Microwave remediation of soil contaminated with hexachlorobenzene

This study describes the remediation of hexachlorobenzene (HCB) contaminated soils by microwave (MW) radiation in a sealed vial. When powdered MnO2 was used as MW absorber, a complete removal of HCB was obtained with 10 min MW by the addition of H2SO4 (50%). But no significant decomposition was observed by the addition of NaOH (10 mol/L) or H2O in the same conditions. In contrast, when powdered Fe was used instead of MnO2, the difference of HCB removals between H2SO4 and NaOH were not obvious. It is noteworthy that more than 95% removal was achieved in any case when the sole aqueous solution of H2SO4, NaOH, H2O or Na2SO4 was added without MnO2 or Fe. As a result, it is possible that water itself contained in the damp soil may act as MW absorber and remediate the contaminated soil without addition of any other MW absorbers. Gas chromatograph/mass spectrum (GC/MS) analysis detected no intermediates in all the processes. The decomposition mechanism of HCB by MW radiation was suggested as the binding of HCB and soil. Whatever fragments formed from HCB by heat were tightly bound to the soil, making it impossible to extract them out. In the end, treatment of practical HCB contaminated soil by MW reduced HCB from 55.8 mg/kg to 0.91 mg/kg.     

Desorption and dissolution of heavy metals from contaminated soil using Shewanella sp. (HN-41) amended with various carbon sources and synthetic soil organic matters

Heavy metals in soil are considered a major environmental problem facing many countries around the world. Contamination of heavy metals occurs in soil due to both anthropogenic and natural causes. During the last two decades, extensive attention has been paid to the management and control of soil contamination. Decontamination of heavy metals in the soil has been a challenge for a long time. Microbial solubilization is one of promising process for remediation of heavy metals from contaminated sites. In this study, we attempted to treat soil contaminated with heavy metals using a facultative anaerobic bacterium Shewanella sp. (HN-41). The effect of carbon sources on the dissolution and conversion of heavy metals was first investigated using a defined medium containing 1 g of highly contaminated soil to select the most effective carbon source. Among three carbon sources, namely glucose, acetic acid and lactic acid, glucose at 10 mM was found to be the most effective. Therefore, glucose was used as a representative carbon source for the second part of the biological treatment in the defined medium, amended with humic acid (HA) and anthraquinone-2,6-disulfonate (ADQS), respectively. Among the heavy metals, iron and manganese exhibited the highest dissolution efficiency in the medium supplemented with glucose at 10mM. The rates of dissolution and removal of heavy metals were little bit higher in the medium amended with humic acid and ADQS. Per these results outlined above, a combined system of humic acid and ADQS incorporated with glucose was found to be effective for the removal of heavy metals from soil.     

Immobilization and phytotoxicity of Cd in contaminated soil amended with chicken manure compost

The experiment was conducted to evaluate the effect of compost application on the immobilization and biotoxicity of Cd in winter wheat (Triticum aestivum L.) potted soils. Soils treated with various levels of Cd (0-50 mg Cd kg(-1) soil) were amended with 0, 30, 60 and 120 g compost kg(-1) soil. The fractions of Cd in soil were evaluated by a sequential extraction procedure. Compost application resulted in more than 70% lower soluble/exchangeable Cd (KNO(3)) but increased the concentration of organic-bound (NaOH) and inorganic precipitates (EDTA) Cd in soils. Addition of compost was effective in reducing the phytotoxicity of Cd by decreasing more than 50% Cd uptake by wheat tissue and improving wheat growth. Alleviation of Cd phytotoxicity by compost was attributed primarily to the increase of soil pH, complexation of Cd by the organic matter and coprecipitation with P content. Compost was effective in the immobilization of Cd in soils and can be used to remediate Cd-contaminated soils.     

Pre- and post-cyclic behaviour of an unsaturated clayey soil contaminated with crude oil

Besides adverse impacts on the environment, pollution with hydrocarbon compounds such as crude oil affects the geotechnical parameters like deformation modulus and shear strength. The present research involves evaluation of clayey soil properties changes in an unsaturated state due to application of cyclic loads before and after contamination with crude oil. A series of constant water content (CW) static and dynamic triaxial tests were conducted on samples that were compacted to the same dry density but different degrees of saturation and net confining pressures. The soil studied was provided from a place near an oil refinery located in Iran’s capital city and was artificially polluted with 3%, 6% and 9% crude oil. Deformation modulus reduction due to cyclic loads application was considerably more than reduction of shear strength. Also, these parameters increased due to increasing net confining pressure and initial matric suction. Several chemical tests and techniques were employed to investigate the chemical variations in soil structure and the role of different chemical components of crude oil on quantitative variations of soil characteristics.     

