Analysis of Nitroaromatics and Nitramines in Ammunition Waste Water and in Aqueous Samples from Former Ammunition Plants and Other Military Sites Analyse von Nitroaromaten und Nitraminen in Munitionsabwasser und wäßrigen Proben ehemaliger Munitionsfabriken und anderen Rüstungsaltlasten

Waste water from ammunition production sites and aqueous samples (ground and surface water) on or near former military sites on which explosives were produced or filled, e.g. into shells, may be contaminated by the original explosives—mainly nitrotoluenes (such as dinitrotoluenes, trinitrotoluene (TNT)) and nitramines (such as hexogen (RDX), octogen (HMX), and tetryl) or hexyl, but also by byproducts and compounds formed by biodegradation of the explosives such as aminonitrotoluenes, chlorinated nitrobenzenes and nitrophenols. These compounds can be extracted from aqueous samples by liquid/liquid extraction (using dichloromethane or toluene) or by solid phase extraction using C-18 adsorbents with high recoveries (usually ≥85%) provided they contain only one amino group. Nitrotoluenes, chlorinated nitrobenzenes and aminonitrotoluenes (nitrotoluidines) may be determined by gas chromatography (GC) using selective detectors such as an electron capture detector (ECD), a nitrogen-phosphorus detector (NPD) or a chemiluminescence detector (thermal energy analyzer, TEA). The use of combined gas chromatography/mass spectrometry (GC/MS) under electron impact conditions is even more specific. Detection limits comparable to an ECD or NPD, however, are only achieved if the mass spectrometer is operated under selected ion monitoring (SIM). Nitrophenols are derivatized after extraction by heptafluorobutyric anhydride or by acetic anhydride where the latter method can be directly applied to the aqueous sample. The nitramine explosives, such as RDX, HMX, and tetryl, hexyl, the nitrate esters, such as nitropenta (PETN) and nitroguanidine as well as picric acid cannot, or only with difficulty, be analyzed by gas chromatography. They may be determined by high performance liquid chromatography (HPLC) with UV-detection. The HPLC analysis can be extended to include also nitrotoluenes and nitroaminotoluenes.     

Assessment of the feasibility of utilizing Landsat for detection and monitoring of landfills in a statewide GIS

Use of satellite data could be beneficial and cost effective in detecting and monitoring landfills in a state-wide geographic information system (GIS). To assure the feasibility of this approach, multitemporal Landsat data were used to detect several selected active and inactive landfills in central and southwest Missouri. The landfills were visually delineated from aerial photography of approximately the same two dates. A classification procedure based on homogeneity of the digital numbers was performed on each landfill scene for each time period using four spectral bands: two visible, one near-infrared, and one mid-infrared. The mid-infrared band proved more useful in delineating landfills, especially when spectral change was compared to the near-infrared band. The active landfills were spectrally different from surrounding land cover as were the two landfills which closed after the collection of the first Landsat scene. These landfills showed considerable areal change between the two selected time periods as verified by the aerial photographs. The inactive landfills were more difficult to discern from surrounding land cover types because they were grass covered and spectrally similar to pasture. Consequently, areal change could not be assigned to these older landfills because the reclamation process was practically complete.     

Pilot-scale field model tests for detecting landfill leachate intrusion into the subsurface using a grid-net electrical conductivity measurement system

The grid-net electrical conductivity measurement system for detecting exact locations of landfill leachate intrusion in the subsurface was developed in this study. Laboratory and pilot-scale field model tests were performed to evaluate the direct application of a grid-net electrical conductivity measurement system for the detection of landfill leachate. A significant increase in electrical conductivity of soil was observed by adding landfill leachate. This can be explained as an increase in electrical conductivity of pore fluid due to an increase in leachate constituents as charge carriers. In pilot-scale field model tests, leachate intrusion locations were accurately identified at the initial stage of landfill leachate release by the grid-net electrical conductivity measurement system. The electrical conductivity of the subsurface before leachate injection lay within a small range of 24.8–43.0 S/cm. The electrical conductivity values in detected points were approximately ten times more than the conductivity values of the subsurface without landfill leachate intrusion. The results in this study indicate that the grid-net electrical conductivity measurement method has a possible application for detecting locations of landfill leachate intrusion into the subsurface at the initial stage, and thus has great potential in monitoring leachate leakage at waste landfills.     

