The dissolution of benzene, toluene, m-xylene and naphthalene from a residually trapped non-aqueous phase liquid under mass transfer limited conditions

The results of dissolution experiments for benzene, toluene, m-xylene and naphthalene (BTXN) from a relatively insoluble oil phase (tridecane), residually trapped in a non-sorbing porous medium, are described. This mixture was chosen to simulate dissolution of soluble aromatic compounds from a petroleum hydrocarbon mixture, e.g., crude oil, for which a large fraction of the mixture is relatively insoluble. The experiments were carried out at a small source length to interstitial velocity ratio, L/v, so that dissolution would be mass transfer limited (MTL). When fitted to data for toluene, a multiregion mass transfer model was found to predict the experimental data satisfactorily for the other components without adjustment of the mass transfer rate parameters. These results indicate that the dissolution process can be generalized for various hydrophobic organic compounds present in a multicomponent non-aqueous phase liquid (NAPL) when mass transfer limitations are present. This also suggests that dissolution data obtained for one compound can be useful for predicting the dissolution histories for other compounds from petroleum hydrocarbon mixtures.     

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.     

Quantifying the physical and chemical mass transfer processes for the fate and transport of Co(II)EDTA in a partially-weathered limestone-shale saprolite

The objective of the research is to quantify the relative contributions of physical and chemical mass transfer to the movement of Co(II/III)EDTA (chelates of Cobalt and Ethylene Diamine Tetraacetic Acid or EDTA) through a limestone-shale saprolite soil. Saprolite is a collective term referring to partially-weathered bedrock. It exists extensively in the subsurface. Because the parent bedding structures are maintained during the weathering process, saprolite soils are characterized by intensive fractures and secondary deposits of minerals such as Al-, Fe- and Mn-oxides on the fracture surfaces. Movement of reactive species through the soils may be influenced by diffusion into the rock matrix, a physical mass transfer (PMT) process, and interfacial chemical reactions, a chemical mass transfer (CMT) process. The PMT and CMT processes are phenomenologically similar but mechanistically different. In this research, previous laboratory observations from a Br and Co(II)EDTA tracer injection into an undisturbed saprolite soil column were used. Mechanistic reactive transport models were formulated to quantify the PMT and CMT processes. The PMT process was independently characterized by using the non-reactive tracer Br. Model parameters thus obtained were subsequently used as constraints to quantify the CMT processes involving Co(II)EDTA and its oxidation product Co(III)EDTA. Our calculations indicated that the PMT rates of the less reactive Co(III)EDTA were comparable with their theoretical CMT rates. In contrast, for the more reactive species Co(II)EDTA, CMT rates are higher than PMT rates. Evaluations of alternative CMT process models further confirmed one of our hypotheses on the basis of previous experimental understandings. The hypothesis suggested that competition from Fe-oxide for Co(II)EDTA may account for the majority of the decrease of Co(III)EDTA effluent concentrations that resulted in the separation of total Co and Co(III)EDTA breakthrough curves. Because Co(III)EDTA is more mobile than Co(II)EDTA in the subsurface, the results of this research suggest independent quantifications of CoEDTA PMT and CMT processes if laboratory results are to be interpreted correctly and scaled up for field and predictive uses.     

Bacteria additives to the changes in gaseous mass transfer from stored swine manure

Abstract

A bacteria additives treatment experiment in assessing the changes in gaseous mass transfer from stored swine manure is presented. The experiment is tested for ammonia, methane, hydrogen sulfide, and carbon dioxide emission data sampled from pilot swine manure columns and analyzed by GC/MS. The result shows that bacteria additives slightly reduce the methane and carbon dioxide releases, while the same additives do not show any effect on the reduction of ammonia. The hydrogen sulfide contents of stored swine manure continued to be low. Gas concentrations emitted from treated and untreated stored swine manure were: 3.76 and 2.2 ppm for methane, 0.35 and 0.11 ppm for ammonia, and 1000 and 470 ppm for carbon dioxide, respectively. A simple model to estimate gas emission rates is also developed from the viewpoint of two‐film resistance theory. The average emission rates calculated from the model for methane, ammonia, and carbon dioxide are respectively: 0.01, 0.0005, and 13.98 g/min from untreated stored manure; while 0.07, 0.096, and 0.55 g/min from treated manure. The emission model also indicates that for most gaseous pollutants of environmental concern, liquid phase transfer coefficient controls the rate of volatile compounds emitted from stored swine manure and gas phase transfer coefficient has insignificant effect in the calculation of overall mass transfer coefficient.     

