Immiscible fluid flow in porous media: dielectric properties

The movement and retention of immiscible fluids in porous media was determined using a microwave dielectric measuring technique. The technique was used to monitor the composite dielectric constant of columns containing model soil materials to observe the effect of displacement of various saturating fluids by water and determine the retained immiscible components. Various combinations of displacing fluids, both miscible and immiscible, were studied, yielding time-dependent flow characteristics as well as the total retention factor. The flow circumstances were similar to what would be encountered in an accidental spill of chlorocarbons or crude oil.The retention of chlorocarbons and crude oil was determined for model soils consisting of sand or glass spheres. The storage capacity of the sand for immiscible fluids was dependent on the fluid initially saturating the porous medium. For chlorocarbons, it was increased in water-wet compared to dry sands while the inverse was true for crude oil. The retention of crude oil in the sand was dependent on the water flow velocity and was much larger than that for chlorocarbons. The crude oil could be displaced by solvents such as cyclohexane in the sand but the net volume occupied by the two immiscible fluids after water flushing did not change appreciably, i.e. the crude oil component was replaced by the solvent. Application of a miscible fluid-water mixture or surfactants improved the ability of water to displace the immiscible fluid from the sand column.     

Time-lapse 3-D seismic imaging of shallow subsurface contaminant flow

This paper presents a physical modelling study outlining a technique whereby buoyant contaminant flow within water-saturated unconsolidated sand was remotely monitored utilizing the time-lapse 3-D (TL3-D) seismic response. The controlled temperature and pressure conditions, along with the high level of acquisition repeatability attainable using sandbox physical models, allow the TL3-D seismic response to pore fluid movement to be distinguished from all other effects. TL3-D seismic techniques are currently being developed to monitor hydrocarbon reserves within producing reservoirs in an endeavour to improve overall recovery. However, in many ways, sandbox models under atmospheric conditions more accurately simulate the shallow subsurface than petroleum reservoirs. For this reason, perhaps the greatest application for analogue sandbox modelling is to improve our understanding of shallow groundwater and environmental flow mechanisms. Two fluid flow simulations were conducted whereby air and kerosene were injected into separate water-saturated unconsolidated sand models. In both experiments, a base 3-D seismic volume was recorded and compared with six later monitor surveys recorded while the injection program was conducted. Normal incidence amplitude and P-wave velocity information were extracted from the TL3-D seismic data to provide visualization of contaminant migration. Reflection amplitudes displayed qualitative areal distribution of fluids when a suitable impedance contrast existed between pore fluids. TL3-D seismic reflection tomography can potentially monitor the change in areal distribution of fluid contaminants over time, indicating flow patterns. However, other research and this current work have not established a quantifiable relationship between either normal reflection amplitudes and attenuation and fluid saturation. Generally, different pore fluids will have unique seismic velocities due to differences in compressibility and density. The predictable relationships that exist between P-wave velocity and fluid saturation can allow a quantitative assessment of contaminant migration.     

Visualization by light transmission of oil and water contents in transient two-phase flow fields

The difficulty of determining transient fluid contents in a soil–oil–water system is hampering an understanding of the system's flow characteristics. In this paper, we describe a light transmission method (LTM) which can rapidly obtain oil and water contents throughout a large two-dimensional flow field of silica sand. By appropriately coloring the water with 0.005% FD&C blue #1, the hue of the transmitted light is found to be directly related to the water content within the porous media. The hue provides a high resolution measurement of the water and oil contents in transient flow fields (such as unstable flow). Evaluation of the reliability of LTM was assessed by checking the mass balance for a known water injection and its utility in visualizing a whole flow field was exemplified for unstable fingered flow by comparing fluid contents to those obtained with synchrotron X-ray radiation.     

