A functional relation for field-scale nonaqueous phase liquid dissolution developed using a pore network model

A pore network model with cubic chambers and rectangular tubes was used to estimate the nonaqueous phase liquid (NAPL) dissolution rate coefficient, Kdissai, and NAPL/water total specific interfacial area, ai. Kdissai was computed as a function of modified Peclet number (Pe') for various NAPL saturations (SN) and ai during drainage and imbibition and during dissolution without displacement. The largest contributor to ai was the interfacial area in the water-filled corners of chambers and tubes containing NAPL. When Kdissai was divided by ai, the resulting curves of dissolution coefficient, Kdiss versus Pe' suggested that an approximate value of Kdiss could be obtained as a weak function of hysteresis or SN. Spatially and temporally variable maps of Kdissai calculated using the network model were used in field-scale simulations of NAPL dissolution. These simulations were compared to simulations using a constant value of Kdissai and the empirical correlation of Powers et al. [Water Resour. Res. 30(2) (1994b) 321]. Overall, a methodology was developed for incorporating pore-scale processes into field-scale prediction of NAPL dissolution.     

Laboratory evidence of natural remobilization of multicomponent DNAPL pools due to dissolution

Mixtures of dense non-aqueous phase liquids (DNAPLs) trapped in the subsurface can act as long-term sources of contamination by dissolving into flowing groundwater. In general, the components of higher solubility are removed more quickly, thus altering the composition of the remaining DNAPL, and possibly leading to changes in its physical properties. Through the development of a simple compositional model, Roy et al. [J. Contam. Hydrol. 2002 (59) 163] showed that preferential dissolution of a mixed DNAPL could potentially result in changes in density and interfacial tension that could subsequently lead to remobilization of an initially static DNAPL pool. The laboratory experiments presented in this next paper provide a proof-of-concept for the previously presented theory, demonstrating and quantifying this process of remobilization. In addition, the experiments provide a data set for evaluation of the model presented by Roy et al. [J. Contam. Hydrol. 2002 (59) 163]. In the four experiments, a DNAPL pool comprised of tetrachloroethene and benzene was created as an open pool overlying glass beads within a water-saturated 2-D flow box. Experiments included rectangular and triangular pools. In each of the experiments, remobilization (as breakthrough) was observed more than 2 weeks after formation of the initial pool. During each experiment, the pool height declined as mass was lost by dissolution, while sampling indicated a decrease in the mole fraction of benzene, the more soluble component. Small protuberances formed along the bottom of the pool as its composition changed with time and the displacement pressure was achieved for various pore throats. Eventually one of the protuberances extended further, forming a finger (breakthrough). In general, the pool emptied as the finger proceeded further into the beads. It was also shown theoretically and experimentally that remobilization will occur sooner for pools with a triangular (pointing down), rather than rectangular, shape. The experimental results were simulated using the model developed by Roy et al. [J. Contam. Hydrol. 2002 (59) 163]. The model matched the observations well, suggesting that it accurately represents the primary mechanisms involved with natural remobilization under the conditions of the study.     

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.     

Adsorption of Cu and Mn on covalently cross-linked alginate gel beads

The covalently cross-linked alginate gel beads were prepared by the reactions of Ca(2+)-doped alginate gel beads, which were formed by spraying a viscous alginate solution into a calcium chloride solution, with cyanogen bromide and following 1,6-diaminohexane. The cross-linking of alginate matrix decreased the mean bead diameter by about 30% and made the beads durable in some extent under alkaline conditions. The adsorption of metal ions on the covalently cross-linked alginate gel beads was rapid and reached at equilibrium within 30 min at 25 degrees C. Adsorption isotherms of Cu(II), Mn(II), and Ca2+ on the beads possessed a stepwise shape, which was firstly determined by Rorrer et al. [Ind. Eng. Chem. Res. 32 (1993) 2170] for cross-linked chitosan gel beads and explained by a pore-blockage mechanism. Higher selectivity was determined against Cu(II) over Mn(II) and Ca2+, especially at a low concentration region. These metal adsorption profiles for the covalently cross-linked alginate gel beads was almost the same as those for the un-cross-linked beads, indicating that the cross-linking reactions were performed without interfering the adsorption characteristics of alginate gel beads.     