A method for estimating distributions of mass transfer rate coefficients with application to purging and batch experiments

Mass transfer between aquifer material and groundwater is often modeled as first-order rate-limited sorption or diffusive exchange between mobile zones and immobile zones with idealized geometries. Recent improvements in experimental techniques and advances in our understanding of pore-scale heterogeneity demonstrate that two (or even a few) rate coefficients are insufficient in many cases. Here, we investigate a piece-wise linear model for a continuous distribution of rate coefficients, that has several advantages over previously used ‘statistical' distribution models (with functional form from gamma or lognormal PDF's): (1) distributions of arbitrary, even bimodal, shapes can be represented; (2) linear estimation methods can be applied to determine the distribution from experimental data; (3) the uncertainty in the distribution can be determined for each of its sections; and (4) the relationship between the time scales of available data and those of estimatable mass transfer processes can be investigated. A statistical model refinement algorithm is presented that reduces the number of parameters (sections of the piece-wise linear model) to the admissible minimum. We show that purging experiments allow estimation of a wider zone of the rate distribution than do batch experiments, and hence will provide predictions that are accurate over a wider range of time scales. Finally, in an application to TCE gas-purging desorption data, the piece-wise linear rate-distribution model has a higher probability of being adequate than those using a gamma or lognormal distribution or a single rate coefficient.     

生物化学法净化低浓度甲苯废气的传质研究

通过试验和理论分析,研究生物化学法净化低浓度甲苯废气这一传质一生化反应过程的控制因素,结果表明生物化学法净化低学本废气为传播控制过程,并以气膜控制为主,研究为工业化装置的设计和操作提供了理论依据。     

The significance of heterogeneity on mass flux from DNAPL source zones: an experimental investigation

Understanding the process of mass transfer from source zones of aquifers contaminated with organic chemicals in the form of dense non-aqueous phase liquids (DNAPL) is of importance in site management and remediation. A series of intermediate-scale tank experiments was conducted to examine the influence of aquifer heterogeneity on DNAPL mass transfer contributing to dissolved mass emission from source zone into groundwater under natural flow before and after remediation. A Tetrachloroethylene (PCE) spill was performed into six source zone models of increasing heterogeneity, and both the spatial distribution of the dissolution behavior and the net effluent mass flux were examined. Experimentally created initial PCE entrapment architecture resulting from the PCE migration was largely influenced by the coarser sand lenses and the PCE occupied between 30 and 60% of the model aquifer depth. The presence of DNAPL had no apparent effect on the bulk hydraulic conductivity of the porous media. Up to 71% of PCE mass in each of the tested source zone was removed during a series of surfactant flushes, with associated induced PCE mobilization responsible for increasing vertical DNAPL distributions. Effluent mass flux due to water dissolution was also found to increase progressively due to the increase in NAPL-water contact area even though the PCE mass was reduced. Doubling of local groundwater flow velocities showed negligible rate-limited effects at the scale of these experiments. Thus, mass transfer behavior was directly controlled by the morphology of DNAPL within each source zone. Effluent mass flux values were normalized by the up-gradient DNAPL distributions. For the suite of aquifer heterogeneities and all remedial stages, normalized flux values fell within a narrow band with mean of 0.39 and showed insensitivity to average source zone saturations.     

Multiphase flow and transport caused by spontaneous gas phase growth in the presence of dense non-aqueous phase liquid

Disconnected bubbles or ganglia of trapped gas may occur below the top of the capillary fringe through a number of mechanisms. In the presence of dense non-aqueous phase liquid (DNAPL), the disconnected gas phase experiences mass transfer of dissolved gases, including volatile components from the DNAPL. The properties of the gas phase interface can also change. This work shows for the first time that when seed gas bubbles exist spontaneous gas phase growth can be expected to occur and can significantly affect water-gas-DNAPL distributions, fluid flow, and mass transfer. Source zone behaviour was observed in three different experiments performed in a 2-dimensional flow cell. In each case, a DNAPL pool was created in a zone of larger glass beads over smaller glass beads, which served as a capillary barrier. In one experiment effluent water samples were analyzed to determine the vertical concentration profile of the plume above the pool. The experiments effectively demonstrated a) a cycle of spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone, b) DNAPL redistribution caused by gas phase growth and mobilization, and c) that these processes can significantly affect mass transport from a NAPL source zone.     

Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface

The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.     

The interfacial mass transfer resistances of the ozone dry deposition over the field soil of Taichung County in Taiwan

This study aims to design a dry deposition chamber and to measure ozone depletion over the Taichung field soil. This study seeks to verify the phenomena by an experimental and mathematical model. It is demonstrated that interfacial mass transfer resistances of ozone dry deposition involve reactive resistance (R(sr)) and kinetic resistance (R(sk)). It reveals the chemical reaction (O3 + NO --> NO2) to produce the reactive resistance, and verifies that the interfacial mass transfer resistances depend on nitrogen oxide emission and soil temperature. It shows that the interfacial mass transfer resistances are reduced with increasing soil temperature (T(S)). The model profiles are smaller than the observed data within a relative error of 15%. The reactive resistance decreases exponentially with increasing soil temperature; R(sr)(-1) (cm x sec(-1)) = 0.0001 exp (0.1455T(S)). The kinetic resistance decreases linearly with increasing soil temperature; R(sk)(-1)(cm x sec(-1)) = 0.0108T(S) + 1.4012. This model is more accurate with higher soil temperature and larger ozone concentration. Results are consistent with thermodynamics and reaction kinetics. Ozone dry deposition over agricultural soil causes conversion of nitrogen oxide (NO) to nitrogen dioxide (NO2).     

高效液相色谱-串联质谱法同时检测地表水中13种药物及个人护理品

采用高效液相色谱-串联质谱(HPLC-MS/MS)检测,建立了地表水中13种药物及个人护理品的测定方法。水样用盐酸与氢氧化钠溶液调pH值至7.0左右,过固相萃取小柱进行富集,用14 mL甲醇洗脱。以C18柱为分离柱,0.01%甲酸的甲醇-0.01%甲酸水溶液为流动相,目标物在10 min内分离,在0.50~250 μg/L范围内,13种化合物峰面积与内标物质峰面积之比与质量浓度的线性关系良好(>0.99),检出限在0.05~0.5 ng/L范围内。基质加标实验结果表明,13种化合物在水中的回收率分别在56.2%~123.2%之间(加标水平5 ng/mL)和58.0%~107.8%(加标水平50 ng/mL),相对标准偏差在1.60%~19.9%(n=6)之间。应用该方法测定了从2条纳污河流采集的10份水样,结果表明,除美托诺尔和普洛萘尔未被检出外,其余11药物的检出频率在30%~100%之间。在13种目标物质中,咖啡因的检测浓度最高达287.5 ng/L,舒必利次之,为277.5 ng/L。本方法快速、准确,适用于地表水中PPCPs类的快速测定。     

水环境中磺胺类抗生素固相萃取-液质联用检测方法的建立及效果评估

为快速、同步检测分析磺胺类抗生素,有效削减并控制水体中磺胺类上抗生素含量,基于已有检测仪器和分析测试方法,建立了一种用于同时测定水体中8种磺胺类抗生素(磺胺氯哒嗪、磺胺间二甲氧嘧啶、磺胺二甲基嘧啶、磺胺甲恶唑、磺胺喹恶啉、磺胺甲氧哒嗪、磺胺甲噻二唑、磺胺吡啶)残留的固相萃取-液相色谱-三重四极杆串联质谱检测方法;在检测过程中,调节水样的pH为3,用HLB固相萃取柱进行净化、富集,在40 ℃条件下用氮吹浓缩吹干,用超纯水复溶至1 mL;以0.1%甲酸水溶液和0.1%甲酸乙腈溶液作为流动相,使用Phenomenex Kinetex F5 色谱柱(50 mm×3.0 mm, 2.6 μm)进行分离,在多反应监测模式(MRM)下对样品进行定量、定性分析。结果表明：8种磺胺类抗生素线性关系良好,且拟合度均大于0.999 0;检出限为0.1~0.5 μg·L⁻¹,定量限为0.5~2.0 μg·L⁻¹;质量浓度为1、5、50 μg·L⁻¹的混标溶液的加标回收率分别为78.85%~127.96%、76.69%~114.38%和73.55%~125.92%, 相对标准偏差均在15%以内。该方法快捷、高效、灵敏,能够满足水中磺胺类抗生素的定性、定量检测,可为我国检测方法标准体系的建设提供参考。     

