Soil science
Z. Movahedi Rad; M. Hamidpour; A. Tajabadipour
Abstract
Introduction
Recently, layered double hydroxides (LDHs) with a unique structure and unbeatable characteristics have been widely studied and investigated in various fields. One of these fields is the investigating the potential of these compounds to supply essential nutrients for plants. Several studies ...
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Introduction
Recently, layered double hydroxides (LDHs) with a unique structure and unbeatable characteristics have been widely studied and investigated in various fields. One of these fields is the investigating the potential of these compounds to supply essential nutrients for plants. Several studies have reported the application of LDHs as fertilizers for macronutrients and micronutrients. These compounds have a very high potential as fertilizers and can increase agricultural productivity. Micronutrients such as Zn, Cu and Mn can be structurally incorporated in the metal hydroxide layer. According to recent research, LDHs have shown a suitable potential to release micronutrients. However, more studies are needed to enhance our understanding of the mechanism and reaction of layered double hydroxides in different conditions. Although various studies have explored the potential of LDHs as slow-release fertilizers, our research focuses on the role of citric acid and tartaric acid and as well as the ratio of divalent to trivalent cations on the kinetics of Zn, Mn and Mg release from Mg-Zn-Mn-Al-LDH intercalated with nitrate.
Materials and Methods
All chemicals used in this study including citric acid (C6H8O7.H2O), tartaric acid (C4H6O6) KCl, Zn (NO3)2.6H2O, Mn(NO3)2.4H2O Mg(NO3)2.6H2O and Al(NO3).9H2O were of analytical grades, purchased from Chem-Lab or Merck Chemical Corporations. Solutions were prepared using decarbonated ultrapure water (electrical resistivity = 18 MΩcm). The LDHs were synthesized by co-precipitation method at constant pH = 9.2-9.6. Two types of LDHs were synthesized by varying the M+2(Zn+Mn+Mg)/M+3(Al) ratios of 3:1 and 4:1 in the precursor solution while stirring vigorously in a nitrogen atmosphere. The pH was kept at 9.2-9.6 by adding volumes of 3 M NaOH. The LDH crystals were allowed to ripen in the mixture for 2 hours, after which the precipitates were centrifuged at 3000 rpm for 20 min and washed several times with distilled water and placed in an oven at 70°C for 8 hours to dry.
The chemical composition of the synthesized layered double hydroxides (LDHs) was analyzed using furnace atomic absorption spectrophotometry (SavantAA, GBC) following acid digestion. The physical, chemical, and morphological characteristics of the LDHs were assessed through several techniques, including X-ray diffraction (Panalytical X Pert Pro X-ray diffractometer), field emission scanning electron microscopy (FE-SEM, Sigma VP), Fourier-transform infrared spectroscopy (FT-IR, Nicolet iS10 spectrometer), and Brunauer-Emmett-Teller (BET, BELSORP Mini II) analysis.
A batch study was conducted to evaluate the effects of varying M²⁺/M³⁺ ratios in LDHs and the influence of citric acid and tartaric acid on the release of Zn, Mn, and Mg from LDH (3:1) and LDH (4:1). In brief, 0.01 g of synthesized LDH was placed in a centrifuge tube and mixed with 10 ml of background electrolyte (0.01 M KCl) and 1.25 mM of citric acid or tartaric acid, maintaining an initial pH of 6–7 at a constant temperature of 25 ± 0.5 °C. Blank samples (without ligands) were also included for comparison. The suspensions were shaken for time periods ranging from 5 to 720 minutes at an agitation speed of 180 rpm. After shaking, the supernatant was separated by centrifugation at 4000 rpm for 20 minutes. The concentrations of Zn, Mn, and Mg in the supernatant solutions were determined using graphite furnace atomic absorption spectrophotometry.
To describe the time-dependent release of Zn, Mn, and Mg, several kinetic models were tested. Among the five models evaluated, the pseudo-second-order and power function models provided the best fit for the kinetic data. Additionally, the chemical species present in the initial solution and the saturation index (SI) of various minerals were predicted using the Visual MINTEQ 3.1 computer code.
