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نوع مقاله : مقالات پژوهشی

نویسندگان

1 گروه کشاورزی، دانشگاه پیام نور، تهران، ایران

2 گروه علوم خاک، دانشکده کشاورزی، دانشگاه ولی‌عصر (عج) رفسنجان، رفسنجان، ایران

چکیده

اخیراً پتانسیل هیدروکسیدهای دوگانه لایه­ای در تأمین عناصر ضروری گیاهان به­طور گسترده مورد توجه قرار گرفته است. در این پژوهش Mg-Zn-Mn-Al-LDH با آنیون بین لایه­ای نیترات با دو نسبت کاتیون دو به سه ظرفیتی 3:1 (LDH (3:1)) و 4:1 (LDH (4:1)) به روش هم­رسوبی تهیه شد. پس از بررسی ویژگی­های ساختاری و مورفولوژیکی با استفاده از تکنیک­های XRD، SEM، FTIR و BET، روند رهاسازی عناصر روی، منگنز و منیزیم از آن­ها در حضور و عدم حضور اسیدهای آلی سیتریک و تارتاریک با مطالعات پیمانه­ای مورد بررسی قرار گرفت. از بین مدل­های سینتیکی مختلف، مدل­های تابع توانی و شبه مرتبه دوم به‌دلیل دارا بودن ضریب تبیین (R2) بیشتر و خطای تخمین استاندارد کمتر (SE) جهت برازش بر داده­های سینتیکی مورد استفاده قرار گرفتند. نتایج نشان داد اسیدهای آلی نقش مهمی در رهاسازی عناصر از ساختار LDH داشته به­گونه­ای که در حضور اسید سیتریک، از LDH (3:1) مقدار رهاسازی روی، منگنز و منیزیم به­ترتیب 99، 99 و 91 درصد و از LDH (4:1) به­ترتیب 97، 98 و 85 درصد بیشتر از عدم حضور این اسید بود. همچنین در حضور اسید تارتاریک مقدار رهاسازی روی، منگنز و منیزیم از LDH (3:1) به­ترتیب 99، 90 و 89 درصد و از LDH (4:1) این مقادیر 93، 86 و 69 درصد بیشتر از عدم حضور این اسید بود. نسبت کاتیون دو به سه ظرفیتی در ساختار LDH تأثیر مستقیم بر پایداری LDH داشته و افزایش این نسبت منجر به کاهش پایداری LDH گردید. با توجه به نتایج حاصل می­توان در رویکردی جدید هیدروکسیدهای دوگانه لایه­ای را به­عنوان ترکیبات کودی با قابلیت آزادسازی آرام عناصر غذایی در شرایط کمبود آن­ها و در حضور گیاه مورد بررسی بیشتر قرار داد.

کلیدواژه‌ها

موضوعات

عنوان مقاله [English]

Kinetics of Zinc, Manganese and Magnesium Release from Layered Double Hydroxides (Mg-Zn-Mn-Al-LDH): Effect of Citric Acid and Tartaric Acid

نویسندگان [English]

  • Z. Movahedi Rad 1
  • M. Hamidpour 2
  • A. Tajabadipour 2

1 Department of Agriculture, Payame Noor University, Tehran, Iran

2 Soil Science Department, Faculty of Agriculture, Vali-e-Asr University of Rafsanjan, Rafsanjan, Iran

چکیده [English]

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.

کلیدواژه‌ها [English]

  • Kinetic models
  • Low molecular weight organic acid
  • Micronutrients
  • Slow-release fertilizer

©2025 The author(s). This is an open access article distributed under Creative Commons Attribution 4.0 International License (CC BY 4.0).