Speciation of Cd and Zn in contaminated soils assessed by DGT-DIFS, and WHAM/Model VI in relation to uptake by spinach and ryegrass

A pot experiment was carried out to investigate the impact of Cd and Zn extractability in soil and speciation in pore water of industrial contaminated soils, on metal concentration in a metal sensitive species like spinach (Spinacia oleracea) and a more metal tolerant species like Italian ryegrass (Lolium multiflorum). For chemical speciation of Cd and Zn in pore water, WHAM/Model VI version 6.0 was used. The DGT technique was used to determine the effective concentration, C(E), of Cd and Zn in soils. The free ion activity in pore water correlated well with the contents in plants, and there was a linear relationship between the C(E) values and the concentration of Cd and Zn in both spinach and ryegrass in the non-toxic range. However, the C(E) values usually overestimated the plant contents when plants, particularly the spinach plants, were subjected to toxic concentration in the pore water. Metal uptake decreased in plants affected by toxicity, whereas metal binding to the Chelex resin did not. Thus, we found no linear relationship between the C(E) and metal contents in spinach, whereas a linear relationship was found between C(E)-Zn and the Zn concentration in ryegrass (r2=0.96, p<0.001). For Cd in ryegrass this relationship was weak (r2=0.53, p=0.18). This study indicates that the transport of metals from labile metal pools to the DGT-resin is linearly related to plant uptake only when plants are growing well, and that the applicability of DGT as an indicator for plant uptake seems species dependent.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Contribution of the diffusive exchange method to the characterization of pore-water in consolidated argillaceous rocks

Consolidated argillaceous rocks, potential host rocks for nuclear waste disposal, display particular properties (low water content, very small pore size) that require specific methods, especially for the characterization of their pore-water. The diffusive exchange method was applied to the claystone of Tournemire by taking into account the effect of swelling or micro-cracks induced by drilling. The good agreement of diffusion parameters with those obtained from the through-diffusion method showed that the extent of this disturbance was low. This method led to stable isotope content values in pore-water in good agreement with those measured in the fracture fluids located in the vicinity, validating the method. On the contrary, the vacuum distillation technique gave a systematic depletion in heavy isotopes of water, probably induced by an incomplete extraction of pore-water. For the chloride tracer, the determination of the accessible porosity on each sample allowed the estimate of chloride concentration of pore-water to be improved, by taking into account all the petrophysical heterogeneities.     

Residual gasoline saturation in unsaturated soil with and without organic matter

The goal of this study was to investigate the influence of one variable, natural organic matter, on residual gasoline saturation in sandy soils. Capillary pressure-saturation (P_c−S) relationships (air-gasoline) were determined for three physically-similar sandy soils, with different organic carbon contents (0.086%, 0.89% and 1.65%) and residual gasoline saturations were compared. Two initial moisture conditions, residual water saturation and air-dry, were evaluated. One soil type was packed to two different bulk densities. Visualization of the soils using cryo-scanning electron microscopy was performed to aid in better understanding the role of the organic matter in the soil. The results showed that soils with higher organic contents had higher residual gasoline saturations when starting with an initially air-dry soil. Increasing the bulk density of the same air-dried soil resulted in an increase in residual gasoline saturation. In the presence of a residual water saturation, however, residual gasoline saturations were virtually identical for the three soils and independent of bulk density; approximately 5–10 times lower than in soil that was initially air-dry. The presence of the residual water effectively coated the surface of the soil thereby reducing or eliminating gasoline/soil interactions. Some residual water may also be occupying very small pore spaces, making these locations inaccessible to the gasoline.     

Bacterial deposition in unsaturated porous media as related to surface properties

Transport of Escherichia coli, Pseudomonas fluorescens and Bacillus subtilis in silica sand under water-unsaturated conditions was investigated using column experiments. It was hypothesised that bacterial deposition was due to their interactions within the pore environment, which was a function of their surface physicochemical properties as well as pore water chemistry. Surface thermodynamic properties of these bacterial strains were measured independently by means of contact angle measurements under different water saturation conditions using variable lawn moisture contents. Bacterial interactions with the liquid-gas interface and the porous media were calculated based on their surface properties and were related to their transport observations.     

