Skip to main content
SpringerLink
Log in

Effect of solution pH on aging dynamics and surface structural evolution of mZVI particles: H2 production and spectroscopic/microscopic evidence

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

A microscale zero-valent iron (mZVI)-based in situ reactive zone is a promising technology for contaminated groundwater remediation. Estimation of mZVI aging behavior after its injection into the subsurface is essential for efficiency and longevity assessments. In this study, batch tests were conducted to investigate the effect of initial pH on mZVI aging dynamics, as well as the formation and evolution of aging products over 112 days. Results indicated that mZVI aging accelerated with decreasing initial pH. Corrosion rates of mZVI particles under pH 6.0 and 7.5 were approximately two orders of magnitude higher than those observed at pH 9.0. The morphological, structural, and compositional evolution of mZVI particles in three systems (pH = 6.0, 7.5, and 9.0) were investigated using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. In acidic and neutral solutions, a thick passivation layer with loosely and unevenly distributed aging precipitates was observed, and Fe3O4 was the final aging precipitate. Nevertheless, in alkaline solutions, minute aging precipitates were detected on the mZVI surface at 112 day. Characterization results suggested that mZVI was oxidized via the Fe0–Fe(OH)2–Fe3O4 route. These findings shed new light on mZVI aging mechanisms, particularly its physicochemical characteristics and the structural evolution of mZVI in field-scale groundwater remediation applications.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Abdel-Samad H, Watson PR (1997) An XPS study of the adsorption of chromate on goethite (α-FeOOH). Appl Surf Sci 108:371–377

    Article  CAS  Google Scholar 

  • Bae S, Hanna K (2015) Reactivity of nanoscale zero-valent iron in unbuffered systems: effect of pH and Fe (II) dissolution. Environ Sci Technol 49:10536–10543

    Article  CAS  Google Scholar 

  • Bhargava G, Gouzman I, Chun CM, Ramanarayanan TA, Bernasek SL (2007) Characterization of the “native” surface thin film on pure polycrystalline iron: a high resolution XPS and TEM study. Appl Surf Sci 253:4322–4329

    Article  CAS  Google Scholar 

  • Chen J, Al-Abed SR, Ryan JA, Li Z (2001) Effects of pH on dechlorination of trichloroethylene by zero-valent iron. J Hazard Mater 83:243–254

    Article  CAS  Google Scholar 

  • Comba S, Molfetta AD, Sethi R (2011) A comparison between field applications of nano-, micro-, and millimetric zero-valent iron for the remediation of contaminated aquifers. Water Air Soil Poll 215:595–607

    Article  CAS  Google Scholar 

  • Crane RA, Scott TB (2012) Nanoscale zero-valent iron: future prospects for an emerging water treatment technology. J Hazard Mater 211:112–125

    Article  Google Scholar 

  • Fan D, O’Brien Johnson G, Tratnyek PG, Johnson RL (2016) Sulfidation of nano zerovalent iron (nZVI) for improved selectivity during in-situ chemical reduction (ISCR). Environ Sci Technol 50(17):9558–9565

    Article  CAS  Google Scholar 

  • Farrell J, Kason M, Melitas N, Li T (2000) Investigation of the long-term performance of zero-valent iron for reductive dechlorination of trichloroethylene. Environ Sci Technol 34:514–521

    Article  CAS  Google Scholar 

  • Gao J, Ran X, Shi C, Cheng H, Cheng T, Su Y (2013) One-step solvothermal synthesis of highly water-soluble, negatively charged superparamagnetic Fe3O4 colloidal nanocrystal clusters. Nano 5:7026–7033

    CAS  Google Scholar 

  • Grosvenor AP, Kobe BA, McIntyre NS, Tougaard S, Lennard WN (2004) Use of QUASES™/XPS measurements to determine the oxide composition and thickness on an iron substrate. Surf Interface Anal 36:632–639

    Article  CAS  Google Scholar 

  • Han J, Jia X, Zheng X, Kolditz O, Shao H (2016) Remediation of trichloroethylene-contaminated groundwater by three modifier-coated microscale zero-valent iron. Environ Sci Pollut Res 23:1–9

    Article  Google Scholar 

  • Jia X, Tang F, Zheng X, Shao H, Kolditz O, Xin L (2016) Distinct kinetics and mechanisms of mZVI particles aging in saline and fresh groundwater: H2 evolution and surface passivation. Water Res 100:80–87

    Article  Google Scholar 

  • Kim H, Kim T, Ahn J, Hwang K, Park J, Lim T, Hwang I (2012a) Aging characteristics and reactivity of two types of nanoscale zero-valent iron particles (FeBH and FeH2) in nitrate reduction. Chem Eng J 197:16–23

    Article  CAS  Google Scholar 

  • Kim W, Suh C, Cho S, Roh K, Kwon H, Song K, Shon I (2012b) A new method for the identification and quantification of magnetite-maghemite mixture using conventional X-ray diffraction technique. Talanta 94:348–352

    Article  CAS  Google Scholar 

  • Klas S, Kirk DW (2013) Advantages of low pH and limited oxygenation in arsenite removal from water by zero-valent iron. J Hazard Mater 252-253:77–82

    Article  CAS  Google Scholar 

  • Kumar N, Auffan M, Gattacceca J, Rose J, Olivi L, Borschneck D, Kvapil P, Jublot M, Kaifas D, Malleret L (2014) Molecular insights of oxidation process of iron nanoparticles: spectroscopic, magnetic, and microscopic evidence. Environ Sci Technol 48:13888–13894