Heavy metal pollution and acid drainage from the abandoned Balya Pb-Zn sulfide Mine,NW Anatolia,Turkey

This study was conducted to determine the effects of the waste-rock dump (WRD) of the underground polymetallic Balya Mine on the Kocacay River and eventually on Lake Manyas in Turkey. Data presented in this paper include geochemical characteristics of various kinds of water (mine, surface and groundwater) and of suspended-particle samples in the vicinity of Balya. The more polluted mine waters have low pH and high conductivity, while high concentrations of Zn, Cd, Mn tend to be found in the dry and wet seasons. High concentrations of Pb, As, Cr, Cu and S appear only in the wet season. The sources of the heavy metal concentration within the Kocacay River are leached waste, surface run off, and overflow from the spillway of the WRD. To minimize the formation of acids and dissolved metal, and for the remediation of the harmful effects of extreme contamination conditions, it is recommended that lime or alkali materials and organic carbon be added to simulate the action of sulfate-reducing bacteria.     

Experimental study of migration of potassium ion through a two-layer soil system

A barrier system based on the hydraulic trap design concept for a landfill was proposed. To study the field scenario in which a clay liner is underlain by a granular layer functioning as a secondary leachate drain layer, a laboratory advection–diffusion test was performed to investigate factors controlling the transport of contaminants in a two-layer soil system. The soils used for this study were Ariake clay and, the underlying layer, Shirasu soil from the Kyushu region of Japan. Potassium (K⁺) was selected as the target chemical species with an initial concentration of 905 mg L⁻¹. The effective diffusion coefficients (D _e) of K⁺ for Ariake clay and Shirasu soil were back-calculated using an available computer program, Pollute V 6.3. Values of D _e derived from this experiment are consistent with previously published ones. The Ariake clay has lower D _e than the Shirasu soil. The hypothesis that mechanical dispersion can be considered negligible is reasonable based on both the observation that the predicted values well fit the experimental data and the analyses of two dimensionless parameters. Parametric analyses show that transport of K⁺ through soils is controlled by advection–diffusion rather than diffusion only, whereas at low Darcy velocity (i.e., ≤10⁻⁹ m s⁻¹), transport of K⁺ will be controlled by diffusion. Applications of the test results and parametric analysis results in practical situations were reviewed.     

Contaminant dispersion at the rehabilitated Mary Kathleen uranium mine, Australia

This study reports on the transfer of contaminants from waste rock dumps and mineralised ground into soils, sediments, waters and plants at the rehabilitated Mary Kathleen uranium mine in semi-arid northwest Queensland. Numerous waste rock dumps were partly covered with benign soil and the open pit mine was allowed to flood. The mineralised and waste calc-silicate rock in the open pit and dumps has major (>1 wt%) Ca, Fe and Mg, minor (>1,000 ppm) Ce, La, Mn, P and S, subminor (>100 ppm) Ba, Cu, Th and U, and trace (<100 ppm) As, Ni, Pb, Y and Zn values. Consequently, chemical and physical weathering processes have acted on waste rock and on rock faces within the open pit, mobilising many elements and leading to their dispersion into soils, stream sediments, pit water and several plant species. Chemical dispersion is initiated by sulfide mineral breakdown, generation of sulfuric acid and formation of several soluble, transient sulfate minerals as evaporative efflorescent precipitates. Radiation doses associated with the open pit average 5.65 mSv year⁻¹; waste dumps commonly have lower values, especially where soil-covered. Surface pit water is slightly acid, with high sulfate values accompanied by levels of U, Cu and Ni close to or above Australian water guideline values for livestock. Dispersion of U and related elements into soils and stream sediments occurs by physical (erosional) processes and from chemical precipitation. Plants growing in the mine void, on waste dumps and contaminated soil display evidence of biological uptake of U, LREE, Cu and Th and to a lesser degree of As, Ni, Pb, Y and Zn, with values being up to 1–2 orders of magnitude above background sites for the same species. Although rehabilitation procedures have been partly successful in reducing dispersion of U and related elements into the surrounding environment, it is apparent that 20 years after rehabilitation, there is significant physical and chemical mobility, including transfer into plants.     