Clearance and recovery of Cd(II) from aqueous solution by magnetic separation technology

An effective method to actualize the recycling use of Cd(II) in industrial wastewater was developed by using the magnetic beads, which was modified with ethylenediamine. When the industrial wastewater was treated with these magnetic beads, the Cd(II) concentration in the solution was sharply reduced to the governmental standard (0.1 μg mL⁻¹) of China. Based on the monolayer adsorption of Cd(II) on the surface of these magnetic beads, the saturation capacity for Cd(II) reached to 68 mg g⁻¹ dried magnetic beads. On the other hand, the binding Cd(II) could be easily recovered in acid conditions and the recovery efficiency exceeded 99%. Thus, in the process of the wastewater purification, the recycling utilization of Cd(II) was realized. Additionally, the excellent capability of regeneration and recycling utilization of these magnetic beads made this technology much suitable for the large-scale application. Compared with the conventional purification methods, the rapid process, simple equipments, easy operation and high efficiency, brought this technology with great potentialities in the treatment of industrial wastewater.     

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.     

SAGA: a decision support system for air pollution management around a coal-fired power plant

Air quality models are currently feasible approaches to prevent air pollution episodes. From one of the first source-oriented modelling approaches for air pollution forecasting (Souto et al., 1994, 1996, 1998), a new decision support system for air quality management, SAGA, was developed to provide support to As Pontes Power Plant (APPP) staff. SAGA can provide air pollution forecasts and manage meteorological and air quality measurements. Power plant decisions are supported by the results of a non-hydrostatic meteorological model (ARPS, Xue et al., 2001) to produce Meteorological Forecasts (MFs), and to be coupled to different Lagrangian dispersion models.     

Cleanup of biological extracts by a Pasteur pipette column and a comparison of in vivo-accumulated chlorinated pesticide residues with other clean up systems

Biological samples are extracted with n-hexane/acetone (60:40) and 1 mL of the concentrated extract is eluted through a pasteur pipette column prepacked with alumina (0.3 g) and silicic acid (0.25 g) with 10 mL n-hexane (containing 4% acetone). The fat and other co-extractives are retained by the column and clear eluate is directly injected on a GLC column for determination on electron capture detector. A comparison of the Pasteur pipette cleanup with the modified method of Cole et al. (1967) on 41 samples of fish, One Step Method, (Ahmad and Marolt (1986] on 86 samples of fish and Maunder et al. (1964) on 10 type of wildlife (100 samples) was made. The Pasteur pipette method gives results which are significantly higher (p greater than 0.5) than the other methods except the One step method. The Pasteur pipette method has a detection limit of 0.01 microgram/g for DDT and its metabolites.     

Changes in air saturation and air-water interfacial area during surfactant-enhanced air sparging in saturated sand

Reduction in the surface tension of groundwater, prior to air sparging for removal of volatile organic contaminant from aquifer, can greatly enhance the air content and the extent of influence when air sparging is implemented. However, detailed information on the functional relationship between water saturation, air-water contact area induced by air sparging and the surface tension of water has not been available. In this study, the influence of adding water-soluble anionic surfactant (sodium dodecyl benzene sulfonate) into groundwater before air sparging on the air-water interfacial area and water saturation was investigated using a laboratory-scale sand packed column. It was found that water saturation decreases with decreasing surface tension of water until it reaches a point where this trend is reversed so that water saturation increases with further decrease in the surface tension. The lowest water saturation of 0.58 was achieved at a surface tension of 45.4 dyn/cm, which is considered as the optimum surface tension for maximum de-saturation for the initially water-saturated sand used in this study. The air-water contact area generated in the sand column due to air sparging was measured using a gaseous interfacial tracer, n-decane, and was found to monotonically increase with decreasing water saturation. The results of this study provide useful design information for surfactant-enhanced air sparging removal of volatile contaminants from aquifers.     

