A review of biochars’ potential role in the remediation, revegetation and restoration of contaminated soils

Biochars are biological residues combusted under low oxygen conditions, resulting in a porous, low density carbon rich material. Their large surface areas and cation exchange capacities, determined to a large extent by source materials and pyrolysis temperatures, enables enhanced sorption of both organic and inorganic contaminants to their surfaces, reducing pollutant mobility when amending contaminated soils. Liming effects or release of carbon into soil solution may increase arsenic mobility, whilst low capital but enhanced retention of plant nutrients can restrict revegetation on degraded soils amended only with biochars; the combination of composts, manures and other amendments with biochars could be their most effective deployment to soils requiring stabilisation by revegetation. Specific mechanisms of contaminant-biochar retention and release over time and the environmental impact of biochar amendments on soil organisms remain somewhat unclear but must be investigated to ensure that the management of environmental pollution coincides with ecological sustainability.

Investigation about the efficiency of the bioaugmentation technique when applied to diesel oil contaminated soils

Este trabalho investigou a eficiência da técnica do bioaumento quando aplicada a solos contaminados com óleo diesel coletados em três postos de combustíveis. Experimentos de biodegradação foram realizados em frascos de Bartha (250 mL), usados para medir a produção microbiana de CO2. A eficiência de biodegradação também foi quantificada pela concentração de hidrocarbonetos. Conjuntamente aos experimentos de biodegradação, a capacidade das culturas estudadas e dos microrganismos nativos em biodegradar óleo diesel comprado de um posto de combustíveis local, foi verificada utilizando-se a técnica baseada no indicador redox 2,6 - diclorofenol indofenol (DCPIP). Resultados obtidos com esse teste mostraram que os inóculos empregados nos experimentos de biodegradação foram capazes de biodegradar óleo diesel e os testes com os microrganismos nativos indicaram que estes solos previamente apresentavam uma microbiota adaptada para degradar hidrocarbonetos. em suma, nenhum ganho foi obtido com a adição dos microrganismos ou mesmo efeitos negativos foram observados nos experimentos de biodegradação.

Remediation of crude oil contaminated soils by means of bitumen emulsions

Effective remediation of contaminated sites with oils, heavy metals and other chemical agents is one of the most important environmental problems all over the world. Contaminated soils by petroleum from different sites and origins, might contaminate groundwater aquifers and then be spread by rain. Many years and the requirement of remedial techniques may be needed to remediate them. However, previous experiences show the uselessness of these methods for the solution of all problems. As any case of soil contamination is different, specific studies with relevant factors at financial aspects, legal limits and waste and soil characteristics are needed. In this work, a study of the use of bitumen asphalt emulsion to remediate contaminated soils by crude oils is exposed. By means of the soil stabilization technology, using the contaminated soils as aggregates and the tailor made emulsion as binder, the feasibility of the mix application to produce stable and resistant pavements is demonstrated

Experimental analysis of soil and dust stabilizers for controlling displacement of contaminated soils by wind tunnel experiments

During the remediation of burial grounds at the US Department of Energy's (DOE's) Hanford Site in Washington State, the dispersion of contaminated soil particles and dust is an issue that is faced by site workers on a daily basis. This contamination problem is even more of a concern when one takes into account the semi-arid characteristics of the region where the site is located. To mitigate this problem, workers at the site use a variety of engineered methods to minimize the dispersion of contaminated soil and dust (i.e. use of water and/or suppression agents that stabilizes the soil prior to soil excavation, segregation, and removal activities). A primary contributor to the dispersion of contaminated soil and dust is wind soil erosion. The erosion process occurs when the wind speed exceeds a certain threshold value which depends on a number of factors including wind force loading, particle size, surface soil moisture, and the geometry of the soil. Thus under these circumstances, the mobility of contaminated soil and generation and dispersion of particulate matter are significantly influenced by these parameters. This dependence of soil and dust movement on threshold shear velocity, fixative dilution and/or application rates, soil moisture content, and soil geometry were studied for Hanford's sandy soil through a series of wind tunnel experiments, laboratory experiments and theoretical analysis. In addition, the behavior of plutonium (Pu) powder contamination in the soil was studied by introducing a Pu simulant (cerium oxide). The results showed that soil dispersion and PM10 concentrations decreased with increasing soil moisture. Also, it was shown that the mobility of the soil was affected by increasing wind velocity. It was demonstrated that the use of fixative products greatly decreased the amount of soil and PM10 concentrations when exposed to varying wind conditions. In addition, it was shown that geometry of the soil sample affected the velocity profile and calculation of roughness surface coefficient when comparing round and flat soil samples. Finally, threshold shear velocities were calculated for soil with flat surface and their dependency on surface soil moisture was demonstrated. A theoretical framework was developed to explain these dependencies.

