Influence of rate-limited sorption on the cleanup of layered soils by vapor extraction

The conditions under which rate-limited sorption is important for cleanup of layered soils by vapor extraction are investigated. The investigation includes two steps: (a) the cleanup time is estimated for a number of scenario cases by means of a numerical model and (b) the numerical results are approximated using analytical solutions derived for simplified models. In this way, equations are derived, which give insight into the influence of different parameters characterizing the properties of the soil, the geometry of the formation, the mass transfer mechanisms in it, and the distribution of the contaminant mass in the different phases (gas phase, water phase and solid phase). The numerical model used is based on the advection-dispersion differential equations for Darcian isothermal airflow, local equilibrium contaminant mass transfer between gas phase and soil water and first-order kinetics for mass transfer between soil water and solid phase. The numerical results are approximated combining an analytical solution to estimate cleanup time in layered formations for local equilibrium sorption, which has been presented in a previous work (J. Contam. Hydrol., 36 (1999) 105). with an analytical solution based on the well-mixed reservoir model under consideration of rate-limited sorption. The analytical approximation of the cleanup time is in reasonable agreement with the numerical results and allows its estimation with small computational effort.     

Sorption of hydrophobic organic compounds (HOC) in rapeseed oil bodies

Oil-bodies are minute plant organelles (0.5-2.0microm diameter) consisting of an oil core surrounded by a phospholipid monolayer/proteinaceous membrane. Oil-bodies have been isolated from rapeseed seeds and demonstrated to constitute a novel type of micro-capsule suitable for the extraction of hydrophobic organic compounds from aqueous environments. Three hydrophobic pesticides: atrazine (2-chlor-4-ethyl-amino-6-isopropylamino-1,3,5-triazine), carbaryl (1-naphthyl methylcarbamate) and parathion (O,O-diethyl O-(4-nitrophenyl) phosphorothioate), as well as naphthalene and 2-phenylethanol were successfully extracted from aqueous solutions, with absorption in the inner oily core of OB as sorption mechanism. The OB membrane does not represent a barrier for the mass transfer of the compound towards the inner oily core of OB. Moreover, due to very high surface area to volume ratio, oil-bodies exhibit very good mass transfer properties compared with larger synthetic microcapsules or two-phase liquid-liquid extraction (LLE) techniques, which diminishes the need for strong agitation and avoids the formation of difficult to separate stable emulsions.     

膜萃取邻甲酚废水的传质特性研究

构造了卷绕式及管束式两种膜组件,采用均质硅橡胶膜,以氢氧化钠溶液为萃取液来萃取邻甲酚废水.通过考察邻甲酚初始浓度、两相流动状态、两相压差(△P)和温度等因素对传质过程的影响,研究了邻甲酚废水的膜萃取过程与机制.结果表明,初始质量浓度为21.93 g/L的邻甲酚废水很适合直接进行膜萃取;当△P<0.07 MPa时,总传质系数(Kov)随△P的增大而略有减小.当△P>0.07 MPa时,Kov随△P增大而显著增大,由实验数据拟合得到总的膜萃取传质模型.且该模型的实验值与理论值的相对误差在5%以内,满足工业设计要求.     

Effect of scale and dimensionality on the surfactant-enhanced solubilization of a residual DNAPL contamination