Agro-improving method of phytoextracting heavy metal contaminated soil

Phytoextraction of heavy metal contaminated soils is a promising remediation technology. Till now, more than several hundreds of hyperaccumulators or non-hyperaccumulators which can be used to clean polluted soils with heavy metals have been reported. However, phytoextraction is still not extensively applied. Thus, some measurements should be taken to improve phytoremediation. This paper introduced the basic mechanisms of phytoextration, its main restrictive factors, its relationship with agricultural technology and some agricultural improvement methods. We suggested that unavailable heavy metal activation, crop breeding, seed-coating and felicitous utilization of fertilizer and water, as well as the use of two-phase planting may be important and indispensable paths for phytoextraction to be widely applied at a commercial level in the future.     

Remediation of soil contaminated with the heavy metal (Cd2+)

Soil contamination by heavy metals is increasing. The biosorption process for removal of the heavy metal Cd(2+) from contaminated soil is chosen for this study due to its economy, commercial applications, and because it acts without destroying soil structure. The study is divided into four parts (1) soil leaching: the relationships between the soil leaching effect and agitation rates, solvent concentrations, ratios of soil to solvent, leaching time and pH were studied to identify their optimum conditions; (2) adsorption Cd(2+) tests of immobilized Saccharomycetes pombe beads: different weight percentages of chitosan and polyvinyl alcohol (PVAL) were added to alginate (10 wt.%) and then blended or cross-linked by epichlorohydrin (ECH) to increase their mechanical strength. Next, before blending or cross-linking, different weight percentages of S. pombe 806 or S. pombe ATCC 2476 were added to increase Cd(2+) adsorption. Thus, the optimum beads (blending or cross-linking, the percentages of chitosan, PVAL and S. pombe 806 or S. pombe ATCC 2476) and the optimum adsorption conditions (agitation rate, equilibrium adsorption time, and pH in the aqueous solution) were ascertained; (3) regeneration tests of the optimum beads: the optimum beads adsorbing Cd(2+) were regenerated by various concentrations of aqueous HCl solutions. The results indicate that the reuse of immobilized pombe beads was feasible; and (4) adsorption model/kinetic model/thermodynamic property: the equilibrium adsorption, kinetics, change in Gibbs free energy of adsorption of Cd(2+) on optimum beads were also investigated.     

Remediation of heavy metal contaminated soil washing residues with amino polycarboxylic acids

Removal of Cu, Pb, and Zn by the action of the two biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS) and methylglycinediacetic acid (MGDA), as well as citric acid, was tested. Three soil samples, which had previously been treated by conventional soil washing (water), were utilized in the leaching tests. Experiments were performed in batches (0.3 kg-scale) and with a WTC-mixer system (Water Treatment Construction, 10 kg-scale). EDDS and MGDA were most often equally efficient in removing Cu, Pb, and Zn after 10–60 min. Nonetheless, after 10 d, there were occasionally significant differences in extraction efficiencies. Extraction with citric acid was generally less efficient, however equal for Zn (mainly) after 10 d. Metal removal was similar in batch and WTC-mixer systems, which indicates that a dynamic mixer system could be used in full-scale. Use of biodegradable amino polycarboxylic acids for metal removal, as a second step after soil washing, would release most remaining metals (Cu, Pb and Zn) from the present soils, however only after long leaching time. Thus, a full-scale procedure, based on enhanced metal leaching by amino polycarboxylic acids from soil of the present kind, would require a pre-leaching step lasting several days in order to be efficient.     

