Peroxydisulfate activation by one-step pyrolysis iron-rich sludge biochar for tetracycline removal in water: performance, mechanism and degradation pathway

Xunli Bao , Lu Zhou , Bei Liu , Guanhao Zhang , Yi Fang , Yulin Zeng

Biochar ›› 2025, Vol. 7 ›› Issue (1) : 87

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Biochar ›› 2025, Vol. 7 ›› Issue (1) : 87 DOI: 10.1007/s42773-025-00471-1
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Peroxydisulfate activation by one-step pyrolysis iron-rich sludge biochar for tetracycline removal in water: performance, mechanism and degradation pathway

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Abstract

Steel sludge, a byproduct generated from wastewater treatment in the steel industry, has high levels of iron salts and heavy metals, while traditional treatment technologies such as land application, sanitary landfilling, and incineration make resource recovery and utilization challenging. In this study, iron-rich sludge biochar (FSB) was prepared by one-step pyrolysis of iron-rich sludge generated from a steel factory and utilized to activate peroxydisulfate (PS) for tetracycline (TC) removal. Results showed that FSB pyrolyzed at 450 ºC (FSB450) exhibited excellent degradation performance under the optimal conditions (FSB450 dosage of 0.4 g L−1, initial solution pH of 3, and PS dosage of 8 mM). In the FSB450/PS system, oxygen-containing functional groups, edge defects, and inherent iron oxides in FSB provided abundant active sites that can facilitate the generation of reactive oxygen species (ROS), including SO4˙,.OH, O2˙, and 1O2, thus accelerating TC degradation by both radical and non-radical processes. Combining with density functional theory (DFT) calculations, the degradation pathways of TC may include demethylation, decarbonylation, dealkylation, dehydroxylation, etc. Meanwhile, the overall toxicity of TC intermediates was reduced after FSB450/PS treatment. Overall, this study provides a novel and feasible approach for the resource utilization of iron-enrich sludge and the treatment of TC wastewater treatment.

Keywords

Iron-rich sludge / Peroxydisulfate / Tetracycline degradation / Biochar / Mechanism

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Xunli Bao, Lu Zhou, Bei Liu, Guanhao Zhang, Yi Fang, Yulin Zeng. Peroxydisulfate activation by one-step pyrolysis iron-rich sludge biochar for tetracycline removal in water: performance, mechanism and degradation pathway. Biochar, 2025, 7(1): 87 DOI:10.1007/s42773-025-00471-1

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References

[1]

BriganteM, SchulzPC. Remotion of the antibiotic tetracycline by titania and titania–silica composed materials. J Hazard Mater, 2011, 192(3): 1597-1608

[2]

ChenJ, BaiX, YuanY, ZhangY, SunJ. Printing and dyeing sludge derived biochar for activation of peroxymonosulfate to remove aqueous organic pollutants: Activation mechanisms and environmental safety assessment. Chem Eng J, 2022, 446 ArticleID: 136942

[3]

DengY, XiaoL, ZhouH, CuiB, ZhangL, ChenD, GuC, ZhanZ, WangR, MeiS, PeiX, LiQ, YeY, PanF. Phytic acid pre-modulated and Fe/N co-doped biochar derived from ramie fiber to active persulfate for efficient degradation of tetracycline via radical and non-radical pathways. Sep Purif Technol, 2024, 342 ArticleID: 126976

[4]

DuanX, SuC, ZhouL, SunH, SuvorovaA, OdedairoT, ZhuZ, ShaoZ, WangS. Surface controlled generation of reactive radicals from persulfate by carbocatalysis on nanodiamonds. Appl Catal B, 2016, 194: 7-15

[5]

FengY, LiuM, ShiQ, SongY, YangL, ZhangJ, LiZ, ZhuW. Sludge-derived biochar applied in peroxymonosulfate (PMS) activation: reactive oxygen species (ROS) dominated process and characteristics. J Environ Chem Eng, 2023, 11(6) ArticleID: 111365

[6]

GongW, HeD, WangX, YanY, DionysiouDD, BlaneyL, PengG. The role of Fe(IV) in the zero-valent iron biochar activated persulfate system for treatment of contaminants of emerging concern. Chem Eng J, 2024, 487 ArticleID: 150553

[7]

GuoP, ZhouY, ZhangY, LiY, LeiH, ZhangH, LiS. Insights into the well-dispersed nano-Fe3O4 catalyst supported by N-doped biochar prepared from steel pickling waste liquor for activating peroxydisulfate to degrade tetracycline. Chem Eng J, 2023, 464 ArticleID: 142548

