Citation: Jinyan Yang, Ying Chen, Minghan Yu, Lan Zhu, Yilin Wang, Jingsong Chen, Hui Ma, Shengyan Pu. Different natural iron-bearing minerals activated peroxymonosulfate for in-situ chemical oxidation process: Insights into the active Fe sites and activation mechanism[J]. Chinese Chemical Letters, ;2026, 37(7): 112210. doi: 10.1016/j.cclet.2025.112210 shu

Different natural iron-bearing minerals activated peroxymonosulfate for in-situ chemical oxidation process: Insights into the active Fe sites and activation mechanism

Jinyan Yang ^{a, b} ,
Ying Chen ^{a, b} ,
Minghan Yu ^{a, b} ,
Lan Zhu ^{a, b} ,
Yilin Wang ^{a, b} ,
Jingsong Chen ^{a, b} ,
Hui Ma ^{a, b, *,} ,
Shengyan Pu ^{a, b, c, *,}

a.
State Key Laboratory of Geohazard Prevention and Geoenvironment Protection, Chengdu University of Technology, Chengdu 610059, China
b.
State Environmental Protection Key Laboratory of Synergetic Control and Joint Remediation for Soil&Water Pollution, Chengdu University of Technology, Chengdu 610059, China
c.
Tianfu Jiangxi Laboratory, Chengdu 610059, China

mahui@cdut.edu.cn

pushengyan@gmail.com

pushengyan13@cdut.edu.cn

Received Date: 11 June 2025
Revised Date: 26 November 2025
Accepted Date: 3 December 2025
Available Online: 3 December 2025

Figures(6)