Effective treatment of PAH contaminated Superfund site soil with the peroxy-acid process

Peroxy-organic acids are formed by the chemical reaction between organic acids and hydrogen peroxide. The peroxy-acid process was applied to two Superfund site soils provided by the U.S. Environmental Protection Agency (EPA). Initial small-scale experiments applied ratios of 3:5:7 (v/v/v) or 3:3:9 (v/v/v) hydrogen peroxide:acetic acid:deionized (DI) water solution to 5g of Superfund site soil. The experiment using 3:5:7 (v/v/v) ratio resulted in an almost complete degradation of the 14 EPA regulated polycyclic aromatic hydrocarbons (PAHs) in Bedford LT soil during a 24-h reaction period, while the 3:3:9 (v/v/v) ratio resulted in no applicable degradation in Bedford LT lot 10 soil over the same reaction period. Specific Superfund site soil characteristics (e.g., pH, total organic carbon content and particle size distribution) were found to play an important role in the availability of the PAHs and the efficiency of the transformation during the peroxy-acid process. A scaled-up experiment followed treating 150g of Bedford LT lot 10 soil with and without mixing. The scaled-up processes applied a 3:3:9 (v/v/v) solution resulting in significant decrease in PAH contamination. These findings demonstrate the peroxy-acid process as a viable option for the treatment of PAH contaminated soils. Further work is necessary in order to elucidate the mechanisms of this process.     

Comparison of analytical error and sampling error for contaminated soil

Investigation of soil from contaminated sites requires several sample handling steps that, most likely, will induce uncertainties in the sample. The theory of sampling describes seven sampling errors that can be calculated, estimated or discussed in order to get an idea of the size of the sampling uncertainties. With the aim of comparing the size of the analytical error to the total sampling error, these seven errors were applied, estimated and discussed, to a case study of a contaminated site. The manageable errors were summarized, showing a range of three orders of magnitudes between the examples. The comparisons show that the quotient between the total sampling error and the analytical error is larger than 20 in most calculation examples. Exceptions were samples taken in hot spots, where some components of the total sampling error get small and the analytical error gets large in comparison. Low concentration of contaminant, small extracted sample size and large particles in the sample contribute to the extent of uncertainty.     

Electroosmotic flow behaviour of metal contaminated expansive soil

It is important to study the flow behaviour through soil during electrokinetic extraction of contaminants to understand their removal mechanism. The flow through the expansive soil containing montmorillonite is monitored during laboratory electrokinetic extraction of heavy metal contaminants. The permeability of soil, which increases due to the presence of contaminants, is further enhanced during electrokinetic extraction of contaminants due to osmotic permeability. The variations in flow rates through the soil while the extracting fluid is changed to dilute acetic acid (used to control the increase of pH) and EDTA solution (used to desorb the metal ions from soil) are studied. The trends of removal of contaminants vis-a-vis the changes in the flow through the soil during different phases of electrokinetic extraction are established. Chromium ions are removed by flushing of water through the soil and increased osmotic flow is beneficial. Removal of iron ions is enhanced by induced osmotic flow and desorption of ions by electrokinetic processes.     

Electrochemical EDTA recycling after soil washing of Pb, Zn and Cd contaminated soil

Recycling of chelant decreases the cost of EDTA-based soil washing. Current methods, however, are not effective when the spent soil washing solution contains more than one contaminating metal. In this study, we applied electrochemical treatment of the washing solution obtained after EDTA extraction of Pb, Zn and Cd contaminated soil. A sacrificial Al anode and stainless steel cathode in a conventional electrolytic cell at pH 10 efficiently removed Pb from the solution. The method efficiency, specific electricity and Al consumption were significantly higher for solutions with a higher initial metal concentration. Partial replacement of NaCl with KNO₃ as an electrolyte (aggressive Cl⁻ are required to prevent passivisation of the Al anode) prevented EDTA degradation during the electrolysis. The addition of FeCl₃ to the acidified washing solution prior to electrolysis improved Zn removal. Using the novel method 98, 73 and 66% of Pb, Zn and Cd, respectively, were removed, while 88% of EDTA was preserved in the treated washing solution. The recycled EDTA retained 86, 84 and 85% of Pb, Zn and Cd extraction potential from contaminated soil, respectively.     