[8]

HeJ, TangJ, ZhangZ, WangL, LiuQ, LiuX. Magnetic ball-milled FeS@biochar as persulfate activator for degradation of tetracycline. Chem Eng J, 2021, 404 ArticleID: 126997

[9]

HeL, YangS, YangL, ShenS, LiY, KongD, ChenZ, YangS, WangJ, WuL, ZhangZ. Ball milling-assisted preparation of sludge biochar as a novel periodate activator for nonradical degradation of sulfamethoxazole: Insight into the mechanism of enhanced electron transfer. Environ Pollut, 2023, 316 ArticleID: 120620

[10]

HuangZ, LiuH. Insights into the pathways, intermediates, influence factors and toxicological properties in the degradation of tetracycline by TiO2-based photocatalysts. J Environ Chem Eng, 2023, 11 5) ArticleID: 110587

[11]

IoannidiA, OulegoP, ColladoS, PetalaA, ArniellaV, FrontistisZ, AngelopoulosGN, DiazM, MantzavinosD. Persulfate activation by modified red mud for the oxidation of antibiotic sulfamethoxazole in water. J Environ Manage, 2020, 270 ArticleID: 110820

[12]

KangX, ZhangQ, LiuX, SongJ, GuoH, WangL. The interface mechanism of sludge biochar activating persulfate to remove tetracycline: the role of the C-O-Fe bridge at the carbon surface. J Clean Prod, 2023, 384 ArticleID: 135514

[13]

KemmouL, FrontistisZ, VakrosJ, ManariotisID, MantzavinosD. Degradation of antibiotic sulfamethoxazole by biochar-activated persulfate: factors affecting the activation and degradation processes. Catal Today, 2018, 313: 128-133

[14]

LiZ, SunY, LiuD, YiM, ChangF, LiH, DuY. A review of sulfate radical-based and singlet oxygen-based advanced oxidation technologies: recent advances and prospects. Catalysts, 2022, 12 10): 1092

[15]

LiX, CaoH, CaoY, ZhaoY, ZhangW, ShenJ, SunZ, MaF, GuQ. Insights into the mechanism of persulfate activation with biochar composite loaded with Fe for 2,4-dinitrotoluene degradation. J Environ Manage, 2023, 341 ArticleID: 117955

[16]

LiC, LiuZ, FangN, YuW, YangC, ChuY, LiuW. 10Extrinsic defects-rich biochar for efficient peroxydisulfate activation: electronic structure modulation and disparate nonradical mechanisms. Sep Purif Technol, 2024, 336 ArticleID: 126338

[17]

LiS, ZhouY, WangJ, DouM, ZhangQ, HuoK, HanC, ShiJ. Sewage sludge pyrolysis ‘kills two birds with one stone’: biochar synergies with persulfate for pollutants removal and energy recovery. Chemosphere, 2024, 363 ArticleID: 142824

[18]

LiX, ZengL, ZhuL, JiangH, LiuC, DaiY. Strong adsorption of tetracycline on carbon blacks: an in-depth study of the adsorption mechanism. J Water Process Eng, 2025, 70, ArticleID: 106784

[19]

LiangJ, ChenK, DuanX, ZhaoL, QiuH, XuX, CaoX. pH-dependent generation of radical and nonradical species for sulfamethoxazole degradation in different carbon/persulfate systems. Water Res, 2022, 224 ArticleID: 119113

[20]

LinL, FangW, LiangQ, XingY, SunM, LuoH. Synthesis of Fe-doped sludge biochar from Fenton sludge for efficient activation of peroxymonosulfate in tetracycline hydrochloride degradation. J Environ Chem Eng, 2024, 12(3) ArticleID: 112590

[21]

LiuC, ChenL, DingD, CaiT. From rice straw to magnetically recoverable nitrogen doped biochar: efficient activation of peroxymonosulfate for the degradation of metolachlor. Appl Catal B, 2019, 254: 312-320

[22]

LiuH, LiuY, TangL, WangJ, YuJ, ZhangH, YuM, ZouJ, XieQ. Egg shell biochar-based green catalysts for the removal of organic pollutants by activating persulfate. Sci Total Environ, 2020, 745 ArticleID: 141095

[23]