Experimental study and modeling of the transfer of zinc in a low reactive sand column in the presence of acetate

Nowadays, it is necessary to understand and identify the reactions governing the fate of heavy metals introduced into the environment with low complexing organic compounds, particularly when they are transferred through soils in urban areas. In this work the concomitant influence of pH and acetate on the fate of zinc on siliceous sand was studied in batch and non-saturated column experiments. Total zinc concentrations varied between 2 and 20 mg/l, and total acetate concentrations were fixed at 22, 72, 132, and 223 mM to obtain solution pHs of 4, 5, 6 and 7, respectively. Natural sand (diameter, 0.3-2 mm), mainly constituted of silica, was used. In batch adsorption experiments, zinc adsorption is insignificant at pH 4, low and linear at pH 5, and increasingly nonlinear, of the Langmuir type, at pH 6 and 7 indicating near-saturation conditions of surface sites at these high pH values. In column experiments, Zn retardation increases and the maximum outlet concentration of Zn decreases with rising pH and acetate concentrations. Previous column tracer experiments revealed the occurrence of regionalized water transport in the column. Modeling these data was based on a non-electrostatic approach. Batch and column data modeling was based on the PHREEQC code that allows concomitant resolution of chemical speciation and regionalized water transport. The speciation calculation indicates that the ZnAcetate+ species is the dominant Zn species in the solutions used. Batch experimental curves are correctly modeled assuming the formation of the three surface species triple bond SiOZn+, triple bond SiOH-Zn Acetate+ and triple bond SiO-Zn(Acetate)2-. The column data could be adequately modeled assuming a two-region water transport and the formation of the same three species with the same thermodynamic constants determined in the batch experiments. The hypothesis of the modeling leads to a slight overestimation of the quantities of zinc eluted (10%) at pH 6 and 7, mostly in the desorption phase. These results show that the methodology used facilitates the correct modeling of both batch and transport experiments and formulation of the hypothesis on the interactions between the low reactive sand and a complex solution.     

The evolution of mass balance models of persistent organic pollutant fate in the environment

Current approaches to modelling the fate of persistent organic pollutants (POPs) in the environment have evolved in response to four dominant characteristics of these substances; namely: (1) the presence of POPs in virtually all environmental phases and the ease with which they move from one to the other requires multi-compartmental modelling. Describing transport across phase boundaries becomes as, or even more, important as quantifying transport within the phases; (2) POPs may persist in the environment for many decades. For chemicals that 'have time', concepts such as equilibrium partitioning and steady-state become more important than for short-lived substances whose fate is more controlled by the rates of transformation; (3) measuring POPs is difficult and expensive and observed concentrations of POPs are not available in high spatial or temporal resolution. Consequently, high resolution tends not to be a high priority in POP models; and (4) detrimental effects of POPs often manifest themselves in top predators, which has led to a focus on modelling biotic uptake and transfer within food chains. The task of building a POPs model is viewed as combining the four 'building blocks' of partitioning, transport, transformation and source data with the help of the law of the conservation of mass. Process models, evaluative models, models of real local, regional and global fate, as well as biological uptake models are presented and references to numerous examples are provided. An attempt is made to forecast future directions in the field of POPs modelling. It is expected that modelling techniques that do not rely on quantitative emission estimates as well as approaches that take into account spatial, temporal and climatic variability as well as parameter uncertainty will increase in importance. Finally, the relationship between modelling POPs and models of other pollutant issues is addressed, as are potential interactions between POPs and pollutant issues such as eutrophication, acidification and global climate change.     

