The role of natural clays in the sustainability of landfill liners

Engineered synthetic liners on their own cannot protect the environment and human health against landfill leachate pollution. Despite their initial impermeability, they are susceptible to failure during and after installation and have no attenuation properties. Conversely, natural clay liners can attenuate leachate pollutants by sorption, redox transformations, biodegradation, precipitation, and filtration, decreasing the pollutant flux. Depending on the clay, significant differences exist in their shrinkage potential, sorption capacity, erosion resistance and permeability to fluids, which affects the suitability and performance of the potential clay liner. Here, the physico-chemical, mineralogical and geotechnical characteristics of four natural clayey substrata were compared to discuss their feasibility as landfill liners. To study their chemical compatibility with leachate and rainwater, hydraulic conductivities were measured every ≈2 days spread over 7 weeks of centrifugation at 25 gravities. At field-scale, this is equivalent to every 3.4 yrs spread over 80 yrs. All the clayey substrata had favourable properties for the attenuation of leachate pollutants, although different management options should be applied for each one. London Clay (smectite-rich) is the best material based on the sorption capacity, hydraulic conductivity and low erodibility, but has the greatest susceptibility to excessive shrinkage and alterable clay minerals that partially collapse to illitic structures. Oxford Clay (illite rich) is the best material for buffering acid leachates and supporting degradation of organic compounds. The Coal Measures Clays (kaoline-rich) have the lowest sorption capacity, but also the lowest plasticity and have the most resistant clay minerals to alteration by leachate exposure

Effect of physical heterogeneity on the electromigration of nitrate in layered granular porous media

The effect of physical heterogeneity on the electrokinetic (EK) transport of nitrate, an electron acceptor frequently used for anaerobic biodegradation, was investigated experimentally within saturated granular porous media comprising two layers of high and low hydraulic conductivity (K) material. Two hypotheses were tested: firstly, that the presence of layered physical heterogeneity will generate non-uniformities in the electric field; and secondly that this would create non-uniform electromigration of ions resulting in an additional nitrate flux into the lower-K layer. Experiments were conducted in bench-top test cells that contained electrode and sediment chambers. An aqueous nitrate solution (0, 0.1, 1 and 5 g-NO3 L−1) was added at the cathode and the experiments run with an idealised mixture of glass beads and kaolinite, and natural sediment and kaolinite. A constant current (1.6 A m−2) was applied in all experiments. Results showed elevated voltage differences between layers in heterogeneous experiments compared to equivalent homogenous experiments. Furthermore, nitrate concentrations are elevated in the low-K material in heterogeneous compared with homogeneous systems. Using predicted values this is shown to be a function of a transverse flux associated with the voltage difference between layers. The importance of this phenomena at field scale for delivery of an amendment (i.e., electron acceptor, donor or nutrient) by EK for bioremediation is presented in an electron balance model. Overall, this research establishes and quantifies a previously unreported important phenomenon in the electrokinetic transport literature that enhance the application of this technology for bioremediation of contaminated aquifers

Influence of contaminant exposure on the development of aerobic ETBE biodegradation potential in microbial communities from a gasoline-impacted aquifer

Aerobic biodegradation of ethyl tert butyl ether (ETBE) in a gasoline-impacted aquifer was investigated in laboratory microcosms containing groundwater and aquifer material from ETBE-impacted and non-impacted locations amended with either ETBE, or ETBE plus methyl tert butyl ether (MTBE). As sole substrate, ETBE was biodegraded (maximum rate of 0.54 day^−1) without a lag in ETBE-impacted microcosms but with a lag of up to 66 days in non-impacted microcosms (maximum rate of 0.38 day^−1). As co-substrate, ETBE was biodegraded preferentially (maximum rate of 0.25 and 0.99 day^−1 in non-impacted and impacted microcosms, respectively) before MTBE (maximum rate of 0.24 and 0.36 day^−1 in non-impacted and impacted microcosms, respectively). Further addition of ETBE and MTBE reduced lags and increased biodegradation rates. ethB gene copy numbers increased significantly (>100 fold) after exposure to ETBE, while overall cell numbers remained constant, suggesting that ethB-containing microorganisms come to dominate the microbial communities. Deep sequencing of 16S rRNA genes identified members of the Comamonadaceae family that increased in relative abundance upon exposure to ETBE. This study demonstrates the potential for ETBE biodegradation within the unsaturated and saturated zone, and that ETBE biodegrading capability is rapidly developed and maintained within the aquifer microbial community over extended timescales

Enhancing in situ biodegradation in groundwater using pump and treat remediation: a proof of concept and modelling analysis of controlling variables