Results and Discussion
The results indicated that the calculated molar ratio of divalent cations to trivalent cations closely matched the molar ratios used in the synthesis of the layered double hydroxide (LDH) samples. The X-ray diffraction (XRD) patterns for both LDH (3:1) and LDH (4:1) samples exhibited strong and sharp peaks corresponding to the 003 and 006 reflections, confirming the layered structure of the synthesized materials. Fourier-transform infrared (FT-IR) spectroscopy revealed two significant absorption bands around 3480 cm⁻¹ and 1620 cm⁻¹ in all synthesized LDH materials, which are indicative of stretching vibrations associated with the O-H groups in the hydroxide layers and the interlayer water molecules. Additionally, a sharp band at approximately 1382 cm⁻¹ in LDH (3:1) and a band at around 1354 cm⁻¹ in LDH (4:1) were attributed to the antisymmetric stretching mode of the nitrate anion present in the LDH structure. The specific surface areas of LDH (3:1) and LDH (4:1) were measured at 5.50 m²/g and 16.54 m²/g, respectively. Correspondingly, the average pore diameters were found to be 1.92 nm for LDH (3:1) and 2.55 nm for LDH (4:1), indicating differences in porosity between the two samples. The time-dependent cumulative release of Zn, Mn, and Mg from LDH (3:1) and LDH (4:1) in the presence and absence of citric acid and tartaric acid was investigated. The release of these micronutrients was accelerated in the presence of both organic acids. The release process appeared to occur in two stages: during the initial stage (0 to 50 minutes), the release rate of Zn, Mn, and Mg was rapid, followed by a period from 50 to 720 minutes where the release rate either fixed or slightly increased.
In this research, among the non-linear models which were used to determine the release kinetics of Zn, Mn, and Mg, the one with the highest R2 values was chosen. The R² values ranged from 0.81 to 0.99 for the pseudo-first-order model, 0.89 to 0.93 for the pseudo-second-order model, 0.97 to 0.99 for the Elovich model, 0.89 to 0.99 for the power function model, and 0.55 to 0.86 for the parabolic diffusion model. Ultimately, the pseudo-second-order and power function models were chosen to analyze the kinetic data. The amount of Zn, Mn and Mg released at equilibrium (qe) were higher in the presence of citric acid (42%) compared to tartaric acid. Additionally, the release of these elements was greater from LDH (4:1) than from LDH (3:1). This suggests that increasing the ratio of divalent cations to trivalent cations reduces the stability of LDH, enhancing the release of micronutrients.
Conclusion
The results of this study demonstrated that the release of Zn, Mn, and Mg from layered double hydroxides (LDHs) was influenced by time, the type of low molecular weight organic acid, and the ratio of divalent to trivalent cations in the LDH structure. Kinetic modeling revealed that the release rates of Zn, Mn, and Mg from LDH with a 4:1 ratio were higher than those from LDH with a 3:1 ratio. Additionally, the dissolution rates of LDHs were faster in the presence of citric acid compared to tartaric acid. To further assess the potential of LDHs as slow-release micronutrient fertilizers in calcareous soils, additional greenhouse and soil experiments are recommended.
Soil science
Z. Movahedi Rad; M. Hamidpour
Abstract
Introduction Recently, layered double hydroxides (LDHs) have attracted significant attention due to their various applications, particularly as slow-release fertilizers for essential plant nutrients. Several studies have reported the release of nitrate and phosphorus from LDHs. Additionally, micronutrients ...
