原位热修复过程中土壤内热质传递研究现状与展望

近年来,原位热修复技术因其具有修复周期短、可靠性高、适用性强、二次污染可控等优点,已被广泛应用于有机污染地块修复领域。概述了国内外原位热修复技术研究进展,对比了蒸汽强化抽提技术(SEE)、电阻加热技术(ERH)和热传导加热技术(TCH) 3种典型原位热修复技术的优缺点和适用条件,并分析了污染物性质、土壤非均质性、含水率及加热温度等主要因素对不同技术的修复效果的影响。在此基础上,从理论、实验和数值3方面阐述了原位热修复过程中热质传递机理的研究现状。     

原位热传导修复过程中热量传递的数值模拟

目前原位热传导修复技术存在热量传递机理不明、主要影响因子作用关系不清的问题,通过模拟室内土柱实验实现对土壤内部热湿耦合迁移机理的验证,并应用到室外场地尺寸,明确场地尺寸下热源温度、初始含水率对原位热传导修复的影响作用.建立了原位热传导修复耦合模型,利用小试实验对其进行了数值模拟验证,在场地尺寸下探究了热源温度、初始含水...     

Sensitivity analysis of mass balance receptor modeling: Methyl chloride as an indicator of wood smoke

The Singular Value Decomposition (SVD) approach to stability analysis of the Chemical Mass Balance (CMB) receptor model is extended to incorporate uncertainties in both source and ambient compositions. SVD is applied to determine the improved precision with which the impact of residential wood smoke can be estimated by including methyl chloride in a CMB analysis. Wood smoke impacts in Hillsboro and Medford, Oregon, are examined. The results indicate that including methyl chloride will dramatically improve the precision of estimating wood smoke impacts for Medford, while estimates for Hillsboro are changed to a much lesser extent. This result is reasonable since the Medford airshed includes many industrial sources of particulate matter with chemical compositions similar to residential wood smoke, while Hillsboro is predominantly a residential community. The precision improvements estimated by SVD are verified by CMB analysis of a series of ambient samples collected in Hillsboro. Finally, the applicability of SVD as a receptor model study design tool is discussed.     

Interphase mass transfer during chemical oxidation of TCE DNAPL in an aqueous system

The chemical oxidation of trichloroethene dense non-aqueous phase liquid by permanganate was studied in an aqueous system using micro-reaction/extraction vessels in a novel approach. Experiments were conducted at ambient temperature ( approximately 20 degrees C) under static and mixed conditions to evaluate the rate of TCE(DNAPL) dissolution as a function of permanganate concentration. Chemical oxidation by permanganate was shown to increase the rate of TCE(DNAPL) dissolution under static conditions and decrease the rate of dissolution under mixed conditions. The apparent inconsistency in results appears to result from the local deposition of a film at the DNAPL interface composed of manganese oxide solids as discovered through visual observation with the aid of a Goniometer. Data from interfacial deposition experiments suggest that the film formed rapidly and reached maturation within approximately 2 h with little or no growth occurring thereafter. A conceptual model of the reaction and mass transfer processes occurring at the DNAPL interface was proposed based on the experimental results.     

臭氧在柱式反应器中的强化传质过程

结合理论分析,提出了影响臭氧在水中传质效率的三大因素：表观气速μobs、初始气泡直径d、液位高H。通过实验设计,以臭氧氧化柱式反应器中气泡的行为为研究对象,以废水COD去除率及臭氧利用率为指标,考察了这三大因素对臭氧传质效率的影响,且探讨了体系中引入搅拌对强化臭氧传质的贡献。结果表明,适当地提高表观气速μobs、初始气泡直径d及液位高H都可强化气液传质、提高废水处理效果,而对于传质控制型反应效果更为显著。在低、中表观气速下,搅拌能促使气泡均匀分散,从而提高气液传质效率;而在高表观气速下,搅拌作用的强化能力是有限的。通过对搅拌作用下反应器内流体热视图分析可知,反应器内中心气泡密度、尺寸均高于近壁面位置。n=100 r·min-1时,反应器内气泡直径小且分布均匀;n=200 r·min-1时,反应器内气泡破碎严重,搅拌杆有气穴生成;n=500 r·min-1时,反应器中心出现明显旋流与气液分层现象。     