In situ chemical oxidation (ISCO) technology using peroxymonosulfate (PMS) and natural iron-bearing minerals for groundwater remediation has received increasing interest. The interaction between PMS and active Fe sites in minerals significantly influences the effectiveness of groundwater remediation. Nevertheless, there has been limited research investigating the relationship between the minerals active Fe sites and PMS activation. Herein, we distinguished and quantified the active Fe sites of common natural iron-bearing minerals in groundwater aquifers. Lewis acid sites (Fe-OH) were confirmed as the reaction sites in iron oxide/hydroxide/bearing clay minerals. The activation performance of minerals is positively correlated with their Lewis acid content. In iron sulfide minerals, Fe-S sites act as electron transfer mediators, facilitating PMS adsorption and activation. The activation of PMS by Lewis acid and Fe-S sites free radical both led to the generation of free radicals (SO₄^·- and ^·OH) for CPs removal. Moreover, typical ferrihydrite/PMS and pyrite/PMS systems exhibited resistance to environmental interference and broad pH adaptability. A one-dimensional sand column experiment further proved their feasibility and long-term applicability in saturated porous media. These findings highlight the critical influence of active Fe sites of natural iron-bearing minerals and provide technical support for the application of PMS-ISCO strategies for groundwater remediation.
- Groundwater remediation,
- In situ chemical oxidation,
- Natural iron-bearing minerals,
- Peroxymonosulfate activation,
- Active Fe sites
1. [1]
  A. Peng, J. Gao, Z. Chen, et al., Environ. Sci. Tech. 52 (2018) 5208–5217. doi: 10.1021/acs.est.7b06664
2. [2]
  T. Chen, C. Zou, F. Chen, et al., J. Hazard. Mater. 426 (2022) 128066. doi: 10.1016/j.jhazmat.2021.128066
3. [3]
  M. Yu, J. Yang, J. Chen, et al., J. Environ. Chem. Eng. 13(2) (2025) 116048. doi: 10.1016/j.jece.2025.116048
4. [4]
  M. Hao, Q. Wang, F. Yu, Z. et al., J. Clean. Prod. 458 (2024) 142415. doi: 10.1016/j.jclepro.2024.142415
5. [5]
  X. Chen, Z. Li, Z. Zhang, et al., Water Res. 273 (2025) 123014. doi: 10.1016/j.watres.2024.123014
6. [6]
  J.Q. Yang, Z.L. Li, B. Wu, et al., J. Hazard. Mater. 441 (2023) 129978. doi: 10.1016/j.jhazmat.2022.129978
7. [7]
  W. Wang, T. Gong, H. Li, et al., Water Res. 217 (2022) 118422. doi: 10.1016/j.watres.2022.118422
8. [8]
  L. McGachy, D.L. Sedlak, Environ. Sci. Tech. 58 (2024) 17–32. doi: 10.1021/acs.est.3c07409
9. [9]
  J. Dou, X. Su, J. Wu, et al., Environ. Sci. Tech. 58 (2024) 8065–8075. doi: 10.1021/acs.est.3c08759
10. [10]
  X. Liu, H. Qin, S. Xing, et al., Environ. Sci. Tech. 57 (2023) 13710–13720. doi: 10.1021/acs.est.3c04870
11. [11]
  A Wang, B.Z. Zhu, C.H. Huang, et al., Water Res. 235 (2023) 119904. doi: 10.1016/j.watres.2023.119904
12. [12]
  C. Liang, S. Yin, P. Huang, et al., Chem. Eng. J. 482 (2024) 148969. doi: 10.1016/j.cej.2024.148969
13. [13]
  J. Liang, X. Duan, X. Xu, et al., Environ. Sci. Tech. 58 (2024) 915–924. doi: 10.1021/acs.est.3c07253
14. [14]
  Z. Yang, Y. Cui, B. Pan, J.J. Pignatello, Environ. Sci. Tech. 57 (2023) 18918–18928. doi: 10.1021/acs.est.3c00777
15. [15]
  A. Chen, M. Cheng, G. Wang, et al., Sep. Purif. Technol. 354 (2025) 129432. doi: 10.1016/j.seppur.2024.129432
16. [16]
  R.H. Wang, Q.K. Shi, W.J.Wang He, et al., Environ. Sci.: Nano. 12 (2025) 2407–2420. doi: 10.1039/d5en00004a
17. [17]
  W. Xiao, A. Chen, M. Cheng, et al., Water Res. 268 (2025) 122735. doi: 10.1016/j.watres.2024.122735
18. [18]
  W.X. Jiang, Y.W. Wang, H. Guo, J. Hazard. Mater. 49 (2025) 138138.
19. [19]
  W.X. Jiang, Y.W. Wang, C. D. P. Y, et al., J. Colloid Interface Sci. 685 (2025) 975–987. doi: 10.1016/j.jcis.2025.01.226
20. [20]
  C. Guo, L. Qi, Y. Bai, et al., Ecotoxicology Environ. Saf. 224 (2021) 112649. doi: 10.1016/j.ecoenv.2021.112649