Stochastic analysis of the effect of heterogeneity and fractures on radionuclide transport in a low-permeability clay layer

Deep low-permeability clay layers are considered as safe environments for disposal of high-level radioactive waste. In Belgium, the Boom Clay is a candidate host rock for deep geological disposal. In this study, we analyze the effects of fractures and spatially variable hydraulic conductivity on radionuclide migration through the clay. Fracture geometry and properties are simulated with Monte Carlo simulation. The heterogeneity of hydraulic conductivity is simulated by direct sequential co-simulation using measurements of hydraulic conductivity and four types of secondary variables. The hydraulic conductivity and fracture simulations are used as input for a transport model. Radionuclide fluxes computed with this heterogeneous model are compared with fluxes obtained with a homogeneous model. The output fluxes of the heterogeneous model differ at most 8% from the homogeneous model. The main safety function of the Boom Clay is thus not affected by the fractures and the spatial variability of hydraulic conductivity.     

Three-dimensional stability analysis of the Kettleman Hills landfill slope failure based on observed sliding-block mechanism

Previous studies of the Kettleman landfill slope failure of 1988 had concluded that the failure, which slid along the underlying liner interfaces with low shearing resistance, occurred as a result of attaining the critical waste fill height. These studies showed, however, some discrepancies in regard to the adopted material strength data as well as the computed factors of safety. Based on the observed sliding-block mechanism, a 3D analysis model was established herein which allowed for variations in material strength mobilization within the sliding mass and at the slip surface. With a careful consideration on the interface strength data, results of forward analysis for the pre-slide slope generally showed better agreement with the field observations. Results of backward analysis for the post-slide slope indicated a consistency in the estimated material strength with the laboratory test data. The current study also showed slightly higher computed 3D factors of safety than the associated 2D values, in both pre-slide and post-slide cases.     

Assessment of crushed shales for use as compacted landfill liners

The possibility of using crushed shales as landfill liners is investigated in this study. Two types of shales were studied by performing the following laboratory tests: hydraulic conductivity, compaction, swelling, consolidation, X-ray diffraction (XRD), scanning electron microscope (SEM) and chemical analysis. For both compacted shales, the hydraulic conductivity was in order of 10^− 7 cm/s or less which satisfies the specifications for landfill liners. The results of XRD and SEM support the low values of the hydraulic conductivity. Because of the dominant presence of low-activity kaolinite, there was no significant change in the hydraulic conductivity when the compacted shales are exposed to calcium chloride solution. The compressibility of the compacted clay was low and no serious post-construction settlement is expected. The shear strength of the compacted shales was within the usual expected range for earthen liners and, therefore, should pose no challenges with respect to shear strength. The crushed shales also satisfy the other criteria related to Atterberg limits and grain size.     

Stochastic analysis of the effect of spatial variability of diffusion parameters on radionuclide transport in a low permeability clay layer

Most studies that incorporate subsurface heterogeneity in groundwater flow and transport models only analyze and simulate the spatial variability of hydraulic conductivity. Heterogeneity of the other flow and transport parameters are usually neglected. This approach is often justified, but there are, however, cases in which disregarding the heterogeneity of the other flow and transport parameters can be questionable. In low permeability media, for instance, diffusion is often the dominant transport mechanism. It therefore seems logical to incorporate the spatial variability of the diffusion parameters in the transport model. This study therefore analyses and simulates the spatial variability of the effective diffusion coefficient and the diffusion accessible porosity with geostatistical techniques and incorporates their heterogeneity in the transport model of a low permeability formation. The formation studied was Boom clay (Belgium), a candidate host rock for the deep geological disposal of high-level radioactive waste. The calculated output radionuclide fluxes of this model are compared with the fluxes calculated with a homogeneous model and a model with a heterogeneous hydraulic conductivity distribution. This analysis shows that the heterogeneity of the diffusion parameters has a much larger effect on the calculated output radionuclide fluxes than the heterogeneity of hydraulic conductivity in the low permeability medium under study.