Fossil rootlet biopores as conduits for contaminant transport through clay horizons: a case study of DNAPL behaviour in Severn alluvium, UK

This paper presents a case study of several DNAPL contaminated sites around the Severn Estuary (UK) where a combination of detailed observations, core dissections and physicochemical characterisation of alluvial clay–silt horizons have revealed the presence of fossil rootlet biopores which act and have the potential to act as conduits for contaminant migration through up to 13 m of clay–silt. The biopores are shown to penetrate the low-permeability (K ~ 10−10 m/s) clay–silt matrix throughout its entire depth (up to 13 m) and provide a preferential transport pathway for DNAPLs from near surface to the underlying aquifer, with particularly high concentrations measured in the biopores themselves. Capillary rise experiments with coal tar distillate demonstrate that DNAPLs are drawn into biopores, with values of surface interfacial tension for the system calculated as 8 × 10−2 J/m2. Wicking by residual plant fibres was demonstrated qualitatively and is thought to be an important additional transport mechanism. The DNAPL contamination below and throughout the Severn alluvial clay–silt horizons demonstrates that the assumption that these horizons act as an effective seal protecting underlying aquifers from severe pollution from the legacy sites around the Severn is flawed and highlights the failure of current protocols for sampling of clay horizons for hydraulic conductivity assessments, since current methods can destroy delicate in situ biopore structures. The study demonstrates that the interplay between ecological and the geological depositional environment can, at a regional scale, result in a network of biopores that can potentially act as conduits for contaminant transport

Changes in metal leachability through stimulation of iron reducing communities within waste sludge

Bioreduction of ferric iron-rich wastes is a rapidly emerging technology for the extraction/ recovery of metals from low-grade ores and metallurgical wastes. However, despite studies being successful, they have only been demonstrated at laboratory scale and issues relating to economic, industrial scale application have yet to be studied. Using bioreduction as a pre-treatment to increase recovery yield is a relatively new concept. This study examines the biostimulation of microbial communities to induce bioreduction of metalliferous sludge and the effect that this has on the leachability of metals from the waste using dilute sulphuric acid. Data shows an increase in both zinc and copper leachability after bioreduction, with maximum six fold and eleven fold increase (compared to pre-treatment) in the amount of zinc and copper leached respectively.</jats:p

Physicochemical characterization of sludge originating from vegetable oil–based cutting fluids

Vegetable oil–based cutting fluids are a relatively recent development in large-scale metal machining. A metal machining factory in Wales that switched from mineral oil-based to vegetable oil-based cutting fluids has experienced the occurrence of a problematic floating sludge within the settling and holding tanks at the on-site effluent treatment plant. Physicochemical analyses have found that the sludge is composed of on average 33% water, 20% oleic acid, and 18% palmitic acid, originating from the vegetable oil–based cutting fluids used at the factory. A solvent separation step was devised and used successfully to separate water inherent within the sludge so as to study the division of the inorganic elements within the water and organic phases of the sludge. It was found that only a minor constituent of the sludge can be accounted for by Ca-bonded fatty acids. Formation of the sludge is suspected to be due to the biologically induced hydrolysis and oxidation of the oils from esters to the free fatty acids and subsequent creaming, forming a layer of stable floating sludge on the surface of the effluent storage tanks

Altered chemical evolution in landfill leachate post implementation of biodegradable waste diversion

Within the UK implementation of the European Union Landfill Directive (1999) has led to the diversion of biodegradable waste (BW) from municipal solid wastes away from landfills. It has been widely anticipated, but thus far not verified, that the diversion of BW and consequent reduction in BW reaching landfill would lead to a change in the degradation processes occurring within landfills and that this would be reflected in an altered evolution in leachate chemistry compared to pre-Directive landfills. This paper provides evidence based on leachate chemistry from two operational landfills together with calculations of the reduced BW content, that demonstrate the acetogenic phase that characterised pre-Directive landfill leachates is missing and is now more typical of methanogenic phase leachate. The paper demonstrates how data from national datasets and detailed landfill records can be used to constrain likely and upper estimates of the amount of BW going into post-Directive landfills, and the observed change in the evolution of leachate chemistry which has resulted from a decrease in BW content from typical values of BW (pre-Landfill Directive) of 22% to an inferred 12% in the case-study landfills. Data provided here add to the growing literature that estimates the amount of BW in recent post-Directive landfills which importantly allow the quantitative linkage between a decrease in landfilled BW and observed changes in leachate chemistry to be established such that future landfill operators can increase confidence in the effect of Directive implementation on landfill operational parameters

In situ resource recovery from waste repositories: exploring the potential for mobilization and capture of metals from anthropogenic ores

Wastes and the waste repositories in which they reside are becoming targets for resource recovery, both for legacy wastes and for future waste arisings as part of a desire to move toward a circular economy. There is an urgent requirement to explore concepts for practicable technologies that can be applied to these ends. This paper presents a synthesis of concepts concerning in situ technologies (developed from mining and contaminated land remediation industries) that have enormous potential for application to technospheric mining. Furthermore, potential target waste streams and their mineralogy and character are presented along with a discussion concerning lixiviant and metal capture systems that could be applied. Issues of preferential flow (critical to the success of in situ techniques) and how to control it with engineering measures are discussed in detail. It is clear that in situ recovery of metals from anthropogenic ores is a novel technology area that links new sustainable remediation approaches for contaminated materials and technospheric mining for closing material loops, and warrants the further research and development of technologies applicable to major waste streams

Delignification and enhanced gas release from soil containing Lignocellulose by treatment with bacterial lignin degraders