Assessment of interfacial mass transfer in water-unsaturated soils during vapor extraction

This paper presents results of a numerical investigation of soil vapor extraction (SVE) systems at the laboratory scale. The SVE technique is used to remove volatile chlorinated hydrocarbons (VCHC) from the water-unsaturated soil zone. The developed numerical model solves equations of flow, transport and interfacial mass transfer regarding an isothermal n-component and three-phase system. The mathematical model is based on a simple pore network and phase distribution model and designed to be scaled by a characteristic length. All mathematical expressions are structured into VCHC specific and VCHC non-specific parameters. Furthermore, indicators are introduced that help to separate thermodynamic equilibrium from thermodynamic non-equilibrium domains and to determine the controlling physical parameters. For numerical solution, the system of partial differential equations is discretized by a finite volume method and an implicit Euler time stepping scheme. Computational effort is reduced notably through techniques that enable spatial and temporal adaptivity, through a standard multigrid method as well as through a problem-oriented sparse-matrix storage concept. Computations are carried out in two dimensions regarding the laboratory experiment of Fischer et al. [Water Resour. Res. 32 (12) 1996 3413]. By varying the characteristic length scale of the pore network and phase distribution model, it is shown that the experimental gas phase concentrations cannot be explained only by the volatility and diffusivity of the VCHC. The computational results suggest a sorption process whose significance grows with the aqueous activity of the less or non-polar organic compounds.     

A comparison of models to estimate in-canopy photosynthetically active radiation and their influence on canopy stomatal resistance

The models for photosynthetically active radiation (PAR) used in a multi-layer canopy stomatal resistance (CSR) model developed by Baldocchi et al. (Atmospheric Environment 21 (1987) 91–101) and in a two-big-leaf CSR model developed by Hicks et al. (Water, Air and Soil Pollution 36 (1987) 311) are investigated in this study. The PAR received by shaded leaves in Baldocchi et al. (1987) is found to be larger than that predicted by a canopy radiative-transfer model developed by Norman (in: Barfield, Gerber, (Eds.), Modification of the Aerial Environment of Crops. ASAE Monograph No. 2. American Society for Agricultural. Engineering, St. Joseph, MI, 1979, p. 249) by as much as 50% even though the Baldocchi et al. (1987) model is indirectly based on Norman's model. This larger value of PAR results in turn in a smaller CSR by as much as 30% for canopies with larger leaf area indexes. A new formula to predict vertical profiles for PAR received by shaded leaves inside a canopy is suggested in the present study based on Norman (1979) and agrees well with the original model of Norman (1979). The simple treatment used in Hicks et al. (1987) for canopy-average PAR received by shaded leaves is found to diverge for canopies with leaf area indexes not close to two A new empirical formula for canopy-average PAR is then suggested for use in a two-big-leaf model, and it is shown that under most conditions the modified two-big-leaf CSR model can predict reasonable values when compared with the more complex multi-layer CSR model. Both the modified multi-layer CSR model and the modified two-big-leaf CSR model are also shown to predict reasonable dry deposition velocities for O₃ when compared to several sets of measurements.     

On performing long-term predictions of ozone using the SOMS model

This study examined the potential of using the Simplified Ozone Modeling System (SOMS) (Venkatram et al., 1994. Atmospheric Environment 28, 3665–3678) to generate long-term ozone predictions that may be used to complement the results from more complex air quality models for creating control strategies and establishing long-term trends. A sensitivity study was performed using SOMS to study the application of a model, which is an exponential function of temperature, to estimate the intra-annual biogenic VOC concentration at the receptor in a 1-year run (i.e. 1988). The predictions were made for a core urban site in Baltimore, Maryland. After the sensitivity analyses was completed, the daily maximum ozone concentration (DMOC) was predicted for a 3-year (1987–1989) period for the Baltimore site. The results of the 3-year model prediction were compared with observations.     

The EU-project ERAPharm. Incentives for the further development of guidance documents?

