sperry's chemoaffinity process allows a mechanistic approach to this important issue. In Syrian hamsters, neonatal, partial (PT) ablation of posterior superior colliculus (SC) leads to compression of the retinotopic map, independent of neural activity. Graded, repulsive EphA receptor/ephrin‐A ligand interactions direct the formation of the retinocollicular map, but whether ephrins might also be involved in map compression is unknown. To examine whether map compression might be directed by changes in the ephrin expression pattern, we compared ephrin‐A2 and ephrin‐A5 mRNA expression between normal SC and PT SC using in situ hybridization and quantitative real‐time PCR. We found that ephrin‐A ligand expression in the compressed maps was low anteriorly and high posteriorly, as in normal animals. Consistent with our hypothesis, the steepness of the ephrin gradient increased in the lesioned colliculi. Interestingly, overall levels of ephrin‐A2 and ‐A5 expression declined immediately after neonatal target damage, perhaps promoting axon outgrowth. These data establish a correlation between changes in ephrin‐A gradients and map compression, and suggest that ephrin‐A expression gradients may be regulated by target size. This in turn could lead to compression of the retinocollicular map onto the reduced target. These findings have important implications for mechanisms of recovery from traumatic brain injury. © 2012 Wiley Periodicals, Inc. Develop Neurobiol, 2013     

The effect of interfacial tension on hydrocarbon entrapment and mobilization near a dynamic water table

The entrapment of residual hydrocarbon ganglia during water table fluctuations can produce a long‐term contamination threat to groundwater supplies that is difficult to remove. The mobilization of entrapped hydrocarbon ganglia depends on the balance between capillary and gravitational forces represented by the Bond number. The present work focuses on the influence of the interfacial tension between the hydrocarbon and the surrounding water on the entrapment and mobilization of the residual ganglia. Laboratory column tests using glass beads as the porous medium have been conducted to determine the residual saturation of a hydrocarbon (Soltrol 170) trapped during vertical displacements due to a rising water table and the necessary decrease in interfacial tension to mobilize these trapped ganglia. The interfacial tension was decreased by the addition of isopropyl alcohol to the water phase. Saturations of the three phases (water, hydrocarbon, and air) were measured with a dual‐beam y‐densitometer. The results for residual hydrocarbon saturation at various interfacial tensions were combined with previous results for different particle diameters to provide a general relationship between residual saturation and Bond number. The relationship is expressed in an empirical correlation valid for Bond numbers between 0.001 and 1.2.     

An evaluation of abiotic carbon sinks in deserts

Recent field studies have reported anomalous CO₂ uptake using eddy‐covariance techniques in arid and semiarid ecosystems. The rates of CO₂ uptake are incompatible with changes in situ of organic carbon pools. Here, I examine several potential mechanisms of abiotic CO₂ uptake in arid and semiarid soils: atmospheric pressure pumping, carbonate dissolution, and percolation of soil water through the vadose zone. Each mechanism is deemed inadequate to explain the observations of the eddy‐covariance systems, which must now be questioned for their accuracy in desert ecosystems.     

Thermal variation of organic fluid properties and impact on thermal remediation feasibility

Preliminary evaluations of the feasibility of thermal remediation techniques such as hot water flooding and steam flushing can be conducted with a knowledge of the influence of temperature on organic fluid properties such as interfacial tension, density, viscosity, solubility, vapor pressure, and Henry's constant. Relationships quantifying the effect of these fluid properties on organic removal and empirical equations for predicting the thermal variation of fluid properties are reviewed. Methods for measuring these properties are reviewed and applied to the characterization of perchloroethylene and a transformer oil. The importance of various removal mechanisms associated with thermal remediation is evaluated for these two fluids. Perchloroethylene solubilities increased by approximately 60% as temperature increased from 30°C to 90°C, suggesting that increased solubilization at higher temperatures would not be a significant removal mechanism. Viscosity and density reductions for both NAPLs were small, indicating that hydraulic displacement of NAPL would not be greatly enhanced with hot water or steam flushing. Interfacial tension decreases were not great enough to cause concem about downward remobilization of pools and residual zones of NAPLs. Capillary numbers for hot water flooding decreased for both NAPL, suggesting that hot water flooding would not enhance hydraulic removal of entrapped NAPL.     

Protons,pumps, and potentials: Control of cytochrome oxidase

Cytochromec oxidase oxidizes cytochromec and reduces molecular oxygen to water. When the enzyme is embedded across a membrane, this process generates electrical and pH gradients, and these gradients inhibit enzyme turnover. This respiratory control process is seen both in intact mitochondria and in reconstituted proteoliposomes. Generation of pH gradients and their role in respiratory control are described. Both electron and proton movement seem to be implicated. A topochemical arrangement of redox centers, like that in the photosynthetic reaction center and the cytochromebc ₁ complex, ensures charge separation as a result of electron movement. Proton translocation does not require such a topology, although it does require alternating access to the two sides of the membrane by proton-donating and accepting groups. The sites of respiratory control within the enzyme are discussed and a model presented for electron transfer and proton pumping by the oxidase in the light of current knowledge of the transmembranous location of the redox centers involved.     

Stem and leaf hydraulic properties are finely coordinated in three tropical rain forest tree species

Coordination of stem and leaf hydraulic traits allows terrestrial plants to maintain safe water status under limited water supply. Tropical rain forests, one of the world's most productive biomes, are vulnerable to drought and potentially threatened by increased aridity due to global climate change. However, the relationship of stem and leaf traits within the plant hydraulic continuum remains understudied, particularly in tropical species. We studied within‐plant hydraulic coordination between stems and leaves in three tropical lowland rain forest tree species by analyses of hydraulic vulnerability [hydraulic methods and ultrasonic emission (UE) analysis], pressure‐volume relations and in situ pre‐dawn and midday water potentials (Ψ). We found finely coordinated stem and leaf hydraulic features, with a strategy of sacrificing leaves in favour of stems. Fifty percent of hydraulic conductivity (P₅₀) was lost at ?2.1 to ?3.1 MPa in stems and at ?1.7 to ?2.2 MPa in leaves. UE analysis corresponded to hydraulic measurements. Safety margins (leaf P₅₀ – stem P₅₀) were very narrow at ?0.4 to ?1.4 MPa. Pressure‐volume analysis and in situ Ψ indicated safe water status in stems but risk of hydraulic failure in leaves. Our study shows that stem and leaf hydraulics were finely tuned to avoid embolism formation in the xylem.