Remediation of soils contaminated with petrol and diesel with lime

Lime treatment of hydrocarbon-contaminated soils offers the potential to stabilize and solidify these materials, with a consequent reduction in the risks associated with the leachate emanating from them. This can aid the disposal of contaminated soils or enable their on-site treatment. In this study, the addition of hydrated lime and quicklime significantly reduced the leaching of total petroleum hydrocarbons (TPH) from soils polluted with a 50:50 petrol/diesel mixture. Treatment with quicklime was slightly more effective, but hydrated lime may be better in the field because of its ease of handling. It is proposed that this occurs as a consequence of pozzolanic reactions retaining the hydrocarbons within the soil matrix. There was some evidence that this may be a temporary effect, as leaching increased between seven and 21 days after treatment, but the TPH concentrations in the leachate of treated soils were still one order of magnitude below those of the control soil, offering significant protection to groundwater. The reduction in leaching following treatment was observed in both aliphatic and aromatic fractions, but the latter were more affected because of their higher solubilty. The results are discussed in the context of risk assessment, and recommendations for future research are made.

Effects of metals on life cycle parameters of the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils

Two control and eight field-contaminated, metal-polluted soils were inoculated with Eisenia fetida (Savigny, 1826). Three, 7, 14, 21, 28 and 42 days after inoculation, earthworm survival, body weight, cocoon production and hatching rate were measured. Seventeen metals were analysed in E.fetida tissue, bulk soil and soil solution. Soil organic carbon content, texture, pH and cation exchange capacity were also measured. Cocoon production and hatching rate were more sensitive to adverse conditions than survival or weight change. Soil properties other than metal concentration impacted toxicity. The most toxic soils were organic-poor (1-10 g C kg(-1)), sandy soils (c. 74% sand), with intermediate metal concentrations (e.g. 7150-13, 100 mg Ph kg(-1), 2970-53,400 mg Zn kg(-1)). Significant relationships between soil properties and the life cycle parameters were determined. The best coefficients of correlation were generally found for texture, pH, Ag, Cd, Mg, Pb, Tl, and Zn both singularly and in multivariate regressions. Studies that use metal-amended artificial soils are not useful to predict toxicity of field multi-contaminated soils. (c) 2007 Elsevier Ltd. All rights reserved.

Effects of soluble humic acids on the uptake of heavy metals by Vetiveria zizanioides (L.) Nash in contaminated mining soils

In the past, mining wastes were left wherever they might lie in the surroundings of the mine area. Unfortunately, inactive and abandoned mines continue to pollute our environment, reason why these sites should be restored with minimum impact. Phytoextraction is an environmental-friendly and cost-effective technology less harmful than traditional methods that uses metal hyperaccumulator or at least tolerant plants to extract heavy metals from polluted soils. One disadvantage of hyperaccumulator species is their slow growth rate and low biomass production. Vetiveria zizanioides (L.) Nash, perennial species adapted to Mediterranean climate has a strong root system which can reach up to 3 m deep, is fast growing, and can survive in sites with high metal levels (Chen et al., 2004). Due to the fact that metals in abandoned mine tailings become strongly bonded to soil solids, humic acids used as chelating agents could increase metal bioavailability (Evangelou et al., 2004; Wilde et al., 2005) and thereby promote higher accumulation in the harvestable parts of the plant. The objective of this study was to examine the performance of humic acid assisted phytoextraction using Vetiveria zizanioides (L.) Nash in heavy metals contaminated soils.

