Leaching mechanisms of Cr(VI) from chromite ore processing residue

Batch leaching tests, qualitative and quantitative x-ray powder diffraction (XRPD) analyses, and geochemical modeling were used to investigate the leaching mechanisms of Cr(VI) from chromite ore processing residue (COPR) samples obtained from an urban area in Hudson County, New Jersey. The pH of the leaching solutions was adjusted to cover a wide range between 1 and 12.5. The concentration levels for total chromium (Cr) and Cr(VI) in the leaching solutions were virtually identical for pH values >5. For pH values <5, the concentration of total Cr exceeded that of Cr(VI) with the difference between the two attributed to Cr(III). Geochemical modeling results indicated that the solubility of Cr(VI) is controlled by Cr(VI)-hydrocalumite and Cr(VI)-ettringite at pH >10.5 and by adsorption at pH <8. However, experimental results suggested that Cr(VI) solubility is controlled partially by Cr(VI)-hydrocalumite at pH >10.5 and by hydrotalcites at pH >8 in addition to adsorption of anionic chromate species onto inherently present metal oxides and hydroxides at pH <8. As pH decreased to <10, most of the Cr(VI) bearing minerals become unstable and their dissolution contributes to the increase in Cr(VI) concentration in the leachate solution. At low pH ( <1.5), Cr(III) solid phases and the oxides responsible for Cr(VI) adsorption dissolve and release Cr(III) and Cr(VI) into solution.     

Heavy metal immobilization in soil near abandoned mines using eggshell waste and rapeseed residue

Heavy metal contamination of agricultural soils has received great concern due to potential risk to human health. Cadmium and Pb are largely released from abandoned or closed mines in Korea, resulting in soil contamination. The objective of this study was to evaluate the effects of eggshell waste in combination with the conventional nitrogen, phosphorous, and potassium fertilizer (also known as NPK fertilizer) or the rapeseed residue on immobilization of Cd and Pb in the rice paddy soil. Cadmium and Pb extractabilities were tested using two methods of (1) the toxicity characteristics leaching procedure (TCLP) and (2) the 0.1 M HCl extraction. With 5 % eggshell addition, the values of soil pH were increased from 6.33 and 6.51 to 8.15 and 8.04 in combination with NPK fertilizer and rapeseed residue, respectively, compared to no eggshell addition. The increase in soil pH may contribute to heavy metal immobilization by altering heavy metals into more stable in soils. Concentrations of TCLP-extracted Cd and Pb were reduced by up to 67.9 and 93.2 % by addition of 5 % eggshell compared to control. For 0.1 M HCl extraction method, the concentration of 0.1 M HCl-Cd in soils treated with NPK fertilizer and rapeseed residue was significantly reduced by up to 34.01 and 46.1 %, respectively, with 5 % eggshell addition compared to control. A decrease in acid phosphatase activity and an increase in alkaline phosphatase activity at high soil pH were also observed. Combined application of eggshell waste and rapeseed residue can be cost-effective and beneficial way to remediate the soil contaminated with heavy metals.     

Characterizing As(III,V) adsorption by soils surrounding ash disposal facilities

Leachate derived from unlined coal ash disposal facilities is a potential anthropogenic source of arsenic to the environment. To establish a theoretical framework for predicting attenuation of arsenic by soils subject to ash landfill leachate, which is typically enriched in calcium and sulfate, the adsorption of As(V) and As(III) was characterized from 1 mM CaSO₄ for 18 soils obtained down-gradient from three ash landfill sites and representing a wide range in soil properties. As(V) consistently exhibited an order of magnitude greater adsorption than As(III). As(V) adsorption was best described by coupling pH with 15 s DCB-Fe (R² = 0.851,  = 0.001), although pH coupled to clay, DCB-Fe, or DCB-Al also generated strong correlations. For As(III), pH coupled to Ox–Fe (R² = 0.725,  = 0.001) or Ox–Fe/Al (R² = 0.771,  = 0.001) provided the best predictive relationships. Ca²⁺ induced increases in As(V) adsorption whereas sulfate suppressed both As(V) and As(III) adsorption. Attenuation of arsenic from ash leachate agreed well with adsorption measured from 1 mM CaSO₄ suggesting that the use of 1 mM CaSO₄ in laboratory adsorption tests is a reasonable approach for estimating arsenic behavior in soils surrounding ash landfills. We also showed that the impact of leachate-induced changes in soil pH over time may not be significant for As(V) adsorption at pH < 7; however, As(III) adsorption may be impacted over a wider pH range especially if phyllosilicate clays contribute significantly to adsorption. The benefits and limitations of predicting arsenic mobility using linearized adsorption coefficients estimated from nonlinear adsorption isotherms or from the relationships generated in this study are also discussed.     

