Approximate evaluation of contaminant transport through vertical barriers

Containment of groundwater contamination using physical barriers can be an important element of a subsurface remediation program. This work presents simple analytical tools for predicting the performance of barriers in terms of the steady-state contaminant flux across the barrier, the duration of the transient period following barrier installation, and the time-dependent contaminant concentration distribution within the barrier. The analytical expressions are developed from approximate boundary layer (BL) solutions to the advective–dispersive equation subject to conservative fixed concentration boundary conditions. Critical ranges of important dimensionless quantities are identified for use in barrier performance assessment, for both steady-state and transient conditions. Comparative calculations made with the BL equations and more exact semi-analytical solutions are used to characterize the accuracy and applicability of the BL approach.     

Use of tracer tests to evaluate the impact of enhanced-solubilization flushing on in-situ biodegradation

Tracer tests were conducted to evaluate the effect of a complexing sugar flush (CSF) on in-situ biodegradation potential at a site contaminated by jet fuel, solvents, and other organic compounds. Technical-grade hydroxypropyl-beta-cyclodextrin was used during the CSF study, which was conducted in a hydraulically isolated cell emplaced in a surficial aquifer. In-situ biodegradation potential was assessed with the use of tracer tests, which were conducted prior to and immediately following the CSF study. Ethanol, hexanol, and benzoate were used as the biodegradable tracers, while bromide was used as a nonreactive tracer. The results indicate that the biodegradation of benzoate was similar for both tracer tests. Conversely, the biodegradation of ethanol (23% increase) and hexanol (41% increase) was greater for the post-CSF tracer test. In addition, analysis of core samples collected from within the test cell indicates that the population density of aerobic jet-fuel degraders increased in the vicinity of the injection wells during the CSF. These results indicate that the cyclodextrin flush did not deleteriously affect the indigenous microbial community. This study illustrates that tracer tests can be used to evaluate the impact of remediation activities on in-situ biodegradation potential.     

Transport of a non-volatile contaminant in unsaturated porous media in the presence of colloids

Stable colloidal particles can travel long distances in subsurface environments and carry particle-reactive contaminants with them to locations further than predicted by the conventional advective-dispersive transport equation. When such carriers exist in a saturated porous medium, the system can be idealized as consisting of three phases: an aqueous phase, a carrier phase, and a stationary solid matrix phase. However, when colloids are present in an unsaturated porous medium, the system representation should include one more phase, i.e. the air phase. In the work reported, a mathematical model was developed to describe the transport and fate of the colloidal particles and a non-volatile contaminant in unsaturated porous media. The model is based on mass balance equations in a four-phase porous medium. Colloid mass transfer mechanisms among aqueous, solid matrix, and air phases, and contaminant mass transfer between aqueous and colloid phases are represented by kinetic expressions. Governing equations are non-dimensionalized and solved to investigate colloid and contaminant transport in an unsaturated porous medium. A sensitivity analysis of the transport model was utilized to assess the effects of several parameters on model behavior. The colloid transport model matches successfully with experimental data of Wan and Wilson. The presence of air-water interface retards the colloid transport significantly counterbalancing the facilitating effect of colloids. However, the retardation of contaminant transport by colloids is highly dependent on the properties of the contaminant and the colloidal surface.     

Local and distant residence times of contaminants in multi-compartment models. Part I: a review of the theoretical basis

In this, Part I of a two-part series, a review is presented of some generally appreciated residence time properties of multimedia models. The novel concept of “distant residence time” (DRT) is developed to provide additional insights into the characterization of environmental transport. DRT is the proportionality constant between the rate of emission of a contaminant into one compartment or region and the mass that results at steady-state in a distant compartment. The concept, which can be viewed as an expression of environmental mobility, is illustrated for various configurations of compartments and is shown to be consistent with the concepts of global fractionation and cold condensation. The dynamic responses of chemical quantities at distant locations to changing emission rates are also discussed. It is shown that approximate solutions for DRTs and their time dependence are useful for characterizing the long-range transport of chemicals and for interpreting monitoring data.     