Differential sorption behaviour of aromatic hydrocarbons on charcoals prepared at different temperatures from grass and wood

Naturally occurring charcoals are increasingly being recognized as effective sorbents for organic compounds. In this study we investigated the sorption of benzene and toluene in single-sorbate and bi-sorbate systems on different types of charcoals produced in laboratory, employing the batch sorption technique. Air dried plant materials from Phalaris grass (Phalaris tuberosa) and Red Gum wood (Eucalyptus camadulensis) were combusted under limited oxygen supply at 250 degrees C, 450 degrees C, and 850 degrees C. The resulting charcoals were characterized for their specific surface areas, total cation content, and pore size distributions (pore size distribution only for wood combusted at 450 degrees C and 850 degrees C). For the materials treated at 850 degrees C not only the surface area, microporosity, and total amount of sorbed sorbate increased markedly, but also the non-linearity of the sorption isotherm. The pore size distributions and surface areas as well as an indifferent sorption behaviour and competition effects for both sorbates indicated that pore filling mechanisms were the dominating processes governing the sorption on these microporous, high temperature treated materials. For the materials treated at lower temperatures the affinity of toluene was higher compared to that of benzene. In the bi-sorbate system the overall uptake of benzene increased. These phenomena might be due to the stronger hydrophobicity of toluene, and to a varying potential for swelling of the matrix and pore deformation by the two sorbates. The significantly lower sorption capacity of the Phalaris-derived material compared to the Red Gum charcoal correlated with its smaller surface area and higher cation content.     

A set of constitutive relationships accounting for residual NAPL in the unsaturated zone

Although laboratory experiments show that non-aqueous phase liquid (NAPL) is retained in the unsaturated zone, no existing multiphase flow model has been developed to account for residual NAPL after NAPL drainage in the unsaturated zone. We developed a static constitutive set of saturation-capillary pressure relationships for water, NAPL and air that accounts for both this residual NAPL and entrapped NAPL. The set of constitutive relationships is formulated similarly to the set of scaled relationships that is frequently applied in continuum models. The new set consists of three fluid-phase systems: a three-phase system and a two-phase system, that both comply with the original constitutive model, and a newly introduced residual NAPL system. The new system can be added relatively easily to the original two- and three-phase systems. Entrapment is included in the model. The constitutive relationships of the non-drainable residual NAPL system are based on qualitative fluid behavior derived from a pore scale model. The pore scale model reveals that the amount of residual NAPL depends on the spreading coefficient and the water saturation. Furthermore, residual NAPL is history-dependent. At the continuum scale, a critical NAPL pressure head defines the transition from free, mobile NAPL to residual NAPL. Although the Pc-S relationships for water and total liquid are not independent in case of residual NAPL, two two-phase Pc-S relations can represent a three-phase residual system of Pc-S relations. A newly introduced parameter, referred to as the residual oil pressure head, reflects the mutual dependency of water and oil. Example calculations show consistent behavior of the constitutive model. Entrapment and retention in the unsaturated zone cooperate to retain NAPL. Moreover, the results of our constitutive model are in agreement with experimental observations.     

Water-based condensation particle counters for environmental monitoring of ultrafine particles