Molecular Biomonitoring during Rhizoremediation of Oil-Contaminated Soil

Rhizoremediation is the use of microbial populations present in the rhizosphere of plants for environmental cleanup. The idea of this work was that bacteria living in the rhizosphere of a nitrogen-fixing leguminous plant, goat's rue (Galega orientalis), could take part in the degradation of harmful monoaromatic hydrocarbons, such as benzene, toluene and xylene (BTEX), from oil-contaminated soils. In addition to chemical (e.g. pollutant concentration) and physical (e.g. soil structure) information, the knowledge of biological aspects (e.g. bacteria and their catabolic genes) is essential when developing the rhizoremediation into controlled and effective bioremediation practice. Therefore, the need for reliable biomonitoring methods is obvious. The main aims of this thesis were to evaluate the symbiotic G. orientalis - Rhizobium galegae system for rhizoremediation of oil-contaminated soils, to develop molecular methods for biomonitoring, and to apply these methods for studying the microbiology of rhizoremediation. In vitro, Galega plants and rhizobia remained viable in m-toluate concentrations up to 3000 mg/l. Plant growth and nodulation were inhibited in 500 mg/l m-toluate, but were restored when plants were transferred to clean medium. In the greenhouse, Galega showed good growth, nodulation and nitrogen fixation, and developed a strong rhizosphere in soils contaminated with oil or spiked with 2000 mg/l m-toluate. The high aromatic tolerance of R. galegae and the viability of Galega plants in oil-polluted soils proved this legume system to be a promising method for the rhizoremediation of oil-contaminated soils. Molecular biomonitoring methods were designed and/or developed further for bacteria and their degradation genes. A combination of genomic fingerprinting ((GTG)5-PCR), taxonomic ribotyping of 16S rRNA genes and partial 16S rRNA gene sequencing were chosen for molecular grouping of culturable, heterogeneous rhizosphere bacteria. PCR primers specific for the xylE gene were designed for TOL plasmid detection. Amplified enzyme-coding DNA restriction analysis (AEDRA) with AluI was used to profile both TOL plasmids (xylE primers) and, in general, aromatics-degrading plasmids (C230 primers). The sensitivity of the direct monitoring of TOL plasmids in soil was enhanced by nested C23O-xylE-PCR. Rhizosphere bacteria were isolated from the greenhouse and field lysimeter experiments. High genetic diversity was observed among the 50 isolated, m-toluate tolerating rhizosphere bacteria in the form of five major lineages of the Bacteria domain. Gram-positive Rhodococcus, Bacillus and Arthrobacter and gram-negative Pseudomonas were the most abundant genera. The inoculum Pseudomonas putida PaW85/pWW0 was not found in the rhizosphere samples. Even if there were no ecological niches available for the bioaugmentation bacterium itself, its conjugative catabolic plasmid might have had some additional value for other bacterial species and thus, for rhizoremediation. Only 10 to 20% of the isolated, m-toluate tolerating bacterial strains were also able to degrade m-toluate. TOL plasmids were a major group of catabolic plasmids among these bacteria. The ability to degrade m-toluate by using enzymes encoded by a TOL plasmid was detected only in species of the genus Pseudomonas, and the best m-toluate degraders were these Pseudomonas species. Strain-specific differences in degradation abilities were found for P.oryzihabitans and P. migulae: some of these strains harbored a TOL plasmid - a new finding observed in this work, indicating putative horizontal plasmid transfer in the rhizosphere. One P. oryzihabitans strain harbored the pWW0 plasmid that had probably conjugated from the bioaugmentation Pseudomonas. Some P. migulae and P. oryzihabitans strains seemed to harbor both the pWW0- and the pDK1-type TOL plasmid. Alternatively, they might have harbored a TOL plasmid with both the pWW0- and the pDK1-type xylE gene. The breakdown of m-toluate by gram-negative bacteria was not restricted to the TOL pathway. Also some gram-positive Rhodococcus erythropolis and Arthrobacter aurescens strains were able to degrade m-toluate in the absence of a TOL plasmid. Three aspects of the rhizosphere effect of G. orientalis were manifested in oil-contaminated soil in the field: 1) G. orientalis and Pseudomonas bioaugmentation increased the amount of rhizosphere bacteria. G. orientalis especially together with Pseudomonas bioaugmentation increased the numbers of m-toluate utilizing and catechol positive bacteria indicating an increase in degradation potential. 2) Also the bacterial diversity, when measured as the amount of ribotypes, was increased in the Galega rhizosphere with or without Pseudomonas bioaugmentation. However, the diversity of m-toluate utilizing bacteria did not significantly increase. At the community level, by using the 16S rRNA gene PCR-DGGE method, the highest diversity of species was also observed in vegetated soils compared with non-vegetated soils. Diversified communities may best guarantee the overall success in rhizoremediation by offering various genetic machineries for catabolic processes. 3) At the end of the experiment, no TOL plasmid could be detected by direct DNA analysis in soil treated with both G. orientalis and Pseudomonas. The detection limit for TOL plasmids was encountered indicating decreased amount of degradation plasmids and thus, the success of rhizoremediation. The use of G. orientalis for rhizoremediation is unique. In this thesis new information was obtained about the rhizosphere effect of Galega orientalis in BTEX contaminated soils. The molecular biomonitoring methods can be applied for several purposes within environmental biotechnology, such as for evaluating the intrinsic biodegradation potential, monitoring the enhanced bioremediation, and estimating the success of bioremediation. Environmental protection by using nature's own resources and thus, acting according to the principle of sustainable development, would be both economically and environmentally beneficial for society. Keywords: molecular biomonitoring, genetic fingerprinting, soil bacteria, bacterial diversity, TOL plasmid, catabolic genes, horizontal gene transfer, rhizoremediation, rhizosphere effect, Galega orientalis, aerobic biodegradation, petroleum hydrocarbons, BTEX