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Introduction Recently, layered double hydroxides (LDHs) have attracted significant attention due to their various applications, particularly as slow-release fertilizers for essential plant nutrients. Several studies have reported the release of nitrate and phosphorus from LDHs. Additionally, micronutrients such as zinc (Zn), copper (Cu), and manganese (Mn) can be structurally incorporated into the metal hydroxide layers. Recent research indicates that LDHs have considerable potential for releasing these micronutrients. However, further studies are needed to enhance our understanding of the mechanisms and reactions of LDHs under different conditions. Currently, there is a lack of information regarding the divalent (M2+) to trivalent cation (M3+) ratios in LDHs and the influence of malic acid on the release of Zn, Mn, and magnesium (Mg) from these compounds. This study aimed to investigate the effects of malic acid and the ratio of M2+/M3+ on the kinetics release of Zn, Mn and Mg from Mg-Zn-Mn-Al-LDH intercalated with nitrate. Materials and MethodsAll chemicals used in this study including malic acid (C4H6O5), KCl, Zn(NO3)2.6H2O, Mn(NO3)2.4H2O, Mg(NO3)2.6H2O and Al(NO3).9H2O were of analytical grades, purchased from Chem-Lab or Merck Chemical Corporations. The solutions were made with the decarbonated ultrapure water (electrical resistivity = 18 MΩcm). The LDHs were synthesized by co-precipitation method at constant pH=9.2-9.6. Two types of LDHs were synthesized with varying the M+2(Zn+Mn+Mg)/M+3(Al) 3:1 and 4:1 in the precursor solution while being stirred vigorously in a nitrogen atmosphere. The pH was kept at 9.2-9.6 by adding volumes of 3 M NaOH. The crystals of LDH were ripened in the mixture for 2 h and after that, the precipitates were centrifuged at 3000 rpm for 20 min and washed several times with distilled water and placed in an oven at 70 °C for 8 h to dry. The chemical composition of the synthesized LDHs was determined by furnace atomic absorption spectrophotometry (SavantAA, GBC) after acid digestion. The physical, chemical, and morphological characteristics of the LDHs were determined using X-ray diffraction analysis (Panalytical x Pert ProX-ray diffractometer), Fe-SEM (Sigma VP), FT-IR (Nicolet iS10 spectrometer), and BET (BELSORP Mini II) techniques. A batch study was done to determine the effect of different ratios of M2+/M3+ in LDHs and the effect of malic acid on release of Zn, Mn, and Mg from LDH (3:1) and LDH (4:1). Briefly, 0.01 g of synthesized LDH were put in a centrifuge tube mixed with 10 ml background electrolyte (KCl 0.01 M) and 1.25 mM malic acid in initial pH=6-7 and constant temperature (25±0.5 °C). Blank samples (without ligand) were also considered. Suspensions were shaken at periods ranging from 5 to 720 min agitation (180 rpm). Then, the supernatant solution was separated using a centrifuge at a speed of 4000 rpm for 20 min. Zn, Mn, and Mg concentrations in supernatants solutions were determined by graphite furnace atomic absorption spectrophotometry. The effect of pH in the range of 5 to 10 on the release of Zn, Mn, and Mg from LDH was also studied. Two equations (pseudo-second-order and Elovich) were used to fit the kinetics data. Results and DiscussionThe results showed that the calculated molar ratio of divalent cation to trivalent cation was similar to their molar ratio in the solution prepared for the synthesis of LDH samples. The X-ray diffraction patterns of LDH (3:1) and LDH (4:1) samples showed the existence of strong and sharp peaks for 003 and 006 plates. Accordingly, the reflections of the 003 and 006 plates revealed the layered structure of the synthesized LDH materials. Two bands of FT-IR spectrums around 3480 and 1620 cm-1 for all synthesized LDH materials designated stretching vibrations of the O-H group of hydroxide layers and the interlayer water molecules. The sharp characteristic band around 1382 cm−1 in LDH (3:1) and band around 1354 cm-1 in LDH (4:1) was attributed to the antisymmetric stretching mode of nitrate anion in LDH. The specific surface area of LDH (3:1) and LDH (4:1) were 5.50 m2g-1 and 16.54 m2g-1 respectively. The average pore diameters in LDH (3:1) and LDH (4:1) were 1.92 nm and 2.55 nm, respectively. Time-dependent cumulative release of Zn, Mn, and Mg from LDH (3:1) and LDH (4:1) in the presence and absence of malic