杂质对白泥-石膏法烟气脱硫传质反应的影响

白泥中含有大量的杂质,如钠、镁、氯及黑色胶状物,在脱硫过程中可能会对二氧化硫的吸收传质过程存在影响。为明确各杂质在脱硫过程中作用,详细考察了上述物质对二氧化硫的吸收传质过程的影响。结果表明,硫酸钠、高浓度硫酸镁均对传质反应具有增强作用;而氯离子、黑色胶状物、低浓度硫酸镁却对传质反应起阻碍作用。实验同时研究了杂质浓度对传质反应的影响,在硫酸镁低浓度范围内K/β-c符合高斯函数形式。     

Hexachlorobenzene as an indicator of dioxin production from combustion

The production of polychlorinated dioxins and dibenzofurans shows a strong correlation with the production of hexachlorobenzene. Hexachlorobenzene can be used as an indicator for the production of chlorinated aromatics.     

Synthetic fibers as an indicator of land application of sludge

Synthetic fabric fibers have been proposed as indicators of past spreading of wastewater sludge. Synthetic fiber detectability was examined in sludges (dewatered, pelletized, composted, alkaline-stabilized) and in soils from experimental columns and field sites applied with those sludge products. Fibers (isolated by water extraction and examined using polarized light microscopy) were detectable in sludge products and in soil columns over 5 years after application, retaining characteristics observed in the applied sludge. Concentrations mirrored (within a factor of 2) predictions based on soil dilution. Fibers were detectable in field site soils up to 15 years after application, again retaining the characteristics seen in sludge products. Concentrations correlated with residual sludge metal concentration gradients in a well-characterized field site. Fibers found along preferential flow paths and/or in horizons largely below the mixed layer suggest some potential for translocation. Synthetic fibers were shown to be rapid and semi-quantitative indicators of past sludge application.     

Validation of in-situ measurements of volatile organic compounds through flask sampling and gas chromatography/mass spectrometry analysis

Continuous monitoring of ambient non-methane hydrocarbons (NMHCs) by automated gas chromatographs equipped with flame ionization detection (termed in-situ GC/FID) with hourly data resolution was instated in ozone non-attainment areas throughout Taiwan. Performance of these on-site in-situ GCs was validated by manual flask sampling, as well as by in-lab gas chromatography/mass spectrometry (GC/MS) analysis. More than 50 VOCs from C₂ to C₁₁ were analyzed by both methods. Ninety flask samples were collected in series near an in-situ GC monitoring station in order to closely compare with the in-situ measurements. Both time-series and scatter plots from the two methods are displayed and discussed. It was found that over-simplified, un-humidified single-point calibration leading to surface loss was responsible for the bias in the in-situ method, resulting in greater error in accuracy as VOC volatility decreased. Although this over-estimate of the concentrations was found across all target VOCs, both methods were able to consistently capture the variability of ambient VOCs, with R² values greater than 0.9 for most of the major VOCs.     

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.     

Use of pine needles as an indicator of atmospheric contamination by pentachlorophenol

The use of pine needles as an inexpensive and natural device for collecting atmospheric organic contaminants was investigated. The widespread existence of pentachlorophenol in the atmosphere was investigated by analyzing pine needle extracts by GC-MS. PCP was found at low ppb levels in all pine needle samples which were analyzed.     

Sphagnum fuscum moss as an indicator of atmospheric cadmium deposition across Canada

The concentration of cadmium was determined in samples of Sphagnum fuscum moss collected from 37 sites across Canada from the Pacific Ocean to the Atlantic Ocean and Labrador Sea. At 22 of the sites, Cd was less than 0.2 mg kg(-1), the detection limit. Elevated Cd levels were only found in mosses collected in the vicinity of the smelters at Flin Flon, Manitoba, and Rouyn-Noranda, Quebec, where a maximum concentration of 12 mg kg(-1) was measured.     