A remediation approach which uses pump and treatment (PAT) to enhance the biodegradation of organic contaminants by increasing dispersive mixing between plumes and groundwater was evaluated for a phenol-contaminated aquifer, using a reactive transport model which simulates kinetic reactions between an electron donor (ED) in the plume and electron acceptor (EA) in the groundwater. The influence of system design and operation was examined in six modelling scenarios. Injection or extraction of groundwater increases biodegradation above no action and the location, pumping rate, and distance between well(s) are important variables which influence biodegradation. An increase in pumping rate, distance of the wells from the plume centreline, and changing the flow direction increase dispersive mixing between the plume and groundwater. This increases plume spreading and the plume fringe interface, providing a greater flux of dissolved EAs for biodegradation. In general, injection of groundwater containing natural EAs enhances biodegradation more than extraction. The enhancement of biodegradation is sensitive to the relative fluxes of ED and EA, as controlled by the arrangement of the wells. In the best performing scenario, biodegradation was enhanced by 128%, compared with no action

Natural attenuation of dissolved petroleum fuel constituents in a fractured Chalk aquifer: Contaminant mass balance with probabilistic analysis

A plume-scale mass balance is developed to assess the natural attenuation (NA) of dissolved organic contaminants in fractured, dual porosity aquifers. This methodology can be used to evaluate contaminant distribution within the aquifer, plume source term, contaminant biodegradation and plume status. The approach is illustrated for a site on the UK Upper Chalk aquifer impacted by petroleum fuel containing MTBE and TAME. Variability in site investigation data and uncertainty in the mass balance was assessed using probabilistic analysis. The analysis shows that BTEX compounds are biodegraded primarily by denitrification and sulphate reduction in the aquifer, with an equivalent plume-scale first-order biodegradation rate of 0.49 year-1. Other biodegradation processes are less important. Sorption contributes to hydrocarbon attenuation in the aquifer but is less important for MTBE and TAME. Uncertainty in the plume source term and site hydrogeological parameters had the greatest effect on the mass balance. The probabilistic analysis enabled the most likely long-term composition of the plume source term to be deduced and provided a site-specific estimate of contaminant mass flux for the prediction of plume development. The mass balance methodology provides a novel approach to improve NA assessments for petroleum hydrocarbons and other organic contaminants in these aquifer settings

High Attenuation Recycled Materials as landfill liners (the HARM project) – a new concept for improved landfill liner design

A new approach in landfill liner design which combines hydraulic containment of leachate with contaminant attenuation to improve the performance of these environmental control systems at landfills is described. The idea is to re-use readily available industrial waste residues (construction and biomass waste) as additives for natural clay liners, wherein the additives have specific properties which enhance the attenuation of contaminants by the mixture. The aim is to (1) evaluate the contaminant attenuation capacity of these mixtures, (2) develop design guidelines to construct liners for waste containment systems and similar applications, and (3) interpret their performance using numerical modelling. This is evaluated in permeation studies using a geotechnical centrifuge, which enables the performance of liner compositions to be tested for representive time-scales (100 years), pressures and temperatures at realistic experimental time-scales of days-weeks in the laboratory. The permeation experiments include liner compositions flushed with leachate to deduce contaminant transport and attenuation mechanisms, followed by rainwater to assess the potential for release of attenuated contaminants. This experimental methodology is illustrated with depth profiles from permeation studies conducted on different clay-additive compositions. The concept will be applicable for liner design at other waste disposal facilities and is a timely improvement which addresses the problem of managing large quantities of industrial residues. Instead of disposal these can be recycled as an additive in host clay to construct these liners, thus conserving natural resources (clay) and reducing construction costs. It also provides an effective and more environmentally sustainable basis to reduce risks from leachate leakage

Biogeochemical processes in the active layer and permafrost of a high Arctic fjord valley

Warming of ground is causing microbial decomposition of previously frozen sedimentary organic carbon in Arctic permafrost. However, the heterogeneity of the permafrost landscape and its hydrological processes result in different biogeochemical processes across relatively small scales, with implications for predicting the timing and magnitude of permafrost carbon emissions. The biogeochemical processes of iron- and sulfate-reduction produce carbon dioxide and suppress methanogenesis. Hence, in this study, the biogeochemical processes occurring in the active layer and permafrost of a high Arctic fjord valley in Svalbard are identified from the geochemical and stable isotope analysis of aqueous and particulate fractions in sediment cores collected from ice-wedge polygons with contrasting water content. In the drier polygons, only a small concentration of organic carbon (<5.40 dry weight%) has accumulated. Sediment cores from these drier polygons have aqueous and solid phase chemistries that imply sulfide oxidation coupled to carbonate and silicate dissolution, leading to high concentrations of aqueous iron and sulfate in the pore water profiles. These results are corroborated by δ34S and δ18O values of sulfate in active layer pore waters, which indicate the oxidative weathering of sedimentary pyrite utilising either oxygen or ferric iron as oxidising agents. Conversely, in the sediments of the consistently water-saturated polygons, which contain a high content of organic carbon (up to 45 dry weight%), the formation of pyrite and siderite occurred via the reduction of iron and sulfate. δ34S and δ18O values of sulfate in active layer pore waters from these water-saturated polygons display a strong positive correlation (R2 = 0.98), supporting the importance of sulfate reduction in removing sulfate from the pore water. The significant contrast in the dominant biogeochemical processes between the water-saturated and drier polygons indicates that small-scale hydrological variability between polygons induces large differences in the concentration of organic carbon and in the cycling of iron and sulfur, with ramifications for the decomposition pathway of organic carbon in permafrost environments