LiuF, DingJ, ZhaoG, ZhaoQ, WangK, WangG, GaoQ. Catalytic pyrolysis of lotus leaves for producing nitrogen self-doping layered graphitic biochar: performance and mechanism for peroxydisulfate activation. Chemosphere, 2022, 302 ArticleID: 134868

[24]

LiuX, ShaoZ, WangY, LiuY, WangS, GaoF, DaiY. New use for Lentinus edodes bran biochar for tetracycline removal. Environ Res, 2023, 216 ArticleID: 114651

[25]

LuY-W, FanY-H, ChenM. Synthesis of invasive plant biochar catalyst with carbon nitride structure for peroxymonosulfate activation toward efficient ciprofloxacin degradation. Biochar, 2024, 6 1): 1-17

[26]

MaH, ZhangB, WangS, LiuC, ZhuL, ZhaoZ, LiW, ShaoZ, LiuX, DaiY. Enhanced removal of tetracycline by vitamin C-modified cow manure biochar in water. Sci Rep, 2024, 14(1): 22362

[27]

MengX, PengG, YanY, WangX, ZhuJ, BelverC, GongW, BlaneyL. Analysis of the steady-state concentrations of reactive species and their role in contaminant degradation by the iron-biochar/persulfate advanced oxidation process: comparison of probe compound and quenching agent methods. Sep Purif Technol, 2025, 354 ArticleID: 128502

[28]

MiaoX, ChenX, WuW, LinD, YangK. Intrinsic defects enhanced biochar/peroxydisulfate oxidation capacity through electron-transfer regime. Chem Eng J, 2022, 438 ArticleID: 135606

[29]

Olmez-HanciT, Arslan-AlatonI. Comparison of sulfate and hydroxyl radical based advanced oxidation of phenol. Chem Eng J, 2013, 224: 10-16

[30]

Olmez-HanciT, Arslan-AlatonI, DursunD. Investigation of the toxicity of common oxidants used in advanced oxidation processes and their quenching agents. J Hazard Mater, 2014, 278: 330-335

[31]

PuM, WanJ, ZhangF, BrusseauML, YeD, NiuJ. Insight into degradation mechanism of sulfamethoxazole by metal-organic framework derived novel magnetic Fe@C composite activated persulfate. J Hazard Mater, 2021, 414 ArticleID: 125598

[32]

QianL, YanS, YongX, SelvarajM, GhramhHA, AssiriMA, ZhangX, AwasthiMK, ZhouJ. Effective degradation of chloramphenicol in wastewater by activated peroxymonosulfate with Fe-rich porous biochar derived from petrochemical sludge. Chemosphere, 2023, 310 ArticleID: 136839

[33]

QuJ, WangS, JinL, LiuY, YinR, JiangZ, TaoY, HuangJ, ZhangY. Magnetic porous biochar with high specific surface area derived from microwave-assisted hydrothermal and pyrolysis treatments of water hyacinth for Cr(VI) and tetracycline adsorption from water. Biores Technol, 2021, 340 ArticleID: 125692

[34]

QuJ, XueJ, SunM, LiK, WangJ, ZhangG, WangL, JiangZ, ZhangY. Superefficient non-radical degradation of benzo[a]pyrene in soil by Fe-biochar composites activating persulfate. Chem Eng J, 2024, 481 ArticleID: 148585

[35]

SamuelMS, SavunthariKV, EthirajS. Synthesis of a copper (II) metal–organic framework for photocatalytic degradation of rhodamine B dye in water. Environ Sci Pollut Res, 2021, 28(30): 40835-40843

[36]

SamuelMS, ShangM, KlimchukS, NiuJ. Novel regenerative hybrid composite adsorbent with improved removal capacity for lead ions in water. Ind Eng Chem Res, 2021, 60(14): 5124-5132

[37]

SamuelMS, ShangM, NiuJ. Photocatalytic degradation of perfluoroalkyl substances in water by using a duo-functional tri-metallic-oxide hybrid catalyst. Chemosphere, 2022, 293 ArticleID: 133568

[38]

SamuelMS, KadarkaraiG, RyanDR, McBeathST, MayerBK, McNamaraPJ. Enhanced perfluorooctanoic acid (PFOA) degradation by electrochemical activation of peroxydisulfate (PDS) during electrooxidation for water treatment. Sci Total Environ, 2024, 942 ArticleID: 173736

[39]

ShaoF, WangY, MaoY, ShaoT, ShangJ. Degradation of tetracycline in water by biochar supported nanosized iron activated persulfate. Chemosphere, 2020, 261 ArticleID: 127844