- Triggered by the detection of a large variety of pharmaceuticals in surface waters, soils and groundwaters across the world (e.g. Halling- Sørensen et al. 1998, Daughton & Ternes 1999, Jones et al. 2001, Heberer 2002) and the widespread occurrence of endocrine active compounds and related effects in the environment (e.g. Purdom et al. 1994, Tyler et al. 1998, Vethaak et al. 2002), pharmaceuticals in the environment have become an issue for both the scientific and the public community. During the last few years, our understanding of the fate and effects of pharmaceuticals in the environment has progressed significantly. However, there are still a number of uncertainties concerning the effects of pharmaceuticals on the environment and the assessment of potential exposure (e.g. Hanisch et al. 2004, Salomon 2005). These uncertainties will be addressed by the EU-project ‘Environmental risk assessment of pharmaceuticals’ (ERAPharm). This project, a specific targeted research project, is carried out within the priority ‘Global change and ecosystems’ of the 6th framework programme of the European Union. ERAPharm has started on 1st October 2004; the project duration is three years.     

The re-imagining of a framework for agricultural land use: A pathway for integrating agricultural practices into ecosystem services,planetary boundaries and sustainable development goals: This article belongs to Ambio’s 50th Anniversary Collection. Theme: Agricultural land use

This paper reflects on the legacy of the Ambio papers by Sombroek et al. (1993), Turner et al. (1994), and Brussaard et al. (1997) on the study of agricultural land use and its impacts on global carbon storage and nutrient dynamics. The papers were published at a time of transition in ecology that involved the integration of humans as components of ecosystems, the formulation of the ecosystem services, and emergence of sustainability science. The papers offered new frameworks to studying agricultural land use across multiple scales in a way that captured causality from interacting components of the system. Each paper argued for more comprehensive data sets; foreseeing the power of network-based science, the potential of molecular technologies to assess biodiversity, and advances in remote sensing. The papers have contributed both conceptual framings and methodological approaches to an ongoing movement to identify a pathway to study agricultural land use and environmental change that fit within the concepts of ecosystem services, planetary boundaries and sustainable development goals.     

Fe3+(NTA)还原菌的固定化小球制备及还原特性

采用海藻酸钠包埋驯化得到的优势铁还原菌,用于还原络合吸收法脱除NOx过程中形成的中间副产物Fe³⁺(NTA)。结果表明,最佳包埋条件为海藻酸钠质量浓度4%,菌体质量浓度0.2%,CaCl₂质量浓度3%,此条件下制备的小球还原性能好,在微生物用量为20 g（湿重）/L时还原10 mmol/L Fe³⁺(NTA),经12 h反应后还原率达到96.1％,而相同条件下游离微生物的还原率仅为11.8％,但反应16 h后游离微生物与固定化小球的还原率相近,均为97％左右。但此法制备的小球机械强度不高,溶胀、破裂现象严重。通过添加聚乙烯醇和硅藻土改良固定化小球,可强化小球的机械强度、降低小球的溶胀及破裂现象,对Fe³⁺(NTA)的还原效果也较改良前的小球有所提高,两者最佳添加量均为20 g/L。改良后的小球与游离微生物相比,耐酸性增强,在pH=5的条件下,仍具有79.8％的还原效率,远高于相同条件下游离微生物的39.5％,但对温度的适应范围两者基本一致。     

Extensions to minimum relative entropy inversion for noisy data

Minimum relative entropy (MRE) and Tikhonov regularization (TR) were compared by Neupauer et al. [Water Resour. Res. 36 (2000) 2469] on the basis of an example plume source reconstruction problem originally proposed by Skaggs and Kabala [Water Resour. Res. 30 (1994) 71] and a boxcar-like function. Although Neupauer et al. [Water Resour. Res. 36 (2000) 2469] were careful in their conclusions to note the basis of these comparisons, we show that TR does not perform well on problems in which delta-like sources are convolved with diffuse-groundwater contamination response functions, particularly in the presence of noise. We also show that it is relatively easy to estimate an appropriate value for epsilon, the hyperparameter needed in the minimum relative entropy solution for the inverse problem in the presence of noise. This can be estimated in a variety of ways, including estimation from the data themselves, analysis of data residuals, and a rigorous approach using the real cepstrum and the Akaike Information Criterion (AIC). Regardless of the approach chosen, for the sample problem reported herein, excellent resolution of multiple delta-like spikes is produced from MRE from noisy, diffuse data. The usefulness of MRE for noisy inverse problems has been demonstrated.     

