Partial aging can counter-intuitively couple with sulfidation to improve the reactive durability of zerovalent iron

Abstract

● Partial aging of SZVI can enhance its reactive durability toward Cr(VI).

● Partial aging can couple with sulfidation to reconstruct the interface of ZVI.

● Partial aging can retain the conductive FeS _x in the subshell of SZVI.

● Iron (hydr)oxides and FeS _x improve the mass and electron transfer of ZVI to Cr(VI).

Sulfated zero-valent iron (SZVI) has shown promising applications in wastewater treatment. However, the rapid decline in the reactivity of SZVI with time limits its real practice. To mediate this problem, partial aging was proposed to improve the reactive durability of SZVI. Taking Cr(VI) as the target contaminant, we found that the aged ZVI (AZVI) gradually lost reactivity as aging time increased from 0.5 to 2 d. Counter-intuitively, the partially aged SZVI (ASZVI) showed greater reactivity than SZVI when exposed to oxygenated water for a period ranging from 0.5 to 14 d. In addition, the ASZVI with 0.5 d of aging time (ASZVI-0.5) not only maintained reactivity in successive runs but also increased the Cr(VI) removal capacity from 9.1 mg/g by SZVI to 19.1 mg/g by ASZVI-0.5. Correlation analysis further revealed that the electron transfer from the Fe⁰ core to the shell was mediated by the conductive FeS and FeS₂ in the subshell of ASZVI. Meanwhile, the lepidocrocite and magnetite on the surface of ASZVI facilitated Cr(VI) adsorption and subsequent electron transfer for Cr(VI) reduction. Moreover, the iron (hydr)oxide shell could retain the conductive FeS and FeS₂ in the subshell, allowing ASZVI to reduce Cr(VI) efficiently and sustainably. In general, partial aging can enhance the reactive durability of ZVI when coupled with sulfidation and this synergistic effect will be beneficial to the application of SZVI-based technology for wastewater treatment.

Graphical abstract

Keywords

Zerovalent iron / Sulfidation / Partial aging / Interface reconstruction / Electron transfer

References

[1] Agrawal A , Tratnyek P . (1995). Reduction of nitro aromatic compounds by zero-valent iron metal. Environmental Science & Technology, 30(1): 153–160

[2] Cai S , Chen B , Qiu X , Li J , Tratnyek P G , He F . (2021). Sulfidation of zero-valent iron by direct reaction with elemental sulfur in water: efficiencies, mechanism, and dechlorination of trichloroethylene. Environmental Science & Technology, 55(1): 645–654

[3] Cao Z , Li H , Lowry G V , Shi X , Pan X , Xu X , Henkelman G , Xu J . (2021a). Unveiling the role of sulfur in rapid defluorination of florfenicol by sulfidized nanoscale zero-valent iron in water under ambient conditions. Environmental Science & Technology, 55(4): 2628–2638

[4] Cao Z , Li H , Xu X , Xu J . (2020a). Correlating surface chemistry and hydrophobicity of sulfidized nanoscale zerovalent iron with its reactivity and selectivity for denitration and dechlorination. Chemical Engineering Journal, 394: 124876

[5] Cao Z , Li H , Zhang S , Hu Y , Xu J , Xu X . (2021b). Properties and reactivity of sulfidized nanoscale zero-valent iron prepared with different borohydride amounts. Environmental Science. Nano, 8(9): 2607–2617

[6] Cao Z , Xu J , Li H , Ma T , Lou L , Henkelman G , Xu X . (2020b). Dechlorination and defluorination capability of sulfidized nanoscale zerovalent iron with suppressed water reactivity. Chemical Engineering Journal, 400: 125900

[7] Fan D , Lan Y , Tratnyek P G , Johnson R L , Filip J , O’Carroll D M , Nunez Garcia A , Agrawal A . (2017). Sulfidation of iron-based materials: a review of processes and implications for water treatment and remediation. Environmental Science & Technology, 51(22): 13070–13085

[8] Fan P , Li L , Sun Y , Qiao J , Xu C , Guan X . (2019a). Selenate removal by Fe⁰ coupled with ferrous iron, hydrogen peroxide, sulfidation, and weak magnetic field: a comparative study. Water Research, 159: 375–384

[9] Fan P , Sun Y , Zhou B , Guan X . (2019b). Coupled effect of sulfidation and ferrous dosing on selenate removal by zerovalent iron under aerobic conditions. Environmental Science & Technology, 53(24): 14577–14585

