Remediation of soils contaminated with polychlorinated biphenyls by microwave-irradiated manganese dioxide

The removal of polychlorinated biphenyls (PCBs) using microwave-irradiated manganese dioxide (MnO₂) in PCB-contaminated soils under different conditions is investigated. The removal of PCB77 in two actual soil samples exhibits strong pH-dependent behavior, and the removal efficiency is higher in acidic soil (Ali-Perudic Ferrosols) than that in neutral soil (Udic Argosols). The removal kinetics of PCB77 using microwave-irradiated MnO₂ under different experimental conditions fits a pseudo-first-order kinetic model well. Both the removal efficiency and the kinetic constant (k) values of PCB77 in Ali-Perudic Ferrosols considerably increase, although in a nonlinear fashion, as the initial amount of MnO₂ is increased, as the treated soil mass is increased, and as the microwave power is increased. The reactivity of three PCBs (PCB28, PCB77, and PCB118) did not present as a function of the degree of chlorination in the reaction with microwave-irradiated MnO₂. The pronounced removal of three PCBs in contaminated soil (all above 95%) indicates that MnO₂ in combination with microwave irradiation is promising for technological applications that seek to remediate sites critically polluted with PCBs.     

Remediation of petroleum contaminated soils through composting and rhizosphere degradation

Composting along with rhizodegradation was used to remediate petroleum-contaminated soils in the Yellow River Delta, China. The average concentration of total petroleum hydrocarbons (TPH) in these soils was reduced from 7900-17,900 mg kg(-1) to 1400-3700 mg kg(-1) after field composting. The best volume ratio of amendment to contaminated soil was 2/1 and the best C/N ratio was 15/1. After composting, four local dominant plant species, Seepweed, Sealavander, Central Asia Saltbush and Reed, were selected and planted in composted soils for rhizodegradation in the field. After 90 days of cultivation, the highest net TPH degradation rate was over 40% for Seepweed, probably because of strong root system and active microbial community. In addition, Seepweed roots significantly reduced the surface and volume of soil micropores (which are able to sequestrate organic compounds inside), thus increasing the bioavailability of TPH. In sum, composting followed with planting Seepweed was most effective in remediating the contaminated soil in the Yellow River Delta.     

Remediation of dinitrotoluene contaminated soils from former ammunition plants: soil washing efficiency and effective process monitoring in bioslurry reactors

A pilot-scale bioslurry system was used to test the treatment of soils highly contaminated with 2,4-dinitrotoluene (2,4-DNT) and 2,6-dinitrotoluene (2,6-DNT). The treatment scheme involved a soil-washing process followed by two sequential aerobic slurry reactors augmented with 2,4-DNT- and 2,6-DNT-mineralizing bacteria. Test soils were obtained from two former army ammunition plants, the Volunteer Army Ammunition Plant (VAAP, Chattanooga, TN) and the Badger Army Ammunition Plant (BAAP, Baraboo, WI). Soil washing was used to minimize operational problems in slurry reactors associated with large particulates. The Eimco slurry reactors were operated in a draw-and-fill mode for 3 months and were monitored for the biodegradation of 2,4-DNT and 2,6-DNT, nitrite production, NaOH consumption, and oxygen uptake rate. Results show that soil washing was very effective for the removal of sands and the recovery of soil fines containing 2,4-DNT and 2,6-DNT. Bioslurry reactors offered rapid and nearly complete degradation of both DNT isomers, but require real time monitoring to avoid long lag periods upon refeeding. Results found a significant discrepancy between the measured DNT concentrations and calculated DNT concentrations in the slurry reactors because of solids profiles in the slurry reactors and the presence of floating crystal of DNTs. Based on the actual amount of dinitrotoluene degradation, nitrite release, NaOH consumption, and oxygen uptake were close to the theoretical stoichiometric coefficients of complete DNT mineralization. Such stoichiometric relationships were not achieved if the calculation was based on the measured DNT concentrations due to the heterogeneity of DNT in the reactor. Results indicate that nitrite release, NaOH consumption, and oxygen uptake rates provide a fast assessment of 2,4-DNT degradation and microbial activity in a slurry reactor, but could not be extended to a second reactor in series where the degradation of a much lower concentration of 2,6-DNT degradation was achieved.     