21. [21]
  S. He, Y. Chen, X. Li, et al., ACS EST Eng. 2 (2022) 527–546. doi: 10.1021/acsestengg.1c00330
22. [22]
  J. Peng, H. Zhou, W. Liu, et al., Chem. Eng. J. 397 (2020) 125387. doi: 10.1016/j.cej.2020.125387
23. [23]
  J. Zhao, P. Zhong, W. Luo, et al., Chem. Eng. J. 433 (2022) 133835. doi: 10.1016/j.cej.2021.133835
24. [24]
  D. Wu, S. Huang, X. Zhang, et al., Environ. Sci. Tech. 55 (2021) 9569–9578. doi: 10.1021/acs.est.1c01016
25. [25]
  P. Wang, X. Liu, W. Qiu, et al., Water Res. 182 (2020) 116030. doi: 10.1016/j.watres.2020.116030
26. [26]
  C. Li, L. Jin, W. Wang, et al., J. Hazard. Mater. 436 (2022) 129079. doi: 10.1016/j.jhazmat.2022.129079
27. [27]
  Y. Zhou, X. Wang, C. Zhu, et al., Water Res. 142 (2018) 208–216. doi: 10.1016/j.watres.2018.06.002
28. [28]
  S. Xiao, M. Cheng, H. Zhong, et al., Chem. Eng. J. 384 (2020) 123265. doi: 10.1016/j.cej.2019.123265
29. [29]
  Q. Qin, T. Liu, J. Zhang, et al., J. Hazard. Mater. 419 (2021) 126447. doi: 10.1016/j.jhazmat.2021.126447
30. [30]
  K. Hou, Z. Pi, F. Yao, et al., Chem. Eng. J. 407 (2021) 127078. doi: 10.1016/j.cej.2020.127078
31. [31]
  Y. Zhao, H. An, J. Feng, et al., Environ. Sci. Tech. 53 (2019) 4500–4510. doi: 10.1021/acs.est.9b00658
32. [32]
  M. Wu, W. Sun, X. Meng, et al., ACS EST Water 3 (2023) 3265–3273. doi: 10.1021/acsestwater.3c00266
33. [33]
  R.L. Parfitt, J.D. Russell, V.C. Farmer, J. Chem. Soc. 72 (1976) 1082–87.
34. [34]
  C. Tian, C. Dai, X. Tian, et al., Sep. Purif. Technol. 286 (2022) 120437. doi: 10.1016/j.seppur.2021.120437
35. [35]
  P. Zhang, S. Yuan, Geochim. Cosmochim. Acta 218 (2017) 153–166. doi: 10.1016/j.gca.2017.08.032
36. [36]
  C.A. Emeis, J. Catal. 141 (1993) 347–354. doi: 10.1006/jcat.1993.1145
37. [37]
  X. Li, T. Li, T. Zhang, et al., Environ. Sci. Tech. 52 (2018) 4031–4039. doi: 10.1021/acs.est.7b05479
38. [38]
  K.B. Gregory, P. Larese-Casanova, G.F. Parkin, et al., Sci. Tech. 38 (2004) 1408–1414. doi: 10.1021/es034588w
39. [39]
  J. Lee, U. von Gunten, J.H. Kim, Environ. Sci. Tech. 54 (2020) 3064–3081. doi: 10.1021/acs.est.9b07082
40. [40]
  Y. Lei, Y. Yu, X. Lei, et al., Environ. Sci. Tech. 57 (2023) 5433–5444. doi: 10.1021/acs.est.2c09338
41. [41]
  X. Zhang, C. Zhou, J. Zhang, et al., Chin. Chem. Lett. 37 (2026) 111630. doi: 10.1016/j.cclet.2025.111630
42. [42]
  L. Huang, R. Gan, X. Han, et al., Chin. Chem. Lett. 37 (2026) 111840. doi: 10.1016/j.cclet.2025.111840
43. [43]
  B. Barrios, B. Mohrhardt, P.V. Doskey, et al., Environ Sci Tech, 2021, 55(12): 8054–67. doi: 10.1021/acs.est.1c01712
44. [44]
  X.Q. Cao, X. Liu, Y. Wang, et al., Chin. Chem. Lett. (2025) 112112, doi:10.1016/j.cclet.2025.112112. doi: 10.1016/j.cclet.2025.112112
45. [45]
  J. Li, Y. Ren, J. Gao, et al., Chin. Chem. Lett. (2025) 111355, doi:10.1016/j.cclet.2025.111355. doi: 10.1016/j.cclet.2025.111355
46. [46]
  L. Zou, D, WANG, S. Lai, et al., Chin. Chem. Lett. 36 (2025) 111094. doi: 10.1016/j.cclet.2025.111094
47. [47]
  S. You, R. Li, H. Lu, et al., Chin. Chem. Lett. 36 (2025) 110955. doi: 10.1016/j.cclet.2025.110955
48. [48]
  G. Li, Y. Zhang, X. Zhang, et al., Environ. Sci. Tech. 58(35) (2024) 15864–15873. doi: 10.1021/acs.est.4c06675
49. [49]
  L.J. Ting, Kai Wang, Y. Li, et al., Appl. Catal. B: Environ. 286 (2021) 119883. doi: 10.1016/j.apcatb.2021.119883
50. [50]
  A. Gu, X. Zhou, C. Gong, et al., Chem Eng. J. 468 (2023) 143444. doi: 10.1016/j.cej.2023.143444
51. [51]
  J. Miao, W. Geng, P.J.J. Alvarez, et al., Environ. Sci. Tech. 54(13) (2020) 8473–8481. doi: 10.1021/acs.est.0c03207
52. [52]
  T. Günay, Y. Çimen, Environ. Pollut. 231 (2017) 1013–1020. doi: 10.1016/j.envpol.2017.08.059
53. [53]
  W. Li, Z. Wang, H. Liao, et al., Chem. Eng. J. 417 (2021) 128121. doi: 10.1016/j.cej.2020.128121
54. [54]
  Z. Cheng, B. Yang, Q. Chen, et al., Chem. Eng. J. 354 (2018) 12–20. doi: 10.5539/ass.v14n12p12
