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.     

Sensitivity of the DERMA long-range Gaussian dispersion model to meteorological input and diffusion parameters

The Danish Emergency Response Model of the Atmosphere (DERMA) is described and applied to the first ETEX experiment. By using analysed low-resolution numerical weather-prediction data from the global model of the European Centre for Medium-range Weather Forecast (ECMWF) as well as higher-resolution data from two versions of the High Resolution Limited Area Model (HIRLAM), which are operational at the Danish Meteorological Institute (DMI), the sensitivity of DERMA to the resolution of meteorological data is analysed by comparing DERMA results with concentration measurements. Furthermore, the sensitivity to boundary-layer height and diffusion parameters is studied. These parameters include the critical bulk Richardson number, which is used to estimate the atmospheric boundary-layer height, the horizontal eddy diffusivity and the Lagrangian turbulence time scale. The parameters, which provide the best performance of DERMA, are 0.25 for the critical bulk Richardson number, 6×10³ m² s^-1 for the horizontal eddy diffusivity, and 3 h for the Lagrangian time scale. DERMA is much more sensitive to boundary-layer parameters when using high-resolution DMI-HIRLAM data than when using data of lower resolution from the ECMWF. Finally, the bulk Richardson number method of boundary-layer height calculation applied to DMI-HIRLAM data is verified directly against routine radiosondes released under the tracer gas plume. The boundary-layer height estimates based on analysed NWP model data agree well with observations, and the agreement deteriorates as a function of forecast length.