acid was investigated. Time-dependent Zn, Mn, and Mg release from LDH (3:1) and LDH (4:1) was accelerated in the presence of malic acid. The Zn, Mn, and Mg release from the LDHs was likely to be separated into two stages. In the initial stage from 0 to 60 min, the release rate of Zn, Mn, and Mg was rapid, then either remained constant or slightly enhanced during 60–720 min. In this research, among the non-linear models used to determine the release kinetics of Zn, Mn, and Mg, the result with the highest R2 values was chosen. The R2 values were 0.91–0.99, 0.93–0.99, 0.93–0.99, 0.89-0.99, and 0.55–0.86 for pseudo-first-order, pseudo-second-order, Elovich, power function, and parabolic diffusion, respectively. So, pseudo-second-order and Elovich models were used to analyze kinetic data. The amounts of release of Zn, Mn and Mg were higher from LDH (4:1) than from LDH (3:1) because of greater specific surface area, volume, and pore diameter in LDH (4:1). A comparison of metal release versus time profiles exhibited that dissolution was greatly dependent on the pH. ConclusionThe results of this research indicated that the release of Zn, Mn, and Mg from layered double hydroxides (LDHs) was influenced by factors such as time, ligand, solution pH, and the type of LDH. According to the kinetics models fitted to the experimental data, the release rate of Zn, Mn, and Mg from LDH (4:1) was higher than that from LDH (3:1). In both types of LDHs, the presence of malic acid significantly increased both the rate and amount of Zn, Mn, and Mg release compared to the absence of malic acid. While this study demonstrated that varying the ratios of divalent to trivalent cations can influence the amount and rate of Zn and Mn release, further greenhouse studies are required to confirm the effectiveness of LDH as a slow-release fertilizer in calcareous soils.
Soil science
A. Hassanzadeh; M. Hamidpour
Abstract
IntroductionLayered double hydroxides (LDH) have gained considerable attention for their potential application in agriculture, serving as a slow release sources of essential nutrients for plants. The appraising of LDH as a favorable fertilizer is in the early development, and more studies on the nutrient ...
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IntroductionLayered double hydroxides (LDH) have gained considerable attention for their potential application in agriculture, serving as a slow release sources of essential nutrients for plants. The appraising of LDH as a favorable fertilizer is in the early development, and more studies on the nutrient release mechanism of LDH are needed to answer the question of how LDH could replace commercial fertilizers for providing the stable nutrients for plants. Although several studies on the release of P from LDH exist in the literature, no information regarding ratios of divalent cation (M2+) to trivalent cation (M3+) in LDHs on phosphate release from LDHs is available. So, it is important to raise our knowledge about various parameters like pH and time on the solubility of LDHs. This study aimed to investigate the effects of pH and the ratios of M2+/M3+on the kinetics release of P from Mg-Al-LDH. Materials and MethodsAll the chemicals in this research, such as magnesium nitrate hexahydrate (Mg (NO3)2.6H2O) and aluminum nitrate nonahydrate Al(NO3)3.9H2O were of analytical grade and obtained from Merk (USA). The solutions were made with decarbonated pure water without impurities (electrical resistivity = 18 MΩcm). Two nitrate forms of Mg-Al-LDH were synthesized using the co-precipitation method at constant pH by varying the Mg/Al ratios (2:1 and 3:1) in the precursor solution. Briefly, 50 mL of 1M solution containing nitrate salt of divalent cations (Mg(NO3)2.6H2O) and trivalent cations (Al(NO3)3.9H2O) in the appropriate ratios (2:1 and 3:1) were added simultaneously for 2h to 400 mL of 0.01M solution of sodium hydroxide while being stirred vigorously in a nitrogen atmosphere. The pH was kept at 9.5 by adding volumes of 3 M NaOH. Afterward, the material was ripened in the synthesis mixture for 2 h and centrifuged at 3000 rpm for 20 min. The precipitates were washed by three washing-centrifugation cycles with Milli-Q water and subsequently dried at 70 °C. In this study, LDH-P was made by ion exchange. The LDH-N were treated with 0.05 M KH2PO4 solutions at pH 7.2. The suspensions were shaken end-over-end for 