55. [55]
  W. D, Lai, Y.L. He, H.Y. Zhou, et al., Chem. Eng. J. 416 (2021) 125809.
56. [56]
  B. Huang, Z. Xiong, P. Zhou, et al., J Hazard Mater. 424 (2022): 127641. doi: 10.1016/j.jhazmat.2021.127641
57. [57]
  P. Zhou, J. Zhang, Y. Zhang, et al., J. Hazard. Mater. 344 (2018) 1209–1219. doi: 10.1016/j.jhazmat.2017.11.023
58. [58]
  J. Wang, S. Wang, Chem. Eng. J. 411 (2021) 128392. doi: 10.1016/j.cej.2020.128392
59. [59]
  X. Fu, X. Gu, S. Lu, et al., Chem. Eng. J. 309 (2017) 22–29. doi: 10.1016/j.cej.2016.10.006
60. [60]
  Y. Xiao, X. Liu, Y. Huang, et al., RSC Adv. 11(6) (2021) 3636–3644. doi: 10.1039/d0ra08395j
61. [61]
  J. Bao, Y. Wei, Z. Lu, et al., Chem. Eng. J. 504 (2025) 158290. doi: 10.1016/j.cej.2024.158290
1. [1]
  Xian-Rui Meng , Qian Chen , Mei-Feng Wu , Qiang Wu , Su-Qin Wang , Li-Ping Jin , Fan Zhou , Ren-Li Ma , Jian-Ping Zou . Nano-flowers FeS/MoS2 composites as a peroxymonosulfate activator for efficient p-chlorophenol degradation. Chinese Journal of Structural Chemistry, 2025, 44(3): 100543-100543. doi: 10.1016/j.cjsc.2025.100543
2. [2]
  Chunrui Zhao , Tianren Li , Jiage Li , Yansong Liu , Zian Fang , Xinyu Wang , Mingxin Huo , Shuangshi Dong , Mingyu Li . Doped cobalt for simultaneously promoting active (001) facet exposure of MIL-68(In) and acting as reactive sites in peroxymonosulfate-mediated photocatalytic decontamination. Chinese Chemical Letters, 2025, 36(5): 110201-. doi: 10.1016/j.cclet.2024.110201
3. [3]
  Lina Zou , Dengke Wang , Shiqin Lai , Xunheng Jiang , Siqi Chen , Lanqing Deng , Dong Fan , Hengshuai Li , Zhigang Zhou , Denglong Chen , Xiangyang Yao , Jianping Zou . Local spin-state manipulation of iron single-atom sites induced by sulfur modification to boost Fenton-like reaction. Chinese Chemical Letters, 2025, 36(12): 111094-. doi: 10.1016/j.cclet.2025.111094
4. [4]
  Cunjun Li , Wencong Liu , Xianlei Chen , Liang Li , Shenyu Lan , Mingshan Zhu . Adsorption and activation of peroxymonosulfate on BiOCl for carbamazepine degradation: The role of piezoelectric effect. Chinese Chemical Letters, 2024, 35(10): 109652-. doi: 10.1016/j.cclet.2024.109652
5. [5]
  Ning Liu , Man Tian , Ye Zhang , Jinming Yang , Zhihao Wang , Wangxi Dai , Guixiang Quan , Jianqiu Lei , Xiaodong Zhang , Liang Tang . Three-dimensional MIL-88A(Fe)-derived α-Fe₂O₃ and graphene composite for efficient photo-Fenton-like degradation of ciprofloxacin. Chinese Chemical Letters, 2025, 36(12): 111063-. doi: 10.1016/j.cclet.2025.111063
6. [6]
  Lu Zhang , Baohua Wang , Wei Yang , Lunan Ju , Zihan Fu , Lei Zhao , Yunqi Jiang , Hongyan Wang , Xiansheng Wang , Cong Lyu . CoOOH@COFs S−scheme heterojunction for efficient triclosan degradation in photocatalytic-peroxymonosulfate activation system: Enhanced interfacial electron transfer mechanism. Chinese Chemical Letters, 2026, 37(1): 111142-. doi: 10.1016/j.cclet.2025.111142
7. [7]
  Yingnan Duan , Jinyu Liu , Qian Liu , Tianhao Li , Hexiang Zhao , Zhurui Shen . Remediation of characteristic contaminants in groundwater of chemical industrial by the activation of PMS: Recent developments and challenges-a mini-review. Chinese Chemical Letters, 2026, 37(1): 111120-. doi: 10.1016/j.cclet.2025.111120
8. [8]
  Mingli Jiang , Weihua Xu , Xin Li , Xiaofei Tan , Wei Zhang . Fe-bearing clay minerals as catalysts for oxidant activation in organic pollutant degradation: ROS generation driven by Fe(Ⅱ)/Fe(Ⅲ) redox cycling. Chinese Chemical Letters, 2026, 37(7): 112274-. doi: 10.1016/j.cclet.2025.112274
9. [9]
  Jinxin Li , Yifan Ren , Jianan Gao , Nadeeshani Nanayakkara , Xin Wang , Meng Liu , Yanbiao Liu . Asymmetric triple-atomic sites with modulated electronic structure toward boosted peroxymonosulfate activation. Chinese Chemical Letters, 2026, 37(2): 111355-. doi: 10.1016/j.cclet.2025.111355
10. [10]
