Potentials of emergent plant residue derived biochar to be alternative carbon-based phosphorus fertilizer by Fe(II)/Fe(III) magnetic modification

Abstract

Emergent plants have been remarkably effective in reducing phosphorus (P) discharge from ecological ditches; however, the treatment and recycling of these residues is a great challenge. In this study, magnetic biochars (MB_s, i.e., MB-A, MB-C, and MB-T) were fabricated from three emergent plant residues (Acorus calamus L., Canna indica L., and Thalia dealbata Fraser, respectively) and modified with Fe(II)/Fe(III). Scanning electron microscopy-energy dispersive spectroscopy and X-ray diffraction spectra confirmed the successful loading of Fe₃O₄ and FeO(OH) onto the surfaces of the MB_s. Batch adsorption experiments showed that MB_s exhibited a higher P adsorption capacity than that of the raw biochars. Within the range of 0.8–43.0 mg L⁻¹ in solution, the adsorption capacities of P by MB-A, MB-C, and MB-T were 304.6–5658.8, 314.9–6845.6, and 292.8–5590.0 mg kg⁻¹, with adsorption efficiencies of 95.2–32.9%, 98.4–39.8%, and 91.5–32.5%, respectively. The primary mechanisms that caused P to adsorb onto the MB_s were inner-sphere complexation and electrostatic attraction. Low pH conditions were more beneficial for the P adsorption of the MB_s, while co-existing anions had a negative impact with the following order: HCO₃ ⁻ > SO₄ ²⁻ > Cl⁻≈NO₃ ⁻. The P-31 nuclear magnetic resonance results further demonstrated that the main adsorbed P species on the MB_s was orthophosphate, followed by orthophosphate monoesters and DNA. Overall, MB_s offer a resource utilization strategy for emergent plant residues and P-laden MB_s are promising alternative P fertilizers.

Highlights

•	Emergent plant biochar modified with Fe(II)/Fe(III) enhanced P adsorption capacity.
•	Canna indica residue-derived MB exhibited the best P adsorption efficiency.
•	MBs promoted P adsorption mainly via inner-sphere complexation and electrostatic attraction.
•	P species adsorbed by MBs were mainly orthophosphate followed by orthophosphate monoesters and DNA.

Keywords

Emergent plant / Fe(II)/Fe(III) modification / Magnetic biochar / Phosphorus adsorption / Phosphorus species

References

[1] Ahmad M, Rajapaksha AU, Lim JE, Zhang M, Bolan N, Mohan D, Vithanage M, Lee SS, Ok YS. Biochar as a sorbent for contaminant management in soil and water: a review. Chemosphere, 2014, 99: 19-33,

[2] Ai D, Ma H, Meng Y, Wei T, Wang B. Phosphorus recovery and reuse in water bodies with simple ball-milled Ca-loaded biochar. Sci Total Environ, 2023, 860,

[3] Ajmal Z, Muhmood A, Usman M, Kizito S, Lu JX, Dong RJ, Wu SB. Phosphate removal from aqueous solution using iron oxides: adsorption, desorption and regeneration characteristics. J Colloid Interface Sci, 2018, 528: 145-155,

[4] An X, Wu Z, Yu J, Cravotto G, Liu X, Li Q, Yu B. Copyrolysis of biomass, bentonite, and nutrients as a new strategy for the synthesis of improved biochar-based slow-release fertilizers. ACS Sustain Chem Eng, 2020, 8(8): 3181-3190,

[5] Cade-Menun BJ, Preston CM. A comparison of soil extraction procedures for 31 P NMR spectroscopy. Soil Sci, 1996, 161: 770-785,

[6] Chen H, Gao Y, Li J, Fang Z, Bolan N, Bhatnagar A, Gao B, Hou D, Wang S, Song H, Yang X, Shaheen SM, Meng J, Chen W, Rinklebe J, Wang H. Engineered biochar for environmental decontamination in aquatic and soil systems: a review. Carbon Res, 2022,

[7] Cheng H, Yang S, Bolan N. Biochar for future and futuristic biochar. Pedosphere, 2023, 33: 680-682,