[10] Fan P , Zhang X , Deng H , Guan X . (2021). Enhanced reduction of p-nitrophenol by zerovalent iron modified with carbon quantum dots. Applied Catalysis B: Environmental, 285: 119829

[11] Feng P , Guan X , Sun Y , Choi W , Qin H , Wang J , Qiao J , Li L . (2015). Weak magnetic field accelerates chromate removal by zero-valent iron. Journal of Environmental Sciences (China), 31: 175–183

[12] Fu F , Dionysiou D D , Liu H . (2014). The use of zero-valent iron for groundwater remediation and wastewater treatment: a review. Journal of Hazardous Materials, 267: 194–205

[13] Garcia A N , Zhang Y , Ghoshal S , He F , O’Carroll D M . (2021). Recent advances in sulfidated zerovalent iron for contaminant transformation. Environmental Science & Technology, 55(13): 8464–8483

[14] Geiger C L , Ruiz N E , Clausen C A , Reinhart D R , Quinn J W . (2002). Ultrasound pretreatment of elemental iron: kinetic studies of dehalogenation reaction enhancement and surface effects. Water Research, 36(5): 1342–1350

[15] Gheju M (2011). Hexavalent chromium reduction with zero-valent iron (ZVI) in aquatic systems. Water, Air, and Soil Pollution, 222(1–4): 103–148

[16] Gillham R W , Ohannesin S F . (1994). Enhanced degradation of falogenated aliphatics by zero-valent iron. Ground Water, 32(6): 958–967

[17] Gong Y , Gai L , Tang J , Fu J , Wang Q , Zeng E Y . (2017). Reduction of Cr(VI) in simulated groundwater by FeS-coated iron magnetic nanoparticles. Science of the Total Environment, 595: 743–751

[18] Gu Y , Gong L , Qi J , Cai S , Tu W , He F . (2019). Sulfidation mitigates the passivation of zero valent iron at alkaline pHs: experimental evidences and mechanism. Water Research, 159: 233–241

[19] Gu Y , Wang B , He F , Bradley M J , Tratnyek P G . (2017). Mechanochemically sulfidated microscale zero valent iron: pathways, kinetics, mechanism, and efficiency of trichloroethylene dechlorination. Environmental Science & Technology, 51(21): 12653–12662

[20] Guan X H , Sun Y K , Qin H J , Li J X , Lo I M , He D , Dong H R . (2015). The limitations of applying zero-valent iron technology in contaminants sequestration and the corresponding countermeasures: the development in zero-valent iron technology in the last two decades (1994–2014). Water Research, 75: 224–248

[21] Huang S , Xu C , Shao Q , Wang Y , Zhang B , Gao B , Zhou W , Tratnyek P G . (2018). Sulfide-modified zerovalent iron for enhanced antimonite sequestration: characterization, performance, and reaction mechanisms. Chemical Engineering Journal, 338: 539–547

[22] Huang X , Chen L , Ma Z , Carroll K C , Zhao X , Huo Z . (2022). Cadmium removal mechanistic comparison of three Fe-based nanomaterials: water-chemistry and roles of Fe dissolution. Frontiers of Environmental Science & Engineering, 16(12): 151

[23] Kim E J , Kim J H , Azad A M , Chang Y S . (2011). Facile synthesis and characterization of Fe/FeS nanoparticles for environmental applications. ACS Applied Materials & Interfaces, 3(5): 1457–1462

[24] Li H , Zhang J , Gu K , Li J . (2020a). Sulfidation of zerovalent iron for improving the selectivity toward Cr(VI) in oxic water: involvements of FeS_x. Journal of Hazardous Materials, 409: 124498

[25] Li J , Dou X , Qin H , Sun Y , Yin D , Guan X . (2019). Characterization methods of zerovalent iron for water treatment and remediation. Water Research, 148: 70–85

[26] Li J , Qin H , Guan X . (2015). Premagnetization for enhancing the reactivity of multiple zerovalent iron samples toward various contaminants. Environmental Science & Technology, 49(24): 14401–14408

[27] Li J , Zhang X , Liu M , Pan B C , Zhang W , Shi Z , Guan X . (2018). Enhanced reactivity and electron selectivity of sulfidated zerovalent iron toward chromate under aerobic conditions. Environmental Science & Technology, 52(5): 2988–2997

[28] Li J , Zhang X , Sun Y , Liang L , Pan B C , Zhang W , Guan X . (2017). Advances in sulfidation of zerovalent iron for water decontamination. Environmental Science & Technology, 248(23): 173–182