Influence of indoor transport and mixing time scales on the performance of sensor systems for characterizing contaminant releases

Optimizing real-time sensor systems to detect and identify relevant characteristics of an indoor contaminant event is a challenging task. The interpretation of incoming sensor data is confounded by uncertainties in building operation, in the forces driving contaminant transport, and in the physical parameters governing transport. In addition, simulation tools used by the sensor interpretation algorithm introduce modeling uncertainties. This paper explores how the time scales inherent in contaminant transport influence the information that can be extracted from real-time sensor data. In particular, we identify three time scales (within room mixing, room-to-room transport, and removal from the building) and study how they affect the ability of a Bayesian Monte Carlo (BMC) sensor interpretation algorithm to identify the release location and release mass from a set of experimental data, recorded in a multi-floor building. The research shows that some limitations in the BMC approach do not depend on details of the models or the algorithmic implementation, but rather on the physics of contaminant transport. These inherent constraints have implications for the design of sensor systems.     

Biogeochemical processes at the fringe of a landfill leachate pollution plume: potential for dissolved organic carbon, Fe(II), Mn(II), NH4, and CH4 oxidation

Various redox reactions may occur at the fringe of a landfill leachate plume, involving oxidation of dissolved organic carbon (DOC), CH4, Fe(II), Mn(II), and NH4 from leachate and reduction of O2, NO3 and SO4 from pristine groundwater. Knowledge on the relevance of these processes is essential for the simulation and evaluation of natural attenuation (NA) of pollution plumes. The occurrence of such biogeochemical processes was investigated at the top fringe of a landfill leachate plume (Banisveld, the Netherlands). Hydrochemical depth profiles of the top fringe were captured via installation of a series of multi-level samplers at 18, 39 and 58 m downstream from the landfill. Ten-centimeter vertical resolution was necessary to study NA within a fringe as thin as 0.5 m. Bromide appeared an equally well-conservative tracer as chloride to calculate dilution of landfill leachate, and its ratio to chloride was high compared to other possible sources of salt in groundwater. The plume fringe rose steadily from a depth of around 5 m towards the surface with a few meters in the period 1998-2003. The plume uplift may be caused by enhanced exfiltration to a brook downstream from the landfill, due to increased precipitation over this period and an artificial lowering of the water level of the brook. This rise invoked cation exchange including proton buffering, and triggered degassing of methane. The hydrochemical depth profile was simulated in a 1D vertical reactive transport model using PHREEQC-2. Optimization using the nonlinear optimization program PEST brought forward that solid organic carbon and not clay minerals controlled retardation of cations. Cation exchange resulted in spatial separation of Fe(II), Mn(II) and NH4 fronts from the fringe, and thereby prevented possible oxidation of these secondary redox species. Degradation of DOC may happen in the fringe zone. Re-dissolution of methane escaped from the plume and subsequent oxidation is an explanation for absence of previously present nitrate and anaerobic conditions in pristine groundwater above the plume. Stable carbon isotope (delta13C) values of methane confirm anaerobic methane oxidation immediately below the fringe zone, presumably coupled to reduction of sulfate, desorbed from iron oxide. Methane must be the principle reductant consuming soluble electron-acceptors in pristine groundwater, thereby limiting NA for other solutes including organic micro-pollutants at the fringe of this landfill leachate plume.     

