Comparative study of Mg/Al-LDH and Mg/Fe-LDH on adsorption and loss control of 2,4-dichlorophenoxyacetic acid

Abstract

Low efficiency and high surface runoff of 2,4-dichlorophenoxyacetic acid (2,4-D) from agricultural field threaten crop yield severely. Layered double hydroxides (LDH) have shown promising adsorption properties for 2,4-D. However, the comparison of two environmentally friendly LDHs (i.e. Mg/Al-LDH vs Mg/Fe-LDH) on adsorption of 2,4-D and corresponding intrinsic mechanisms are still unclear, and the studies on the leaching control of 2,4-D by LDHs in soil environment are particularly limited. In this study, Mg/Al-LDH and Mg/Fe-LDH were selected to conduct their adsorption kinetics experiment for 2,4-D combined with the characterization technology. The results showed that the adsorption capacity of Mg/Al-LDH and Mg/Fe-LDH for 2,4-D was up to 242 mg kg⁻¹ and 64 mg kg⁻¹, respectively, which were negatively correlated with pH. Adsorption mechanisms of both Mg/Al-LDH and Mg/Fe-LDH for 2,4-D are dominated by chemical adsorption, including electrostatic attraction and inner sphere complexation, but no interlayer adsorption mechanism. Mg/Al-LDH contains smaller metal ion radius, which provides greater surface charge density, resulting in greater electrostatic attraction and inner sphere complexation to 2,4-D compared to Mg/Fe-LDH. The greater adsorption capacity of Mg/Al-LDH for 2,4-D was driven by the higher adsorption energy (E_ads) and lower electron density, as corroborated by density functional theory (DFT) calculation. The soil column experiment further verified that Mg/Al-LDH could control the loss of 2,4-D more effectively, and the leaching amount could be significantly reduced by 61.7%, while the effect of Mg/Fe-LDH was only 24.2%. This study provides theoretical guidance for screening more potential LDH types to solve the leaching loss of 2,4-D from soil and improve its effectiveness in agricultural production.

Graphical Abstract

Keywords

2,4-D / Mg/Al-LDH / Mg/Fe-LDH / Adsorption mechanisms / Loss control

References

[1] Ahmed IM, Gasser MS. Adsorption study of anionic reactive dye from aqueous solution to Mg–Fe–CO₃ layered double hydroxide (LDH) [J]. Appl Surf Sci. 2012, 259: 650-656

[2] Albadarin A B, Mangwandi C, Al-Muhtaseb A a H, et al. Kinetic and thermodynamics of chromium ions adsorption onto low-cost dolomite adsorbent [J]. Chem Eng J. 2012;179:193–202. https://doi.org/10.1016/j.cej.2011.10.080.

[3] Annadurai G, Juang R, Lee D. Use of cellulose-based wastes for adsorption of dyes from aqueous solutions [J]. J Hazard Mater. 2002, 92: 263-274

[4] Azizian S. Kinetic models of sorption: A theoretical analysis [J]. J Colloid Interface Sci. 2004, 276: 47-52

[5] Balinova AM, Mondesky M. Pesticide contamination of ground and surface water in Bulgarian Danube plain [J]. J Environ Sci Health. 1999, 34(1): 33-46

[6] Cai B-G, Li Q, Empel C, et al. . Dark and Light Reactions of Carbenes─Merging Carbene Transfer Reactions with N-Heterocyclic Carbene Catalysis for the Synthesis of Hydroxamic Acid Esters [J]. ACS Catal. 2022, 12(18): 11129-11136

[7] Calisto JS, Pacheco IS, Freitas LL, et al. . Adsorption kinetic and thermodynamic studies of the 2, 4-dichlorophenoxyacetate (2,4-D) by the [Co–Al–Cl] layered double hydroxide [J]. Heliyon. 2019, 5(12): e02553

[8] Caporale A G, Pigna M, Dynes J J, et al. Effect of inorganic and organic ligands on the sorption/desorption of arsenate on/from Al–Mg and Fe–Mg layered double hydroxides [J]. J Hazard Mater. 2011;198–298. https://doi.org/10.1016/j.jhazmat.2011.10.044.