24h, followed by centrifugation, washing, and drying as described above. After digesting the dried LDHs in aqua regia (3:1 HCl/HNO3), the total P concentration of the LDHs was determined. The chemical composition of the synthesized LDHs was determined by graphite furnace atomic absorption spectrophotometry (SavantAA, GBC) after acid digestion (3:1 HCl/HNO3). Crystallization and morphology of the LDHs were characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD). The XRD patterns were prepared using an x-ray diffractometer (Panalytical x Pert Pro, Netherlands), at scan step time of 1s from 2θ=5° to 2θ=70° (40KV and 30 mA), and with a step size of 0.0260, which were used to identify the mineral phases. The phase purity was surveyed by comparing these XRD diagrams with those found in the literature. The SEM photographs were gained on a scanning electron microscope (Sigma VP, Germany). Fourier Transform Infrared (FTIR) spectrum was done on a Nicolet iS10 FT-IR spectrometer by utilizing KBr pressed disk technique.A batch study was done to determine the effect of different ratios of M2+/M3+ in LDHs at different pH 6.0 and 8.0 on the release of P from LDHs. Briefly, 0.01 g of synthesized LDH were put in a centrifuge tube mixed with 10 ml of 0.03M KNO3 at initial pH=6 and 8. Suspensions were shaken at a constant temperature (25±0.5 °C) and agitation (180 rpm) by using an incubator shaker for 8h. Phosphorus concentration in supernatant solutions was measured by vanadate yellow method at 470 nm wavelength.In order to investigate the kinetics of phosphorus release, LDH-P1 (2:1) and LDH-P2 (3:1) were used at two initial pHs of 6 and 8. First, 0.012 g of LDH sample was placed in 120 ml of KNO3 electrolyte solution (with ionic strength of 0.03 M) in an Erlenmeyer flask. The flasks were shaken for 5 to 1175 min by an incubator shaker at 100 rpm. Then the suspensions were centrifuged at a speed of 4000 rpm for 20 minutes and the phosphorus concentration was determined by the method described previously. All experiments were performed with three repetitions. Two equations (pseudo-second-order and parabolic diffusion) were used to fit the kinetics data. Results and DiscussionAccording to the XRD patterns, the sharpness and reflection of diffraction planes (003) and (006) pertained to layer structures. The basal spacing as calculated by Bragg’s law (nλ = 2d sin θ) were 7.94 and 8.0 Å for Mg-Al-NO3 with M+2/M+3 2:1, 3:1 respectively. The XRD patterns of the LDHs exhibited a distinct characteristic reflection (003), which indicated that the basal spacing decreased as the Mg/Al ratio decreased (higher AEC). In addition, the decreased basal spacing is linked with a decrease in the interlayer spacing. The different basal spacing of LDH were related to the layer charge density, the content of water, and the reorientation of anions in the interlayer of LDH. The intercalation of phosphate anions into Mg/Al LDH is in adaptation with the change toward lower 2θ angles of the (001) reflections corresponding to the expansion of the basal distance d003 compared to the host Mg/Al-NO3-.Two bands of FT-IR spectrums around 3470 and 1655 cm-1 for all synthesized LDH materials designate stretching vibrations of the O-H group of hydroxide layers and the interlayer water molecules. The band vibration of phosphate was perceived at 1051 cm−1 and 1064 cm-1, reflecting the formation of inner-sphere surface complex (M-O-P) between dihydrogen phosphate ions and MgAl-LDH materials. It indicated that the phosphate exchange process may be resulted in the formation of bidentate and monodentate surface complexes. According to the SEM images, the well-crystallized and plate-like morphology were typical for layer double hydroxides. The results of the X-ray energy dispersive spectroscopy (EDS) analysis showed, the only elements that existed in the LDH-N were Mg, Al, N, and O, whereas Mg, Al, P, and O were detected in the LDH-P. The results showed that increasing the pH from 6 to 8 in the presence of 0.03 M potassium nitrate background electrolyte led to an increase in phosphorus released from both types of LDH. For example, by increasing the initial pH of suspensions from 6 to 8, the amount of cumulative phosphorus released from LDH-P1 increased from 38.59 mg kg-1 to 41.91 mg kg-1 at equilibrium. In all studied pHs, phosphorus release from LDH-P1 in background electrolyte was lower than