  1. Adeleke, R., Nwangburuka, C., & Oboirien, B. (2017). Origins, roles and fate of organic acids in soils: A review. South African Journal of Botany, 108, 393-406. https://doi.org/10.1016/j.sajb.2016.09.002
  2. Alexandratos, N., & Bruinsma, J. (2012). World Agriculture Towards 2030/2050: the 2012 revision. ESA Work. Paper No 12-03. Global Perspective Studies Team FAO Agricultural Development Economics Division.
  3. Baranimotlagh, M., & Gholami, M. (2013). Time-dependent zinc desorption in some calcareous soils of Iran. Pedosphere, 23(2), 185-193. https://doi.org/10.1016/S1002-0160(13)60006-5
  4. Benicio, L.P.F., Constantino, V.R.L., Pinto, F.G., Vergutz, L., Tronto, J., & Da Costa, L.M. (2017). Layered double hydroxides: new technology in phosphate fertilizrs based on nanostructured materials. ACS Sustainable Chemistry & Engineering, 5(1), 399-409. https://doi.org/10.1021/acssuschemeng.6b01784
  5. Benicio, L.P.F., Eulalio, D., Guimaraes, L.D.M., Pinto, F.G., Costa, L.M.D., & Tronto, J. (2018). Layered double hydroxides as hosting matrices for storage and slow release of phosphate analyzed by stirred-flow method. Materials Research, 21(6), e20171004. https://doi.org/10.1590/1980-5373-MR-2017-1004
  6. Bernardo, M.P., Moreira, F.K., & Ribeiro, C. (2017). Synthesis and characterization of eco-friendly Ca-Al-LDH loaded with phosphate for agricultural applications. Applied Clay Science, 137, 143-150. https://doi.org/10.1016/ j.clay.2016.12.022
  7. Cardoso, L.P., Celis, R., Cornejo, J., & Valim, J.B. (2006). Layered double hydroxides as supports for the slow release of acid herbicides. Journal of Agricultural and Food Chemistry, 54(16), 5968-5975. https://doi.org/ 10.1021/jf061026y
  8. Dalla Nora, F.B., Lima, V.V., Oliveira, M.L., Hosseini-Bandegharaei, A., de Lima Burgo, T.A., Meili, L., & Dotto, G.L. (2020). Adsorptive potential of Zn–Al and Mg–Fe layered double hydroxides for the removal of 2–nitrophenol from aqueous solutions. Journal of Environmental Chemical Engineering, 8(4), 103913. https://doi.org/10.1016/j.jece.2020.103913
  9. Essington, M.E. (2015). Second edition Soil and Water Chemistry: an Integrative Approach. CRC press.
  10. Evans Jr, A. (1991). Influence of low molecular weight organic acids on zinc distribution within micronutrient pools and zinc uptake by wheat. Journal of Plant Nutrition, 14(12), 1307-1318. https://doi.org/10.1080/ 01904169109364287
  11. Everaert, M., Warrinnier, R., Baken, S., Gustafsson, J.P., De Vos, D., & Smolders, E. (2016). Phosphate-exchanged Mg-Al layered double hydroxides: A new slow release phosphate fertilizer. ACS Sustainable Chemistry & Engineering, 4(8), 4280–4287. https://doi.org/10.1021/acssuschemeng.6b00778
  12. Everaet, M., Andelkovic, I.B., Smolders, E., Degryse, F., Baird, R., & Mclaughlin, M.J. (2023). Layered transition metal molybdates as new slow-release micronutrient fertilizer matrices for Zn, Cu, and Industrial & Engineering Chemistry Research, 62(20), 7859-7867. https://doi.org/10.1021/acs.iecr.3c00498
  13. Figueredo Benicio, L.P., Eulalio, D., Guimaraes, L.D.M., Pinto, F.G., Da Costac, L.M., & Tronto, J. (2018). Layered double hydroxides as hosting matrices for storage and slow release of phosphate. Materials Research-Ibero-American Journal of Materials, 21(6). https://doi.org/10.1590/1980-5373-MR-2017-1004
  14. Hansen, J.C., & Strawn, D.G. (2003). Kinetics of phosphorus release from manure-amended alkaline soil. Soil Science, 168(12), 869-879. https://doi.org/10.1097/01.ss.0000106408.84926.8f
  15. Halajnia, A., Oustan, S., Najafi, N., Khataee, A.R., & Lakzian, A. (2013). Adsorption–desorption characteristics of nitrate, phosphate and sulfate on Mg–Al layered double hydroxide. Applied Clay Science, 80, 305-312. https://doi.org/10.1016/j.clay.2013.05.002
  16. Hassanzadeh, A., Hamidpour, M., Abbaszadeh Dahaji, P., Akhgar, A., & Kariman, K. (2024). Maximizing the efficiency of layered double hydroxides as a slow-release phosphate fertilizer: A study on the impact of plant growth-promoting rhizobacteria. Applied Clay Science, 262, 107620. https://doi.org/10.1016/j.clay.2024.107620