Remediation of hexachlorobenzene contaminated soils by rhamnolipid enhanced soil washing coupled with activated carbon selective adsorption

The present study investigates the selective adsorption of hexachlorobenzene (HCB) from rhamnolipid solution by a powdered activated carbon (PAC). A combined soil washing-PAC adsorption technique is further evaluated on the removal of HCB from two soils, a spiked kaolin and a contaminated real soil. PAC at a dosage of 10 g L(-1) could achieve a HCB removal of 80-99% with initial HCB and rhamnolipid concentrations of 1 mg L(-1) and 3.3-25 g L(-1), respectively. The corresponding adsorptive loss of rhamnolipid was 8-19%. Successive soil washing-PAC adsorption tests (new soil sample was subjected to washing for each cycle) showed encouraging leaching and adsorption performances for HCB. When 25 g L(-1) rhamnolipid solution was applied, HCB leaching from soils was 55-71% for three cycles of washing, and HCB removal by PAC was nearly 90%. An overall 86% and 88% removal of HCB were obtained for kaolin and real soil, respectively, by using the combined process to wash one soil sample for twice. Our investigation suggests that coupling AC adsorption with biosurfactant-enhanced soil washing is a promising alternative to remove hydrophobic organic compounds from soils.     

Enhanced dissolution of TCE in NAPL by TCE-degrading bacteria in wetland soils

The influence of trichloroethene (TCE) dechlorinating mixed cultures in dissolution of TCE in nonaqueous phase liquid (NAPL) via biodegradation was observed. Experiments were conducted in batch reactor system with and without marsh soils under 10 and 20 degrees C for 2 months. The dissolution phenomenon in biotic reactors containing mixed cultures was showed temporal increases compared to abiotic reactors treated with biocide. Effective NAPL-water transfer rate (K(m)) calculated in this study showed more than four times higher in biotic reactors than that in abiotic reactors. The results might be attributed to the biologically enhanced dissolution process via dechlorination in reactors. Temperature would be a factor to determine the dissolution rate by controlling bacterial activity. The TCE dechlorination occurred even in an interface of TCE-NAPL that demonstrated no previous TCE biodegradation, suggesting that microbes may be useful in developing source-zone bioremediation system. In conclusion, dechlorinating mixed culture could enhance dissolution in NAPL that may be useful in the application of source zone bioremediation.     

Remediation of groundwater contaminated with DNAPLs by biodegradable oil emulsion

Emulsion-based remediation with biodegradable vegetable oils was investigated as an alternative technology for the treatment of subsurface DNAPLs (dense non-aqueous phase liquids) such as TCE (trichloroethylene) and PCE (perchloroethylene). Corn and olive oil emulsions obtained by homogenization at 8000rpm for 15min were used. The emulsion droplets prepared with corn and olive oil gave a similar size distribution (1-10microm) and almost all of initially injected oil, >90%, remained in a dispersed state. In batch experiments, 2% (v/v) oil emulsion could adsorb up to 11,000ppm of TCE or 18,000ppm of PCE without creating a free phase. Results of one-dimensional column flushing studies indicated that contaminants with high aqueous solubility could be efficiently removed by flushing with vegetable oil emulsions. Removal efficiencies exceeded 98% for TCE and PCE with both corn and olive oil emulsions. The results of this study show that flushing with biodegradable oil emulsion can be used for the remediation of groundwater contaminated by DNAPLs.     

Assessment of lead bioaccessibility in peri-urban contaminated soils

Lead (Pb) bioaccessibility was assessed in a range of peri-urban soils (n=31) with differing sources of Pb contamination, including shooting range soils, and soils affected by incinerator, historical fill, mining/smelting, and gasworks activities. A gossan soil sample was also included. Lead bioaccessibility was determined using both gastric and intestinal phases of the SBRC in vitro assay and in vitro data was then incorporated into in vivo-in vitro regression equations to calculate Pb relative bioavailability. Lead bioaccessibility ranged from 26.8-105.2% to 5.5-102.6% for gastric and intestinal phase extractions respectively. Generally, Pb bioaccessibility was highest in the shooting range soils and lowest in the gossan soil. Predictions of relative Pb bioavailability derived from in vitro data were comparable for shooting ranges soils, but highly variable for the other soils examined. For incinerator, historical fill, gasworks and gossan soils, incorporating in vitro gastric data into the in vivo-in vitro regression equation resulting in more conservative Pb relative bioavailability values than those derived using the intestinal in vitro data.     