LDH-P2. For example, at pH 6 and 8, the amount of cumulative phosphorus released from LDH-P2 was 1.46 and 1.33 times higher than LDH-P1 at equilibrium, respectively. The cumulative phosphorus release kinetics from the studied LDHs showed that the amount of phosphorus release accelerated with increasing time. Phosphorus release from LDH continued at a higher rate from 0 to 400 minutes in the first stage and at a slower rate during 400-1175 minutes. Also, based on the results, among the studied kinetic equations, pseudo-second-order and parabolic diffusion equations had the best fit on phosphorus release data. ConclusionThe results of this research showed that the release of phosphorus from LDH is dependent on time, pH and the type of LDH. Based on the results of fitting the kinetics models to the experimental data, the release rate of phosphorus from LDH-P2 (3:1) was higher than that of LDH-P1 (2:1). Cumulative phosphorus release from LDH-P2 compared to LDH-P1 was 46.54, 33.61% higher at pH 6 and 8, respectively.
Mohsen Hamidpour; Leila Akbari; Hossein Shirani; Ali akbar Mohammadi
Abstract
Introduction: Soil contamination by heavy metals is a major concern throughout the world, due to persistence of metals in the environment and their toxicity and threat to all living organisms. Several strategies have been used to immobilize heavy metal ions in soils. Immobilization can be achieved by ...
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Introduction: Soil contamination by heavy metals is a major concern throughout the world, due to persistence of metals in the environment and their toxicity and threat to all living organisms. Several strategies have been used to immobilize heavy metal ions in soils. Immobilization can be achieved by adding natural and synthetic amendments such as zeolites and organic materials. Because of large specific surface area, high cation exchange capacity (CEC), low cost and wide spread availability, zeolites are probably the most promising materials interacting with many heavy metal ions in contaminated soils and water. Organic amendments such as vermicompost contains a high proportion of humified organic matter (OM), may decrease the bioavailability of heavy metals in soil by adsorption and by forming stable complexes with surface functional groups, thus permitting the re-establishment of vegetation on contaminated sites. Recent studies showed that the co-application of zeolite and humic acids could be effective in reducing the available fraction of Pb in a garden polluted soil. Fractionation of heavy metals cations in amended polluted-soils is needed to predict elemental mobility in soil and phyto-availability to plants. Therefore, the objective of this study was to investigate the effects of co-application of zeolite and vermicompost on Zn redistribution in a contaminated soil.
Material and Methods: A contaminated soil was collected from the top 20 cm in the vicinity of zinc mine in Zanjan province, western north of Iran. The soil sample was air-dried, passed through 2-mm sieve and stored at room temperature. The soil sample was thoroughly mixed to ensure uniformity. Sub-samples were then digested using the hot-block digestion procedure for total Zn concentration. The experiment was conducted under greenhouse condition. The polluted soil was put in polyethylene pots and mixed well vermicompost and zeolite at the rate of 0, 50 and 100 g kg-1 soil. The treatments were evaluated in a 3 × 3 factorial design and were arranged in a randomized block design with three replications. After incubation for 45 days, five seeds of corn were sown in each pot. After germination the seedlings were thinned to 3 per pot. Plants were grown for 2 months under control conditions. After the corn had been harvested, soil samples were air-dried, and analyzed for pH, cation exchange capacity (CEC), and electrical conductivity (EC). Chemical fractionations of Zn in soils collected after the pot trial were investigated using the procedure of Salbu et al. (1998). This procedure subdivides the heavy-metal distribution into an water-extractable+exchangeable fraction, a form bound to carbonates, a form bound to Fe and Mn oxides, a form bound to organics, and a residual form. An analysis of variance was used to test significance (P≤0.05) of treatment effects and Duncan multiple range test (P≤0.05) was used to compare the means (SAS, 2002).