TSI Inc. (Shoreview, MN) has introduced three new water-based condensation particle counters (WCPCS) that were designed to detect airborne particles larger than 2.5 nm (model 3786), 5 nm (model 3785), and either 10 or 20 nm (model 3782). These WCPCs are well suited for real-time, environmental monitoring of number concentration of airborne ultrafine particles. Their unique design incorporates the use of water as the working fluid instead of alcohol. Water is odor free, readily available, and eliminates the problem of water condensation and absorption into alcohol working fluids during operation in humid environments. In this study, the performance of three TSI WCPCs was characterized for several aerosol compositions, including sucrose, salt (NaCl), dioctyl sebacate (DOS), dioctyl phthalate (DOP), emery oil (poly-alpha-olefin), silver, impurity residue particles, and ambient aerosol particles. All particles were size selected using a nano differential mobility analyzer (nano-DMA; model 3085, TSI Inc.) to create monodisperse challenge aerosols. The challenge aerosol was mixed uniformly with clean makeup flow and split into a WCPC and a reference instrument to determine the counting efficiency of the WCPC. For the model 3785 WCPC, the D50 (i.e., the particle diameter with 50% counting efficiency) was determined to be 3.1 nm for salt particles, 4.7 nm for sucrose and ambient particles, 5.6 nm for silver particles, and >50 nm for ultrapure oil particles. The sensitivity to oil droplets increased dramatically (D50 < 10 nm) when the oil was slightly contaminated. The D50 of model 3786 ultrafine water-based CPC (UWCPC) was 2.4 nm for impurity residue particles. The D50 of the model 3782 WCPC was 10.8 (with a nominal setting of 10 nm) or 19.8 nm (with a nominal setting of 20 nm) for sucrose particles. All three WCPCs have response times of less than 2 or 3 sec and are therefore able to detect fast-changing events.     

Combination of biodegradable organic matter quantification and XAD-fractionation as effective working parameter for the study of biodegradability in environmental and anthropic samples

The present work proposes to couple quantification of biodegradable organic matter (BOM) with XAD-fractionation. Biodegradable dissolved organic carbon (BDOC) and assimilable organic carbon (AOC) analysis were applied to fractions extracted by XAD resin. An examination of mechanisms during consumption of BOM has been carried out, using comparison of biodegradability between the bulk BOM of samples (landfill leachate and surface water) and the sum of BOM contents obtained for the extracted fractions. Results point out that a cometabolism mechanism seems to be involved during the degradation of the surface water fractions. On the other hand, fractions extracted from the leachate seem to be degraded as primary substratum. The more reactive fractions of the leachate (HPO*) and the water (HPI) have been identified as well the less reactive (HPI* and HPO, respectively). The BDOC contents determined for the bulk leachate and surface water are 10+/-2% and 28+/-2%, respectively. The values of AOC are 107+/-18 microg C acetate L(-1) and 163+/-21 microg C acetate L(-1), respectively.     

Behavior and stability of organic contaminant droplets in aqueous solutions

The behavior of several hydrophobic organic compounds (HOCs) in water at concentrations close to and above their maximum solubility values was studied. For this purpose, solutions of benzene, toluene, xylene, trichloroethylene (TCE) and a mixture of them were prepared in excess in freshwater and in saltwater, and solution stability was examined. High organic concentrations were found to remain stable in both freshwater and saltwater. In saltwater, for example, toluene and xylene concentrations remained as high as 14 and 26 times their solubilities, respectively, over a period of 6 days, while in freshwater, their concentrations remained 8 and 30 times their solubilities over the same period. This phenomenon is attributed to the presence of stable organic droplets, which were observed using optical microscopy. In addition, the transport of HOC droplets through sand is demonstrated, using an experimental system consisting of a saltwater source reservoir connected by a porous inactive sand layer to a freshwater collector reservoir.     

Surfactant-induced changes in gravity fingering of water through a light oil

Gravity-driven preferential flow (fingering) can greatly affect how one fluid displaces another in the subsurface. We have studied the internal properties of these preferential flow paths for water, with and without surfactants, infiltrating into oil saturated porous media using synchrotron X-rays, and miniature tensiometers to characterize fluid content and pressure relationships. We also used a light transmission technique to visualize overall flow pattern. Capillary pressure and water content decrease behind the front, similar to fingers in air-dry sand, with quantitative differences for five different surfactants with surface tensions ranging from 4–21 g/s². Using unstable flow theory, the finger widths, capillary pressure drops within the fingers, finger tip lengths, and finger splitting dynamics were scaled successfully with interfacial tension, fluid density, and the contact angle using the fingers in air–water systems as the reference.     