[8] Christopher C. Emergent macrophyte biomass production. Methods Biogeochem Wetlands, 2013, 10: 137-153,

[9] Conley DJ, Paerl HW, Howarth RW, Boesch DF, Seitzinger SP, Havens KE, Lancelot C, Likens GE. Controlling eutrophication: nitrogen and phosphorus. Science, 2009, 323: 1014-1015,

[10] Dai J, Meng X, Zhang Y, Huang Y. Effects of modification and magnetization of rice straw derived biochar on adsorption of tetracycline from water. Bioresource Technol, 2020, 311,

[11] Dong X, He L, Hu H, Liu N, Gao S, Piao Y. Removal of 17β-estradiol by using highly adsorptive magnetic biochar nanoparticles from aqueous solution. Chem Eng J, 2018, 352: 371-379,

[12] Drenkova-Tuhtan A, Mandel K, Paulus A, Meyer C, Hutter F, Gellermann C, Sextl G, Franzreb M, Steinmetz H. Phosphate recovery from wastewater using engineered superparamagnetic particles modified with layered double hydroxide ion exchangers. Water Res, 2013, 47: 5670-5677,

[13] Fang Y, Ali A, Gao Y, Zhao P, Li R, Li X, Liu J, Luo Y, Peng Y, Wang H, Liu H, Zhang Z, Pan J. Preparation and characterization of MgO hybrid biochar and its mechanism for high efficient recovery of phosphorus from aqueous media. Biochar, 2022, 4: 40,

[14] Gao R, Fu Q, Hu H, Wang Q, Liu Y, Zhu J. Highly-effective removal of pb by co-pyrolysis biochar derived from rape straw and orthophosphate. J Hazard Mater, 2019, 371: 191-197,

[15] Gong H, Tan Z, Zhang L, Huang Q. Preparation of biochar with high absorbability and its nutrient adsorption–desorption behaviour. Sci Total Environ, 2019, 694,

[16] Gusain R, Pandey B, Suthar S. Composting as a sustainable option for managing biomass of aquatic weed Pistia: a biological hazard to aquatic system. J Clean Prod, 2018, 177: 803-812,

[17] Hao S, Li Q, Qu J, An F, Zhang Y, Yu Z. Neuron-inspired Fe₃O₄/conductive carbon filament network for high-speed and stable lithium storage. Acs Appl Mater Inter, 2018, 10: 17923-17932,

[18] Hartley AM, House WA, Callow ME, Leadbeater BSC. Coprecipitation of phosphate with calcite in the presence of photosynthesizing green algae. Water Res, 1997,

[19] Huang Q, Song S, Chen Z, Hu B, Chen J, Wang X. Biochar-based materials and their applications in removal of organic contaminants from wastewater: state-of-the-art review. Biochar, 2019, 1: 45-73,

[20] Huang H, Guo T, Wang K, Li Y, Zhang G. Efficient activation of persulfate by a magnetic recyclable rape straw biochar catalyst for the degradation of tetracycline hydrochloride in water. Sci Total Environ, 2021, 758,

[21] Iamchaturapatr J, Yi SW, Rhee JS. Nutrient removals by 21 aquatic plants for vertical free surface-flow (VFS) constructed wetland. Ecol Eng, 2007, 29: 287-293,

[22] Jiang D, Chu B, Amano Y, Machida M. Removal and recovery of phosphate from water by Mg-laden biochar: batch and column studies. Colloids Surf, A, 2018, 558: 429-437,

[23] Jiang Z, Yan L, Wu J, Liu X, Zhang J, Zheng Y, Pei Y. Low-temperature synthesis of carbonate-intercalated Ni_XFe-layered double hydroxides for enhanced adsorption properties. Appl Surf Sci, 2020, 531,

[24] Klinar D. Universal model of slow pyrolysis technology producing biochar and heat from standard biomass needed for the techno-economic assessment. Bioresource Technol, 2016, 206: 112-120,

[25] Kröger R, Moore MT. Phosphorus dynamics within agricultural drainage ditches in the lower Mississippi Alluvial Valley. Ecol Eng, 2011, 37: 1905-1909,