Integrated treatment of PAH contaminated soil by soil washing, ozonation and biological treatment

The aim of the study was to optimise three different treatment methods and to find out if the integration of soil washing, ozonation and biological treatment could be a feasible method for the remediation of aged oil contaminated with PAHs. Three different ozone doses and soil washing were studied in different pHs in order to assess their effect to the degradation and enhancement of biodegradability of PAH in the soil and water phase. Main target of the study was to find out a method with which the PAH concentrations could be decreased below the Finnish guideline level for total PAHs. In this case, the initial concentration of PAHs was 1200 mg kg(-1) and therefore almost 85% degradation of PAHs was required. Any of the methods studied was not able to reach this target level alone, but by several combinations of the methods studied achieved 90% reduction of PAHs. The consumption of ozone was 5-10 times lower in the integrated treatments of soil washing, ozonation and biological treatment than without prewashing.     

Use of poultry litter for biodegradation of soil contaminated with 2,4- and 2,6-dinitrotoluene

Pseudomonas sp. and Pseudomonas putida can utilize dinitrotoluene (DNT) as N-source after the enzymatic removal of nitro groups from the aromatic ring. Addition of nutrients is known to stimulate the biodegradation process. Poultry litter has consortia of microorganisms (including Pseudomonas) along with many nutrients. The objective of this research was to study the biodegradation of 2,4- and 2,6-DNT contaminated soil (from Badger Army Ammunition Plant) using poultry litter. Complete biodegradation of both 2,4- and 2,6-DNT in the soil was observed after 1-day interaction with poultry litter. No degradation was observed using autoclaved litter.     

Kinetics of electrodialytic extraction of Pb and soil cations from a slurry of contaminated soil fines

The objective of this work was to investigate the kinetics of Pb-removal from soil fines during electrodialytic remediation in suspension, and study the simultaneous dissolution of common soil cations (Al, Ca, Fe, Mg, Mn, Na and K). This was done to evaluate the possibilities within control of the remediation process to leave a final product suitable for reuse. The Pb-remediation process could be divided into four phases: (1) a "lag-phase", (2) a period with a high removal rate (7.4 mg/day in average at 40 mA), (3) a period with a low removal rate, and (4) a period where no further Pb-removal was obtained. During the first phase, dissolution of carbonates was the prevailing process, resulting in a corresponding loss of soil mass. During this phase, the investigated ions accounted for the major current transfer, while, as remediation proceeded, hydrogen ions increasingly dominated the transfer. During phase (3) the high conductivity and low voltage suggested that removal may be accelerated by increasing the current density. Overall, 97% of the Pb could be extracted, reducing the final Pb-concentration to 25 mg/kg. The order of removal rates was: Ca>Pb>Mn>Mg>K>(Al and Fe).     

Leaching of metals from soil contaminated by mining activities

Stabilization/solidification (s/s) is one of the most effective methods of dealing with heavy metal contaminated sites. The ability of lime and cement stabilization to immobilize Pb, Cu and Fe contained in a contaminated soil originating from an old mining and smelting area located along the Mediterranean Sea shore in northern Cyprus was investigated. The stabilization was evaluated by applying leaching tests. A series of tests were conducted to optimize the additive soil ratio for the best immobilization process. Additive/soil=1/15 (m/m) ratio was found to be the optimum for both lime and cement. Application of the US EPA toxicity characteristic leaching procedure (TCLP) on the soil samples treated with lime at additive/soil=1/15 (m/m) mixing ratios showed that Cu and Fe solubility was reduced at 94 and 90%, respectively. The results of cement treatment using the same ratio, reduced the solubility 48 and 71% for Cu and Fe, respectively. The Pb solubility was found to be below the regulatory limit of 5mg/l so no additive treatment was needed. The optimum additive/soil amount (1/15) was selected for more detailed column studies, that were carried out in the acidic pH range. According to the results of column leaching tests, it was found that, the degree of heavy metal leaching is highly dependent on pH.     

Technological prospecting: Patent mapping of bioremediation of soil contaminated with agrochemicals using fungi

The purpose of this study was to investigate the development of biotechnologies related to the bioremediation of soil contaminated by agrochemicals using fungi through technological prospecting with patent mapping and analysis of scientific products. Due to the high complexity of biotechnologies involving microorganisms, it is observed that the state of the art is still in development, with several technological advantages already elucidated and important challenges to be overcome. Patent mapping revealed that the number of granted or pending patents showed a positive trend. In this context, a high number of patent documents were observed that describe processes and methods aimed at the preparation and application of fungi in soil bioremediation, as well as biotechnologies that use consortia of different strains of fungi or fungi and bacteria and advanced approaches involving genetic engineering. In short, it was found that inventions related to the investigated biotechnology have been protected mainly in China, the USA, Japan, and the European Union, with emphasis on the technological impact of patents in India. Finally, the findings indicated that soil bioremediation with the use of fungi presents a potential for development due to a series of technological and environmental aspects.     