The mass transfer rate from residual dense non-aqueous phase liquids (DNAPLs) to the mobile aqueous phase is an important parameter for the efficiency of surfactant-enhanced remediation through solubilization of this type of contamination. The mass transfer kinetics are highly dependent on the dimensionality of the system. In this study, irregularly shaped residual TCE saturations in two-dimensional saturated flow fields were flushed with a 2% polyoxyethylene sorbitan (20) monooleate (POESMO) solution until complete removal had been achieved. A numerical model was developed and used for the simulation of the various surfactant-flushing experiments with different initial saturation patterns and flow rates. Through optimization against in situ concentration and saturation data, a phenomenological power-law model for the relationship between the mass transfer rate from the DNAPL to the mobile aqueous phase on the one hand and the residual DNAPL saturation and the flow velocity on the other hand was derived. The obtained mass transfer rate parameters provide a reasonable fit to the experimental data, predicting the cleanup time and the general saturation and concentration pattern quite well but failing to predict the concentration curves at every individual sampling port. The obtained mass transfer rate model gives smaller values for the predicted mass transfer rate but shows a comparable dependence on water flow and saturation as in earlier published one-dimensional column experiments with identical characteristics for porous medium, DNAPL and surfactant. Mass transfer rate predictions were about one order of magnitude lower in the 2-D flow cell experiment than in 1-D column experiments. These results give an indication for the importance of dimensionality during surfactant remediation.     

Rate-limited mass transfer of octane, decane, and dodecane into nonionic surfactants solutions under laminar flow conditions

A key component to predicting the success of utilizing surfactants to enhance the removal of organic liquids from soil system is quantifying micellar solubilization kinetics. In this study, a flow reactor was employed to investigate the influence of surfactant ethoxylate chain length on the rates of solubilization of octane, decane, and dodecane in micellar solutions of a homologous series of purified dodecyl alcohol ethoxylates. Effluent concentration data were fit using a finite element model utilizing a linear-driving-force model to represent mass transfer at the interface. For flow rates between 0.1 and 2 ml min(-1), mass transfer coefficients ranged from 5 x 10(-8) to 7 x 10(-7)m s(-1) and did not vary in a systematic way with either solute structure or surfactant ethoxylate chain length and were lower than those found in pure water. Correlations developed for the Sherwood number based on diffusion coefficients of surfactant micelles containing organic material (organic-laden micelle) exhibit a velocity dependence similar to that found for systems based on aqueous diffusion. These results suggest that under gentle flowing conditions, the mass transfer is limited by diffusion of the organic-laden micelle. Although these trends are specific for this experimental system, the results demonstrate the importance of selecting the proper diffusion coefficient when modeling surfactant solubilization processes.     

膜基活化溶液中活化剂在回收温室气体CO2过程中的作用

将AMP和PZ作为活化剂添加于MDEA溶液中,形成活化溶液,研究了膜基活化溶液回收温室气体CO₂性能,着重考察活化剂的活化作用和对膜接触器传质加强的影响,提出一个活化机理来解释活化现象,建立了阻力层方程模型, 并模拟膜基活化溶液回收CO₂的传质过程。结果表明,活化剂对膜接触器传质的加强起到重要作用,具有双氨基环状结构的PZ对传质的加强作用高于具有空间位阻结构的AMP;活化溶液的CO2回收率和传质通量明显高于未活化的MDEA溶液,活化性能PZ＞AMP;活化剂的活化效应与分子结构有关;流体力学的改变对传质的影响有限,活化剂的反应动力学对传质的加强起主导作用;阻力层方程模型能较好地模拟膜基活化溶液回收CO₂传质过程,传质通量和总传质系数的模型值与实验值符合较好。     

Effect of water content on transient nonequilibrium NAPL-gas mass transfer during soil vapor extraction

The effect of water content on the volatilization of nonaqueous phase liquid (NAPL) in unsaturated soils was characterized by one-dimensional venting experiments conducted to evaluate the lumped mass transfer coefficient. An empirical correlation based upon the modified Sherwood number, Peclet number, and normalized mean grain size was used to estimate initial lumped mass transfer coefficients over a range of water content. The effects of water content on the soil vapor extraction SVE process have been investigated through experimentation and mathematical modeling. The experimental results indicated that a rate-limited NAPL-gas mass transfer occurred in water-wet soils. A severe mass transfer limitation was observed at 61.0% water saturation where the normalized effluent gas concentrations fell below 1.0 almost immediately, declined exponentially from the initiation of venting, and showed long tailing. This result was attributed to the reduction of interfacial area between the NAPL and mobile gas phases due to the increased water content. A transient mathematical model describing the change of the lumped mass transfer coefficient was used. Simulations showed that the nonequilibrium mass transfer process could be characterized by the exponent beta, a parameter which described the reduction of the specific area available for NAPL volatilization. The nonequilibrium mass transfer limitations were controlled by the soil mean grain size and pore gas velocity, were well described by beta values below 1.0 at low water saturation, and were well predicted with beta values greater than 1.0 at high water saturation.     