Summer cover crops reduce atrazine leaching to shallow groundwater in southern Florida

At Florida's southeastern tip, sweet corn (Zea Mays) is grown commercially during winter months. Most fields are treated with atrazine (6-chloro-N-ethyl-N'-[1-methylethyl]-1,3,5-triazine-2,4-diamine). Hydrogeologic conditions indicate a potential for shallow groundwater contamination. This was investigated by measuring the parent compound and three degradates--DEA (6-chloro-N-[1-methylethyl]-1,3,5-triazine-2,4-diamine), DIA (6-chloro-N-ethyl)-1,3,5-triazine-2,4-diamine, and HA (6-hydroxy-N-[1-methylethyl]-1,3,5-triazine-2,4-diamine)--in water samples collected beneath sweet corn plots treated annually with the herbicide. During the study, a potential mitigation measure (i.e., the use of a cover crop, Sunn Hemp [Crotalaria juncea L.], during summer fallow periods followed by chopping and turning the crop into soil before planting the next crop) was evaluated. Over 3.5 yr and production of four corn crops, groundwater monitoring indicated leaching of atrazine, DIA, and DEA, with DEA accounting for more than half of all residues in most samples. Predominance of DEA, which increased after the second atrazine application, was interpreted as an indication of rapid and extensive atrazine degradation in soil and indicated that an adapted community of atrazine degrading organisms had developed. A companion laboratory study found a sixfold increase in atrazine degradation rate in soil after three applications. Groundwater data also revealed that atrazine and degradates concentrations were significantly lower in samples collected beneath cover crop plots when compared with concentrations below fallow plots. Together, these findings demonstrated a relatively small although potentially significant risk for leaching of atrazine and its dealkylated degradates to groundwater and that the use of a cover crop like Sunn Hemp during summer months may be an effective mitigation measure.     

Influence of a soil enzyme on iron-cyanide complex speciation and mineral adsorption

Cyanide is commonly found as ferrocyanide [Fe(II)(CN)(6)](-4) and in the more mobile form, ferricyanide [Fe(III)(CN)(6)](-3) in contaminated soils and sediments. Although soil minerals may influence ferrocyanide speciation, and thus mobility, the possible influence of soil enzymes has not been examined. In a series of experiments conducted under a range of soil-like conditions, laccase, a phenoloxidase enzyme derived from the fungi Trametes versicolor, was found to exert a large influence on iron-cyanide speciation and mobility. In the presence of laccase, up to 93% of ferrocyanide (36-362ppm) was oxidized to ferricyanide within 4h. No significant effect of pH (3.6 and 6.2) or initial ferrocyanide concentration on the extent or rate of oxidation was found and ferrocyanide oxidation did not occur in the absence of laccase. Relative to iron-cyanide-mineral systems without laccase, ferrocyanide adsorption to aluminum hydroxide and montmorillonite decreased in the presence of laccase and was similar to or somewhat greater than that of ferricyanide without laccase. Laccase-catalyzed conversion of ferrocyanide to ferricyanide was extensive though up to 33% of the enzyme was mineral-bound. These results demonstrate that soil enzymes can play a major role in ferrocyanide speciation and mobility. Biotic soil components must be considered as highly effective oxidation catalysts that may alter the mobility of metals and metal complexes in soil. Immobilized enzymes should also be considered for use in soil metal remediation efforts.     

Highly siliceous MCM-48 from rice husk ash for CO2 adsorption

Mesoporous MCM-48 silica was synthesized using a cationic-neutral surfactant mixture as the structure-directing template and rice husk ash (RHA) as the silica source. The MCM-48 samples were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N₂ physisorption and SEM. X-ray diffraction pattern of the resulting MCM-48 revealed typical pattern of cubic Ia3d mesophase. BET results showed the MCM-48 to have a surface area of 1024 m²/g and FT-IR revealed a silanol functional group at about 3460 cm⁻¹. Breakthrough experiments in the presence of MCM-48 were also carried out to test the material's CO₂ adsorption capacity. The breakthrough time for CO₂ was found to decrease as the temperature increased from 298 K to 348 K. The steep slopes observed shows the CO₂ adsorption occurred very quickly, with only a minimal mass transfer effect and very fast kinetics. In addition, amine grafted MCM-48, APTS-MCM-48 (RHA), was prepared with the 3-aminopropyltriethoxysilane (APTS) to investigate the effect of amine functional group in CO₂ separation. An order of magnitude higher CO₂ adsorption capacity was obtained in the presence of APTS-MCM-48 (RHA) compared to that with MCM-48 (RHA). These results suggest that MCM-48 synthesized from rice husk ash could be usefully applied for CO₂ removal.     

A numerical simulation model of cyclic hardening behavior of AC4C-T6 for LNG cargo pump using finite element analysis

This paper is concerned with the evaluation of cyclic hardening models within the stress–strain behavior of aluminum alloy AC4C-T6 that can be used to LNG cargo pump operating in cryogenic temperature. To insure the strength assessment of LNG cargo pump, material model of cyclic hardening and plasticity for aluminum alloy AC4C-T6 is investigated through FEA (Finite Element Analysis) with various hardening options including linear and non-linear hardening, isotropic and kinematic hardening, and combined hardening model. Monotonic tensile and cyclic tensile experiments for AC4C-T6 alloy were performed at room temperature and temperature of ?165 °C. Parameters of each hardening model are obtained from the experimental data; thus five hardening models are numerically simulated thereafter. Appropriate hardening models which describe the cyclic stress–strain relationship are investigated through the simulations of cyclic hardening behavior by FEA. In order to verify the predicted behavior of cyclic hardening obtained by FEA, the results of FEA and those measured by experiments are compared.