Removal of depleted uranium from contaminated soils

Contamination of soil and water with depleted uranium (DU) has increased public health concerns due to the chemical toxicity of DU at elevated dosages. For this reason, there is great interest in developing methods for DU removal from contaminated sources. Two DU laden soils, taken from U.S. Army sites, were characterized for particle size distribution, total uranium concentration and removable uranium. Soil A was found to be a well graded sand containing a total of 3210 mg/kg DU (3.99 x 10(4) Bq/kg, where a Becquerel (Bq) is a unit of radiation). About 83% of the DU in the fines fraction (particle diameter <0.075 mm, total DU 7732 mg/kg (9.61 x 10(4) Bq/kg)) was associated with the carbonate, iron and manganese oxide and organic matter fractions of the material. Soil B was classified as a sandy silt with total DU of 1560 mg/kg (1.94 x 10(4) Bq/kg). The DU content in the fines fraction was 5171 mg/kg (6.43 x 10(4) Bq/kg). Sequential extraction of the Soil B fines fraction indicated that 64% of the DU was present either as soluble U(VI) minerals or as insoluble U(IV). Citric acid, sodium bicarbonate and hydrogen peroxide were used in batch experiments to extract DU from the fines fraction of both soils. Citric acid and sodium bicarbonate were relatively successful for Soil A (50-60% DU removal), but not for Soil B (20-35% DU removal). Hydrogen peroxide was found to significantly increase DU extraction from both soils, attaining removals up to 60-80%.     

Electromigration of cadmium in contaminated soils driven by single and multiple primary cells

This study tentatively used an iron (Fe) and carbon (C) primary cell, instead of dc electric power, to drive the electromigration of cadmium in contaminated soils. The addition of acid to C compartment increased the electric potential, while the addition of acid to Fe compartment had a slight influence on the potential. It was feasible using the primary cell to drive the electromigration of cadmium in kaolin. The electromigration efficiencies were highly related to the soil pH. Lower pH led to greater migration efficiency. The mechanisms involved the desorption of cadmium from soils to pore solution and the electromigration of cadmium in the pore solution. The desorption was critical to the electromigration process. The series of primary cells could expand the treatment area, but the electromigration efficiencies of cadmium in each cell were less than that achieved by single primary cell. Since the potential gradient produced by the primary cell was rather low, the electromigration rate of pollutants was very low and remediation duration was long. The application would be acceptable in some specific sites, such as acidic soils or artificially controlled acid conditions so that heavy metals have been desorbed from soils.     

Bioremediation of Cr(VI) in contaminated soils

Ex situ treatment of hexavalent chromium (Cr(VI)) contaminated soil using a bioreactor-biosorption system was evaluated as a novel remediation alternative. Leaching of Cr(VI) from the contaminated soil using various eluents showed that desorption was strongly affected by the solution pH. The leaching process was accelerated at alkaline conditions (pH 9). Though, desorption potential of ethylene diamine tetra acetic acid (EDTA) was the maximum among various eluents tried, molasses (5 g/L) could also elute 72% of Cr(VI). Cr(VI) reduction studies were carried out under aerobic and facultative anaerobic conditions using the bacterial isolates from contaminated soil. Cr(VI) reduction was moderately higher in aerobic conditions than in facultative anaerobic conditions. The effect of various electron donors on Cr(VI) reduction was also investigated. Among five electron donors screened, peptone (10 g/L) showed maximum Cr(VI) reduction followed by molasses (10 g/L). The time required for complete Cr(VI) reduction was increased with increase in the initial Cr(VI) concentration. However, specific Cr(VI) reduction was increased with increase in initial Cr(VI) concentration. Sulfates and nitrates did not compete with Cr(VI) for accepting the electrons. A bioreactor was developed for the detoxification of Cr(VI). Above 80% of Cr(VI) reduction was achieved in the bioreactor with an initial Cr(VI) concentration of 50 mg/L at an HRT of 8 h. An adsorption column was developed using Ganoderm lucidum (a wood rooting fungus) as the adsorbent for the removal of trivalent chromium (Cr(III)) and excess electron donor from the effluent of the bioreactor. The specific Cr(III) adsorption capacity of G. lucidum in the column was 576 mg/g. The new biosystem seems to be a promising alternative for the ex situ bioremediation of Cr(VI) contaminated soils.     