Effect of microbial activity, soil water content and added copper on the temporal distribution patterns of HCB and DDT among different soil organic matter fractions

Temporal changes in the distribution of exogenous HCB and DDT among different soil organic matter fractions were studied under sterile and non-sterile conditions, different soil water contents, and different concentrations of added Cu(2+). The residence time was 311days. Soil organic matter was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions by a methyl isobutyl ketone (MIBK) method. Results revealed that there is a mass transfer tendency of DDT and HCB from FA, HA and BHA to IR and lipid fractions with increasing residence time. Microbial activity accelerated the mass transfer, while the addition of Cu(2+) slowed it down. The HCB and DDT transfer rate decreased as the soil moisture increased from 1.9% to 60%, but increased when soil moisture increased further to 90%. A two-compartment first order kinetic model was used to describe the mass transfer from FA, HA and BHA.     

Assessment of influential range and characteristics of fugitive dust in limestone extraction processes

Fugitive dust emission from limestone extraction areas is a significant pollution source. The cracking operation in limestone extraction areas easily causes high total suspended particulate (TSP) concentrations in the atmosphere, occasionally exceeding the 1-hr national emission standard of Taiwan (500 microg/m3). The concentration and size distribution were measured at different distances (0.05-15 km) in the extraction areas. The highest hourly concentrations of TSP, PM10 (suspended particulate matter [PM] smaller than 10 microm), and PM2.5 (suspended PM smaller than 2.5 microm) are 1111, 825, and 236 microg/m3, respectively, during the cracking process. Measurement results obtained from the Micro-Orifice Uniform Deposit Impactor indicated that the mass median aerodynamic diameter is approximately 0.7 microm, with the geometric standard deviation exceeding 7. In addition, the emission factors are 0.143 and 0.211 kg/t for both vertical well and stair extraction operations, respectively. Experimental results demonstrate that the corresponding TSP control efficiencies for spraying water, planting grass, setting short walls, paving gravel roads, and establishing vertical well transportation are approximately 55, 50, 44, 22, and 30%, respectively. Furthermore, the PM10 control efficiencies are approximately 45, 41, 54, 35, and 30%, respectively, whereas the PM2.5 control efficiencies are roughly 23, 31, 15, 11, and 10%, individually.     

Uptake of aromatic hydrocarbon vapors (benzene and phenanthrene) at the air-water interface of micron-size water droplets

Uptake of aromatic hydrocarbon vapors (benzene and phenanthrene) by typical micrometer-sized fog-water droplets was studied using a falling droplet reactor at temperatures between 296 and 316 K. Uptake of phenanthrene vapor greater than that predicted by bulk (air-water)-phase equilibrium was observed for diameters less than 200 microm, and this was attributed to surface adsorption. The experimental values of the droplet-vapor partition constant were used to obtain the overall mass transfer coefficient and the mass accommodation coefficient for both benzene and phenanthrene. Mass transfer of phenanthrene was dependent only on gas-phase diffusion and mass accommodation at the interface. However, for benzene, the mass transfer was limited by liquid-phase diffusion and mass accommodation. A large value of the mass accommodation coefficient, alpha = (1.4 +/- 0.4) x 10(-2) was observed for the highly surface-active (hydrophobic) phenanthrene, whereas a small alpha = (9.7 +/- 1.8) x 10(-5) was observed for the less hydrophobic benzene. Critical cluster numbers ranging from 2 for benzene to 5.7 for phenanthrene were deduced using the critical cluster nucleation theory for mass accommodation. The enthalpy of mass accommodation was more negative for phenanthrene than it was for benzene. Consequently, the temperature effect was more pronounced for phenanthrene. A linear correlation was observed for the enthalpy of accommodation with the excess enthalpy of solution. A natural organic carbon surrogate (Suwannee Fulvic acid) in the water droplet increased the uptake for phenanthrene and benzene, the effect being more marked for phenanthrene. A characteristic time constant analysis showed that uptake and droplet scavenging would compete for the fog deposition of phenanthrene, whereas deposition would be unimpeded by the uptake rate for benzene vapor. For both compounds, the characteristic atmospheric reaction times were much larger and would not impact fog deposition.     

