Horticulture, Environment, and Biotechnology : HEB
/
v.59
no.6
/
pp.775-786
/
2018
To test the hypothesis that humic acid (HA), anaerobically digested pig slurry filtrate (APS), and their combination would differently affect the chemical speciation and extractability of metals (cadmium, copper, and zinc) and their uptake by plants, we conducted a pot experiment using wormwood in two texturally contrasting soils (sandy loam and clay loam) collected from a field near an abandoned Cu mine. Four treatments were laid out: HA at $ 23.5g\;kg^{-1}$ (HA), APS at $330mL\;kg^{-1}$ (APS), HA at $ 23.5g\;kg^{-1}$ and APS at $330mL\;kg^{-1}$ (HA + APS), and a control. Each treatment affected the chemical speciation and mobility of the metals, and thereby resulting in variable patterns of plant biomass yield and metal uptake. The APS supported plant growth by increasing nutrient availability. HA supported or hindered plant growth by impacting the soil's water and nutrient retention capacity and aeration, in a soil texture-dependent manner, while consistently enhancing the immobilization of heavy metals. Temporal increases in whole-plant dry matter yield and metal accumulation suggested that the plants were capable of metal hyperaccumulation. The results were discussed in terms of the mobility of metals and plant growth and corroborated by the $^{15}N$ recovery of soil- and plant-N pools under H and HS treatments. Therefore, for effective phytoremediation of polluted soils, an appropriate combination of plant growth promoters (APS) and chelating agents (HA) should be predetermined at the site where chemical stabilization of pollutants is desired.
The mixing treatment process using lime (CaO) and limestone ($CaCO_3$) as the immobilization amendments was applied for heavy metal contaminated filmland soils around Goro abandoned Zn-mine, Korea in the batch and pilot scale continuous column experiments. For the batch experiments, with the addition of 0.5 wt.% commercialized lime or limestone, leaching concentrations of As, Cd, Pb, and Zn from the contaminated filmland soil decreased by 70, 77, 94, and 95 %, respectively, compared to those without amendments. For the continuous pilot scale column experiments, the acryl column (30 cm in length and 20 cm in diameter) was designed and granulated lime and limestone were used. From the results of column experiments, with only 2 wt.% of granulated lime, As, Cd, and Zn leaching concentrations decreased by 63%, 97%, and 98%, respectively. With 2 wt.% of granulated limestone, As leaching concentration reduced from 135.6 to 30.2 ${\mu}g/L$ within 5 months and maintained mostly below 10 ${\mu}g/L$, representing that more than 46% diminution of leaching concentration compared to that without the amendment mixing. For Cd and Zn, their leaching concentrations with only 2 wt.% of limestone mixing decreased by 97%, respectively compared to that without amendment mixing, suggesting that the capability of limestone to immobilize heavy metals in the filmland soil was outstanding and similar to that of lime. From the column experiments, it was investigated that if the efficiency of limestone to immobilize heavy metals from the soil was similar to that of lime, the limestone could be more available to immobilize heavy metals from the soil than lime because of low pH increase and thus less harmful side effect.
ACKGROUND: Cadmium (Cd) has long been recognized as one of most toxic elements. Application of organic amendments and phosphate fertilizers can decrease the bioavailability of heavy metals in contaminated soil. METHODS AND RESULTS: This study was conducted to evaluate effect of combined application of phosphate fertilizer and manure in reducing cadmium phytoavailability in heavy metal contaminated soil. Phosphate fertilizers [Fused and super phosphate (FSP) and $K_2HPO_4$ (DPP)] and manure (M) were applied as single application (FSP, DPP, and M) to combined application (FSP+M and DPP+M) before radish seeding. $K_2HPO_4$ decreased $NH_4OAc$ extractable Cd and plant Cd concentration, mainly due to increases in soil pH and negative charge. However, FSP increased $NH_4OAc$ extractable Cd and plant Cd concentration. Manure significantly increased soil pH and negative charge. Combined application of phosphate fertilizer and manure were much more effective in reducing Cd phytoavailability than a simple application of each component. Calculated solubility diagram indicated that Cd concentrations in the solution of soils amended with phosphate fertilizers and manure were undersaturated with respect to all potential Cd minerals [$Cd_3(PO_4)_2$, $CdCO_3$, $Cd(OH)_2$, and $CdHPO_4$]. Plant Cd concentration and $NH_4OAc$ extractable Cd were negatively related to soil pH and negative charge. CONCLUSION: Alleviation of Cd phytoavailability with phosphate fertilizer and manure can be attributed primarily to Cd immobilization due to the increase in soil pH and negative charge rather than Cd and phosphate precipitation. Therefore, combined application of alkaline phosphate materials and manure is effective for reducing Cd phytoavailability.
