Contaminant degradation in physically and chemically heterogeneous aquifers

This paper examines the importance of the correlation between hydraulic conductivity (K) and degradation rate constant (k) during the transport of reactive contaminants in heterogeneous aquifers. We simulated reactive transport in an ensemble of two-dimensional heterogeneous aquifers. Two sets of transport simulations were conducted: one in which a perfect positive correlation was assumed between ln(K) and ln(k), and one in which a perfect negative correlation was assumed. We found that the sign of the correlation has important consequences for the contaminant transport. Qualitatively, a negative correlation leads to significantly more pronounced "fingering" of the contaminant plume than does a positive correlation, with potentially important consequences for downgradient receptors. Quantitatively, the expected behavior (as quantified by the contaminant mass remaining in the aquifer) is statistically different between the positive and negative cases: on average, more contaminant mass persists when K and k are negatively correlated. Also, the negative correlation leads to more variability between realizations of the ensemble, whereas a positive correlation induces relatively little variability between realizations. We discuss the implications of these findings for the management of contaminated aquifers.     

How Plants Cope with Foreign Compounds. Translocation of xenobiotic glutathione conjugates in roots of barley (Hordeum vulgare) (9 pp)

Background, Aim and Scope Numerous herbicides and xenobiotic organic pollutants are detoxified in plants to glutathione conjugates. Following this enzyme catalyzed reaction, xenobiotic GS-conjugates are thought to be compartmentalized in the vacuole of plant cells. In the present study, evidence is presented for long range transport of these conjugates in plants, rather than storage in the vacuole. To our knowledge this is the first report about the unidirectional long range transport of xenobiotic conjugates in plants and the exudation of a glutathione conjugate from the root tips. This could mean that plants possess an excretion system for unwanted compounds which give them similar advantages as animals. Materials and Methods: Barley plants (Hordeum vulgare L. cv. Cherie) were grown in Petri dishes soaked with tap water in the greenhouse. - Fluorescence Microscopy. Monobromo- and Monochlorobimane, two model xenobiotics that are conjugated rapidly in plant cells with glutathione, hereby forming fluorescent metabolites, were used as markers for our experiments. Their transport in the root could be followed sensitively with very good temporal and spatial resolution. Roots of barley seedlings were cut under water and the end at which xenobiotics were applied was fixed in an aperture with a thin latex foil and transferred into a drop of water on a cover slide. The cover slide was fixed in a measuring chamber on the stage of an inverse fluorescence microscope (Zeiss Axiovert 100). - Spectrometric enzyme assay. Glutathione S-transferase (GST) activity was determined in the protein extracts following established methods. Aliquots of the enzyme extract were incubated with 1-chloro-2,4-dinitrobenzene (CDNB), or monochlorobimane. Controls lacking enzyme or GSH were measured. - Pitman chamber experiments. Ten days old barley plants or detached roots were inserted into special incubation chambers, either complete with tips or decapitated, as well as 10 days old barley plants without root tips. Compartment A was filled with a transport medium and GSH conjugate or L-cysteine conjugate. Compartments B and C contained sugar free media. Samples were taken from the root tip containing compartment C and the amount of conjugate transported was determined spectro-photometrically. Results: The transport in roots is unidirectional towards the root tips and leads to exsudation of the conjugates at rates between 20 and 200 nmol min-1. The microscopic studies have been complemented by transport studies in small root chambers and spectroscopic quantification of dinitrobenzene-conjugates. The latter experiments confirm the microscopic studies. Furthermore it was shown that glutathione conjugates are transported at higher rates than cysteine conjugates, despite of their higher molecular weights. This observation points to the existence of glutathione specific carriers and a specific role of glutathione in the root. Discussion: It can be assumed that long distance transport of glutathione conjugates within the plant proceeds like GSH or amino acid transport in both, phloem and xylem. The high velocity of this translocation of the GS-X is indicative of an active transport. For free glutathione, a rapid transport-system is essential because an accumulation of GSH in the root tip inhibits further uptake of sulfur. Taking into account that all described MRP transporters and also the GSH plasmalemma ATPases have side activities for glutathione derivatives and conjugates, co-transport of these xenobiotic metabolites seems credible. - On the other hand, when GS-B was applied to the root tips from the outside, no significant uptake was observed. Thus it can be concluded that only those conjugates can be transported in the xylem which are formed inside the root apex. Having left the root once, there seems to be no return into the root vessels, probably because of a lack of inward directed transporters. Conclusions: Plants seem to possess the capability to store glutathione conjugates in the vacuole, but under certain conditions, these metabolites might also undergo long range transport, predominantly into the plant root. The transport seems dependent on specific carriers and is unidirectional, this means that xenobiotic conjugates from the rhizosphere are not taken up again. The exudation of xenobiotic metabolites offers an opportunity to avoid the accumulation of such compounds in the plant. Recommendations and Perspectives: The role of glutathione and glutathione related metabolites in the rhizosphere has not been studied in any detail, and only scattered data are available on interactions between the plant root and rhizosphere bacteria that encounter such conjugates. The final fate of these compounds in the root zone has also not been addressed so far. It will be interesting to study effects of the exuded metabolites on the biology of rhizosphere bacteria and fungi.     