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.     

Impact of nonaqueous phase liquid (NAPL) source zone architecture on mass removal mechanisms in strongly layered heterogeneous porous media during soil vapor extraction

An existing multiphase flow simulator was modified in order to determine the effects of four mechanisms on NAPL mass removal in a strongly layered heterogeneous vadose zone during soil vapor extraction (SVE): a) NAPL flow, b) diffusion and dispersion from low permeability zones, c) slow desorption from sediment grains, and d) rate-limited dissolution of trapped NAPL. The impacts of water and NAPL saturation distribution, NAPL-type (i.e., free, residual, or trapped) distribution, and spatial heterogeneity of the permeability field on these mechanisms were evaluated. Two different initial source zone architectures (one with and one without trapped NAPL) were considered and these architectures were used to evaluate seven different SVE scenarios. For all runs, slow diffusion from low permeability zones that gas flow bypassed was a dominant factor for diminished SVE effectiveness at later times. This effect was more significant at high water saturation due to the decrease of gas-phase relative permeability. Transverse dispersion contributed to fast NAPL mass removal from the low permeability layer in both source zone architectures, but longitudinal dispersion did not affect overall mass removal time. Both slow desorption from sediment grains and rate-limited mass transfer from trapped NAPL only marginally affected removal times. However, mass transfer from trapped NAPL did affect mass removal at later time, as well as the NAPL distribution. NAPL flow from low to high permeability zones contributed to faster mass removal from the low permeability layer, and this effect increased when water infiltration was eliminated. These simulations indicate that if trapped NAPL exists in heterogeneous porous media, mass transfer can be improved by delivering gas directly to zones with trapped NAPL and by lowering the water content, which increases the gas relative permeability and changes trapped NAPL to free NAPL.     

Measuring concentrations of volatile organic compounds in vinyl flooring

The initial solid-phase concentration of volatile organic compounds (VOCs) is a key parameter influencing the emission characteristics of many indoor materials. Solid-phase measurements are typically made using solvent extraction or thermal headspace analysis. The high temperatures and chemical solvents associated with these methods can modify the physical structure of polymeric materials and, consequently, affect mass transfer characteristics. To measure solid-phase concentrations under conditions resembling those in which the material would be installed in an indoor environment, a new technique was developed for measuring VOC concentrations in vinyl flooring (VF) and similar materials. A 0.09-m2 section of new VF was punched randomly to produce -200 0.78-cm2 disks. The disks were milled to a powder at -140 degrees C to simultaneously homogenize the material and reduce the diffusion path length without loss of VOCs. VOCs were extracted from the VF particles at room temperature by fluidized-bed desorption (FBD) and by direct thermal desorption (DTD) at elevated temperatures. The VOCs in the extraction gas from FBD and DTD were collected on sorbent tubes and analyzed by gas chromatography/mass spectrometry (GC/MS). Seven VOCs emitted by VF were quantified. Concentration measurements by FBD ranged from 5.1 microg/g VF for n-hexadecane to 130 microg/g VF for phenol. Concentrations measured by DTD were higher than concentrations measured by FBD. Differences between FBD and DTD results may be explained using free-volume and dual-mobility sorption theory, but further research is necessary to more completely characterize the complex nature of a diffusant in a polymer matrix.     