As 3D printing technology is used in the medical field, interest in metal materials is increasing. The Department of Radiation Oncology uses a shielding block to shield the patient's normal tissue from unnecessary exposure during electron beam therapy. However, problems such as handling of heavy metal materials such as lead and cadmium, reproducibility according to skill level and uncertainty of arrangement have been reported. In this study, candidate materials that can be used for metal 3D printing are selected, and the physical properties and radiation dose of each material are analyzed to develop a customized shielding block that can be used in electron beam therapy. As candidate materials, aluminum alloy (d = 2.68 g/cm3), titanium alloy (d = 4.42 g/cm3), and cobalt chromium alloy (d = 8.3 g/cm3) were selected. The thickness of the 95% shielding rate point was derived using the Monte Carlo Simulation with the irradiation surface and 6, 9, 12, and 16 energies. As a result of the simulation, among the metal 3D printing materials, cobalt chromium alloy (d = 8.3 g/cm3) was similar to the existing shielding block (d = 9.4 g/cm3) in shielding thickness for each energy. In a follow-on study, it is necessary to evaluate the usefulness in clinical practice using customized shielding blocks made by metal 3D printing and to verify experiments through various radiation treatment plan conditions.
The objective of this study was to understand the physiological response and cadmium accumulation of MuS1 transgenic tobacco exposed to high concentration of Cd in soil. For this, a pot experiment was carried out in a greenhouse for a month, with two lines of MuS1 transgenic tobaccos (S4 and S6) and non-transgenic tobacco cultivated in the soils spiked at three different Cd concentrations (0, 60 and 180 mg $kg^{-1}$). Both transgenic and non-transgenic tobacco showed visible toxic symptoms such as chlorosis and leaf roll as treated concentration increased. The net photosynthetic rates of MuS1 plants (S4 and S6) exposed at 180 mg $kg^{-1}$ Cd were 6.3 and $7.7{\mu}mol\;m^{-2}s^{-1}$, being higher than those of the non-transgenic plant ($4.8{\mu}mol\;m^{-2}s^{-1}$). Values of stomatal conductance of MuS1 transgenic plants (0.05 and 0.008 mmol $H_2O\;m^{-2}s^{-1}$) were also higher than those of non-transgenic plant (0.03 mmol $H_2O\;m^{-2}s^{-1}$). In addition, fresh and dry weights of MuS1 transgenic plants were heavier than those of non-transgenic plant. Likewise, MuS1 transgenic plants appeared to be better physiological performance than non-transgenic tobacco when exposed at high concentration of Cd in soil. With regard to metal accumulation, MuS1 transgenic tobaccos accumulated more Cd in their roots than non-transgenic tobacco implying that MuS1 transgenic tobacco is suggested to be used for phytostabilization of heavy metals.