  17. Hatami, H., & Fotovat, A. (2023). Evaluation of Zn[Mn]-Al LDHs as matrices for release of B, Zn and Mn in A simulated soil solution. Journal of Water and Soil, 36(6), 761-771. (In Persian with English abstract). https://doi.org/10.1134/s1061933x20060058
  18. Hatami, H., Fotovat, A., & Halajnia, A. (2018). Comparison of adsorption and desorption of phosphate on synthesized Zn-Al LDH by two methods in a simulated soil solution. Applied Clay Science, 152, 333-341. https://doi.org/10.1016/j.clay.2017.11.032
  19. Imran, A., López-Rayo, S., Magid, J., & Hansen, H.C.B. (2016). Dissolution kinetics of pyroaurite-type layered double hydroxide doped with Zn: perspectives for pH controlled micronutrient release. Applied Clay Science, 123, 56–63. https://doi.org/10.1016/j.clay.2015.12.016
  20. Kameliya, J., Verma, A., Dutta, P., Arora, C., Vyas, S., & Varma, R.S. (2023). Layered double hydroxide materials: A Review on their preparation characterization and applications. Inorganics, 11(121), 1-22. https://doi.org/10.3390/inorganics11030121
  21. Khan, A.A., Tahir, M., & Khan, N. (2023). LDH-based nanomaterials for photocatalytic applications: A comprehensive review on the role of bi/trivalent cations, anions, morphology, defect engineering, memory effect, and heterojunction formation. Journal of Energy Chemistry, 84, 242-276. https://doi.org/10.1016/j.jechem.2023. 04.049
  22. Klemkaite, K., Prosycevas, I., Taraskevicius, R., Khinsky, A., & Kareiva, A. (2011). Synthesis and characterization of layered double hydroxides with different cations (Mg, Co, Ni, Al), decomposition and reformation of mixed metal oxides to layered structures. Open Chemistry, 9(2), 275-282. https://doi.org/10.2478/ s11532-011-0007-9
  23. Koilraj, P., & Kannan, S. (2010). Phosphate uptake behavior of ZnAlZr ternary layered double hydroxides through surface precipitation. Journal of Colloid and Interface Science, 341(2), 289-297. https://doi.org/10.1016/ j.jcis.2009.09.059
  24. Lakshani, N., Wijerathne, H.S., Sandaruwan, C., Kottegoda, N., & Karunarathne, V. (2023). Release kinetic models and release mechanisms of controlled-release and slow-release fertilizers. ACS Agricultural Science & Technology, 3(11), 939-956. https://doi.org/10.1021/acsagscitech.3c00152
  25. Li, F., & Duan, X. (2005). Applications of layered double hydroxides. Struct Bond, 119, 193–223.
  26. Lozano-Lunar, A., Otero, R., Álvarez, J.I., Jiménez, J.R., & Fernández-Rodríguez, J.M. (2023). Application of layer double hydroxide in cementitious matrices for the improvement of the double barrier technique in the immobilisation of lead waste. Applied Clay Science, 238, 106938. https://doi.org/10.1016/j.clay.2023.106938
  27. López-Rayo, S., Imran, A., Bruun Hansen, H.C., Schjoerring, J.K., & Magid, J. (2017). Layered double hydroxides: Potential release-on-demand fertilizers for plant zinc nutrition. Journal of Agricultural and Food Chemistry, 65(40), 8779–8789. https://doi.org/10.1021/acs.jafc.7b02604
  28. Meili, L., Lins, P.V., Zanta, C.L.P.S., Soletti, J.I., Ribeiro, L.M.O., Dornelas, C.B., & Vieira, M.G.A. (2019). MgAl-LDH/Biochar composites for methylene blue removal by adsorption. Applied Clay Science, 168, 11-20. https://doi.org/10.1016/j.clay.2018.10.012
  29. Mishra, G., Dash, B., & Pandey, S. (2018). Layered double hydroxides: A brief review from fundamentals to application as evolving biomaterials. Applied Clay Science, 153, 172-186. https://doi.org/10.1016/j.clay.2017. 12.021
  30. Motaghian, H.R., Hosseinpur, A., & Kiani, S. (2016). Zinc and copper release kinetics in a calcareous soil amended with manure and vermicompost. Journal of Water and Soil, 30(2), 581-593. (In Persian with English abstract).
  31. Motaghian, H.R., & Hosseinpur, A.R. (2014). Impact of sewage sludge application on zinc desorption kinetics in some calcareous soils. Environmental Earth Sciences, 71, 4647-4655. https://doi.org/10.1007/s12665-013-2855-4
  32. Movahedirad, Z., & Hamidpour, M. (2024). Release of zinc, manganese and magnesium from Mg-Zn-Mn-Al-LDH: Effect of malic acid and divalent to trivalent cation ratios in mineral structure. Water and Soil, 38(4), 495-509. (In Persian with English abstract).