Comparison of three extraction methods for 17beta-estradiol in sand, bentonite, and organic-rich silt loam

Extraction is an important procedure for samples that contain soil because other compounds in soil may affect analysis of estrogens. This study was conducted to evaluate three different extraction methods for 17beta-estradiol in soil. Sand, bentonite, and organic-rich silt loam were spiked with 1 mg kg(-1) of 17beta-estradiol as a model compound of estrogens. 17beta-estradiol and its metabolites, estrone and estriol, were extracted using (i) a modified Bligh and Dyer extraction, (ii) a pressurized fluid extraction, and (iii) a diethyl ether extraction, and measured by liquid chromatography tandem mass spectrometry. There were significant differences in the extraction efficiency for 17beta-estradiol among the extraction methods and the soils: the efficiencies ranged from 10% to 97%. Overall, the diethyl ether extraction method had the largest efficiency of 17beta-estradiol with 45% and 57% for bentonite and silt loam, respectively. Transformation of 17beta-estradiol to estrone and estriol in the different extraction methods was less than 3.6% during the extraction procedures. This study underlined the importance of sample preparation for estrogen analysis in soil samples.     

Ozonation of azo dye Acid Red 14 in a microporous tube-in-tube microchannel reactor: decolorization and mechanism

Despite the great success of time-weighted average passive sampling of hydrophobic contaminants, such as PCBs and PAHs, the sampling of polar organic compounds still presents a challenge because the equilibrium between water and most sampling phases is attained in a relatively short time. In this study, we proposed a new time-integrative sampler using in situ solvent extraction (TISIS) for polar organic chemicals. The sampler was composed of a 15 cm poly(dimethylsiloxane) (PDMS) tubing, with an internal diameter of 0.5 mm and wall thickness of 0.5 mm, through which an extraction solvent (acetonitrile) was passed. Four polar organic contaminants, caffeine, atrazine, diuron and 17α-ethynylestradiol, were chosen for the evaluation of the performance of the sampler. Without the use of in situ solvent extraction, the PDMS tubing when exposed to a constant aqueous concentration of the four model compounds was able to linearly accumulate those compounds for less than 12 h and equilibrium between the PDMS tubing and water was attained in 2 d under our laboratory conditions. However, TISIS when exposed to a constant aqueous concentration was able to linearly accumulate all the model compounds without any exposure time limitation. The measured sampling rates at three different extraction flow rates (0.2, 0.5, 1.5 mL min⁻¹) were similar, regardless of the chemicals, indicating that the overall mass transfer from aqueous solution to the extraction solvent was most likely dominated by partitioning to the PDMS tubing and the internal diffusion within PDMS. In addition, a pulsed exposure experiment confirmed that TISIS operated in a time-integrative mode when the environmental concentration was highly fluctuated.     

Soil remediation time to achieve clean-up goals II: Influence of natural organic matter and water contents

This work reports a relatively rapid procedure for the forecasting of the remediation time (RT) of sandy soils contaminated with cyclohexane using vapour extraction. The RT estimated through the mathematical fitting of experimental results was compared with that of real soils. The main objectives were: (i) to predict the RT of soils with natural organic matter (NOM) and water contents different from those used in experiments; and (ii) to analyse the time and efficiency of remediation, and the distribution of contaminants into the soil matrix after the remediation process, according to the soil contents of: (ii1) NOM; and (ii2) water. For sandy soils with negligible clay contents, artificially contaminated with cyclohexane before vapour extraction, it was concluded that: (i) if the NOM and water contents belonged to the range of the prepared soils, the RT of real soils could be predicted with relative differences not higher than 12%; (ii1) the increase of NOM content from 0% to 7.5% increased the RT (1.8-13 h) and decreased the remediation efficiency (RE) (99-90%) and (ii2) the increase of soil water content from 0% to 6% increased the RT (1.8-4.9 h) and decreased the RE (99-97%). NOM increases the monolayer capacity leading to a higher sorption into the solid phase. Increasing of soil water content reduces the mass transfer coefficient between phases. Concluding, NOM and water contents influence negatively the remediation process, turning it less efficient and more time consuming, and consequently more expensive.     