[26] Kumwimba MN, Zhu B, Muyembe DK. Assessing the influence of different plant species in drainage ditches on mitigation of non-point source pollutants (N, P, and sediments) in the Purple Sichuan Basin. Environ Monit Assess, 2017, 189: 1-14,

[27] Lei J, Lin J, Zhan Y, Zhang Z, Ma J. Effectiveness and mechanism of aluminum/iron co-modified calcite capping and amendment for controlling phosphorus release from sediments. J Environ Manage, 2021, 298,

[28] Li R, Wang JJ, Zhou B, Awasthi MK, Ali A, Zhang Z, Lahori AH, Mahar A. Recovery of phosphate from aqueous solution by magnesium oxide decorated magnetic biochar and its potential as phosphate-based fertilizer substitute. Bioresource Technol, 2016, 215: 209-214,

[29] Li J, Li B, Huang H, Lv X, Zhao N, Guo G, Zhang D. Removal of phosphate from aqueous solution by dolomite-modified biochar derived from urban dewatered sewage sludge. Sci Total Environ, 2019, 687: 460-469,

[30] Liu J, Cade-Menun BJ, Yang J, Hu Y, Liu CW, Tremblay J, LaForge K, Schellenberg M, Hamel C, Bainard LD. Long-term land use affects phosphorus speciation and the composition of phosphorus cycling genes in agricultural soils. Front Microbiol, 2018, 9: 1643,

[31] Liu X, Fu J, Tang Y, Smith RL Jr, Qi X. Mg-coordinated self-assembly of MgO-doped ordered mesoporous carbons for selective recovery of phosphorus from aqueous solutions. Chem Eng J, 2021, 406,

[32] Liu M, Li R, Wang J, Liu X, Li S, Shen W. Recovery of phosphate from aqueous solution by dewatered dry sludge biochar and its feasibility in fertilizer use. Sci Total Environ, 2022, 814,

[33] Loganathan P, Vigneswaran S, Kandasamy J, Bolan NS. Removal and recovery of phosphate from water using sorption. Crit Rev Env Sci Tec, 2014, 44: 847-907,

[34] Malash GF, El-Khaiary MI. Piecewise linear regression: a statistical method for the analysis of experimental adsorption data by the intraparticle-diffusion models. Chem Eng J, 2010, 163: 256-263,

[35] MEP. . Discharge standard of pollutants for municipal wastewater treatment plant (GB18918-2002), 2002 Beijing China Environment Press

[36] Min L, Zhang ZS, Zhe L, Haitao W. Removal of nitrogen and phosphorus pollutants from water by FeCl₃- impregnated biochar. Ecol Eng, 2020, 149,

[37] Mitrogiannis D, Psychoyou M, Koukouzas N, Tsoukalas N, Palles D, Kamitsos E, Pantazidis A, Oikonomou G, Baziotis I. Phosphate recovery from real fresh urine by Ca(OH)₂ treated natural zeolite. Chem Eng J, 2018, 347: 618-630,

[38] Nash DM, Haygarth PM, Turner BL, Condron LM, McDowell RW, Richardson AE, Watkins M, Heaven MW. Using organic phosphorus to sustain pasture productivity: a perspective. Geoderma, 2014, 221: 11-19,

[39] Ou W, Lan X, Guo J, Cai A, Liu P, Liu N, Liu Y, Lei Y. Preparation of iron/calcium-modified biochar for phosphate removal from industrial wastewater. J Clean Prod, 2023, 383,

[40] Padilla J, Watts D, Novak J, Cerven V, Ippolito J, Szogi A, Johnson M. Magnesium activation affects the properties and phosphate sorption capacity of poultry litter biochar. Biochar, 2023, 5: 64,

[41] Palansooriya KN, Kim S, Igalavithana AD, Hashimoto Y, Choi Y, Mukhopadhyay R, Sarkar B, Ok YS. Fe(III) loaded chitosan-biochar composite fibers for the removal of phosphate from water. J Hazard Mater, 2021, 415,