Microbial activities in boreal soils: Biodegradation of organic contaminants at low temperature and ammonia oxidation

This thesis deals with the response of biodegradation of selected anthropogenic organic contaminants and natural autochthonous organic matter to low temperature in boreal surface soils. Furthermore, the thesis describes activity, diversity and population size of autotrophic ammonia-oxidizing bacteria (AOB) in a boreal soil used for landfarming of oil-refinery wastes, and presents a new approach, in which the particular AOB were enriched and cultivated in situ from the landfarming soil onto cation exchange membranes. This thesis demonstrates that rhizosphere fraction of natural forest humus soil and agricultural clay loam soil from Helsinki Metropolitan area were capable of degrading of low to moderate concentrations (0.2 50 µg cm-3) of PCP, phenanthrene and 2,4,5-TCP at temperatures realistic to boreal climate (-2.5 to +15 °C). At the low temperatures, the biodegradation of PCP, phenanthrene and 2,4,5-TCP was more effective (Q10-values from 1.6 to 7.6) in the rhizosphere fraction of the forest soil than in the agricultural soil. Q10-values of endogenous soil respiration (carbon dioxide evolution) and selected hydrolytic enzyme activities (acetate-esterase, butyrate-esterase and β-glucosidase) in acid coniferous forest soil were 1.6 to 2.8 at temperatures from -3 to +30 °C. The results indicated that the temperature dependence of decomposition of natural autochthonous soil organic matter in the studied coniferous forest was only moderate. The numbers of AOB in the landfarming (sandy clay loam) soil were determined with quantitative polymerase chain reaction (real-time PCR) and with Most Probable Number (MPN) methods, and potential ammonium oxidation activity was measured with the chlorate inhibition technique. The results indicated presence of large and active AOB populations in the heavily oil-contaminated and urea-fertilised landfarming soil. Assessment of the populations of AOB with denaturing gradient gel electrophoresis (DGGE) profiling and sequence analysis of PCR-amplified 16S rRNA genes showed that Nitrosospira-like AOB in clusters 2 and 3 were predominant in the oily landfarming soil. This observation was supported by fluorescence in situ hybridization (FISH) analysis of the AOB grown on the soil-incubated cation-exchange membranes. The results of this thesis expand the suggested importance of Nitrosospira-like AOB in terrestrial environments to include chronically oil-contaminated soils.

Mechanical and leaching behaviour of slag-cement and lime-activated slag stabilised/solidified contaminated soil.

Stabilisation/solidification (S/S) is an effective technique for reducing the leachability of contaminants in soils. Very few studies have investigated the use of ground granulated blast furnace slag (GGBS) for S/S treatment of contaminated soils, although it has been shown to be effective in ground improvement. This study sought to investigate the potential of GGBS activated by cement and lime for S/S treatment of a mixed contaminated soil. A sandy soil spiked with 3000mg/kg each of a cocktail of heavy metals (Cd, Ni, Zn, Cu and Pb) and 10,000mg/kg of diesel was treated with binder blends of one part hydrated lime to four parts GGBS (lime-slag), and one part cement to nine parts GGBS (slag-cement). Three binder dosages, 5, 10 and 20% (m/m) were used and contaminated soil-cement samples were compacted to their optimum water contents. The effectiveness of the treatment was assessed using unconfined compressive strength (UCS), permeability and acid neutralisation capacity (ANC) tests with determination of contaminant leachability at the different acid additions. UCS values of up to 800kPa were recorded at 28days. The lowest coefficient of permeability recorded was 5×10(-9)m/s. With up to 20% binder dosage, the leachability of the contaminants was reduced to meet relevant environmental quality standards and landfill waste acceptance criteria. The pH-dependent leachability of the metals decreased over time. The results show that GGBS activated by cement and lime would be effective in reducing the leachability of contaminants in contaminated soils.

