Utilisation of Supernatants of Pure Cultures of Streptomyces thermocarboxydus NH50 to Reduce Chromium Toxicity and Mobility in Contaminated Soils

Chromium is a heavy metal used in various industrial sectors. Improper handling and storage of chromium-laden effluents or wastes can lead to the pollution of the environment. The most toxic form is the more mobile one: hexavalent chromium Cr(VI). The reduction of Cr(VI) results in the immobilisation of chromium into its less toxic trivalent form Cr(III). This phenomenon may prevent the contamination of groundwater when the soil in the vadose zone is contaminated. Many bacteria have been isolated from contaminated soils and described to reduce Cr(VI) into Cr(III). A new Cr(VI)-reducing strain, identified as a Streptomyces thermocarboxydus,has been isolated and studied in our laboratories for its ability to reduce Cr(VI). This aerobic bacterium, in contrast to other genera described which mediate reduction via enzymes, produces reducing agents into the culture supernatants. Cr(VI) reduction by these substances is accelerated by the presence of small concentration of cupric ions (Cu²⁺). The reducing agent(s) can be easily recovered from the bacterial cultures and used as cell-free solution to treat contaminated soils by an in situ or ex situ processes.     

Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

Removal of Cr(VI) from contaminated soil by electrokinetic remediation

A new process for the removal of hexavalent chromium [Cr(VI)] contaminated soil is described. The process provides for an efficient removal of anionic chemicals from contaminated soils. Chromate anions were removed from the soil to the anodic reservoir by the moving force of electromigration. In this process, the chromate anions that accumulate in the anodic reservoir are simultaneously eliminated by using a column packed adsorbent. The adsorbent (immobilized tannin) used was chemically incorporated into cellulose. Cr(VI) was found to be adsorbed to this adsorbent efficiently. In the electrokinetic process, the pH of the aqueous solution in the anodic reservoir was decreased by the electrolysis of water. In the present study, the pH of the solution in the anodic reservoir is maintained at pH 6 by the addition of an aqueous alkaline solution during the electrokinetic process. The advantage of pH control is that it promotes the release of Cr(VI) from the soil by electromigration, thus permitting the maximum adsorption of Cr(VI) on the immobilized tannin. Simultaneous collection of Cr(VI) from the anodic reservoir leads to the protection from secondary contamination with Cr(VI).     

Electrokinetic remediation of heavy metal-contaminated soils under reducing environments

This paper describes the migration of hexavalent chromium, Cr(VI), nickel, Ni(II), and cadmium, Cd(II), in clayey soils that contain different reducing agents under an induced electric potential. Bench-scale electrokinetic experiments were conducted using two different clays, kaolin and glacial till, both with and without a reducing agent. The reducing agent used was either humic acid, ferrous iron, or sulfide, in a concentration of 1000 mg/kg. These soils were then spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1000, 500 and 250 mg/kg, respectively, and tested under an induced electric potential of 1 VDC/cm for a duration of over 200 h. The reduction of chromium from Cr(VI) to Cr(III) occurred prior to electrokinetic treatment. The extent of this Cr(VI) reduction was found to be dependent on the type and amount of reducing agents present in the soil. The maximum reduction occurred in the presence of sulfides, while the minimum reduction occurred in the presence of humic acid. The concentration profiles in both soils following electrokinetic treatment showed that Cr(VI) migration was retarded significantly in the presence of sulfides due both to the reduction of Cr(VI) to Cr(III) as well as an increase in soil pH. This low migration of chromium is attributed to: (1) migration of Cr(VI) and the reduced Cr(III) fraction in opposite directions, (2) low Cr(III) migration due to adsorption and precipitation in high pH regions near the cathode in kaolin and throughout the glacial till, and (3) low Cr(VI) migration due to adsorption in low pH regions near the anode in both soils. Ni(II) and Cd(II) migrated towards the cathode in kaolin; however, the migration was significantly retarded in the presence of sulfides due to increased pH through most of the soil. Initial high pH conditions within the glacial till resulted in Ni(II) and Cd(II) precipitation, so the effects of reducing agenets were inconsequential. Overall, this study demonstrated that the reducing agents, particularly sulfides, in soils may affect redox chemistry and soil pH, ultimately affecting the electrokinetic remediation process.     