Aims The aim of the study was to isolate bacterial lignin-degrading bacteria from municipal solid waste soil, and to investigate whether they could be used to delignify lignocellulose-containing soil, and enhance methane release. Methods and Results A set of 20 bacterial lignin degraders, including 11 new isolates from municipal solid waste soil, were tested for delignification and phenol release in soil containing 1% pine lignocellulose. A group of 7 strains were then tested for enhancement of gas release from soil containing 1% lignocellulose in small-scale column tests. Using an aerobic pre-treatment, aerobic strains such as Pseudomonas putida showed enhanced gas release from the treated sample, but four bacterial isolates showed 5-10 fold enhancement in gas release in an in situ experiment under microanaerobic conditions: Agrobacterium sp., Lysinibacillus sphaericus, Comamonas testosteroni, and Enterobacter sp.. Conclusions The results show that facultative anaerobic bacterial lignin degraders found in landfill soil can be used for in situ delignification and enhanced gas release in soil containing lignocellulose. Significance & impact of the study The study demonstrates the feasibility of using an in situ bacterial treatment to enhance gas release and resource recovery from landfill soil containing lignocellulosic waste

Changes in metal speciation and mobility during electrokinetic treatment of industrial wastes: implications for remediation and resource recovery

Industrial waste deposits contain substantial quantities of valuable metals and other resources, although often in a recalcitrant form that hinders their recovery. This paper reports an experimental programme on the application of electrokinetic (EK) processing to two different waste materials (a mine tailings deposit and a metallurgical furnace dust), with the aim of exploring the effect of EK on metal speciation and extractability, with a focus on Pb and Zn due to their prevalence in these materials. The speciation of metals within the waste was determined based on a selective sequential extraction (SSE) procedure which was applied to the materials before, during and after the application of the EK treatment. The results demonstrate the generation of an acidic front in the mine tailings, which enhanced the transport of ions associated with the more labile fractions, a behaviour typical of materials characterized by a lower buffering capacity. The application of the EK in the furnace dust showed much less effect due to a very high starting pH (10) with the higher buffering capacity posing an obstacle to transport. It is shown that EK has altered the geochemical speciation of the metals in both materials, typically redistributing them from less available SSE fractions to the more labile fractions. Zn was redistributed with the SSE fractions and mobilised to a greater extent than Pb in both samples. The changes in pH and redox potential arising as a result of the application of an electric field are likely to be the main causes of the changes in speciation of both Zn and Pb. The considerable changes in metal fractionation, including removal from more recalcitrant fractions, suggest that EK may facilitate metal recovery processes. This, combined with its applicability to fine grained materials and heterogeneous environments, demonstrates that the technique may be particularly suited to both remediation of, and in-situ resource recovery from, such materials

Thermal degradation of monoethanolamine and its effect on CO2 capture capacity.

Amine scrubbing is a proven technology in the oil and gas industries. Its use in coal fired power plants is not fully understood and the likelihood of solvent degradation is high. Decreased absorption efficiency, undesirable by-products and the environmental impact of their disposal are the main consequences. In the present study, samples of monoethanolamine were thermally degraded, at 160 °C for between 2 and 8 weeks, and their CO2 removal capacity deterioration was determined. The findings show that thermal degradation at 160 °C for 8 weeks reduced monoethanolamine concentration by 95%, but the remaining solvent still retained 22% of its capacity to remove CO2, probably due to the capacity of some of the degradation products to remove CO2. Therefore, the requirement for monoethanolamine make-up in operational amine scrubbing systems may not be quite as serious as initially believed. A 20% higher MEA loss was determined in the samples with 0.37 initial CO2 loading (mol CO2/mol MEA). 2-Oxazolidone, N-(2-hydroxyethyl)-ethylenediamine and 1-(2-hydroxyethyl)-2-imidazolidinone were identified as the major monoethanolamine degradation products, the latter being indicated as the most stable product with concentrations of up to 17% (v/v). Corrosion (1.95 mm/year) of the stainless steel (type 316) equipment, used during the experiments, was also observed

Conversion of coal mine drainage ochre to water treatment reagent: Production, characterisation and application for P and Zn removal

Coal mine drainage ochre is a ferruginous precipitate that forms from mine water in impacted watercourses and during treatment. With thousands of tonnes per annum of such ochre arising from mine water treatment in the UK alone, management of these wastes is a substantive issue. This paper demonstrates that the ochre from both active and passive treatment of coal mine drainage can be transformed into an effective water treatment reagent by simple acid dissolution and that the reagent can be used for the removal of dissolved phosphorous from municipal wastewater and zinc from non-coal mine waters. Ochre is readily soluble in H2SO4 and HCl. Ochre is more soluble in HCl with solubilities of up to 100 g/L in 20% (w/w) HCl and 68 g/L in 10% (w/w) H2SO4. For four of the eight tested ochres solubility decreased in higher concentrations of H2SO4. Ochre compositional data demonstrate that the coal mine ochres tested are relatively free from problematic levels of elements seen by other authors from acid mine drainage-derived ochre. Comparison to British Standards for use of iron-based coagulants in drinking water treatment was used as an indicator of the acceptability of use of the ochre-derived reagents in terms of potentially problematic elements. The ochre-derived reagents were found to meet the ‘Grade 3’ specification, except for arsenic. Thus, for application in municipal wastewater and mine water treatment additional processing may not be required. There was little observed compositional difference between solutions prepared using H2SO4 or HCl. Ochre-derived reagents showed applicability for the removal of P and Zn with removals of up to 99% and 97% respectively measured for final pH 7–8, likely due to sorption/coprecipitation. Furthermore, the results demonstrate that applying a Fe dose in the form of liquid reagent leads to a better Fe:P and Fe:Zn removal ratio compared to ochre-based sorption media tested in the literature