Results and Discussion: Soil pH gradually decreased with application of both vermicompost and zeolite amendments. This may be due to degradation of organic matter and releasing of organic and inorganic acids such as carbonic, citric and malic acids as well as H+ produced from mineralization of nitrogen in the organic matter. Electrical conductivity (EC) of soils increased with increasing amounts of vermicompost and zeolite applications. The highest EC was observed in pots containing 10% w/w zeolite and 10% w/w vermicompost. Addition of zeolite significantly increased soil CEC. The overall distribution of Zn in different fractions was in the sequence residual (38.6%)> Fe and Mn oxides bound (31.0 %) > carbonated (21.6%)> organic (4.3%)≈exchangeable +water soluble (4.4 %). The application of vermicompost significantly decreased concentration of Zn in water+exchangeable fraction as compared to the control soil. Although singly zeolite amendment had not significant effect on water+exchangeable Zn concentration, this form decreased significantly with co-application of vermicompost and zeolite. This may be due to redistribution of Zn from this form to less available forms (e.g. organic and residual fractions). The addition of vermicompost had not significant effect on the carbonated fraction of Zn, whereas co-application of zeolite and vermicompost significantly decreased concentration of Zn bound in carbonates. Singly zeolite and co-application of amendments decreased the concentration of Zn in Fe and Mn oxides bound. Although singly compost and zeolite amendments increased concentration of Zn bound to organics, this form decreased furthest with co-application of them. Zeolite and vermicompost alone had not significant effect on mobility factor (MF) of Zn over the un-amended soil. Co-application of vermicompost and zeolite to polluted soil resulted in a significant decrease in MF values of Zn compared to control.
Conclusion: Co-application of vermicompost and zeolite to polluted soil resulted in redistribution of Zn from available forms (exchangeable +water soluble) to less available form (e.g. organic), thus may be useful for the immobilization of Zn from polluted sites.
F. Zareapour Rafsanjani; M. Hamidpour; Hossein Shirani; M. Heshmati; seyed javad hosseinifard
Abstract
Introduction: Boron is one of the eight essential micronutrients required for plant growth and development. The optimal concentration range (between deficiency and phytotoxicity) for boron is narrower than for other plant essential nutrients. Generally, irrigating water containing concentrations of B ...
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Introduction: Boron is one of the eight essential micronutrients required for plant growth and development. The optimal concentration range (between deficiency and phytotoxicity) for boron is narrower than for other plant essential nutrients. Generally, irrigating water containing concentrations of B greater than 1 mg L-1 would be detrimental for most plants. Although, there are a large number of different studies on the removal of B ions from aqueous solutions using different adsorbents, every special adsorbent material requires individual research. Information about the chemical behavior of muscovite for boron is very limited. Therefore, the objective of this study was to investigate boron adsorption on muscovite as a function of solution pH, ionic strength of the background electrolyte, kinds of cation, and initial boron concentration.
Materials and Methods: The muscovite sample was obtained from a mine near Hamadan city in western Iran. It was powdered in a mortar and sieved before sorption experiment. Boron adsorption experiments were performed in batch systems using 15 mL polyethylene (PE) bottles in 0.01 M Ca(NO3)2 electrolyte solution at a adsorbent concentrations of 10 g L-1, and at room temperature (23±2 ◦C). All samples were prepared in duplicate. Blank samples (without adsorbent) were prepared for all experiments. For pH dependent B adsorption, aliquots of B stock solution (1000 mg L−1) were added to obtain initial B concentrations of 5 and 15 mg L-1. The pH of the solutions were adjusted to values of 6.8, 7.7 and 8.8 by adding negligible predetermined volumes of 0.03M NaOH or 0.03M HNO3 solution. To study the effects of kinds of cation on boron adsorption, samples of adsorbent (0.1 g) were mixed with 10 mL background electrolyte solutions (0.01M Ca(NO3)2, Mg(NO3)2 and NaNO3) in 15 mL centrifuge tubes. Then, predetermined amount of B were added to the centrifuge tubes to obtain final concentrations of 5 mg L-1 B. For determination of boron adsorption isotherm, after 10 ml 0.01 M of Ca(NO3)2 was transferred into 15 ml centrifuge tubes, 0.1 g sample of muscovite was added to obtain adsorbent concentration of 10 g L-1. Then a predetermined amount of boron from the stock solution was added to give final concentration range between 1 and 15 mg B per liter. Initial pH of the solution was adjusted to 8.2 ± 0.1 by predetermined amount of 0.03 M NaOH solution. Suspensions were then shaken for 24h. At the end of equilibrium time, final pH was measured in the suspensions and the tubes were then centrifuged for 10 min at 5000 g. Half of the supernatant volume (5 mL) was pipetted out from each tube and then B in the supernatants were measured using the colorimetric Azomethin-H method. The amount of B adsorbed on the adsorbent was calculated as the difference between the B concentration in the blanks and the concentration in the solution after equilibration. Chemical species in the solutions were also predicted using Visual MINTEQ, a chemical speciation program developed to simulate equilibrium processes in aqueous systems.
