Ute Kalbe

Transport of organic contaminants within composite liner systems

Abstract Composite liners (a geomembrane in intimate contact with a mineral liner) are frequently used to line landfills and contaminated sites. It is therefore very important to characterise the behaviour of these systems even under extreme conditions. An investigation was undertaken to determine the influence of a mixture of concentrated organic contaminants on composite liner materials taken from test cells that had been dismantled after a 12-year permeation test. The organic hydrocarbons had permeated the HDPE-geomembrane and had then migrated or had been adsorbed within the mineral liners, depending on their properties. The obtained concentration profiles of the contaminant mixture components indicate that the various mineral layer materials have selective retardation abilities which correspond to the different parameters of the organic compounds as well as of the mineral layer. In addition, contaminant transport in the composite liners tested was modelled and the results of the model analysis compared with measurement data. An example (acetone) illustrates the calculated spatial and temporal contaminant concentration. The composite liners investigated exhibit a very good sealing capacity against the concentrated organic contaminants used.

Comparison of stir bar sorptive extraction (SBSE) and liquid-liquid extraction (LLE) for the analysis of polycyclic aromatic hydrocarbons (PAH) in complex aqueous matrices.

Stir bar sorptive extraction (SBSE) is an equilibrium extraction method used amongst others for the analysis of polycyclic aromatic hydrocarbons (PAH) in aqueous samples. We compared SBSE to liquid-liquid extraction (LLE) for aqueous eluates obtained from batch and column tests of PAH contaminated soils to check whether SBSE might be considered as an alternative sample preparation method. We used soils with different particle size distribution, organic matter content, and resulting eluate turbidity to test the sample preparation methods on eluates with matrices of varying complexity. Furthermore, we studied the influence of diluted organic matter (DOM) on the PAH sorption process to the polymer coating of the stir bar during SBSE. In the majority of cases, we found higher PAH concentrations (up to 288%) with SBSE than with LLE. The turbidity correlates with the difference in PAH results, i.e. the greater the turbidity in the eluate, the more PAH we found with SBSE compared to LLE. We observed no similar trend regarding the amount of total organic carbon (TOC). The presence of DOM in the eluate seems to hamper the SBSE slightly, the PAH recovery varied between 82 and 104%.

Column and batch tests of sulfonamide leaching from different types of soil

Sulfonamides (SAs) and their metabolites present severe hazards to human health and the environment, mainly because of antibiotic resistance. Knowledge of their bioavailability, including their sorption to soils and their impact on the soil-groundwater pathway, is crucial to their risk assessment. Laboratory batch and column leaching tests are important tools for determining the release potential of contaminants from soil or waste materials. Batch and column tests were carried out with soils differing in particle size distribution, organic matter content and pH, each spiked with sulfonamides (sulfadimethoxine (SDM), sulfaguanidine (SGD), sulfisoxazole (SX)). In order to test the applicability of leaching tests to polar contaminants batch and column tests were also compared. In the column tests, release was found to depend on the properties of both soil and sulfonamides. The fastest release was observed for coarse-grained soil with the smallest organic matter content (MS soil; 100% decrease in concentration until liquid-to-solid ratio (L/S) of 0.9 L kg(-1) for all SAs). The slowest release was established for sulfadimethoxine (24.5% decrease in concentration until L/S 1.22 L kg(-1)). The results of the batch and column tests were comparable to a large extent, with slightly higher concentrations being obtained in the column test experiments of fine-grained soils with a high organic matter content.

Effect of contact time on the release of contaminants from granular waste materials during column leaching experiments.

When reusing or disposing of contaminated granular waste materials there is a need to evaluate how the contaminants will interact on the pathway soil-groundwater and the effect this interaction will have on the surrounding environment. While column testing can provide a closer approximation to field percolation conditions than batch testing, there is still a need to develop column testing procedures that consider the requirements of practical testing time frames. This study evaluates the effect of different column contact times (2.5, 5, and 16h) on the release of inorganic constituents from bottom ash and demolition waste, two commonly reused granular materials. Leaching data for representative constituents of concern, such as copper, chromium, sulfate and chloride, as well as pH and electrical conductivity was compared for all different contact times studied. Results for the materials investigated in this study showed that variations in contact time have no significant effect on the release of the selected constituents and leaching parameters at low liquid to solid ratios. However, after a liquid to solid ratio of 1L/kg, the effect is more noticeable, and higher contact times show lower pH values as well as a reduction in the release of constituents of concern from bottom ash. In the case of demolition waste, the variation of contact time did not have a strong effect on the leaching behavior.

Leaching experiments on the release of heavy metals and PAH from soil and waste materials

Leaching tests are fundamental tools for the assessment of long-term impact of contaminated waste materials on the soil-groundwater pathway. Experiments were carried out in the framework of standardization and validation of column percolation and batch test procedures, in particular concerning the stipulation of the experimental setup. The colloid release of column and batch experiments was compared and the influence of different column filling heights (12.5-50 cm) on the release of polycyclic aromatic hydrocarbons (PAH) from soil was studied, as well as the effect of varying contact times (2.5-16 h) on the release of chromium from construction and demolition (C&D) waste and municipal solid waste incineration (MSWI) bottom ash. The results indicate that filtration of the eluate, which is required for batch tests, does not always allow the simulation of the actual colloid amount in soil pore water. Medium column heights four times the inner diameter of the column seemed to provide reasonable equilibrium adjustment conditions and avoid major biodegradation. The release of chromium was only marginally affected by the contact time, varied between 0.115 and 0.150 mg/kg for demolition waste eluate at a liquid-to-solid ratio of approximately 5L/kg.