[40]

ShaoZ, ShuangbaoWuS, GaoY, LiuX, DaiY. Two-step pyrolytic preparation of biochar for the adsorption study of tetracycline in water. Environ Res, 2024, 242 ArticleID: 117566

[41]

TongS, ChenD, JiangX, XuZ, LiuX, ShenJ. Persulfate activation by Fe3O4-doped biochar synthesized from Fenton sludge and sewage sludge for enhanced 1-H-1,2,4-triazole degradation. Chem Eng J, 2023, 461 ArticleID: 142075

[42]

WangJ, WangS. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants. Chem Eng J, 2018, 334: 1502-1517

[43]

WangS, WangJ. Nitrogen doping sludge-derived biochar to activate peroxymonosulfate for degradation of sulfamethoxazole: Modulation of degradation mechanism by calcination temperature. J Hazard Mater, 2021, 418 ArticleID: 126309

[44]

WangX, LiW, WangS, ZhangJ, ZhaoQ. Regulated synthesis of cobalt phosphide/biochar utilizing phytic acid: Biochar enhances anion co-catalysis of cobalt phosphides in persulfate activation. Chem Eng J, 2023, 478 ArticleID: 147273

[45]

WangZ-J, LinY-Q, ZhouH-J, LiuZ-L, MiaoR-R, XuX-M, HeL, GuanQ-Q. Boosting persulfate activation via paper mill sludge-based biochar for efficient degradation of bisphenol A: Inherent multiple active sites. Chem Eng J, 2023, 455 ArticleID: 140795

[46]

XiM, CuiK, CuiM, DingY, GuoZ, ChenY, LiC, LiX. Enhanced norfloxacin degradation by iron and nitrogen co-doped biochar: revealing the radical and nonradical co-dominant mechanism of persulfate activation. Chem Eng J, 2021, 420 ArticleID: 129902

[47]

XiaX, ZengS, LiK, ZengL, MiaoS. Unraveling the outstanding catalytic efficiency of unprocessed bone-derived biochar: a deep dive into the mechanisms of native organic encapsulation and defective nitrogen doping in boosting persulfate activation for tetracycline degradation. Sep Purif Technol, 2025, 353 ArticleID: 128571

[48]

XinZ, TongJ, WangJ, RuanC, LyuJ, ShiJ. Research progress on activated persulfate by biochar: soil and water environment remediation, mechanism exploration and simulation calculation. Chem Eng J, 2024, 493 ArticleID: 152718

[49]

XiongS, ZengH, DengY, TangR, WangJ, LiL, ZhouZ, GongD. Unveiling the synergistic effect of internal Fe single atoms and introduced Fe3C in Enteromorpha derived biochar with enhanced peroxymonosulfate activation property towards nitenpyram removal. Biochar, 2023, 5(1): 19

[50]

XiongJ, ZhuJ, ZengQ, ZhaW, LiuJ, FanG, NiuY. Acetic acid-modified nitrogen-doped biochar loaded Fe-Co bimetal promotes persulfate activation for efficient quinoline removal and its 1O2 and O2•- pathways. Surfaces Interfaces, 2024, 54 ArticleID: 105280

[51]

XuM, WeiJ, ChenX, PanG, LiJ, XingL, ZhangY, LiY, WangZ, LiJ. Satisfactory degradation of tetracycline by a pH-universal MnFe-LDH@BC cathode in electric Fenton process: performances, mechanisms and toxicity assessments. J Environ Chem Eng, 2022, 10(5) ArticleID: 108409

[52]

XuK, LinQ, FanX, ZhengJ, LiuY, MaY, HeJ. Enhanced degradation of sulfamethoxazole by activation of peroxodisulfate with red mud modified biochar: synergistic effect between adsorption and nonradical activation. Chem Eng J, 2023, 460 ArticleID: 141578

[53]

XueY, KamaliM, LiyakatA, BruggemanM, MuhammadZ, RossiB, CostaMEV, AppelsL, DewilR. A walnut shell biochar-nano zero-valent iron composite membrane for the degradation of carbamazepine via persulfate activation. Sci Total Environ, 2023, 899 ArticleID: 165535

[54]

YaoB, LuoZ, DuS, YangJ, ZhiD, ZhouY. Magnetic MgFe2O4/biochar derived from pomelo peel as a persulfate activator for levofloxacin degradation: effects and mechanistic consideration. Biores Technol, 2022, 346 ArticleID: 126547