Alginate, a well-known biopolymer, is universally applied for immobilization of microbial cells. Biosorption characteristics of lead by waste biomass of immobilized A. niger beads, used in fermentation industries to produce citric acid, were studied. The immobilized A. niger beads, prepared via capillary extrusion method using calcium chloride, were applied in the removal of lead. Pb uptake was the highest in A. niger beads cells grown for 3 days with medium producing citric acid (12% sucrose, 0.5% $NH_4NO_3$, 0.1% $KH_2PO_4$, and 0.025% $MgSO_4$). Lead uptake by the immobilized A. niger beads and free A. niger mycellia beads increased sharply with time. However, while uptake by the immobilized A. niger beads continued to increase slowly, that by free A. niger mycellia beads stopped after 30 min. The optimum pH and temperature of lead uptake were found to be 6 and $35^{\circ}C$, respectively. The maximum uptake of lead was achieved with $50{\sim}100$ beads and 50 ml lead solution in a 250-ml Erlenmeyer flask, while, at over 100 beads, uptake of the lead decreased. The order of biosorption capacity for heavy metals was Pb>Cu>Cd. Pb uptake capacity of the immobilized A. niger beads treated with 0.1 M $CaCI_2$, 0.1 M NaOH, and 0.1 M KOH decreased compared to the untreated beads. On testing the desorption of Pb from the immobilized A. niger beads, re-uptake of Pb was found possible after desorption of the binding metal with 0.1 M HCI.
BACKGROUND: To determine effect of phosphate (P) application on Cadmium (Cd) extractability and its uptake by rice plant in Cd contaminated paddy soil, dipotassium ($K_2HPO_4$) which was the most effective of P materials to decrease Cd extractability in previous study was selected as P fertilizer. METHODS AND RESULTS: Dipotassium phosphate was applied at the rates of 0, 78, 234, and 390 kg $P_2O_5/ha$, and then rice was cultivated in submerged paddy soil from Jun. to Oct. in 2015. Cadmium concentrations in grain, straw, and root of rice plant decreased significantly with increasing application rate of $K_2HPO_4$. The trend of 1 M $NH_4OAc$ extractable Cd concentration in soil was similar to that of Cd uptake by rice plant. One M $NH_4OAc$ extractable Cd concentration was negatively related to soil pH and negative charge. Alleviation of Cd phytoavailability of rice in paddy soil might be attributed to increase in pH and negative charge of soil. Using a quadratic response model, amount of grain yield were related to $K_2HPO_4$ application rates as Grain yield = $5.38+2.39{\times}10^{-3}K_2HPO_4-6.65{\times}10^{-6}K_2HPO{_4}^2$ (model $R^2=0.968$). Using this equations, the greatest grain yield (5.6 Mg/ha) was at the rate of 180 kg $P_2O_5/ha$. At this application rate of P, the Cd concentration in grain was 0.53 mg/kg, implying ca. 23% lower than the control. CONCLUSION: From the view point of heavy metal safety and crop productivity, it might be good P management to apply P fertilizer with 4 times higher rate than recommendation (45 kg/ha).
The stabilization using limestone ($CaCO_3$) and steel making slag as the immobilization amendments for Cu and Pb contaminated farmland soils was investigated by batch tests, continuous column experiments and the pilot scale feasibility study with 4 testing grounds at the contaminated site. From the results of batch experiment, the amendment with the mixture of 3% of limestone and 2% of steel making slag reduced more than 85% of Cu and Pb compared with the soil without amendment. The acryl column (1 m in length and 15 cm in diameter) equipped with valves, tubes and a sprinkler was used for the continuous column experiments. Without the amendment, the Pb concentration of the leachate from the column maintained higher than 0.1 mg/L (groundwater tolerance limit). However, the amendment with 3% limestone and 2% steel making slag reduced more than 60% of Pb leaching concentration within 1 year and the Pb concentration of leachate maintained below 0.04 mg/L. For the testing ground without the amendment, the Pb and Cu concentrations of soil water after 60 days incubation were 0.38 mg/L and 0.69 mg/l, respectively, suggesting that the continuous leaching of Cu and Pb may occur from the site. For the testing ground amended with mixture of 3% of limestone + 2% of steel making slag, no water soluble Pb and Cu were detected after 20 days incubation. For all testing grounds, the ratio of Pb and Cu transfer to plant showed as following: root > leaves(including stem) > rice grain. The amendment with limestone and steel making slag reduced more than 75% Pb and Cu transfer to plant comparing with no amendment. The results of this study showed that the amendment with mixture of limestone and steel making slag decreases not only the leaching of heavy metals but also the plant transfer from the soil.