[9] Cardoso LP, Celis R, Cornejo J, et al. . Layered double hydroxides as supports for the slow release of acid herbicides [J]. J Agric Food Chem. 2006, 54(16): 5968-5975

[10] Chang C, Lv Y. Adsorption characteristics and mechanism of 2,4-D by two humic acids [J]. Spectrosc Spectr Anal. 2009;29(11):2926–9. https://doi.org/10.3964/j.issn.1000-0593(2009)11-2926-04.

[11] Chen L. Study on soil particle composition determination by hydrometer [J]. J Environ Sci. 2010, 29(04): 97-99

[12] Conte LO, Farias J, Albizzati ED, et al. Photo-Fenton Degradation of the Herbicide 2,4-Dichlorophenoxyacetic Acid in Laboratory and Solar Pilot-Plant Reactors [J]. Ind Eng Chem Res. 2012;51(11):4181–91. https://doi.org/10.1021/ie2023228.

[13] Gao C, Zhang X, Yuan Y, et al. Removal of hexavalent chromium ions by core-shell sand/Mg-layer double hydroxides (LDHs) in constructed rapid infiltration system [J]. Ecotoxicol Environ Saf. 2018;166:285–93. https://doi.org/10.1016/j.ecoenv.2018.09.083.

[14] Gao X, Peng Y, Guo L, et al. Arsenic adsorption on layered double hydroxides biochars and their amended red and calcareous soils [J]. J Environ Manag. 2020;271:111045. https://doi.org/10.1016/j.jenvman.2020.111045.

[15] Gordon N, Beroza M. Spectrophotometric Determination of Small Quantities of 2,4-Dichlorophenoxyacetic Acid and 2,4,5-Trichlorophenoxyacetic Acid Using Partition Chromatography [J]. Anal Chem. 1952;24(12):1968–71. https://doi.org/10.1021/ac60072a026.

[16] Hall JC, Van Deynze TD, Struger J, et al. Enzyme immunoassay based survey of precipitation and surface water for the presence of atrazine, metolachlor and 2,4-D [J]. J Environ Sci Health. 1993;28(5):577–98. https://doi.org/10.1080/03601239309372842.

[17] Ho Y. Review of second-order models for adsorption systems [J]. J Hazard Mater. 2006, 136: 681-689

[18] Hudcová B, Fein JB, Tsang DCW, et al. Mg-Fe LDH-coated biochars for metal(loid) removal: Surface complexation modeling and structural change investigations [J]. Chem Eng J. 2022;432:134360. https://doi.org/10.1016/j.cej.2021.134360.

[19] Hunter R J. Zeta potential in colloid science : principles and applications (New paperback edition) [M]. Academic Press; 1981;0305–9723.

[20] Jiang X, Yan B, Chen J, et al. Transport and retention of phosphorus in soil with addition of Mg-Al layered double hydroxides: Effects of material dosage, flow velocity and pH [J]. Chem Eng J. 2019;378:122154. https://doi.org/10.1016/j.cej.2019.122154.

[21] Kanezaki E, Katoh M. in situ high temperature FT-IR study of the interlayer naphthalene-2,6-disulfonate in Mg and Al layered double hydroxide. [J]. Int J Mod Phys B. 2011;25(31):4185–9. https://doi.org/10.1142/S0217979211066544.

[22] Kang D, Yu X, Tong S, et al. . Performance and mechanism of Mg/Fe layered double hydroxides for fluoride and arsenate removal from aqueous solution [J]. Chem Eng J. 2013, 228: 731-740

[23] Kanmegne J, Bayomock LA, Duguma B, et al. . Screening of 18 agroforestry species for highly acid and aluminum toxic soils of the humid tropics [J]. Agrofor Syst. 2000, 49(1): 31-39

[24] Legrouri A, Lakraimi M, Barroug A, et al. . Removal of the herbicide 2,4-dichlorophenoxyacetate from water to zinc–aluminium–chloride layered double hydroxides [J]. Water Res. 2005, 39(15): 3441-3448

[25] Li B J. Optimization of the synthesis process of 2,4-dichlorophenoxyacetic acid [J]. Contemp Chem Ind. 2011;40(05):457–9. https://doi.org/10.13840/j.cnki.cn21-1457/tq.2011.05.015.