[42] Pitakteeratham N, Hafuka A, Satoh H, Watanabe Y. High efficiency removal of phosphate from water by zirconium sulfate-surfactant micelle mesostructure immobilized on polymer matrix. Water Res, 2013, 47: 3583-3590,

[43] Reguyal F, Sarmah A, Gao W. Synthesis of magnetic biochar from pine sawdust via oxidative hydrolysis of FeCl₂ for the removal sulfamethoxazole from aqueous solution. J Hazard Mater, 2017, 321: 868-878,

[44] Shan X, Zhao Y, Bo S, Yang L, Xiao Z, An Q, Zhai S. Magnetic aminated lignin/CeO₂/Fe₃O₄ composites with tailored interfacial chemistry and affinity for selective phosphate removal. Sci Total Environ, 2021, 796,

[45] Shepherd JG, Joseph S, Sohi SP, Heal KV. Biochar and enhanced phosphate capture: mapping mechanisms to functional properties. Chemosphere, 2017, 179: 57-74,

[46] Singh J, Kumar P, Eid EM, Taher MA, El-Morsy MHE, Osman HEM, Al-Bakre DA, Kumar V. Phytoremediation of nitrogen and phosphorus pollutants from glass industry effluent by using water hyacinth (Eichhornia crassipes (Mart.) Solms): application of RSM and ANN techniques for experimental optimization. Environ Sci Pollut R, 2023, 30: 20590-20600,

[47] Smit AL, Bindraban PS, Conijn JG, van der Meer HG. . Phosphorus in agriculture: global resources, trends and developments, 2009 Wageningen Plant Research International Bv 282

[48] Tang X, Lei Y, Yu C, Wang C, Zhang P, Lu H. Highly-efficient degradation of organic pollutants by oxalic acid modified sludge biochar: mechanism and pathways. Chemosphere, 2023, 325,

[49] Tran HN, You S, Hosseini-Bandegharaei A, Chao H. Mistakes and inconsistencies regarding adsorption of contaminants from aqueous solutions: a critical review. Water Res, 2017, 120: 88-116,

[50] Tu Y, Peng Z, Huang J, Wu X, Kong L, Liang Z, Yang L, Lin Z. Preparation and characterization of magnetic biochar nanocomposites via a modified solvothermal method and their use as efficient heterogeneous Fenton-like catalysts. Ind Eng Chem Res, 2020, 59: 1809-1821,

[51] Villanueva ME, Salinas A, Copello GJ, Díaz LE. Point of zero charge as a factor to control biofilm formation of Pseudomonas aeruginosa in sol-gel derivatized aluminum alloy plates. Surf Coat Technol, 2014, 254: 145-150,

[52] Wang H, Xiao K, Yang J, Yu Z, Yu W, Xu Q, Wu Q, Liang S, Hu J, Hou H, Liu B. Phosphorus recovery from the liquid phase of anaerobic digestate using biochar derived from iron−rich sludge: a potential phosphorus fertilizer. Water Res, 2020, 174,

[53] Wang Z, Hong S, Wen J, Ma C, Tang L, Jiang H, Chen J, Li S, Shen X, Yuan T. Lewis acid-facilitated deep eutectic solvent (DES) pretreatment for producing high-purity and antioxidative lignin. Acs Sustain Chem Eng, 2020, 8: 1050-1057,

[54] Wang B, Hu X, Zhou D, Zhang H, Chen R, Guo W, Wang H, Zhang W, Hong Z, Lyu W. Highly selective and sustainable clean–up of phosphate from aqueous phase by eco–friendly lanthanum cross–linked polyvinyl alcohol/alginate/palygorskite composite hydrogel beads. J Clean Prod, 2021, 298,

[55] Wang Z, Chen L, Liu C, Jin Y, Li F, Khan S, Liang X. Reduced colloidal phosphorus loss potential and enhanced phosphorus availability by manure-derived biochar addition to paddy soils. Geoderma, 2021, 402,

[56] Wang J, Jiang Y, Xu M, Han C, Zhang L, Liu G. Resin-based iron-manganese binary oxide for phosphate selective removal. Environ Sci Pollut Res, 2023, 30(2): 4642-4652,