Laser two-photon ionization of pyrene on contaminated soils

We report a first attempt to use the laser multiphoton ionization method for analysis of trace aromatic compounds on the surface of environmental (soils) and artificial (silica) samples. The measurement setup is composed of a N(2) pulsed laser and a fast conductivity detection system. The technique has been tested for detection of pyrene deposited on moist fine-powdered samples. The observed photoionization signals have indicated a gradual increase in the photoionization current and charge as a function of increasing concentration of pyrene/hexane solutions used for sample contamination. Contaminants have been analyzed in several (organic and inorganic) environmental samples, and a method to compensate for matrix effects is suggested. A contamination model is assumed and applied in order to renormalize all signals and provide an useful calibration plot. This calibration plot provides an upper estimate of pyrene LOD as 35 ng/g.     

Stabilization of cadmium contaminated soils using synthesized zeolite

This research investigates the effect of synthesized zeolite on stabilizing Cd-contaminated soil, using 0.01 M CaCl₂ leaching solution in batch and column experiments. The zeolite was synthesized from fly ash obtained from a Coal-Fired Power Plant, by adding 2 N NaOH and subjecting to 90°C for 24 h. The experiment used two groups of soil samples: (1) addition of Cd to four series of background soils: Pinchen, Jente, Erlin and Chengchung; (2) actual contaminated soils from Chungsing and Tsasta sites. The result of the batch experiment indicates that the addition of zeolite reduces Cd leaching from all types of contaminated soils. The more zeolite added, the lower Cd concentrations were detected in the leaching solution. The stabilized Cd in soils in the presence of zeolite is also demonstrated in the column experiments; the leachate contains insignificant Cd, and Cd depth analysis of the soil columns shows little Cd migration. For example, for Pinchen and Jente soils, after 12 and 49 pore volumes of leaching solution, the remaining Cd levels in the soils were 12% and 35%, respectively, of the original Cd values with no zeolite added, as compared to 96% and 99% in the presence of 16% zeolite. The higher cation exchange capacity of the zeolite/soil mixtures and higher pH are responsible for stabilizing Cd in soils. The effect is most useful in application to the acidic sandy soils to prevent contaminated heavy metals from leaching.     

Characterization and remediation of soils contaminated with uranium

Environmental contamination caused by radionuclides, in particular by uranium and its decay products is a serious problem worldwide. The development of nuclear science and technology has led to increasing nuclear waste containing uranium being released and disposed in the environment. The objective of this paper is to develop a better understanding of the techniques for the remediation of soils polluted with radionuclides (uranium in particular), considering: the chemical forms of uranium, including depleted uranium (DU) in soil and other environmental media, their characteristics and concentrations, and some of the effects on environmental and human health; research issues concerning the remediation process, the benefits and results; a better understanding of the range of uses and situations for which each is most appropriate. The paper addresses the main features of the following techniques for uranium remediation: natural attenuation, physical methods, chemical processes (chemical extraction methods from contaminated soils assisted by various suitable chelators (sodium bicarbonate, citric acid, two-stage acid leaching procedure), extraction using supercritical fluids such as solvents, permeable reactive barriers), biological processes (biomineralization and microbial reduction, phytoremediation, biosorption), and electrokinetic methods. In addition, factors affecting uranium removal from soils are furthermore reviewed including soil characteristics, pH and reagent concentration, retention time.     

Waste green sands as reactive media for groundwater contaminated with trichloroethylene (TCE)

Waste green sands are byproducts of the gray iron foundry industry that consist of sand, binding agents, organic carbon, and residual iron particles. Because of their potential sorptive and reactive properties, tests were conducted to determine the feasibility of using waste green sands as a low cost reactive medium for groundwater treatment. Batch and column tests were conducted to determine the reactivity, sorptive characteristics, and transport parameters for trichloroethylene (TCE) solutions in contact with green sands. Normalized rate constants for TCE degradation in the presence of iron particles extracted from green sands were found to be comparable to those for Peerless iron, a common medium used to treat groundwater. Rate constants and partition coefficients obtained from the batch tests were found to be comparable to those from the column tests. Analytical modeling shows that reactive barriers containing green sand potentially can be used to treat contaminated groundwater containing TCE at typical concentrations observed in the field.     