[26] Lin Y, Fang Q, Chen B. Metal composition of layered double hydroxides(LDHs) regulating ClO^-₄ adsorption to calcined LDHs via the memory effect and hydrogen bonding [J]. J Environ Sci. 2014;26(03):493–501. https://doi.org/10.1016/S1001-0742(13)60462-3.

[27] Liu W, Yang Q, Yang Z, et al. . Adsorption of 2,4-D on magnetic graphene and mechanism study [J]. Colloids Surf, A. 2016, 509: 367-375

[28] Nejati K, Davary S, Saati M. Study of 2,4-dichlorophenoxyacetic acid (2,4-D) removal by Cu-Fe-layered double hydroxide from aqueous solution [J]. Appl Surf Sci. 2013, 280: 67-73

[29] Nelson NH, Faust SD. Acidic dissociation constants of selected aquatic herbicides [J]. Environ Sci Technol. 1969, 3(11): 1186-1188

[30] Oleszczuk P, Jośko I, Futa B, et al. Effect of pesticides on microorganisms, enzymatic activity and plant in biochar-amended soil [J]. Geoderma. 2014:214–5. https://doi.org/10.1016/j.geoderma.2013.10.010.

[31] Poemomo G, Xu R. Direct Assembly of Anisotropic Layered Double Hydroxide (LDH) Nanocrystals on Spherical Template for Fabrication of Drug-LDH Hollow Nanospheres [J]. Chem Mater: A Pub Am Chem Soc. 2009, 21(5): 781-783

[32] Radnia H. Isotherm and Kinetics of Fe(II) Adsorption onto Chitosan in a Batch Process [J]. Iran J Energy Environ. 2011;2(3):250-7. https://doi.org/10.5829/idosi.ijee.2011.02.03.1837.

[33] Ragavan A, Khan A, O’Hare D. Selective intercalation of chlorophenoxyacetates into the layered double hydroxide [LiAl₂(OH)₆]Cl·xH₂O [J]. J Mater Chem. 2006;16:4155–9. https://doi.org/10.1016/j.jhazmat.2013.08.041.

[34] Rodríguez JL, Valenzuela MA, Poznyak T, et al. . Reactivity of NiO for 2,4-D degradation with ozone: XPS studies [J]. J Hazard Mater. 2013, 262: 472-481

[35] Sarkar B, Xi Y, Megharaj M, et al. . Remediation of hexavalent chromium through adsorption by bentonite based Arquad® 2HT-75 organoclays [J]. J Hazard Mater. 2010, 183(1): 87-97

[36] Shi y, Faisal I, Wei j, et al. Degradation of hormone herbicide 2,4-D and its effects on crops and environment. [J]. Zhejiang Agricultural Sciences, 2021, 62(10): 2036–43. https://doi.org/10.16178/j.issn.0528-9017.20211039.

[37] Singh Y B, Sudip D. Effect of time, pH, and temperature on kinetics for adsorption of methyl orange dye into the modified nitrate intercalated MgAl LDH adsorbent [J]. Inorg Chem Commun. 2022;137:109203. https://doi.org/10.1016/j.inoche.2022.109203.

[38] Souza FL, Saéz C, Lanza MRV, et al. . The effect of the sp3/sp2 carbon ratio on the electrochemical oxidation of 2,4-D with p-Si BDD anodes [J]. Electrochim Acta. 2016, 187: 119-124

[39] Su Y, Cui H, Li Q, et al. . Strong adsorption of phosphate by amorphous zirconium oxide nanoparticles [J]. Water Res. 2013, 47(14): 5018-5026

[40] Tan KH, Hameed B. Insight into the adsorption kinetics models for the removal of contaminants from aqueous solutions [J]. J Taiwan Inst Chem Eng. 2017, 74: 25-48

[41] Valente J S, Tzompantzi F, Prince J, et al. Adsorption and photocatalytic degradation of phenol and 2,4 dichlorophenoxiacetic acid by Mg–Zn–Al layered double hydroxides [J]. Appl Catal B: Environ. 2009;90(3):330–8. https://doi.org/10.1016/j.apcatb.2009.03.019.