Measuring the flux at the interface of coal-tar impacted sediment and river water near a former MGP site

Determining water movement through contaminated sediment is critical for characterizing transport of chemicals from the sediment to the overlying water. Field studies to characterize the water flow across the sediment-water interface within a river adjacent to a former manufactured gas plant site were conducted. For this purpose, a new design of an interfacial flow meter was developed and tested. The in situ components of the system consisted of: a cylinder with an interfacial area of 2342 cm2; a dome attached to the cylinder; and a flow tube that allows water to flow from inside the dome to the river at the rate equal to the specific discharge across the sediment-water boundary. A 'heat-pulse' method was used to measure flow by heating the center of the flow tube for a brief time period and measuring the temperature profile within the tube over time. The system was calibrated to measure volumetric flux in the range 1.5-4.0 cm d(-1), however using a flow-addition method, the measurement of lower velocities also was accomplished, and calibration at higher fluxes is possible. From the groundwater flow at the interface of the coal-tar impacted sediment and information on the sediment pore water concentrations of several PAHs (poly-cyclic aromatic hydrocarbons), the mass flux of these PAHs to the river were estimated. Information on PAH mass flux at the sediment-water interface is useful for site assessment, including the evaluation of remediation alternatives and longer term site characterization.     

Solubilization of PAH mixtures by three different anionic surfactants

Solubilization of naphthalene and phenanthrene into the micelles formed by three different anionic surfactants was investigated for single, binary, and ternary mixtures including pyrene. The three surfactants were sodium dodecylbenzene sulfonate (SDDBS), monoalkylated disulfonated diphenyl oxide (MADS-C12), and dialkylated disulfonated diphenyl oxide (DADS-C12). The order of increasing solubility enhancement of naphthalene and phenanthrene was SDDBS < MADS-C12 < < DADS-C12, which indicates that the hydrophobic chains in micellar core play more important role for the solubilization of polycyclic aromatic hydrocarbons (PAHs) than the benzene rings in palisade layer of a micelle. The solubility enhancement of naphthalene was slightly changed in PAH mixtures. The solubility of phenanthrene was greatly enhanced in presence of naphthalene but reduced in presence of pyrene. The explanation for these results could be that less hydrophobic compounds can be solubilized at the interfacial region of a hydrophobic core, which reduces the interfacial tension between the core and water, and then the reduced interfacial tension can support a larger core volume for the same interfacial energy.     

Decoloration of textile dyes by alginate-immobilized Trametes versicolor

Alginate-immobilized Trametes versicolor decolorized Amaranth at similar rates in repeated batch culture when the dye was present in either (i) modified Kirk's medium containing 0.22 gl(-1) ammonium tartrate, (ii) the same buffer, thiamine, trace elements and glucose concentrations as in the modified Kirk's medium, or (iii) glucose alone at either 1, 5 or 10 gl(-1). With glucose alone (0.5 gl(-1)), Amaranth, Reactive Black 5, Reactive Blue 19 and Direct Black 22 had first-order decoloration rate constants of 0.56, 0.76, 0.52, and 0.15 h(-1), respectively. Mixtures of these dyes were also completely decolorized. After four successive decolorations, beads were kept in storage solutions for 48 d at 6 degrees C. CaCl2 (1g l(-1)) was the best storage solution as the beads were easier to handle and had the fastest decoloration rates after storage. Decoloration rates were faster with lower viscosity (less than 2000 cps) alginates and with softer beads which had a lower resistance to compression. Fungal colonization of the beads resulted in higher biomass concentrations with a corresponding higher decoloration rate but the beads became larger, had a lower resistance to compression and a higher percentage of bead breakage in a stirred tank reactor. Biomass, recovered from beads in which there was no growth, could be dispersed while the biomass from colonized beads formed a hollow, spherical shell due to growth on and near the bead surface and no growth in the bead interior. If alginate-immobilized T. versicolor is to be used in a stirred tank reactor, a high biomass loading during the immobilization phase and no fungal growth in the beads is recommended to have high decoloration rates and low bead breakage.     

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30 degrees dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.