Process envelopes for stabilisation/solidification of contaminated soil using lime-slag blend.

PURPOSE: Stabilisation/solidification (S/S) has emerged as an efficient and cost-effective technology for the treatment of contaminated soils. However, the performance of S/S-treated soils is governed by several intercorrelated variables, which complicates the optimisation of the treatment process design. Therefore, it is desirable to develop process envelopes, which define the range of operating variables that result in acceptable performance. METHODS: In this work, process envelopes were developed for S/S treatment of contaminated soil with a blend of hydrated lime (hlime) and ground granulated blast furnace slag (GGBS) as the binder (hlime/GGBS = 1:4). A sand contaminated with a mixture of heavy metals and petroleum hydrocarbons was treated with 5%, 10% and 20% binder dosages, at different water contents. The effectiveness of the treatment was assessed using unconfined compressive strength (UCS), permeability, acid neutralisation capacity and contaminant leachability with pH, at set periods. RESULTS: The UCS values obtained after 28 days of treatment were up to ∼800 kPa, which is quite low, and permeability was ∼10(-8) m/s, which is higher than might be required. However, these values might be acceptable in some scenarios. The binder significantly reduced the leachability of cadmium and nickel. With the 20% dosage, both metals met the waste acceptance criteria for inert waste landfill and relevant environmental quality standards. CONCLUSIONS: The results show that greater than 20% dosage would be required to achieve a balance of acceptable mechanical and leaching properties. Overall, the process envelopes for different performance criteria depend on the end-use of the treated material.

PH-dependent leaching behaviour and other performance properties of cement-treated mixed contaminated soil

Portland cement has been widely used for stabilisation/solidification (S/S) treatment of contaminated soils. However, there is a dearth of literature on pH-dependent leaching of contaminants from cement-treated soils. This study investigates the leachability of Cu, Pb, Ni, Zn and total petroleum hydrocarbons (TPH) from a mixed contaminated soil. A sandy soil was spiked with 3000 mg/kg each of Cd, Cu, Pb, Ni and Zn, and 10,000 mg/kg of diesel, and treated with ordinary Portland cement (CEM I). Four different binder dosages, 5%, 10%, 15% and 20% (m/m) and different water contents ranging from 13%-19% dry weight were used in order to find a safe operating envelope for the treatment process. The pH-dependent leaching behaviour of the treated soil was monitored over an 84-day period using a 3-point acid neutralisation capacity (ANC) test. The monolithic leaching test was also conducted. Geotechnical properties such as unconfined compressive strength (UCS), hydraulic conductivity and porosity were assessed over time. The treated soils recorded lower leachate concentrations of Ni and Zn compared to the untreated soil at the same pH depending on binder dosage. The binder had problems with Pb stabilisation and TPH leachability was independent of pH and binder dosage. The hydraulic conductivity of the mixes was generally of the order, 10-8 m/sec, while the porosity ranged from 26%-44%. The results of selected performance properties are compared with regulatory limits and the range of operating variables that lead to acceptable performance described. © 2012 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences.

Comparisons of operating envelopes for contaminated soil stabilised/solidified with different cementitious binders

This work initiated the development of operating envelopes for stabilised/solidified contaminated soils. The operating envelopes define the range of operating variables for acceptable performance of the treated soils. The study employed a soil spiked with 3,000 mg/kg each of Cd, Cu, Pb, Ni and Zn, and 10,000 mg/kg of diesel. The binders used for treatment involved Portland cement (CEMI), pulverised fuel ash (PFA), ground granulated blast furnace slag (GGBS) and hydrated lime (hlime). The specific binder formulations were CEMI, CEMI/PFA = 1:4, CEMI/GGBS = 1:9 and hlime/GGBS = 1:4. The water contents employed ranged from 13 % to 21 % (dry weight), while binder dosages ranged from 5 % to 20 % (w/w). We monitored the stabilised/solidified soils for up to 84 days using different performance tests. The tests include unconfined compressive strength (UCS), hydraulic conductivity, acid neutralisation capacity (ANC) and pH-dependent leachability of contaminants. The water content range resulted in adequate workability of the mixes but had no significant effect on leachability of contaminants. We produced design charts, representing operating envelopes, from the results generated. The charts establish relationships between water content, binder dosage and UCS; and binder dosage, leachant pH and leachability of contaminants. The work also highlights the strengths and weaknesses of the different binder formulations. © 2013 Springer-Verlag Berlin Heidelberg.