Nitrogen isotope variations in camphor (Cinnamomum Camphora) leaves of different ages in upper and lower canopies as an indicator of atmospheric nitrogen sources

Nitrogen isotopic composition of new, middle-aged and old camphor leaves in upper and lower canopies has been determined in a living area, near a motorway and near an industrial area (Jiangan Chemical Fertilizer Plant). We found that at sites near roads, more positive δ¹⁵N values were observed in the camphor leaves, especially in old leaves of upper canopies, and ?δ¹⁵N = δ¹⁵N_upper − δ¹⁵N_lower > 0, while those near the industrial area had more negative δ¹⁵N values and ?δ¹⁵N < 0. These could be explained by two isotopically different atmospheric N sources: greater uptake from isotopically heavy pools of atmospheric NO_x by old leaves in upper canopies at sites adjacent to roads, and greater uptake of ¹⁵N-depleted NH_y in atmospheric deposition by leaves at sites near the industrial area. This study presents novel evidence that ¹⁵N natural abundance of camphor leaves can be used as a robust indicator of atmospheric N sources.     

Concentration of bioactive compounds in mussels Mytilus galloprovincialis as an indicator of pollution

The polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organotins were analyzed in mussels Mytilus galloprovincialis from polluted and unpolluted sites from Mokpo Bay, Korea. The total PAH's concentrations (10(-3)mgkg(-1)) measured by GC-MS were in the range from 31+/-23 to 1+/-1. Among the eight PAHs the predominant ones were fluoranthene, phenanthrene and pyrene and accounted approximately 63% of the total PAHs. Among the four detected PCBs the highest content was of PCB 153, which accounted about 47% of the total PCBs. The main organotin compounds were dibutyltindichloride (DBT) and tributyltinchloride (TBT) and their composition was approximately 33% and 24%. PAHs, PCBs and organotins were found only in the mussels from polluted site. The antioxidant activity by ABTS [2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonic acid)] test was higher in mussels from polluted than from unpolluted sites (P<0.05). It was found a correlation between the determined compounds (PAHs, PCBs and organotins) and the antioxidant activity of the mussel tissue from polluted site and the correlation coefficients were 0.96, 0.92 and 0.80, respectively. Such correlation can be explained by the properties of mussels. Since the mussel cell wall and tissues are hydrophobic, they can concentrate a number of hydrophobic pollutants like PAHs and PCBs from the marine environment by solubility rules. On the other hand, proteins are lipophilic compounds having antioxidant properties. Certain amino acid residues and thiol (-SH) groups, contained in proteins, respond to the ABTS antioxidant activity assay. Thus there may be a correlation between the total antioxidant activity of the organism and the PAH-PCB pollutants which were concentrated from its environment. The studied properties of mussels from polluted site can be used as an additional indicator of pollution.     

Exploring field vegetation reflectance as an indicator of soil contamination in river floodplains

This study investigated the relation between vegetation reflectance and elevated concentrations of the metals Ni, Cd, Cu, Zn and Pb in river floodplain soils. High-resolution vegetation reflectance spectra in the visible to near-infrared (400-1350 nm) were obtained using a field radiometer. The relations were evaluated using simple linear regression in combination with two spectral vegetation indices: the Difference Vegetation Index (DVI) and the Red-Edge Position (REP). In addition, a multivariate regression approach using partial least squares (PLS) regression was adopted. The three methods achieved comparable results. The best R(2) values for the relation between metals concentrations and vegetation reflectance were obtained for grass vegetation and ranged from 0.50 to 0.73. Herbaceous species displayed a larger deviation from the established relationships, resulting in lower R(2) values and larger cross-validation errors. The results corroborate the potential of hyperspectral remote sensing to contribute to the survey of elevated metal concentrations in floodplain soils under grassland using the spectral response of the vegetation as an indicator. Additional constraints will, however, have to be taken into account, as results are resolution- and location-dependent.     