Fabric studies on contaminated mineral layers in composite liners

Abstract The fabric of mineral liner materials that had been exposed to organic compounds over a 12-year period was investigated as part of a wider research project. Macromorphological and micromorphological changes in the fabric were identified using computed tomography and polarisation microscopy. Special care was taken to ensure artefact free sampling and sample preparation, in particular, the drying method used, has a substantial influence on the quality of the thin sections. Fabric changes due to contaminant permeation over several years are, by and large, relatively small and their intensity is material specific. Silty clay CML1, in particular, contains a somewhat greater number of fissures and voids in comparison with the original material. The superposition of various processes in both test procedures and sample preparation may lead to fabric changes which can impede interpretation of the results.

Sorption effects interfering with the analysis of polycyclic aromatic hydrocarbons (PAH) in aqueous samples

Polycyclic aromatic hydrocarbons (PAH) are severe environmental pollutants that are analyzed frequently. The risk assessment of PAH impact to groundwater can be performed using leaching tests. Therby a liquid-solid separation step including centrifugation may be required, which in turn might lead to loss of analytes due to sorption on the equipment. Thus we determined the PAH recoveries from various container materials (polyethylene (PE), polypropylene (PP), polytetraflourethylene (PTFE), stainless steel (ES), and perflouroalkoxy (PFA)) and compared them to selected PAH properties. We found the best recoveries for PFA (68%) and PTFE (65%) containers. We found good negative correlations (-0.93 and better) between PAH recovery and log partition coefficient organic carbon-water (logKOC) for PFA, PTFE, and ES containers.

Column percolation test for contaminated soils: Key factors for standardization

Column percolation tests may be suitable for prediction of chemical leaching from soil and soil materials. However, compared with batch leaching tests, they are time-consuming. It is therefore important to investigate ways to shorten the tests without affecting the quality of results. In this study, we evaluate the feasibility of decreasing testing time by increasing flow rate and decreasing equilibration time compared to the conditions specified in ISO/TS 21268-3, with equilibration periods of 48h and flow rate of 12mL/h. We tested three equilibration periods (0, 12-16, and 48h) and two flow rates (12 and 36mL/h) on four different soils and compared the inorganic constituent releases. For soils A and D, we observed similar values for all conditions except for the 0h-36mL/h case. For soil B, we observed no appreciable differences between the tested conditions, while for soil C there were no consistent trends probably due to the difference in ongoing oxidation reactions between soil samples. These results suggest that column percolation tests can be shortened from 20 to 30days to 7-9days by decreasing the equilibration time to 12-16h and increasing the flow rate to 36mL/h for inorganic substances.

Laboratory leaching tests on treated wood according to different harmonised test procedures

BackgroundLaboratory leaching tests on treated wood were performed during a European robustness study in the framework of the validation of a tank leaching test procedure that has been proposed for construction products in order to determine the potential release of dangerous substances which can be transferred to soil and groundwater. The release of substances has to be determined also for materials treated with biocidal products according to the requirements of the European Biocidal Products Regulation. A similar leaching test procedure was already harmonised for treated wood for this purpose. Both test procedures were applied in parallel to wood treated with the same preservative to investigate whether the results of these tests can replace each other. Additional experiments were performed to further investigate unexpected effects of L/A ratio on leaching of copper and duration of storage of treated test specimens.ResultsBoth procedures generate similar results concerning cumulative emissions of tebuconazole, copper, dissolved organic carbon and total nitrogen. The emission rates with time are in comparable ranges for both leaching protocols. Emissions of copper increased with decreasing L/A ratios. Strong correlation of copper concentrations and dissolved organic carbon as well as total nitrogen concentrations in eluates indicates that this observation is caused by co-elution of copper with organic substances. Duration of storage of treated test specimens affected emissions for the investigated wood preservative.ConclusionsBased on these findings, results from both test procedures can be used to describe leaching characteristics and avoid double testing of treated wood to fulfil the requirements of the European regulations for either biocides or construction products. Leaching of substances from treated wood is a complex process that depends on its chemical composition and ageing processes.

Laboratory Tools to Quantify Biogenic Dissolution of Rocks and Minerals: A Model Rock Biofilm Growing in Percolation Columns

Sub-aerial biofilms (SAB) are ubiquitous, self-sufficient microbial ecosystems found on mineral surfaces at all altitudes and latitudes. SABs, which are the principal causes of weathering on exposed terrestrial surfaces, are characterised by patchy growth dominated by associations of algae, cyanobacteria, fungi and heterotrophic bacteria. A recently developed in vitro system to study colonisation of rocks exposed to air included two key SAB participants - the rock-inhabiting ascomycete Knufia petricola (CBS 123872) and the phototrophic cyanobacterium Nostoc punctiforme ATCC29133. Both partners are genetically tractable and we used them here to study weathering of granite, K-feldspar and plagioclase. Small fragments of the various rocks or minerals (1 to 6 mm) were packed into flow-through columns and incubated with 0.1% glucose and 10 µM thiamine-hydrochloride (90 µL.min-1) to compare weathering with and without biofilms. Dissolution of the minerals was followed by: analysing (i) the degradation products in the effluent from the columns via Inductively Coupled Plasma Spectroscopy and (ii) by studying polished sections of the incubated mineral fragment/grains using scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analyses. K. petricola/N. punctiforme stimulated release of Ca, Na, Mg and Mn. Analyses of the polished sections confirmed depletion of Ca, Na and K near the surface of the fragments. The abrupt decrease in Ca concentration observed in peripheral areas of plagioclase fragments favoured a dissolution-reprecipitation mechanism. Percolation columns in combination with a model biofilm can thus be used to study weathering in closed systems. Columns can easily be filled with different minerals and biofilms, the effluent as well as grains can be collected after long-term exposure under axenic conditions and easily analysed.