This study aimed to fundamentally understand structural changes of zeolite under pressure and in the presence of different pressure-transmitting media (PTM) for application studies such as immobilization of heavy metal cation or CO2 storage using pressure. High-pressure X-ray powder diffraction study was conducted on the zeolite-W (K6.4Al6.5Si25.8O64× 15.3H2O, K-MER) to understand linear compressibility and the bulk moduli in different PTM conditions. Zeolite-w is a synthetic material having the same framework as natural zeolite merlinoite ((K, Ca0.5, Ba0.5, Na)10 Al10Si22O64× 22H2O). The space group of the sample was identified as I4/mmm belonging to the tetragonal crystal system. Water, carbon dioxide, and silicone-oil were used as pressure-transmitting media. The mixture of sample and each PTM was mounted in a diamond anvil cell (DAC) and then pressurized up to 3 GPa with an increment of ca. 0.5 GPa. Pressure-induced changes of powder diffraction patterns were measured using a synchrotron X-ray light source. Lattice constants, and bulk moduli were calculated using the Le-Bail method and the Birch-Murnaghan equation. In all PTM conditions, linear compressibility of c-axis (𝛽c) was 0.006(1) GPa-1 or 0.007(1) GPa-1. On the other hand, the linear compressibility of a(b)-axis (𝛽a) was 0.013(1) GPa-1 in silicone-oil run, which is twice more compressible than the a(b)-axis in water and carbon dioxide runs, 𝛽a = 0.006(1) GPa-1. The bulk moduli were measured as 50(3) GPa, 52(3) GPa, and 29(2) GPa in water, carbon dioxide, and silicone-oil run, respectively. The orthorhombicities of ac-plane in the water, and carbon dioxide runs were comparatively constant, near 0.350~0.353, whereas the value decreased abruptly in the silicone-oil run following formula, y = -0.005(1)x + 0.351(1) by non-penetrating pressure fluid condition.
This study aimed to fundamentally understand changes of cell parameters of cation-exchanged mordenites using high resolution X-ray powder diffraction for studies that immobilization of various heavy metal cation using synthesis mordenite (Na6.6Al6.6Si41.4O96·20.4H2O, Na-MOR). As a results of measurement by Thermogravimetric analysis (TGA), it was confirmed that 19.4, 20.4 water molecules per unit cell were present in monovalent-cation substituted MOR (Cs-MOR, Na-MOR), and 21, 23.1, 23.2 water molecules per unit cell were present in divalent-cation substituted MOR (Pb-MOR, Sr-MOR, Cd-MOR). The space group of all the samples were identified as Cmcm belonging to the orthorhombic crystal system. Compared to Na-MOR, starting material, relative peak intensity of (110) and (200) is significantly changed after cation substitution whereas peak position is almost similar. Also, (220) peak that was not found in Na-MOR was clearly observed in Pb-, Cd- and Sr-exchanged MOR. Thus, it was estimated that changes of atomic distribution usually occurred on ab-plane while changes of cell parameters were little. Detailed changes in the cell parameters of cation-exchanged mordenites were derived from whole profile fitting method using the GSAS suite program. Changes in the axial lengths and unit cell volume of cation substitution showed different relationship depending on ionic radius and charge number. In case of monovalent-cation substituted MOR, the length of a-axis increases whereas the length of b- and c-axis decrease by absorbed cation radius. In the case of divalent-cation exchanged MOR, the length of a-axis usually decreases while the length of b- and c-axis increases by cation radius. It was confirmed that unit cell volume of monovalent and divalent cation substituted MORs had an independent tendency by cation radius.
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