  33. Nunes, V.L.N., Mulvaney, R.L., Cantarutti, R.B., Pinto, F.G., & Tronto, J. (2020). Improving nitrate fertilization by encapsulating Zn-Al layered double hydroxides in alginate beads. Nitrogen, 1, 125-136. https://doi.org/ 10.3390/nitrogen1020011
  34. Olama, V., Ronaghi, A., Karimian, N., Ghasemi-Fasaei, R., Yasrebi, J., & Tavajjoh, M. (2010). Copper release behavior in two calcareous soils amended with three organic materials. Communications in Soil Science and Plant Analysis, 41(20), 2448-2458. https://doi.org/10.1080/00103624.2010.511376
  35. Peng, L., Liu, P., Feng, X., Wang, Z., Cheng, T., Liang, Y., & Shi, Z. (2018). Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciation. Geochimica et Cosmochimica Acta, 224, 282-300. https://doi.org/10.1016/j.gca.2018.01.014
  36. Reyhanitabar, A., & Gilkes, R.J. (2010). Kinetics of DTPA extraction of zinc from calcareous soils. Geoderma, 154(3-4), 289-293. https://doi.org/10.1016/j.geoderma.2009.10.016
  37. Rojas, R., Barriga, C., De Pauli, C.P., & Avena, M.J. (2010). Influence of carbonate intercalation in the surface-charging behavior of Zn–Cr layered double hydroxides. Materials Chemistry and Physics, 119(1-2), 303-308. https://doi.org/10.1016/j.matchemphys.2009.09.001
  38. Roy, A.S., de Beer, M., Pillai, S.K., & Ray, S.S. (2023). Application of layered double hydroxides as a slow-release phosphate source: A Comparison of hydroponic and soil systems. ACS Omega, 8(17), 15017-15030. https://doi.org/10.1021/acsomega.2c07862
  39. Shafigh, M., Hamidpour, M., & Furrer, G. (2019). Zinc release from Zn-Mg-Fe (III)-LDH intercalated with nitrate, phosphate and carbonate: The effects of low molecular weight organic acids. Applied Clay Science, 170, 135-142. https://doi.org/10.1016/j.clay.2019.01.016
  40. Songkhum, P., Wuttikhun, T., Chanlek, N., Khemthong, P., & Laohhasurayotin, K. (2018). Controlled release studies of boron and zinc from layered double hydroxides as the micronutrient hosts for agricultural application. Applied Clay Science, 152, 311–322. https://doi.org/10.1016/j.clay.2017.11.028
  41. Sparks, D.L. (1986). Kinetics of ionic reactions in clay minerals and soils. Advances in Agronomy, 38, 231-266. https://doi.org/10.1016/S0065-2113(08)60677-X
  42. Thevenot, F., Szymanski, R., & Chaumette, P. (1989). Preparation and characterization of Al-rich Zn-Al hydrotalcite-like compounds. Clays and Clay Minerals, 37(5), 396-402. https://doi.org/10.1346/CCMN.1989. 0370502
  43. Wang, W., & Lu, Y., (2018). Analysis of the mean absolute error (MAE) and the root mean square error (RMSE) in assessing rounding model. IOP Conf. Series: Materials Science Engineering, 324, 012049. https://doi.org/ 10.1088/1757-899X/324/1/012049
  44. Wang, X., Lin, Y., Su, Y., Zhang, B., Li, C., Wang, H., & Wang, L. (2017). Design and synthesis of ternary-component layered double hydroxides for high-performance supercapacitors: understanding the role of trivalent metal ions. Electrochimica Acta, 225, 263-271. https://doi.org/10.1016/j.electacta.2016.12.160
  45. Zabiszak, M., Nowak, M., Taras-Goslinska, K., Kaczmarek, M.T., Hnatejko, Z., & Jastrzab, R. (2018). Carboxyl groups of citric acid in the process of complex formation with bivalent and trivalent metal ions in biological systems. Journal of Inorganic Biochemistry, 182, 37-47. https://doi.org/10.1016/j.jinorgbio.2018.01.017
  46. Zhang, Sh., Gao, N., Shen, T., Yang, Y., Gao, B., Li, Y.C., & Wan, Y. (2019 a). One-step synthesis of superhydrophobic and multifunctional nano copper-modified bio-polyurethane for controlled-release fertilizers with multilayer air shields. new insight of improvement mechanism. Journal of Materials Chemistry, 7, 9503-9509. https://doi.org/10.1039/C9TA00632J
  47. Zhang, Y., Xu, H., & Lu, S. (2021). Preparation and application of layered double hydroxide nanosheets. Royal Society of Chemistry, 11, 24254-24281. https://doi.org/10.1039/d1ra03289e

 

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