  Ruonan Guo , Heng Zhang , Changsheng Guo , Ningqing Lv , Beidou Xi , Jian Xu . Degradation of neonicotinoids with different molecular structures in heterogeneous peroxymonosulfate activation system through different oxidation pathways. Chinese Chemical Letters, 2024, 35(9): 109413-. doi: 10.1016/j.cclet.2023.109413
11. [11]
  Lijuan Huang , Rui Gan , Xin Han , Meilin Sun , Li Chen , Wen Liu , Xiaoxin Zhang , Fei Pan . Peroxymonosulfate activation by Fe(Ⅲ)-phytate co-precipitation for efficient water treatment at circumneutral pH: The critical role of direct electron transfer. Chinese Chemical Letters, 2026, 37(5): 111840-. doi: 10.1016/j.cclet.2025.111840
12. [12]
  Ruiying Liu , Li Zhao , Baishan Liu , Jiayuan Yu , Yujie Wang , Wanqiang Yu , Di Xin , Chaoqiong Fang , Xuchuan Jiang , Riming Hu , Hong Liu , Weijia Zhou . Modulating pollutant adsorption and peroxymonosulfate activation sites on Co3O4@N,O doped-carbon shell for boosting catalytic degradation activity. Chinese Journal of Structural Chemistry, 2024, 43(8): 100332-100332. doi: 10.1016/j.cjsc.2024.100332
13. [13]
  Jin Li , Xin Chen , Aling Chen , Zhi-Qiang Wang , Dengsong Zhang . Theoretical insight into the active sites for chlorobenzene oxidation: From phosphate to M₃ clusters. Chinese Chemical Letters, 2025, 36(8): 110527-. doi: 10.1016/j.cclet.2024.110527
14. [14]
  Zhenfei Tang , Yunwu Zhang , Zhiyuan Yang , Haifeng Yuan , Tong Wu , Yue Li , Guixiang Zhang , Xingzhi Wang , Bin Chang , Dehui Sun , Hong Liu , Lili Zhao , Weijia Zhou . Iron-doping regulated light absorption and active sites in LiTaO₃ single crystal for photocatalytic nitrogen reduction. Chinese Chemical Letters, 2025, 36(3): 110107-. doi: 10.1016/j.cclet.2024.110107
15. [15]
  Yu Yao , Jinqiang Zhang , Yantao Wang , Kunsheng Hu , Yangyang Yang , Zhongshuai Zhu , Shuang Zhong , Huayang Zhang , Shaobin Wang , Xiaoguang Duan . Nitrogen-rich carbon for catalytic activation of peroxymonosulfate towards green synthesis. Chinese Chemical Letters, 2024, 35(11): 109633-. doi: 10.1016/j.cclet.2024.109633
16. [16]
  Zhe Li , Jun Luo , Li Yao , Yonghai Gan , Zheng Wang , Hongcen Zheng , Minhui Cai , Chengcheng Ding , Xiao Luo , Yibin Cui , Yang Zhou , Wenlei Zhu . Electro-chemical nitrate remediation at lower concentrations: Efforts toward practical environmental applications. Chinese Chemical Letters, 2026, 37(7): 112141-. doi: 10.1016/j.cclet.2025.112141
17. [17]
  Shuo Chen , Yuxuan Xiang , Qiulin Yang , Shuang Meng , Chuanshu He , Yang Liu , Jing Zhang , Zhaokun Xiong , Peng Zhou , Bo Lai . Amorphous-boron boosted Fenton-like activation of periodate for water remediation: Multiple routes for generating reactive oxygen species. Chinese Chemical Letters, 2026, 37(5): 111838-. doi: 10.1016/j.cclet.2025.111838
18. [18]
  Yinyin Xu , Yuanyuan Li , Jingbo Feng , Chen Wang , Yan Zhang , Yukun Wang , Xiuwen Cheng . Covalent organic frameworks doped with manganese-metal organic framework for peroxymonosulfate activation. Chinese Chemical Letters, 2024, 35(4): 108838-. doi: 10.1016/j.cclet.2023.108838
19. [19]
  Mengmeng Ao , Jian Wei , Chuan-Shu He , Heng Zhang , Zhaokun Xiong , Yonghui Song , Bo Lai . Insight into the activation of peroxymonosulfate by N-doped copper-based carbon for efficient degradation of organic pollutants: Synergy of nonradicals. Chinese Chemical Letters, 2025, 36(1): 109882-. doi: 10.1016/j.cclet.2024.109882
20. [20]
  Huazhe Wang , Chenghuan Qiao , Chuchu Chen , Bing Liu , Juanshan Du , Qinglian Wu , Xiaochi Feng , Shuyan Zhan , Wan-Qian Guo . Synergistic adsorption and singlet oxygenation of humic acid on alkali-activated biochar via peroxymonosulfate activation. Chinese Chemical Letters, 2025, 36(5): 110244-. doi: 10.1016/j.cclet.2024.110244

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(14)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142