Results and Discussion: The effect of pH on the amount of B retained depended on the initial B concentration. The amount of boron adsorption increased with increasing equilibrium pH. Boron adsorption on muscovite increased with increasing ionic strength. Greater adsorption was observed in the presence of Mg2+ as compared with Ca2+ at the same ionic strength. Calculations using Vminteq showed that the concentration of Mg-borate ion pairs (MgH2BO3+) were higher than the concentration of Ca and Na-borate ion pairs (CaH2BO3+ and NaH2BO3°). It thus seems that the much greater loss of B from solution observed in the Mg system was caused by Mg-borate ion pair adsorption. Sorption isotherm of B were well described by the Freundlich, Langmuir and Sips models but the Sips sorption model describes the interaction between B and the mineral better than the Langmuir model. On the basis of n value of Freundlich model, adsorption isotherm of boron on muscovite was classified as L-type (n≤ 1). This kind of adsorption behavior could be explained by the high affinity of the adsorbent for the adsorptive at low concentrations, which then decreases as concentration increases. Maximum sorption capacity (qmax) was obtained to be 13.98 mmol kg-1 for muscovite.
Conclusion: The experimental data showed that less than 5% of initial boron concentration was adsorbed by muscovite, thus this mineral has not a reasonable adsorption capacity for B.
Keywords: Boron, Adsorption, Muscovite, Speciation.
M. Hamidpour; M. Kalbasi; M. Afyuni; H. Shariatmadari
Abstract
Abstract
Siderophores are of important factors influencing bioavailability and fate of heavy metals in the arid and semi-arid soils. They are low molecular weight organic ligands excreted by aerobic soil microorganisms and some plants roots to acquire Fe. Siderophores may also complex other metals such ...
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Abstract
Siderophores are of important factors influencing bioavailability and fate of heavy metals in the arid and semi-arid soils. They are low molecular weight organic ligands excreted by aerobic soil microorganisms and some plants roots to acquire Fe. Siderophores may also complex other metals such as Pb .The main objective of this study was to investigate the effects of DFOB-siderophore on sorption of Pb on montmorillonite. The sorption of Pb on montmorillonite was studied as a function of pH (sorption envelopes) and as a function of Pb concentration (sorption isotherms) in the presence of siderophore using a 24–h batch equilibration experiment. The results of sorption envelopes showed that the siderophore increased sorption of Pb onto montmorillonite in all solution pH, specially at pH ≥5. The results of equilibrium test (isotherms) revealed that removal of Pb from solution was not affected by siderophore at pH=4.5, while the siderophore strongly influenced the isotherm shape and increased Pb sorption onto montmorillonite at pH=6.5. The equilibrium data is best described by a Freundlich isotherm, in which the values obtained for the KF constant were 4.8 and 196.5 and for n constant were 0.8 and 2.1 in the absence and presence of the siderophore, respectively. These values are indication of high sorption affinity of Pb on montmorillonite in the presence of the siderophore.
Keywords: Lead, Siderophore, Sorption, Montmorillonite