Chromium Removal from Soil by Phytoremediation with Weed Plant Species in Thailand

The possibility of using phytoremediation with weed plant species in Thailand to remove chromium (Cr) from soil was investigated. Six plant species, Cynodon dactylon, Pluchea indica, Phyllanthus reticulatus, Echinochloa colonum, Vetiveria nemoralis, and Amaranthus viridis, were chosen for their abilities to accumulate total chromium (TCr) at tanning industry sites. These plant species were studied in pots at a nursery. Cynodon dactylon and Pluchea indica provided highest TCr accumulation capacities of 152.1 and 151.8 mg/kg of plant on a dry weight basis, respectively, at a pulse hexavalent Cr [Cr(VI)] input of 100 mg Cr(VI)/kg soil. Most of the Cr uptake occurred within 30 days after the input. The TCr accumulation by Pluchea indica was observed in roots, stems, and leaves at 27%, 38%, and 35% of the TCr mass uptake, respectively, whereas 51%, 49% and 0% of the TCr mass uptake accumulated in roots, stems, and leaves of Cynodon dactylon, respectively. The results on Cr accumulation and translocation in plant tissues suggest that Cr was removed mainly via phytoaccumulation and Pluchea indica is more suitable than Cynodon dactylon for the phytoremediation of Cr contaminated soil.     

Synergistic Effects of Multiple Metal Contaminants on Electrokinetic Remediation of Soils

This article presents a bench‐scale study performed to investigate the removal of heavy metals when they exist individually and in combination in soils. Electrokinetic experiments were conducted using two types of clayey soils, kaolin and glacial till. These soils were contaminated with Cr(VI) only, with Ni(II) only, and with Cr(VI), Ni(II), and Cd(II) combined. It was found that in kaolin, a significant pH variation occurred due to electric potential application, affecting the adsorption‐desorption and dissolution‐precipitation, as well as the extent of migration of the contaminants. In glacial till, however, pH changes were not affected significantly. In both kaolin and glacial till, the migration of Cr(VI) and Ni(II) was higher when they were present individually compared to when they existed together with Cd(II). Cr(VI) migration as single or combined contaminant was lower in kaolin as compared to that in glacial till. This result was due to the low pH conditions created near the anode region in kaolin that led to high Cr(VI) adsorption to the clay surfaces. In glacial till, however, nickel precipitated with or without the presence of co‐contaminants due to high pH conditions in the soil. Overall, this study demonstrates that adsorption, precipitation, and reduction are the significant hindering mechanisms for the removal of heavy metals using electrokinetic remediation. The direction of the contaminant migration and overall removal efficiency depend on the polarity of the contaminant, the presence of co‐contaminants, and the type of soil. © 2001 John Wiley & Sons.     

Uptake of chromium by Aspergillus foetidus

Aspergillus foetidus has the ability to take up chromium during the stationary phase of growth and under growth-nonsupportive conditions. We observed a 97% decrease in hexavalent chromium (initial concentration 5 µg/g) at the end of 92 h of growth, which may be due to its reduction to Cr (III) and/or complexation with organic compounds released due to the metabolic activity of the fungus. Replacement culture studies under growth-nonsupportive conditions revealed that the maximum uptake of Cr (VI) at pH 7.0 is 2 mg/g of dry biomass. At low or high pH values, Cr (VI) uptake is significantly reduced. In addition, the initial rate of total chromium uptake is also enhanced by higher biomass concentrations and the presence of glucose. The results obtained through this investigation indicate the possibility of treating waste effluents containing hexavalent chromium using Aspergillus foetidus.     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

Novel pilot-scale washing process and equipment for removing Cr(VI) from contaminated soil

In this study, a novel horizontal rotating soil washing process and equipment were developed and tested for pilot-scale remediation of soils from a site polluted by chromium ore process residue. Operating parameters, including cylinder rotational velocity, cylinder tilt angle, heating temperature and liquid/soil ratio, were investigated. The Taguchi method was used for the experiment design, and the standard L16 orthogonal array with four parameters and four levels was selected for optimising the operating parameters. Optimal removal efficiency was achieved at cylinder rotational velocity of 2.5 rpm, cylinder tilt angle of 2.6°, heating temperature of 200 °C and liquid/soil ratio of 8. The efficiency of citric acid as an extractant in the novel process was compared with that of water. The analysis of the residual Cr(VI) concentration of the soil shows that citric acid could efficiently remove 22.89 % more Cr(VI) than water in one-stage washing. The residual Cr(VI) concentration in the soil after the three-stage washing is as low as 26.16 mg/kg, which meets the screening levels for soil environmental risk assessment of sites in Beijing City (30 mg/kg). Further study is currently underway to optimise the novel process and equipment for commercial-scale use.     

Cr(VI) reduction in aqueous solutions by using copper smelter slag

The ability of Copper Smelter Slag (CSS) to reduce Cr(VI) in aqueous solutions has been investigated. The extent of reduction is dependent on the amounts of acid and reductant, contact time, Cr(VI) concentration, temperature of the solution and particle size of CSS. The amount of acid is the most important variable affecting the reduction process. When twice the amount of acid required with respect to Cr(VI) was used, Cr(VI) in 100 ml solution (100 mg/l) was completely reduced in a contact period less than 5 min by a 10 g/l dosage of CSS. Reduction efficiency increased with increase in temperature of solution, showing that the process is endothermic. Reduced chromium, and iron and other metals dissolved from CSS were effectively precipitated by using NaOH or calcinated carbonatation sludge from sugar plant.     