新型内构件内循环三相流化床流体力学和氧传质特性的研究

对一种导流筒内置静态混合元件的改进型内循环三相流化床 (MITFB)的流体力学和氧传质特性进行了试验研究。结果表明 :相对于普通流化床 (CITFB) ,MITFB上升区气体含率增大 1 8— 3 7倍 ,体积氧转移系数KLa和氧转移效率EA 值平均增大 72 5 % ;而液体循环流量则减小了 2 5 6 %— 37 0 %。上升区气含率和液体循环流速可分别用Fan公式和Chisti公式预测 ,并求出了相应的参数     

Dose transfer of Bacillus thuringiensis from cabbage to the diamondback moth: A graphical simulator

Abstract

The application of agrichemicals is a highly inefficient process and one of the main causes of the environmental and health risks currently associated with pesticide usage. Efforts to mitigate this inefficiency have largely been unsuccessful, due principally to the poor understanding of the processes involved in the spray application of pesticides, from atomization to biological effect. A generalized model of the application system for pesticides from atomization to biological result is described in this overview. The model allows the investigation of the biological consequences of altering the application parameters for the bacterial insecticide Bacillus thuringiensis when used against the diamondback moth (Plutella xylostella L.) with cabbage as the substrate. Parameters input into the model include the in‐flight droplet size frequency distribution of the spray cloud, spatial distribution of the deposit, spread and subsequent environmental degradation of the deposit, and behavioral and toxicological effects.

It is hoped that such a modelling approach can afford insights into the application process, and, through a better understanding of the inefficient but still highly effective hydraulic application systems used worldwide, reduce that inefficiency to tolerable levels.     

Eichhornia crassipes capability to remove naphthalene from wastewater in the absence of bacteria

The aim of the current study was to investigate the potential of an aquatic plant, the water hyacinth (Eichhornia crassipes) devoid rhizospheric bacteria, to reduce naphthalene (a polyaromatic hydrocarbon) present in wastewater and wetlands.The capability of sterile water hyacinth plants to remove naphthalene from water and wastewater was studied in batch systems. Water hyacinths enhance the removal of pollutants through their consumption as nutrients and also through microbial activity of their rhizospheric bacteria.Experimental kinetics of naphthalene removal by water hyacinth coupled with natural rhizospheric bacteria was 100% after 9 d. Plants, decoupled of rhizospheric bacteria, reduced naphthalene concentration up to 45% during 7 d. Additionally, naphthalene uptake by water hyacinth revealed a biphasic behavior: a rapid first phase completed after 2.5 h, and a second, considerably slower rate, phase (2.5-225 h). In conclusion, water hyacinth devoid rhizospheric bacteria reduced significantly naphthalene concentration in water, revealing a considerable plant contribution in the biodegradation process of this pollutant.     

Assessing microbial degradation of o-xylene at field-scale from the reduction in mass flow rate combined with compound-specific isotope analyses

In recent years, natural attenuation (NA) has evolved into a possible remediation alternative, especially in the case of BTEX spills. In order to be approved by the regulators, biodegradation needs to be demonstrated which requires efficient site investigation and monitoring tools. Three methods--the Integral Groundwater Investigation method, the compound-specific isotope analysis (CSIA) and a newly developed combination of both--were used in this work to quantify at field scale the biodegradation of o-xylene at a former gasworks site which is heavily contaminated with BTEX and PAHs. First, the Integral Groundwater Investigation method [Schwarz, R., Ptak, T., Holder, T., Teutsch, G., 1998. Groundwater risk assessment at contaminated sites: a new investigation approach. In: Herbert, M. and Kovar, K. (Editors), GQ'98 Groundwater Quality: Remediation and Protection. IAHS Publication 250, pp. 68-71; COH 4 (2000) 170] was applied, which allows the determination of mass flow rates of o-xylene by integral pumping tests. Concentration time series obtained during pumping at two wells were used to calculate inversely contaminant mass flow rates at the two control planes that are defined by the diameter of the maximum isochrone. A reactive transport model was used within a Monte Carlo approach to identify biodegradation as the dominant process for reduction in the contaminant mass flow rate between the two consecutive control planes. Secondly, compound-specific carbon isotope analyses of o-xylene were performed on the basis of point-scale samples from the same two wells. The Rayleigh equation was used to quantify the degree of biodegradation that occurred between the wells. Thirdly, a combination of the Integral Groundwater Investigation method and the compound-specific isotope analysis was developed and applied. It comprises isotope measurements during the integral pumping tests and the evaluation of delta13C time series by an inversion algorithm to obtain spatially integrated mean isotope values at the control planes. It was shown that the Rayleigh equation is applicable to spatially integrated mean isotope values in order to obtain the mean biodegradation between the consecutive control planes. All three approaches yielded consistently a 98-99% degradation of o-xylene.