危险品道路运输泄漏引发水污染事故的定量风险评估方法研究

介绍了由道路交通事故引发的地表水污染事故风险定量分析方法,重点分析了突发水污染事故源发生概率和危害后果表征方法.以评价水域内道路危险品运输泄漏事故发生概率为水污染事故源发生概率.污染事故后果危害水平的表征:1)敏感区(点)最高浓度; 2)敏感区(点)超标总历时;3)水质超标的范围(如超标河流长度).评估方法为陆源造成的突发水污染事故的预防管理与应急计划的制订实施提供了科学依据.     

Comparison of Microscopic and Macroscopic Modeling Approaches for Subsurface Contaminant Transport

The practice of contaminant transport and remediation has shown significant progress in recent years. However, despite the significant progress made, remediation efforts are often delayed by extremely long breakthrough curve tails that render efforts to bring the level of contaminants below the regulatory standards inefficient. One hypothesis is that these long tails are due to the reservoir-like slow diffusive processes in soil micropore zones. This study compares the effects of micropores at macroscopic and microscopic levels and establishes a link between these approaches for validation and calibration purposes. The link between macroscopic and microscopic levels is established through comparisons and testing of the two models while incorporating appropriate scale and boundary effects. Despite the differences in conceptual approaches and simulation time, the two approaches rendered meaningful results. The link helps forecast the effects of micropore zone transport processes in the subsurface efficiently and thus allows development of numerical tools that could contribute towards more efficient remediation design.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

Identification of key parameters controlling dissolved oxygen migration and attenuation in fractured crystalline rocks

In the crystalline rocks of the Canadian Shield, geochemical conditions are currently reducing at depths of 500-1000 m. However, during future glacial periods, altered hydrologic conditions could potentially result in enhanced recharge of glacial melt water containing a relatively high concentration of dissolved oxygen (O2). It is therefore of interest to investigate the physical and geochemical processes, including naturally-occurring redox reactions, that may control O2 ingress. In this study, the reactive transport code MIN3P is used in combination with 2k factorial analyses to identify the most important parameters controlling oxygen migration and attenuation in fractured crystalline rocks. Scenarios considered are based on simplified conceptual models that include a single vertical fracture, or a fracture zone, contained within a rock matrix that extends from the ground surface to a depth of 500 m. Consistent with field observations, Fe(II)-bearing minerals are present in the fractures (i.e. chlorite) and the rock matrix (biotite and small quantities of pyrite). For the parameter ranges investigated, results indicate that for the single fracture case, the most influential factors controlling dissolved O2 ingress are flow velocity in the fracture, fracture aperture, and the biotite reaction rate in the rock matrix. The most important parameters for the fracture zone simulations are flow velocity in the individual fractures, pO2 in the recharge water, biotite reaction rate, and to a lesser degree the abundance and reactivity of chlorite in the fracture zone, and the fracture zone width. These parameters should therefore receive increased consideration during site characterization, and in the formulation of site-specific models intended to predict O2 behavior in crystalline rocks.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Downward Migration of Dense Bottom Currents

The focus of this paper is on the dynamics of a dense current flowing along the continental slope, and the frictionally induced downward motion it experiences. In particular, the movement of the lateral boundaries where the isopycnals meet the bottom are considered. The current is taken to be wide compared to the Rossby radius, which is in accordance with observations and makes the dynamics quasigeostrophic. The time development of the plume thickness is studied, using three different parameterisations for the bottom friction.Independently of the choice of parameterisation, the following results are obtained: In the central part of the plume friction acts as a diffusive process to minimise the curvature of the upper surface of the plume. At the upper edge the plume quickly approaches a state with small slope, i.e. small geostrophic velocity and small frictionally induced downward flow. At the lower edge a tongue of dense water shoots out creating a widening layer. The thickness of the migrating layer is approximately equal to the boundary layer depth and its downward speed is comparable to the along-slope geostrophic velocity. The downslope end of the migrating layer may form a steep front which requires some precautions in the numerical procedure.     

微生物-光-电化学耦合技术降解污染物和回收能源的研究进展

微生物电化学技术能同时实现污染物去除和能量回收,但存在污染物去除种类有限及产能效率低的局限,近几年将可再生的太阳能引入微生物电化学技术的微生物-光-电化学耦合技术应运而生。本文简要介绍了微生物-光-电化学耦合技术的发展背景和研究现状,对该技术现有的耦合形式进行分类,并对各种形式的耦合机理进行详细的阐释,最后对其未来的发展进行了展望。     

非平衡式双极性离子风消电技术与应用

为实现风送管道物料静电监测与控制,预防料仓静电燃爆事故,提高聚烯烃装置料仓安全水平,基于非平衡式双极性离子风消电技术,开发了双极性离子风消电器;基于离子风消电器和静电监测器,探讨了石化粉体料仓用离子风消电控制系统组成、电路、气路布局;对非平衡式双极性离子风消电系统进行现场应用测试。结果表明:基于此管道粉体消静电技术,合理调节正、负侧控制电压,可有效控制管道物料荷质比稳定在±0.3 μC/kg以内,保障聚烯烃装置料仓安全、稳定运行。