Thermal treatment of soils contaminated with gas oil: influence of soil composition and treatment temperature

Samples of two soils containing different organic matter contents, neat or contaminated with gas oil (diesel fuel oil) at 2.5 wt.% were heated from room temperature to different final temperatures (200-900 degrees C). The experiments, performed in an anaerobic media, simulate conditions pertinent to ex situ thermal desorptive and thermal destructive treatments. The products generated during the heating were collected and light gases were analyzed by gas chromatography. The results indicate that the chemical composition of the soil is a key factor since it strongly influences the quantity and composition of the off-gases. According to the liquid and light gas yields, the gas oil does not affect appreciably the generation of pyrolysis products of the own soil constituents and the gas oil does not suffer significant chemical transformations even at high operating temperatures (e.g. 900 degrees C). With surface areas of 16000 cm(2)/g (Soil A) and 85000 cm(2)/g (Soil B) based on the monolayer adsorbed model, 4 and 20%, respectively, of the original gas oil can be adsorbed. These values are in good agreement with experimental data. Even for high temperatures, the employed thermal treatment is capable to practically remove the gas oil from the soil bed without changing appreciably the original chemical composition of the contaminant.     

Statistical factor-screening and optimization in slurry phase bioremediation of 2,4,6-trinitrotoluene contaminated soil

Since slurry phase bioremediation is a promising treatment for recalcitrant compounds such as 2,4,6-trinitrotoluene (TNT), a statistical study was conducted for the first time to optimize TNT removal (TR) in slurry phase. Fractional factorial design method, 2(IV)(7-3), was firstly adopted and four out of the seven examined factors were screened as effective. Subsequently, central composite design and response surface methodology were employed to model and optimize TR within 15 days. A quadratic model (R(2) = 0.9415) was obtained, by which the optimal values of 6.25 g/L glucose, 4.92 g/L Tween 80, 20.23% (w/v) slurry concentration and 5.75% (v/v) inoculum size were estimated. Validation experiments at optimal factor levels resulted in 95.2% TR, showing a good agreement with model prediction of 96.1%. Additionally, the effect of aeration rate (0-4 vvm) on TR was investigated in a 1-liter bioreactor. Maximum TR of 95% was achieved at 3 vvm within 9 days, while reaching the same removal level in flasks needed 15 days. This reveals that improved oxygen supply in bioreactor significantly reduces bioremediation time in comparison with shake flasks.     

Evaporation and decomposition of Triton X-100 under various gases and temperatures

The thermal behaviour of Triton X-100 (surfactant in PTFE dispersion) under various gases was studied with differential scanning calorimetry (DSC) and IR spectrophotometry below 350° C. In nitrogen or argon gas, Triton X-100 evaporated without decomposition. However, in air or oxygen containing gas, thermal oxidation occurred, where a strong _co band appeared in IR spectra. Oxygen increased the evaporation rate of Triton X-100 remarkably. The heat of vaporization was about 16 kcal mol^–1 which is independent of the oxygen concentration. The evaporation mechanism is discussed briefly.     

Interaction of soil, water and TNT during degradation of TNT on contaminated soil using subcritical water

Subcritical water was used at laboratory scale to reveal information with respect to the degradation mechanism of TNT on contaminated soil. Highly contaminated soil (12% TNT) was heated with water at four different temperatures, 150, 175, 200 and 225 degrees C and samples were obtained at appropriate time intervals. At the same time, similar experiments were performed with TNT spiked on to clean soil, sand and pure water in order to compare and eliminate various factors that may be present in the more complex contaminated soil system. Subcritical water was successful at remediating TNT-contaminated soil. TNT destruction percentages ranged between 98 and 100%. The aim of this work was to study the soil-water-contaminant interaction and determine the main physical parameters that affect TNT degradation. It was shown that the rate-limiting step of the process is the extraction/diffusion of TNT molecules from the soil core to the soil surface, where they degrade. Additionally, it was determined that the soil matrix also catalyses degradation to a lesser extent. Autocatalytic effects were not clearly observed.