[29] Li M , Mu Y , Shang H , Mao C , Cao S , Ai Z , Zhang L . (2020b). Phosphate modification enables high efficiency and electron selectivity of nZVI toward Cr(VI) removal. Applied Catalysis B: Environmental, 263: 118364

[30] Liang L , Sun W , Guan X , Huang Y , Choi W , Bao H , Li L , Jiang Z . (2014a). Weak magnetic field significantly enhances selenite removal kinetics by zero valent iron. Water Research, 49: 371–380

[31] Liang L P , Guan X H , Shi Z , Li J L , Wu Y N , Tratnyek P G . (2014b). Coupled effects of aging and weak magnetic fields on sequestration of selenite by zero-valent iron. Environmental Science & Technology, 48(11): 6326–6334

[32] Ling J , Qiao J , Song Y , Sun Y . (2019). Influence of coexisting ions on the electron efficiency of sulfidated zerovalent iron toward Se(VI) removal. Chemical Engineering Journal, 378: 122124

[33] Liou Y H , Lo S L , Lin C J , Kuan W H , Weng S C . (2005). Effects of iron surface pretreatment on kinetics of aqueous nitrate reduction. Journal of Hazardous Materials, 126(1): 189–194

[34] Liu Y , Qiao J , Sun Y , Guan X . (2022). Simultaneous sequestration of humic acid-complexed Pb(II), Zn(II), Cd(II), and As(V) by sulfidated zero-valent iron: performance and stability of sequestration products. Environmental Science & Technology, 56(5): 3127–3137

[35] Lü Y , Li J , Li Y , Liang L , Dong H , Chen K , Yao C , Li Z , Li J , Guan X . (2019). The roles of pyrite for enhancing reductive removal of nitrobenzene by zero-valent iron. Applied Catalysis B: Environmental, 242: 9–18

[36] Mangayayam M , Dideriksen K , Ceccato M , Tobler D J . (2019). The structure of sulfidized zero-valent iron by one-pot synthesis: impact on contaminant selectivity and long-term performance. Environmental Science & Technology, 53(8): 4389–4396

[37] Matheson L J , Tratnyek P G . (1994). Reductive dehalogenation of chlorinated methanes by iron metal. Environmental Science & Technology, 28(12): 2045–2053

[38] Miehr R , Tratnyek P G , Bandstra J Z , Scherer M M , Alowitz M J , Bylaska E J . (2004). Diversity of contaminant reduction reactions by zerovalent iron: Role of the reductate. Environmental Science & Technology, 38(1): 139–147

[39] Noubactep C . (2008). A critical review on the process of contaminant removal in Fe⁰-H₂O systems. Environmental Technology, 29(8): 909–920

[40] Qiao J , Liu Y , Yang H , Guan X , Sun Y . (2021). Remediation of arsenic contaminated soil by sulfidated zero-valent iron. Frontiers of Environmental Science & Engineering, 15(5): 83

[41] Qin H , Guan X , Bandstra J Z , Johnson R L , Tratnyek P G . (2018). Modeling the kinetics of hydrogen formation by zerovalent iron: effects of sulfidation on micro- and nano-scale particles. Environmental Science & Technology, 52(23): 13887–13896

[42] Qin H J , Li J X , Yang H Y , Pan B C , Zhang W M , Guan X H . (2017). Coupled effect of ferrous ion and oxygen on the electron selectivity of zerovalent iron for selenate sequestration. Environmental Science & Technology, 51(9): 5090–5097

[43] Rajajayavel S R , Ghoshal S . (2015). Enhanced reductive dechlorination of trichloroethylene by sulfidated nanoscale zerovalent iron. Water Research, 78: 144–153

[44] Shao Q , Xu C , Wang Y , Huang S , Zhang B , Huang L , Fan D , Tratnyek P G . (2018). Dynamic interactions between sulfidated zerovalent iron and dissolved oxygen: mechanistic insights for enhanced chromate removal. Water Research, 135: 322–330

[45] Shi J , Zhang J , Wang C , Liu Y , Li J . (2023). Research progress on the magnetite nanoparticles in the fields of water pollution control and detection. Chemosphere, 336: 139220

[46] Song S , Su Y , Adeleye A S , Zhang Y , Zhou X . (2017). Optimal design and characterization of sulfide-modified nanoscale zerovalent iron for diclofenac removal. Applied Catalysis B: Environmental, 201: 211–220