[55]

YiY, FuY, WangY, CaiY, LiuY, XuZ, DiaoZ. 7 Persulfate oxidation of norfloxacin by cobalt doped water hyacinth biochar composite: the key role of cobalt and singlet oxygen. J Water Process Eng, 2024, 59, ArticleID: 104967

[56]

YinR, GuoW, WangH, DuJ, WuQ, ChangJ-S, RenN. Singlet oxygen-dominated peroxydisulfate activation by sludge-derived biochar for sulfamethoxazole degradation through a nonradical oxidation pathway: Performance and mechanism. Chem Eng J, 2019, 357: 589-599

[57]

YinK, WangJ, TianX, YuN, ZhangX, ZhaoY, LiuY, SuiS, WangC, LianF, ZhaiS, LiX, XingB. Effect of biochar-derived dissolved organic matter on tetracycline sorption by KMnO4-modified biochar. Chem Eng J, 2023, 474 ArticleID: 145872

[58]

YuJ, TangL, PangY, ZengG, WangJ, DengY, LiuY, FengH, ChenS, RenX. Magnetic nitrogen-doped sludge-derived biochar catalysts for persulfate activation: Internal electron transfer mechanism. Chem Eng J, 2019, 364: 146-159

[59]

ZangT, WangH, LiuY, DaiL, ZhouS, AiS. Fe-doped biochar derived from waste sludge for degradation of Rhodamine B via enhancing activation of peroxymonosulfate. Chemosphere, 2020, 261 ArticleID: 127616

[60]

ZengS, KanE. Comparative insights into performance and mechanisms of Fenton and persulfate oxidation on iron-functionalized activated biochar for removal of aqueous tetracycline antibiotics. J Water Process Eng, 2024, 65, ArticleID: 105824

[61]

ZengS, ChoiY-K, KanE. Iron-activated bermudagrass-derived biochar for adsorption of aqueous sulfamethoxazole: effects of iron impregnation ratio on biochar properties, adsorption, and regeneration. Sci Total Environ, 2021, 750 ArticleID: 141691

[62]

ZengH, LiJ, XuJ, QiW, HaoR, LinD, LiD, ZhangJ. Magnetic biochar based on platanus leaves and iron sludge for persulfate activation and catalytic degradation of tetracycline. J Clean Prod, 2022, 370 ArticleID: 133336

[63]

ZhangJ, F, ZhangH, ShaoL, ChenD, HeP. Multiscale visualization of the structural and characteristic changes of sewage sludge biochar oriented towards potential agronomic and environmental implication. Sci Rep, 2015, 5 1): 9406

[64]

ZhangP, TanX, LiuS, LiuY, ZengG, YeS, YinZ, HuX, LiuN. Catalytic degradation of estrogen by persulfate activated with iron-doped graphitic biochar: process variables effects and matrix effects. Chem Eng J, 2019, 378 ArticleID: 122141

[65]

ZhaoY, YuanX, LiX, JiangL, WangH. Burgeoning prospects of biochar and its composite in persulfate-advanced oxidation process. J Hazard Mater, 2021, 409 ArticleID: 124893

[66]

ZhouL, ZhuX, ChiT, LiuB, DuC, YuG, WuH, ChenH. Reutilization of manganese enriched biochar derived from Phytolacca acinosa Roxb residue after phytoremediation for lead and tetracycline removal. Bioresource Technol, 2022, 345: 126546

[67]

ZhouX, LaiC, LiuS, LiB, QinL, LiuX, YiH, FuY, LiL, ZhangM, YanH, WangJ, ChenM, ZengG. Activation of persulfate by swine bone derived biochar: Insight into the specific role of different active sites and the toxicity of acetaminophen degradation pathways. Sci Total Environ, 2022, 807 ArticleID: 151059

[68]

ZhuangY, SpahrS, LutzeHV, ReithCJ, HagemannN, PaulA, HaderleinSB. Persulfate activation by biochar and iron: effect of chloride on formation of reactive species and transformation of N, N-diethyl-m-toluamide (DEET). Water Res, 2024, 265 ArticleID: 122267

Funding

National Natural Science Foundation of China(No. 51809019)

Science Fund for Distinguished Young Scholars of Hunan Province(No. 2022JJ30616)

Scientific Research Project of the Education Department of Hunan province(No.22B0338)

Science and Technology Program of Hunan Province(XSKJ2024064-35)

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