Optimizing Cr(VI) adsorption on activated carbon produced from heavy oil fly ash

In order to explore the beneficial utilization of heavy oil fly ash (HOFA) generated in the power plants, the present study is intended to optimize the chromium(VI) [Cr(VI)] adsorption on activated carbon produced from HOFA. The raw HOFA obtained from a power plant was washed by nitric/hydrochloric acid and activated at 800 °C with a holding time of 60 min to produce fly ash activated carbon (FAC). Phosphoric acid was used as a chemical agent to improve the surface characteristics of the HOFA during the activation process. Batch adsorption experiments were employed to evaluate the effects of different parameters such as initial Cr(VI) concentration, pH, and FAC dose on the removal of Cr(VI) from aqueous solution. A total of 17 adsorption experimental runs were carried out employing the detailed conditions followed the response surface methodology based on the Box–Behnken design. The results indicate that developed FAC has the potential for removing Cr(VI) from wastewater. Under the test conditions, a maximum of 91.51 % Cr(VI) removal efficiency was achieved.     

Evaluation of leaching and extraction procedures for soil and waste

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.     

Assessing the potential of using phytoremediation for pyrene‐contaminated soils

Forage crop species representing two biologically distinct families (legumes and grasses) were evaluated on soil spiked with 100 mg/kg of pyrene to determine the potential effectiveness of the rhizospheres of these plants for phytoremediation. In this experiment, pyrene dissipation could not be attributed to the presence of plants. Pyrene dissipation was also not related to rhizosphere biological activity, such as microbial counts and enzyme activity. Planting with reed canarygrass and switchgrass significantly increased the microbial counts in soil; however, the differences in the microbial counts were not correlated to the levels of pyrene dissipation. Reed canarygrass rhizosphere had significantly higher dehydrogenase activity compared to the switchgrass rhizosphere, but this difference in soil dehydrogenase activity was not related to pyrene dissipation. In general, the use of plants was not effective in causing pyrene transformation; however, the presence of vegetation on polycyclic aromatic hydrocarbon–contaminated soils could play a significant role in limiting the spread of contaminants (erosion, leaching) and enhancing ecosystem restoration. © 2004 Wiley Periodicals, Inc.     

Potential Remobilization of Toxic Anions during Reduction of Arsenated and Chromated Schwertmannite by the Dissimilatory Fe(III)-Reducing Bacterium Acidiphilium cryptum JF-5

Schwertmannite, an iron(III)-oxyhydroxysulfate formed in acidic mining-impacted stream or lake waters often contaminated with toxic elements like arsenate or chromate, is able to incorporate high amounts of these oxyanions. Detoxification of the water might be achieved if precipitated arsenated or chromated schwertmannite is fixed in the sediment. However, under reduced conditions, reductive dissolution of iron oxides mediated by the activity of Fe(III)-reducing bacteria might mobilize arsenate and chromate again. In this study, the reduction of synthesized arsenated or chromated schwertmannite by the acidophilic Fe(III)-reducer Acidiphilium cryptum JF-5, isolated from an acidic mining-impacted sediment, was investigated. In TSB medium at pH 2.7 with glucose as electron donor, A. cryptum JF-5 reduced about 10% of the total Fe(III) present in pure synthetic schwertmannite but only 5% of Fe(III) present in arsenated schwertmannite. In contrast to sulfate that was released during the reductive dissolution of pure schwertmannite, arsenate was not released during the reduction of arsenated schwertmannite probably due to the high surface complexation constant of arsenate and Fe(III). In medium containing chromated schwertmannite, no Fe(II) was formed, and no glucose was consumed indicating that chromate might have been toxic to cells of A. cryptum JF-5. Both As(V) or Cr(VI) could not be utilized as electron acceptor by A. cryptum JF-5. A comparison between autoclaved (121 °C for 20 min) and non-autoclaved schwertmannite samples demonstrated that nearly 100%of the bound sulfate was released during heating, and FTIR spectra indicated a transformation of schwertmannite to goethite. This structural change was not observed with autoclaved arsenated or chromated schwertmannite. These results suggest that the mobility of arsenate and chromate is not enhanced by the activity of acidophilic Fe(III)-reducing bacteria in mining-impacted sediments. In contrast, the presence of bound arsenate and chromate seemed to stabilize schwertmannite against reductive dissolution and its further transformation to goethite that is an ongoing process in those sediments.     

