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
Z. Barati; H.R. Owliaie; E. Adhami; M. Najafi-Ghiri
Abstract
IntroductionRecently, layered double hydroxides (LDHs) have attracted significant attention due to their variousapplications, particularly as slow release fertilizers for essential plant nutrients. Several studies have reported therelease of nitrate and phosphorus from LDHs. Additionally, micronutrients ...
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IntroductionRecently, layered double hydroxides (LDHs) have attracted significant attention due to their variousapplications, particularly as slow release fertilizers for essential plant nutrients. Several studies have reported therelease of nitrate and phosphorus from LDHs. Additionally, micronutrients such as zinc (Zn), copper (Cu), andmanganese (Mn) can be structurally incor porated into the metal hydroxide layers. Recent research indicates thatLDHs have considerable potential for releasing these micronutrients. However, further studies are needed toenhance our understanding of the mechanisms and reactions of LDHs under diff erent conditions. Currently, thereis a lack of information regarding the divalent (M 2+2+) to trivalent cation (M 3+3+) ratios in LDHs and the influence ofmalic acid on the release of Zn, Mn, and magnesium (Mg) from these compounds. This study aimed toinvesti gate the effects of malic acid and the ratio of M 2+2+/M 3+ on the kinetics release of Zn, Mn and Mg from MgZn Mn Al LDH intercalated with nitrate 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.ConclusionTheresults 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 thekinetics models fitted to the experimental data, the release rate of Zn, Mn, and Mg from LDH (4:1) was higherthan that from LDH (3:1). In both types of LDH s , the presence of malic acid significantly increased both the rateand amount of Zn, Mn, and Mg release compared to the absence of malic acid. While this study demonstratedthat 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 incalcareous 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.
Hadis Hatami; Amir Fotovat; Akram Halajnia
Abstract
Introduction: After nitrogen, phosphorus is the second most frequently limiting macronutrient for plant growth. It participates in metabolic processes such as photosynthesis, energy transfer and synthesis and breakdown of carbohydrates. H2PO4- and HPO42- are two forms of this element which are present ...
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Introduction: After nitrogen, phosphorus is the second most frequently limiting macronutrient for plant growth. It participates in metabolic processes such as photosynthesis, energy transfer and synthesis and breakdown of carbohydrates. H2PO4- and HPO42- are two forms of this element which are present in the soil solution in the available form. Due to phosphorus reactions with soil components (oxy or hydroxides of Fe and Al in acidic soils and Ca2+ and Mg2+ ions in calcareous soils), the availability of this element is a limiting factor for production of agricultural crops in the whole world. To minimize this problem it is needed to improve the recycling of phosphorus and develop new technologies to reduce phosphorus losses and increase its effectiveness. In the recent decades, layered double hydroxides (LDH) have been extremely used as an effective sorbent for organic and inorganic anions sush as phosphate. Furthermore, some studies have suggested that the phosphate form LDH is applicable as a slow release phosphate fertilizer. Therefore, the objective of the present study was to compare the effect of using Zn-Al LDH and triple superphosphate (TSP) as fertilizers on the availability of phosphorus over time in a calcareous soil.
Materials and Methods: At the first, nitrate containing Zn-Al LDH (N-LDH) was synthesized by urea hydrolysis method and then ion exchange method was used for the phosphate anions intercalation into N-LDH. In this process, 5.0 g of the N-LDH was suspended in 1000 mL of a solution 0.05 mol/L of K2HPO4. The suspension was kept for 12 h at room temperature (25 °C) under stirring. Afterwards, the material was filtered, washed with distilled water and dried at 70 °C for 18 h. The LDH sample produced by the ion exchange method was nominated as P-LDH. To compare the effects of P-LDH and TSP application on the availability of soil phosphorus, an incubation experiment was carried out using a completely randomized factorial design with two sources of phosphorus (P-LDH and TSP), four levels of phosphorus (0 (control), 18, 45 and 90 mg P kg-1), eight levels of time (1, 5, 10, 20, 40, 70, 100 and 150 days) and three replications. Available phosphorus and zinc, pH and EC of samples were measured at the end of each time period. Available phosphorus was extracted with 0.5 M sodium bicarbonate and phosphorus concentration was determined using the ascorbic acid method. Available zinc content was determined by atomic absorption spectrometry following extraction of the sample by DTPA-TEA method. Also, pH and EC were measured in water (soil/water ratio 1:2). Data analysis was performed by MSTAT-C software, and the means were compared at α꞊5% by Duncan test.
Results and Discussion: The results showed that the use of P-LDH and TSP significantly improved available phosphorus compared to control treatment. However, in contrast to TSP, available phosphorus in P-LDH treatments increased with increasing of time, up to significant difference which was observed between the two sources after 150 days. This result is probably due to slow release of phosphorus from P-LDH and reduction of phosphorus reactions with different soil components. Moreover, available zinc was higher for P-LDH treatments than TSP treatments as dissolution of P-LDH may concurrently release zinc ions into the soil solution. It seems that the application of P-LDH not only increased the availability of phosphorus but also improved available zinc. Therefore, due to the zinc deficiency in calcareous soils, P-LDH can be used as a suitable dual purpose fertilizer for these soils. However, the possibility of Zn toxicity risk due to higher level of LDH application in soil is not ruled out. It is worth mentioning that the variation of pH and EC values in P-LDH treatments showed no significant difference compared to TSP tratments. In other words, application of P-LDH increased soil available phosphorus and zinc without any negative effect on soil pH and EC.
Conclusions: The results of this study illustrated that the P-LDH probably can be used as a slow release phosphate fertilizer to increase the phosphorus efficiency; however, care should be taken as the high levels of this fertilizer may not be recommended due to the high zinc content. It should be noted that the high levels of phosphorus are not appropriate for all phosphorus fertilizers but in the present study we used the different levels of fertilizers because the behavior of P-LDH was not clear for us.