Modeling methane oxidation in landfill cover soils as indicator of functional stability with respect to gas management

A performance-based method for evaluating methane (CH₄) oxidation as the best available control technology (BACT) for passive management of landfill gas (LFG) was applied at a municipal solid waste (MSW) landfill in central Washington, USA, to predict when conditions for functional stability with respect to LFG management would be expected. The permitted final cover design at the subject landfill is an all-soil evapotranspirative (ET) cover system. Using a model, a correlation between CH₄ loading flux and oxidation was developed for the specific ET cover design. Under Washington’s regulations, a MSW landfill is functionally stable when it does not present a threat to human health or the environment (HHE) at the relevant point of exposure (POE), which was conservatively established as the cover surface. Approaches for modeling LFG migration and CH₄ oxidation are discussed, along with comparisons between CH₄ oxidation and biodegradation of non-CH₄ organic compounds (NMOCs). The modeled oxidation capacity of the ET cover design is 15 g/m²/day under average climatic conditions at the site, with 100% oxidation expected on an annual average basis for fluxes up to 8 g/m²/day. This translates to a sitewide CH₄ generation rate of about 260 m³/hr, which represents the functional stability target for allowing transition to cover oxidation as the BACT (subject to completion of a confirmation monitoring program). It is recognized that less than 100% oxidation might occur periodically if climate and/or cover conditions do not precisely match the model, but that residual emissions during such events would be de minimis in comparison with published limit values. Accordingly, it is also noted that nonzero net emissions may not represent a threat to HHE at a POE (i.e., a target flux between 8 and 15 g/m²/day might be appropriate for functional stability) depending on the site reuse plan and distance to potential receptors.

Implications: This study provides a scientifically defensible method for estimating when methane oxidation in landfill cover soils may represent the best available control technology for residual landfill gas (LFG) emissions. This should help operators and regulators agree on the process of safely eliminating active LFG controls in favor of passive control measures once LFG generation exhibits asymptotic trend behavior below the oxidation capacity of the soil. It also helps illustrate the potential benefits of evolving landfill designs to include all-soil vegetated evapotranspirative (ET) covers that meet sustainability objectives as well as regulatory performance objectives for infiltration control.     

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.     

The composition of rime ice as an indicator of the quality of winter deposition

Rime ice deposition and snow chemistry has been determined over a 4-year period on the summit of Cairngorm Mountain, NE Scotland. The direction of ice deposition reflected the dominant air mass movement over the summit. Sea salt concentrations in the rime ice were approximately 2.5 times greater than in snow deposited over the same period. Excess sulphate concentrations were double, and those of nitrate nearly four times higher. The direction of deposition influenced concentrations of excess sulphate and nitrogen species (nitrate and ammonium) in rime ice. The same directional effect was found in the snow chemistry indicating increased entrapment of pollutants, or a more polluted air mass, when it prevailed from a Southerly or Easterly direction. The potential surface reactions involving gaseous species of S and N may increase the ionic loading to the rime and reflect natural ionic enrichment of the rimed snowpack surface. Because of such phenomena, rime ice is proposed as a further indicator of winter air quality revealing important information on ionic interactions and total deposition flux measurement, especially at high altitudes.     

PIXE trace element analysis of an aquatic plant as indicator of heavy metal pollution

A new way of detecting trace elements in water is developed by using charged $\text{P}$article $\text{I}$nduced $\text{X}$-ray $\text{E}$mission (PIXE) analysis of cell walls of $\text{Chara corallina}$, a fresh water alga.     

U-series disequilibria in a groundwater flow route as an indicator of uranium migration processes

U-series data relating to groundwater, fracture coatings and the adjoining rock matrix in a groundwater flow system at the Palmottu natural analogue site was examined. The aim was to obtain an experimental reference for migration modelling in a transport section defined within the flow system. The U-series reference obtained turned out to be a very useful tool for fine tuning the flow route and for migration mechanism considerations. The U-series data are well in line with other interpretations of the migration system.