Mineralogy and pore water chemistry of a boiler ash from a MSW fluidized-bed incinerator

This paper presents an investigation of the mineralogy and pore water chemistry of a boiler ash sampled from a municipal solid waste fluidized-bed incinerator, subject to 18 months of dynamic leaching in a large percolation column experiment. A particular focus is on the redox behaviour of Cr(VI) in relation to metal aluminium Al⁰, as chromium may represent an environmental or health hazard. The leaching behaviour and interaction between Cr(VI) and Al⁰ are interpreted on the basis of mineralogical evolutions observed over the 18-month period and of saturation indices calculated with the geochemical code PhreeqC and reviewed thermodynamic data. Results of mineralogical analyses show in particular the alteration of mineral phases during leaching (e.g. quartz and metal aluminium grains), while geochemical calculations suggest equilibria of percolating fluids with respect to specific mineral phases (e.g. monohydrocalcite and aluminium hydroxide). The combination of leaching data on a large scale and mineralogical analyses document the coupled leaching behaviour of aluminium and chromium, with chromium appearing in the pore fluids in its hexavalent and mobile state once metal aluminium is no longer available for chromium reduction.     

Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.     

Thermal valorization of footwear leather wastes in bubbling fluidized bed combustion

Transformation of hide (animal skins) into leather is a complicated process during which significant amounts of wastes are generated. Footwear is the sector that consumes the major part of leather (60%). Logically, this industry is producing the largest quantity of leather wastes. The objective of this work was to demonstrate the technical feasibility of fluidized bed technology to recover the energy from burning footwear leather wastes. Considering the characteristics of leather waste, especially the heating value (12.5-21 MJ/kg), it can be considered a fairly good fuel. Moreover, leather waste has suitable characteristics for combustion, e.g., high volatile matter (76.5%) and low ash content (5.2%). Two factors deserve special attention: N3O and NOx emissions as a consequence of its unusual high nitrogen content (14.1%) and the chromium speciation because chromium is the main element of ash (3.2%) due to its use in leather tanning. A series of experiments has been carried out in a 0.1 MWt bubbling fluidized bed pilot plant. The combustion efficiency, flue gas composition and chromium speciation were investigated. Despite having high nitrogen content, a low conversion rate of fuel-N to NOx and N2O was attained. Chromium was concentrated in the solid streams and it was consistently found as Cr(III+); no presence of Cr(VI+) was detected.     

Using Design-Expert to Optimize the Properties of a Polyethersulfone Ultrafiltration Membrane Through the Incorporation of NH2-MIL-53(Fe) and PVP for Maximum Cr(VI) Removal and Flux

Journal of Polymers and the Environment - In this study, an NH2-MIL-53(Fe) functionalized membrane was fabricated for Cr(VI) removal from contaminated groundwater. Design-Expert was employed to...     

Removal of Cr(VI) Ions from Aqueous Solutions Using Poly 3-Methyl Thiophene Conducting Electroactive Polymers

This paper deals with a new application of poly 3-methyl thiophene synthesized chemically onto sawdust (termed as P3MTh/SD) as an effective adsorbent for removal of Cr(VI) ions from aqueous solutions using column system. Chemical synthesis of poly 3-methyl thiophene was performed by addition of ferric chloride (in chloroform) as oxidant to sawdust which had previously been soaked in monomer solution. All the sorption experiments were conducted using dynamic or column system at room temperature. The effect of important parameters such as pH and initial concentration on uptake of Cr(VI) was investigated. In order to find out the possibility of the regeneration and reuse of the exhausted adsorbent, desorption studies were also performed. The currently introduced adsorbent was found to be an efficient adsorbent for removal of highly toxic and hazardous Cr(VI) ions from aqueous solutions. As our breakthrough analysis has indicated, each gram of P3MTh/SD is able to remove more than 95% of Cr(VI)ions from 300 mL of Cr(VI) polluted solution with the initial concentration of 25 mg L⁻¹ in column system. Sorption/desorption of Cr(VI) ions was found to be a highly pH dependent processes.     

Bioremediation of Chromate by Sulfate-Reducing Bacteria, Cytochromes c3 and hydrogenases

The treatment of soils and ground waters polluted by heavy metals is of economical and environmental interest. Reduction of Cr(VI) to the less toxic Cr(III) associated to its precipitation is a potentially useful process for bioremediation. In order to develop ecological processes using micro-organisms, we have compared various sulfate-reducing bacteria for enzymatic reduction of chromate. The best Cr(VI) reductase activity was obtained with Desulfomicrobium norvegicum. Despite morphological changes induced by the presence of chromate, this strain can grow in the presence of up to 500 M Cr(VI) and can decontaminate waters polluted by Cr(VI) when seeded in bioreactors. We have demonstrated the ability of several metalloenzymes (cytochromes c ₃ and hydrogenases) to reduce chromate. Biophysical investigations of the chromate/protein interaction in order to get further informations on the mechanism of metal reduction by cytochromes c ₃ are under the way.