Using chemical models for evaluating the geochemical confinement capacity of a geological barrier application to the Centre de Stockage de l'Aube (France)

The feasibility of using a chemical reaction-based approach for evaluating and modelling the role of adsorption reactions in determining the geochernical confinement capacity of natural geological barriers is being studied as part of an on-going R & D programme. The confined superficial aquifer underlying the Centre de Stockage de l'Aube facility, a geological barrier for this site, has been used as a case study with the following aims. First, development of a site characterisation protocol and demonstration of its use to determine the principal geochemical characteristics of aquifer materials using batch experiments and to represent the information obtained in terms of a chemical model. The experimental results obtained for Ni²⁺ partitioning as a function of total Ni, pH, total Ca and total solid can be satisfactorily represented in terms of reactions with an ion exchange site and a single amphoteric surface hydroxyl site with ferrihydrite reaction constants. A second objective is the incorporation of the reactions in a coupled geochemistry/transport code, and to verify the applicability of the coupled code predictions for Ni²⁺ mass transfer by comparison with the results obtained during column tracer experiments. The breakthrough curve and equilibrium solid phase Ni loading, predicted by a one-dimensional coupled model for a column tracer experiment, agree closely with observed data.Additional studies are underway to reduce model conditionality, to extend the adsorption model to other analogue cations and anions, to incorporate the effect of natural organic matter and to take into consideration precipitation/dissolution of amorphous Fe surface phases.     

Carbonaceous species in fine particles at the background sites in Korea between 1994 and 1999

Organic carbon (OC) and elemental carbon (EC) in fine particles (PM_2.5) at two background sites, Kosan and Kangwha in Korea were measured during intensive field studies between 1994 and 1999. Fine particles were collected on pre-fired quartz filters in a low-volume sampler and analyzed using the selective thermal oxidation method with MnO₂ catalyst. The OC and EC concentrations at Kosan located at western tip of Cheju Island in southern Korea are lower than those at Kangwha located at western coastal area in mid-Korean peninsula. Still, the OC concentrations at Kosan are generally higher than those at other background areas in Japan and USA. The EC concentrations at Kosan are lower than or comparable to those at other background areas. The total carbon (TC, sum of OC and EC) to EC ratio values at both sites were higher than those at other background areas in Japan and USA. At Kosan, the OC and EC concentrations when air parcels were from southern China were higher than those when air parcels were coming from northern China. However, at Kangwha, the differences were statistically not clear since most air parcels were from northern China. Except when air parcels were from the North Pacific during summer, the OC and EC concentrations are well correlated indicating that both OC and EC share the same emission/transport characteristics. From the gaseous hydrocarbon data and the OC and EC relationship, it was found that during summer local biogenic emissions of OC might be significant at Kosan.     

Relationships between emission sources and air mass characteristics in East Asia during the TRACE-P period

Long-range transport of pollutants influenced by anthropogenic and natural emission sources in East Asia is investigated by using backward trajectory analysis along the NASA TRACE-P flight tracks and a numerical simulation with the three-dimensional chemical transport model (STEM-2k1). Observation-based regional distributions of trace gases are reconstructed using the observations obtained by measurements on board the DC-8 and P3-B aircrafts. Systematic features of the spatial distribution for each species are identified. It is found that the observed concentrations of CO and some NMHCs, and the ratios between these species, are highly associated with the source distribution features and their regional characteristics. Reconstructed fields of the observed and modeled ethane/CO and ethane/propane are found to reproduce well the estimated emission ratios in East Asia. We also investigated the time rate of change of the concentration of species and their ratio along the trajectory. From this analysis the propane/ethane and propane/acetylene ratios are shown to preserve their emission ratios during regional transport. However systematic differences in the propane vs. acetylene/CO relationships are found between the model and observation values. This analysis suggests that further efforts are needed to improve the estimates of biomass burning emissions in SE Asia. The results presented in this paper also suggest ways to further extend the capabilities to derive observation-based inventories.     

On the plausible association between environmental conditions and human eye damage

The increase in solar ultraviolet radiation can have various direct and indirect effects on human health, like the incidence of ocular damage. Data of eye damage in residents of three suburban regions in Greece and in two groups of monks/nuns and fishermen are examined here. The statistics performed on these data provides new information about the plausible association between increased levels of solar ultraviolet radiation, air-pollution at ground level, and the development of ocular defects.