Application of H2O2 lifetime as an indicator of TCE Fenton-like oxidation in soils

Hydrogen peroxide decomposition and trichloroethylene (TCE) oxidation kinetics were studied through batch slurry experiments, performed on two TCE contaminated soils (a sandy soil and a clay soil), characterized by different texture and organic fraction; besides, experiments were also performed on sandy soil columns, in order to more closely reproduce the typical conditions of an in situ treatment. The results of the batch tests indicated that hydrogen peroxide lifetime was correlated to the oxidation efficiency; namely, complete TCE oxidation was achieved only for the conditions characterized by longer hydrogen peroxide lifetime, that was obtained by addition of a proper stabilizer (KH(2)PO(4)). The soil properties were also observed to influence both hydrogen peroxide decomposition and TCE oxidation kinetics, probably as a consequence of the different TOC content. The soil column experiments, performed on 10, 20, and 30 cm long columns, indicated that hydrogen peroxide decomposition, which was almost complete at 30 cm depth, was on the contrary negligible when the stabilizer was added. In agreement with this observation, the performance of TCE oxidation were greatly improved in the latter case. Based upon the collected results, it can be concluded that hydrogen peroxide experiments may be useful, at least in the first screening phase of the design activity, for selecting, among the different operating conditions, those that may be potentially more effective for the oxidation treatment.     

Phenanthrene and pyrene oxidation in contaminated soils using Fenton's reagent

Fenton's reagent has shown its applicability to oxidizing these biorefractory organic contaminants. The purpose of this contribution was to investigate the influence of operating parameters on the process efficiency for soil highly contaminated by PAHs. Five variables were selected: pH, reaction time, UV irradiation, hydrogen peroxide concentration and Fe (II) amendment. Their effects on the oxidation of (i) phenanthrene and on (ii) phenanthrene and pyrene present in freshly contaminated soil samples were studied through batch reactor experiments following factorial designs. For phenanthrene oxidation run with a soil contaminated at 700 mg kg(-1), one set of variables enabled us to reach a residual concentration lower than 40 mg kg(-1) (Dutch legislation threshold). The most important factor was the reaction time, followed at a certain distance by UV irradiation, Fe (II), H(2)O(2) concentration and pH, this last variable being the least significant. The possibility of operating without pH adjustment is of importance in the treatment at the field scale. This shows the feasibility of photo-Fenton-like oxidation for the treatment of soil highly contaminated with PAH and the relative importance of the process variables.     

Combined slurry and solid-phase bioremediation of diesel contaminated soils

This work investigates, at a laboratory and pilot-scale, the influence of various operating parameters on the combined slurry and solid-phase bioremediation technique for a diesel contaminated soil. For slurry-phase bioreactors (SPB), it has been found that, as far as famine conditions are attained at the end of the react cycle, a low hydraulic retention time and a low slurry recycle ratio allows for a better utilization of the reactor volume. A 7-day slurry-phase bioreactor treatment has been shown to provide enough contaminant removal allowing the soil drawn from the slurry-phase bioreactors to be fed effectively to the solid-phase bioreactors (SoPB) for completing the soil cleanup. However, an important improvement of the solid-phase bioreactor performance has been found using soil additives, namely sand and surfactants. While the first soil additive improves pile porosity and consequently oxygen diffusion, the latter increases contaminant bioavailability.     

The activation energy of stabilised/solidified contaminated soils

Developing an understanding of the time-related performance of cement-treated materials is essential in understanding their durability and long-term effectiveness. A number of models have been developed to predict this time-related performance. One such model is the maturity concept which involves use of the 'global' activation energy which derives from the Arrhenius equation. The accurate assessment of the activation energy is essential in the realistic modelling of the accelerated ageing of cement-treated soils. Experimentally, this model is applied to a series of tests performed at different elevated temperatures. Experimental work, related to the results of a time-related performance on a contaminated site in the UK treated with in situ stabilisation/solidification was carried out. Three different cement-based grouts were used on two model site soils which were both contaminated with a number of heavy metals and a hydrocarbon. Uncontaminated soils were also tested. Elevated temperatures up to 60 degrees C and curing periods up to 90 days were used. The resulting global activation energies for the uncontaminated and contaminated soils were compared. Lower values were obtained for the contaminated soils reflecting the effect of the contaminants. The resulting equivalent ages for the uncontaminated and contaminated mixes tested were 5.1-7.4 and 0.8-4.1 years, respectively. This work shows how a specific set of contaminants affect the E(a) values for particular cementitious systems and how the maturity concept can be applied to cement-treated contaminated soils.     

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.     

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.