[42] Wang J, Kang D, Yu X, et al. . Synthesis and characterization of Mg–Fe–La trimetal composite as an adsorbent for fluoride removal [J]. Chem Eng J. 2015, 264: 506-513

[43] Wang W, Tan J, Li S, et al. . Transport, retention and release of phytate in soil with addition of Mg–Al layered double hydroxides [J]. J Clean Prod. 2022, 379: 134774

[44] Wang N, Pan S, Li S, et al. . Combination of magnesium modified biochar and iron oxides down-regulates phosphates transport in porous media [J]. Chem Eng J. 2024, 498: 155151

[45] Wood JA, Anthony DHJ. Herbicide contamination of prairie springs at ultratrace levels of detection [J]. J Environ Qual. 1997;26:1308–18. https://doi.org/10.2134/jeq1997.00472425002600050017x.

[46] Xie Y, Yang J, Li X, et al. Study on removal of phosphorus from water by lanthanum composite materials in river sand [J]. Environ Sci Technol. 2018;41(12):219–25. https://doi.org/10.19672/j.cnki.1003-6504.2018.12.032.

[47] Yang F, Zhang S, Sun Y, et al. . Assembling biochar with various layered double hydroxides for enhancement of phosphorus recovery [J]. J Hazard Mater. 2019, 365: 665-673

[48] Yang T, Xu Y, Huang Q, et al. . Adsorption characteristics and the removal mechanism of two novel Fe-Zn composite modified biochar for Cd(II) in water [J]. Bioresour Technol. 2021, 333: 125078

[49] Zabaloy M C, Garland J L, Gomez M A. Assessment of the impact of 2,4-dichlorophenoxyacetic acid (2,4-D) on indigenous herbicide-degrading bacteria and microbial community function in an agricultural soil [J]. Appl Soil Ecol. 2010;46(2):240–6. https://doi.org/10.1016/j.apsoil.2010.08.006.

[50] Zhang H, Qi R, Duan X. Differences in structure and properties of Mg-Fe and Mg-Al dihydroxyl compound metal oxides [J]. Inorg Chem. 2002, 08: 833-838

[51] Zhang M, Gao B, Yao Y, et al. . Synthesis, characterization, and environmental implications of graphene-coated biochar [J]. Sci Total Environ. 2012, 435–436: 567-572

[52] Zhang F, Du N, Song S, et al. . Mechano-hydrothermal synthesis of SDS intercalated LDH nanohybrids and their removal efficiency for 2,4-dichlorophenoxyacetic acid from aqueous solution [J]. Mater Chem Phys. 2015, 152: 95-103

[53] Zhang L, Tang S, Jiang C, et al. . Simultaneous and Efficient Capture of Inorganic Nitrogen and Heavy Metals by Polyporous Layered Double Hydroxide and Biochar Composite for Agricultural Nonpoint Pollution Control [J]. ACS Appl Mater Interfaces. 2018, 10(49): 43013-43030

[54] Zhang X, Dou Y, Gao C, et al. . Removal of Cd(II) by modified maifanite coated with Mg-layered double hydroxides in constructed rapid infiltration systems [J]. Sci Total Environ. 2019, 685: 951-962

[55] Zhang Y, Wang T, Zhang X, et al. . Porous pie-like nitrogen-doped biochar as a metal-free peroxymonosulfate activator for sulfamethoxazole degradation: Performance, DFT calculation and mechanism [J]. Appl Surf Sci. 2024, 647: 158965

Funding

the National Natural Science Foundation of China(42377323)

RIGHTS & PERMISSIONS

The Author(s)