Application of different single extraction procedures for assessing the bioavailability of heavy metal(loid)s in soils from overlapped areas of farmland and coal resources

Heavy metal(loid) extraction from soils in overlapped areas of farmland and coal resources (OAFCR) is crucial in understanding heavy metal bioavailability in soil and the subsequent risks to crops and consumers. However, limited attention has been paid to the extraction procedure of heavy metal(loid)s in OAFCR soils in the research. This study therefore explored different single and mixed extraction procedures, such as acetic acid (HOAc), citric acid, ammonium bicarbonate-diethylenetriaminepentaacetic acid (AB-DTPA), ethylene diamine tetraacetic acid + ammonium acetate (EDTA+NH₄OAc), and total digestion (HNO₃-HClO₄-HF) to determine the bioavailability of As, Cd, Cr, Cu, Pb, and Zn in OAFCR soil in Xuzhou, China. The results showed the metal(loid) extraction capacity from soil of the different procedures could be ranked as AB-DTPA > EDTA+NH₄OAc > HOA_C > citric acid. The transfer ability of heavy metal(loid)s from soil to wheat tissues and from wheat roots to aerial parts was analyzed by calculating the bioconcentration factor and transfer factor, respectively. Transfer factors of all metal(loid)s were < 1 except Cr whose transfer factor from root to shell and straw were > 1. It is suspected that foliar uptake plays a dominant role in Cr uptake. Correlation analysis between the bioavailability of heavy metal(loid)s in soil and uptake in respective wheat tissues was performed to recommend the best extraction procedures for different studies. The results show that AB-DTPA extraction is recommended for Cu uptake to wheat roots, straws, shells and grains, Zn uptake to roots, and Cd uptake to roots and straws.

     

Lead removal from foundry waste by solvent extraction

Solvent extraction is used to reduce lead concentrations from millpond wastewater solids, a type of foundry process waste. Toluene and toluene mixed with di-(2-ethyl-hexyl) phosphoric acid (HDEHP) have been tried as leaching solvents. Toluene is ineffective as a solvent in extracting lead, but the toluene-HDEHP mixture effectively removes lead from solid foundry waste. The effects of the HDEHP concentration, the contact time, and the amount of solvent used on lead extraction have been investigated. The mass transfer process is rapid: contact time of 1/2 hour has been found to be sufficient to accomplish the leaching process. The concentration of HDEHP significantly impacts lead removal. The optimum concentration of HDEHP is determined to range from 0.05 to 0.1 mol/l. The Toxicity Characteristic Leaching Procedure (TCLP) test of the treated samples gives leachable lead in much lower quantities than those found in the untreated samples. Thus the solvent extraction process appears to be an effective method to significantly reduce the lead content of millpond wastewater solids.     

Inhalation transfer factors for air pollution health risk assessment

To facilitate routine health risk assessments, we develop the concept of an inhalation transfer factor (ITF). The ITF is defined as the pollutant mass inhaled by an exposed individual per unit pollutant mass emitted from an air pollution source. A cumulative population inhalation transfer factor (PITF) is also defined to describe the total fraction of an emitted pollutant inhaled by all members of the exposed population. In this paper, ITFs and PITFs are calculated for outdoor releases from area, point, and line sources, indoor releases in single zone and multizone indoor environments, and releases within motor vehicles. Typical PITFs for an urban area from emissions outdoors are approximately 10(-6)-10(-3). PITFs associated with emissions in buildings or in moving vehicles are typically much higher, approximately 10(-3)-10(-1).