Ammonia removal properties of lightweight aggregates from Si–Al–Fe and Si–Ca rocks

Lightweight aggregates commonly used as construction materials contain high percentages of metal oxides and thus are potential sorbents in aqueous systems. Here, ammonia is used as the model compound to be removed by aggregates since it is toxic for the aquatic life and is regulated in physical systems. The point of zero charge of aggregates is determined at pH values higher than 9. The aggregates made with raw materials from Larisa, Milos, and Samos presented ammonia sorptive capacities of 210, 220 and 400 μmol/kg, respectively. However, the LWA made from wollastonite (Samos) resulted in high pH (10.6) solutions and thus, production of toxic unionized ammonia. Thus, a combination of high sorptive uptake and neutral pH in solution is desired and can be achieved in future studies by selecting the appropriate raw materials for the preparation of aggregates.     

Transport of hydrocarbons from an emplaced fuel source experiment in the vadose zone at Airbase Vaerløse, Denmark

An emplaced hydrocarbon source field experiment was conducted in the relatively homogeneous sandy geology of the vadose zone at Airbase Vaerl?se, Denmark. The source (10.2 l of NAPL) consisted of 13 hydrocarbons (n-, iso- and cyclo-alkanes and aromates) and CFC-113 as a tracer. Monitoring in the 107 soil gas probes placed out to 20 m from the centre of the source showed spreading of all the compounds in the pore air and all compounds were measured in the pore air within a few hours after source emplacement. Seven of the fourteen compounds were depleted from the source within the 1 year of monitoring. The organic vapours in the pore air migrated radially from the source. The CFC-113 concentrations seemed to be higher in the deeper soil gas probes compared with the hydrocarbons, indicating a high loss of CFC-113 to the atmosphere and the lack of degradation of CFC-113. For the first days after source emplacement, the transport of CFC-113, hexane and toluene was successfully simulated using a radial gas-phase diffusion model for the unsaturated zone. Groundwater pollution caused by the vadose zone hydrocarbon vapours was only detected in the upper 30 cm of the underlying groundwater and only during the first 3 months of the experiment. Only the most water-soluble compounds were detected in the groundwater and concentrations decreased sharply with depth (approximately one order of magnitude within 10 cm depth) to non-detect at 30 cm depth. The groundwater table varied more than 1 m within the measurement period. However that did not influence the direction of the groundwater flow. Approximately 7 months after source emplacement the groundwater table rose more than 1 m within 1 month. That did not cause additional pollution of the groundwater.     

Concentrations of persistent organic pollutants and organic matter characteristics as river sediment quality indices

Selected persistent organic pollutants – polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides – were determined in sediments, soils, and crops from the Asopos River area, Greece. The river has been receiving industrial effluents for the last 40 years and has been recently found to be polluted with metals. Sediments were collected in the dry (May) and wet (February) season. Agricultural soils and cultivated crops were sampled from adjacent fields. Polychlorinated biphenyls were below the limit of detection in all samples. In one tomato and two soil samples, DDT and DDE were found. Polycyclic aromatic hydrocarbons were observed in 5% of the sediments and in concentrations ranging from 4 to 57 μg kg^?1 dry weight, quite below sediment quality guidelines. Diagnostic ratios of polycyclic aromatic hydrocarbons indicated a strong influence of petrogenic point discharges. In the sediments, silicate minerals dominate over carbonates and the organic carbon content ranges from 0.4% to 3.5%, more than 70% being of natural origin. Compared to other rivers worldwide, the Asopos River was found to be not contaminated with persistent organic pollutants. Point loadings of organic pollutants were evident but continuous discharge is not occurring throughout the river basin.     