Biodegradation and fate of ethyl tert-butyl ether (ETBE) in soil and groundwater: a review

This review summarises the current state of knowledge on the biodegradation and fate of the gasoline ether oxygenate ethyl tert-butyl ether (ETBE) in soil and groundwater. Microorganisms have been identified in soil and groundwater with the ability to degrade ETBE aerobically as a carbon and energy source, or via cometabolism using alkanes as growth substrates. Aerobic biodegradation of ETBE initially occurs via hydroxylation of the ethoxy carbon by a monooxygenase enzyme, with subsequent formation of intermediates which include acetaldehyde, tert-butyl acetate (TBAc), tert-butyl alcohol (TBA), 2-hydroxy-2-methyl-1-propanol (MHP) and 2-hydroxyisobutyric acid (2-HIBA). Slow cell growth and low biomass yields on ETBE are believed to result from the ether structure and slow degradation kinetics, with potential limitations on ETBE metabolism. Genes known to facilitate transformation of ETBE include ethB (within the ethRABCD cluster), encoding a cytochrome P450 monooxygenase, and alkB-encoding alkane hydroxylases. Other genes have been identified in microorganisms but their activity and specificity towards ETBE remains poorly characterised. Microorganisms and pathways supporting anaerobic biodegradation of ETBE have not been identified, although this potential has been demonstrated in limited field and laboratory studies. The presence of co-contaminants (other ether oxygenates, hydrocarbons and organic compounds) in soil and groundwater may limit aerobic biodegradation of ETBE by preferential metabolism and consumption of available dissolved oxygen or enhance ETBE biodegradation through cometabolism. Both ETBE-degrading microorganisms and alkane-oxidising bacteria have been characterised, with potential for use in bioaugmentation and biostimulation of ETBE degradation in groundwater

Characterisation of microparticle waste from dental resin-based composites

Clinical applications of resin-based composite (RBC) generate environmental pollution in the form of microparticulate waste. Methods: SEM, particle size and specific surface area analysis, FT-IR and potentiometric titrations were used to characterise microparticles arising from grinding commercial and control RBCs as a function of time, at time of generation and after 12 months ageing in water. The RBCs were tested in two states: (i) direct-placement materials polymerised to simulate routine clinical use and (ii) pre-polymerised CAD/CAM ingots milled using CAD/CAM technology. Results: The maximum specific surface area of the direct-placement commercial RBC was seen after 360 s of agitation and was 1290 m2/kg compared with 1017 m2/kg for the control material. The median diameter of the direct-placement commercial RBC was 6.39 μm at 360 s agitation and 9.55 μm for the control material. FTIR analysis confirmed that microparticles were sufficiently unique to be identified after 12 months ageing and consistent alteration of the outermost surfaces of particles was observed. Protonation-deprotonation behaviour and the pH of zero proton charge (pHzpc) ≈ 5–6 indicated that the particles are negatively charged at neutral pH7. Conclusion: The large surface area of RBC microparticles allows elution of constituent monomers with potential environmental impacts. Characterisation of this waste is key to understanding potential mitigation strategies

Properties of layer-by-layer vector stochastic models of force fluctuations in granular materials

We attempt to describe the stress distributions of granular packings using lattice-based layer-by-layer stochastic models that satisfy the constraints of force and torque balance and non-tensile forces at each site. The inherent asymmetry in the layer-by-layer approach appears to lead to an asymmetric force distribution, in disagreement with both experiments and general symmetry considerations. The vertical force component probability distribution is robust and in agreement with predictions of the scalar q model while the distribution of horizontal force components is qualitatively different and depends on the details of implementation.Comment: 18 pages, 12 figures (with subfigures), 1 table. Uses revtex, epsfig,subfigure, and cite. Submitted to PRE. Plots have been bitmapped. High-resolution version is available. Email [email protected] or download from http://rainbow.uchicago.edu/~mbnguyen/research/vm.htm