[47] Stookey L L . (1970). Ferrozine—a new spectrophotometric reagent for iron. Analytical Chemistry, 42(7): 779–781

[48] Sun Y K , Guan X H , Wang J M , Meng X G , Xu C H , Zhou G M . (2014). Effect of weak magnetic field on arsenate and arsenite removal from water by zerovalent iron: an XAFS investigation. Environmental Science & Technology, 48(12): 6850–6858

[49] Ullah S , Guo X , Luo X , Zhang X , Li Y , Zhang Z . (2020). The coupling of sand with ZVI/oxidants achieved proportional and highly efficient removal of arsenic. Frontiers of Environmental Science & Engineering, 14(6): 94

[50] Xu C , Zhang B , Wang Y , Shao Q , Zhou W , Fan D , Bandstra J Z , Shi Z , Tratnyek P G . (2016a). Effects of sulfidation, magnetization, and oxygenation on azo dye reduction by zerovalent iron. Environmental Science & Technology, 50(21): 11879–11887

[51] Xu H , Sun Y , Li J , Li F , Guan X . (2016b). Aging of zerovalent iron in synthetic groundwater: X-ray photoelectron spectroscopy depth profiling characterization and depassivation with uniform magnetic field. Environmental Science & Technology, 50(15): 8214–8222

[52] Xu J , Avellan A , Li H , Clark E A , Henkelman G , Kaegi R , Lowry G V . (2020a). Iron and sulfur precursors affect crystalline structure, speciation, and reactivity of sulfidized nanoscale zerovalent iron. Environmental Science & Technology, 54(20): 13294–13303

[53] Xu J , Avellan A , Li H , Liu X , Noël V , Lou Z , Wang Y , Kaegi R , Henkelman G , Lowry G V . (2020b). Sulfur loading and speciation control the hydrophobicity, electron transfer, reactivity, and selectivity of sulfidized nanoscale zerovalent iron. Advanced Materials, 32(17): 1906910

[54] Xu J , Cao Z , Zhou H , Lou Z , Wang Y , Xu X , Lowry G V . (2019a). Sulfur dose and sulfidation time affect reactivity and selectivity of post-sulfidized nanoscale zerovalent iron. Environmental Science & Technology, 53(22): 13344–13352

[55] Xu J , Li H , Lowry G V . (2021). Sulfidized nanoscale zero-valent iron: tuning the properties of this complex material for efficient groundwater remediation. Accounts of Materials Research, 2(6): 420–431

[56] Xu J , Wang Y , Weng C , Bai W , Jiao Y , Kaegi R , Lowry G V . (2019b). Reactivity, selectivity, and long-term performance of sulfidized nanoscale zerovalent iron with different properties. Environmental Science & Technology, 53(10): 5936–5945

[57] Xu W , Li Z , Shi S , Qi J , Cai S , Yu Y , O’Carroll D M , He F . (2020c). Carboxymethyl cellulose stabilized and sulfidated nanoscale zero-valent iron: characterization and trichloroethene dechlorination. Applied Catalysis B: Environmental, 262: 118303

[58] Yao W , Zhang J , Gu K , Li J , Qian J . (2022). Synthesis, characterization and performances of green rusts for water decontamination: a review. Environmental Pollution, 304: 119205

[59] Yoon I H , Kim K W , Bang S , Kim M G . (2011). Reduction and adsorption mechanisms of selenate by zero-valent iron and related iron corrosion. Applied Catalysis B: Environmental, 104(1): 185–192

[60] Zhang X , Li J , Sun Y , Li L , Pan B , Zhang W , Guan X . (2018). Aging of zerovalent iron in various coexisting solutes: characteristics, reactivity toward selenite and rejuvenation by weak magnetic field. Separation and Purification Technology, 191: 94–100

[61] Zhao J , Su A , Tian P , Tang X , Collins R N , He F . (2021). Arsenic (III) removal by mechanochemically sulfidated microscale zero valent iron under anoxic and oxic conditions. Water Research, 198: 117132

[62] Zhao J M , Wei Z , Zuo Y , Zhao X H . (2005). Effects of some ions on ion-selectivity of ferrous sulfide film. Journal of Applied Electrochemistry, 35(3): 267–271

[63] Zou H , Hu E , Yang S , Gong L , He F . (2019). Chromium(VI) removal by mechanochemically sulfidated zero valent iron and its effect on dechlorination of trichloroethene as a co-contaminant. Science of the Total Environment, 650: 419–426

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