Analysis and comparison of inertinite-derived adsorbent with conventional adsorbents

To increase U.S. petroleum energy-independence, the University of Texas at Arlington (UT Arlington) has developed a coal liquefaction process that uses a hydrogenated solvent and a proprietary catalyst to convert lignite coal to crude oil. This paper reports on part of the environmental evaluation of the liquefaction process: the evaluation of the solid residual from liquefying the coal, called inertinite, as a potential adsorbent for air and water purification. Inertinite samples derived from Arkansas and Texas lignite coals were used as test samples. In the activated carbon creation process, inertinite samples were heated in a tube furnace (Lindberg, Type 55035, Arlington, UT) at temperatures ranging between 300 and 850 degrees C for time spans of 60, 90, and 120 min, using steam and carbon dioxide as oxidizing gases. Activated inertinite samples were then characterized by ultra-high-purity nitrogen adsorption isotherms at 77 K using a high-speed surface area and pore size analyzer (Quantachrome, Nova 2200e, Kingsville, TX). Surface area and total pore volume were determined using the Brunauer Emmet, and Teller method, for the inertinite samples, as well as for four commercially available activated carbons (gas-phase adsorbents Calgon Fluepac-B and BPL 4 x 6; liquid-phase adsorbents Filtrasorb 200 and Carbsorb 30). In addition, adsorption isotherms were developed for inertinite and the two commercially available gas-phase carbons, using methyl ethyl ketone (MEK) as an example compound. Adsorption capacity was measured gravimetrically with a symmetric vapor sorption analyzer (VTI, Inc., Model SGA-100, Kingsville, TX). Also, liquid-phase adsorption experiments were conducted using methyl orange as an example organic compound. The study showed that using inertinite from coal can be beneficially reused as an adsorbent for air or water pollution control, although its surface area and adsorption capacity are not as high as those for commercially available activated carbons. Implications: The United States currently imports two-thirds of its crude oil, leaving its transportation system especially vulnerable to disruptions in international crude supplies. UT Arlington has developed a liquefaction process that converts coal, abundant in the United States, to crude oil. This work demonstrated that the undissolvable solid coal residual from the liquefaction process, called inertinite, can be converted to an activated carbon adsorbent. Although its surface area and adsorption capacity are not as high as those for commercially available carbons, the inertinite source material would be available at no cost, and its beneficial reuse would avoid the need for disposal.     

抗生素废水的GC-MS分析与显色物质的初步确定

为确定抗生素废水中有机污染物构成和显色物质,以二氯甲烷为萃取剂,萃取废水中的有机物,经过浓缩纯化后,利用气相色谱质谱联用(GC-MS)技术对制药废水中的有机成分进行了分析鉴定,结合计算机质谱图库,定性确定了废水中60种有机污染物。其中,脂类为主要污染物成分，经对脱色后的废水进一步GC-MS分析后,初步确定油酸甲酯为此类抗生素废水的主要显色有机物。     

The total carbohydrate: organic carbon ratio as an indicator of sewage-derived organic matter in Burbo Bight sediments, Liverpool Bay, UK

Sediments from the Burbo Bight, Liverpool Bay, were analysed for their total carbohydrate (TCH) and organic carbon (TOC) contents, and the TCH:TOC ratio (when the TCH is expressed as a percentage of the TOC) was used to give an indication of the amount of sewage-derived organic matter in the sediments. The %TCH values found ranged from 17-68 with an average of 40, indicating that sewage-derived organic matter constituted a significant fraction of the organic matter in the sediment. This appears likely to have been derived mainly from the Mersey Estuary outflow and the sewage sludge dumped in Liverpool Bay, but these two sources cannot be distinguished using this technique. It is suggested that further studies are required on the carbohydrates in sewage sludge and coastal sediments to satisfactorily establish this technique.