Effect of ammonoxidation on lignite properties

Oxidised lignite is a potential alternative source of N fertilizers. Ammonoxidation is the reaction of a given substrate with oxygen in aqueous ammonia. Lignite ammonoxidation is used for converting low-rank lignite into slowly nitrogen-releasing artificial humic matter. A lignite sample is compared before and after ammonoxidation in terms of geochemical and petrological properties, as well as the acid–base and physical hydrophobic sorptive behavior. The most obvious change caused by ammonoxidation is the decrease of attrinite, texto-ulminite and textinite in favor mainly of densinite and gelohuminite. In general, the ammonoxidative reactions promote the destruction of the structured humic macerals (texto-ulminite, textinite), and the formation of gels, which resulted in the cementation of the freely fine humic particles (attrinite). The pzc values are 3.4 and 4.3 for oxidised and non-oxidised lignite, respectively. After ammonoxidation the contents of carboxylic and free phenolic groups are found to be lower. The oxidised lignite shows a statistically lower sorptive capacity and affinity than the original sample due to a possible decrease in the hydrophobicity of the lignite.     

Diffusive partitioning tracer test for the quantification of nonaqueous phase liquid (NAPL) in the vadose zone: Performance evaluation for heterogeneous NAPL distribution

A partitioning tracer test based on gas-phase diffusion in the vadose zone yields estimates of the residual nonaqueous phase liquid (NAPL) saturation. The present paper investigates this technique further by studying diffusive tracer breakthrough curves in the vadose zone for a heterogeneous NAPL distribution. Tracer experiments were performed in a lysimeter with a horizontal layer of artificial kerosene embedded in unsaturated sand. Tracer disappearance curves at the injection point and tracer breakthrough curves at some distance from the injection point were measured inside and outside of the NAPL layer. A numerical code was used to generate independent model predictions based on the physicochemical sand, NAPL, and tracer properties. The measured and modeled tracer breakthrough curves were in good agreement confirming the validity of important modeling assumptions such as negligible sorption of chlorofluorocarbon (CFC) tracers to the uncontaminated sand and their fast reversible partitioning between the soil air and the NAPL phase. Subsequently, the model was used to investigate different configurations of NAPL contamination. The experimental and model results show that the tracer disappearance curves of a single-well diffusive partitioning tracer test (DPTT) are dominated by the near-field presence of NAPL around the tip of the soil gas probe. In contrast, breakthrough curves of inter-well tracer tests reflect the NAPL saturation in between the probes, although there is no unique interpretation of the tracer signals if the NAPL distribution is heterogeneous. Numerical modeling is useful for the planning of a DPTT application. Simulations suggest that several cubic meters of soil can be investigated with a single inter-well partitioning tracer test of 24-hour duration by placing the injection point in the center of the investigated soil volume and probes at up to 1 m distance for the monitoring of gaseous tracers.     

Model coupling intraparticle diffusion/sorption, nonlinear sorption, and biodegradation processes

Diffusion, sorption and biodegradation are key processes impacting the efficiency of natural attenuation. While each process has been studied individually, limited information exists on the kinetic coupling of these processes. In this paper, a model is presented that couples nonlinear and nonequilibrium sorption (intraparticle diffusion) with biodegradation kinetics. Initially, these processes are studied independently (i.e., intraparticle diffusion, nonlinear sorption and biodegradation), with appropriate parameters determined from these independent studies. Then, the coupled processes are studied, with an initial data set used to determine biodegradation constants that were subsequently used to successfully predict the behavior of a second data set. The validated model is then used to conduct a sensitivity analysis, which reveals conditions where biodegradation becomes desorption rate-limited. If the chemical is not pre-equilibrated with the soil prior to the onset of biodegradation, then fast sorption will reduce aqueous concentrations and thus biodegradation rates. Another sensitivity analysis demonstrates the importance of including nonlinear sorption in a coupled diffusion/sorption and biodegradation model. While predictions based on linear sorption isotherms agree well with solution concentrations, for the conditions evaluated this approach overestimates the percentage of contaminant biodegraded by as much as 50%. This research demonstrates that nonlinear sorption should be coupled with diffusion/sorption and biodegradation models in order to accurately predict bioremediation and natural attenuation processes. To our knowledge this study is unique in studying nonlinear sorption coupled with intraparticle diffusion and biodegradation kinetics with natural media.