[57] Wu B, Wan J, Zhang Y, Pan B, Lo IMC. Selective phosphate removal from water and wastewater using sorption: process fundamentals and removal mechanisms. Environ Sci Technol, 2020, 54: 50-66,

[58] Wu D, Shen C, Cheng Y, Ding J, Li W. Phosphorus removal by aquatic vegetation in shallow eutrophic lakes: a laboratory study. Environ Sci Pollut R, 2023, 30: 16166-16177,

[59] Xie F, Wu F, Liu G, Mu Y, Feng C, Wang H, Giesy JP. Removal of phosphate from eutrophic lakes through adsorption by in situ formation of magnesium hydroxide from diatomite. Environ Sci Technol, 2014, 48: 582-590,

[60] Xie F, Li L, Song K, Li G, Wu F, Giesy JP. Characterization of phosphorus forms in a eutrophic lake, China. Sci Total Environ, 2019, 659: 1437-1447,

[61] Xu Q, Chen Z, Wu Z, Xu F, Yang D, He Q, Li G, Chen Y. Novel lanthanum doped biochars derived from lignocellulosic wastes for efficient phosphate removal and regeneration. Bioresource Technol, 2019, 289,

[62] Yamashita T, Hayes P. Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials. Appl Surf Sci, 2008, 254: 2441-2449,

[63] Yang Q, Wang X, Luo W, Sun J, Xu Q, Chen F, Zhao J, Wang S, Yao F, Wang D, Li X, Zeng G. Effectiveness and mechanisms of phosphate adsorption on iron-modified biochars derived from waste activated sludge. Bioresource Technol, 2018, 247: 537-544,

[64] Yang J, Wang Z, Li R, Xu X, Liu J, Huang Y, Ye X, Wang W. Effect of Fe (III) modification on the phosphorus removal behavior of Ce (III) carbonate adsorbents. ACS Omega, 2022, 7(36): 31767-31777,

[65] Yao Y, Gao B, Chen J, Yang L. Engineered biochar reclaiming phosphate from aqueous solutions: Mechanisms and potential application as a slow-release fertilizer. Environ Sci Technol, 2013, 47: 8700-8708,

[66] Yi Y, Tu G, Zhao D, Tsang P, Fang Z. Biomass waste components significantly influence the removal of Cr(VI) using magnetic biochar derived from four types of feedstocks and steel pickling waste liquor. Chem Eng J, 2019, 360: 212-220,

[67] Yin Q, Ren H, Wang R, Zhao Z. Evaluation of nitrate and phosphate adsorption on Al-modified biochar: influence of Al content. Sci Total Environ, 2018, 631: 895-903,

[68] Yu C, Shi C, Ji M, Xu X, Zhang Z, Ma J, Wang G. Taste and odor compounds associated with aquatic plants in Taihu lake: distribution and producing potential. Environ Sci Pollut R, 2019, 26: 34510-34520,

[69] Yu J, Feng H, Tang L, Pang Y, Wang J, Zou J, Xie Q, Liu Y, Feng C, Wang J. Insight into the key factors in fast adsorption of organic pollutants by hierarchical porous biochar. J Hazard Mater, 2021, 403,

[70] Zhang B, Wang L, Li Y. Fractionation and identification of iron-phosphorus compounds in sewage sludge. Chemosphere, 2019, 223: 250-256,

[71] Zhao D, Qiu S, Li M, Luo Y, Zhang L, Feng M, Yuan M, Zhang K, Wang F. Modified biochar improves the storage capacity and adsorption affinity of organic phosphorus in soil. Environ Res, 2022, 205,

[72] Zhou Z, Liu Y, Liu S, Liu H, Zeng G, Tan X, Yang C, Ding Y, Yan Z, Cai X. Sorption performance and mechanisms of arsenic (V) removal by magnetic gelatin-modified biochar. Chem Eng J, 2017, 314: 223-231,

Funding

Key Research and Development Project of Science and Technology Department of Zhejiang Province(2023C02016); Key Laboratory in Science and Technology Development Project of Suzhou(2023C02019); Key Technologies Research and Development Program(2022YFD1700704-3); Bingtuan Science and Technology Program(2021DB019)