    Article  CAS  Google Scholar 

  • Lai KC, Lo IM (2008) Removal of chromium (VI) by acid-washed zero-valent iron under various groundwater geochemistry conditions. Environ Sci Technol 42:1238–1244

    Article  CAS  Google Scholar 

  • Li X, Zhang W (2007) Sequestration of metal cations with zerovalent iron nanoparticles a study with high resolution X-ray photoelectron spectroscopy (HR-XPS). J Phys Chem C 111:6939–6946

    Article  CAS  Google Scholar 

  • Li H, Wan J, Ma Y, Huang M, Wang Y, Chen Y (2014) New insights into the role of zero-valent iron surface oxidation layers in persulfate oxidation of dibutyl phthalate solutions. Chem Eng J 250:137–147

    Article  CAS  Google Scholar 

  • Liang L, Yang W, Guan X, Li J, Xu Z, Wu J, Huang Y, Zhang X (2013) Kinetics and mechanisms of pH-dependent selenite removal by zero valent iron. Water Res 47:5846–5855

    Article  CAS  Google Scholar 

  • Lin T, Seshadri G, Kelber JA (1997) A consistent method for quantitative XPS peak analysis of thin oxide films on clean polycrystalline iron surfaces. Appl Surf Sci 119:83–92

    Article  CAS  Google Scholar 

  • Liu Y, Lowry GV (2006) Effect of particle age (Fe0 content) and solution pH on NZVI reactivity: H2 evolution and TCE dechlorination. Environ Sci Technol 40:6085–6090

    Article  CAS  Google Scholar 

  • Liu A, Liu J, Zhang W (2015) Transformation and composition evolution of nanoscale zero valent iron (nZVI) synthesized by borohydride reduction in static water. Chemosphere 119:1068–1074

    Article  CAS  Google Scholar 

  • Liu A, Liu J, Han J, Zhang W (2017) Evolution of nanoscale zero-valent iron (nZVI) in water: microscopic and spectroscopic evidence on the formation of nano-and micro-structured iron oxides. J Hazard Mater 322:129–135

    Article  CAS  Google Scholar 

  • Mu Y, Jia F, Ai Z, Zhang L (2016): Iron oxide shell mediated environmental remediation properties of nano zero-valent iron. Environ. Sci.: Nano, 2017, 4: 27

  • Ningshen S, Mudali UK (2009) Hydrogen effects on pitting corrosion and semiconducting properties of nitrogen-containing type 316L stainless steel. Electrochim Acta 54:6374–6382

    Article  CAS  Google Scholar 

  • Noubactep C (2009) Characterizing the discoloration of methylene blue in Fe0/H2O systems. J Hazard Mater 166:79–87

    Article  CAS  Google Scholar 

  • Paar H, Ruhl AS, Jekel M (2015) Influences of nanoscale zero valent iron loadings and bicarbonate and calcium concentrations on hydrogen evolution in anaerobic column experiments. Water Res 68:731–739

    Article  CAS  Google Scholar 

  • Qin H, Li J, Yang H, Pan B, Zhang W, Guan X (2017) Coupled effect of ferrous ion and oxygen on the electron selectivity of zerovalent iron for selenate sequestration. Environ Sci Technol 51(9):5090–5097

    Article  CAS  Google Scholar 

  • Reardon EJ (2005) Zerovalent irons: styles of corrosion and inorganic control on hydrogen pressure buildup. Environ Sci Technol 39:7311–7317

    Article  CAS  Google Scholar 

  • Reardon EJ, Fagan R, Vogan JL, Przepiora A (2008) Anaerobic corrosion reaction kinetics of nanosized iron. Environ Sci Technol 42:2420–2425

    Article  CAS  Google Scholar 

  • Sarathy V, Tratnyek PG, Nurmi JT, Baer DR, Amonette JE, Chun CL, Penn RL, Reardon EJ (2008) Aging of iron nanoparticles in aqueous solution: effects on structure and reactivity. J Phys Chem C 112:2286–2293

    Article  CAS  Google Scholar 

  • Tang F, Xin J, Zheng T, Zheng X, Yang X, Kolditz O (2017) Individual and combined effects of humic acid, bicarbonate and calcium on TCE removal kinetics, aging behavior and electron efficiency of mZVI particles. Chem Eng J 324:324–335

    Article  CAS  Google Scholar 

  • Velimirovic M, Larsson P, Simons Q, Bastiaens L (2013) Reactivity screening of microscale zerovalent irons and iron sulfides towards different CAHs under standardized experimental conditions. J Hazard Mater 252:204–212

    Article  Google Scholar 

  • Velimirovic M, Simons Q, Bastiaens L (2014b) Guar gum coupled microscale ZVI for in situ treatment of CAHs: continuous-flow column study. J Hazard Mater 265:20–29

    Article  CAS  Google Scholar 

  • Velimirovic M, Carniato L, Simons Q, Schoups G, Seuntjens P, Bastiaens L (2014a) Corrosion rate estimations of microscale zerovalent iron particles via direct hydrogen production measurements. J Hazard Mater 270:18–26

    Article  CAS  Google Scholar 

  • Xia X, Ling L, Zhang W (2017) Solution and surface chemistry of the Se (IV)-Fe (0) reactions: effect of initial solution pH. Chemosphere 168:1597–1603

    Article  CAS  Google Scholar 

  • Xie Y, Cwiertny DM (2010) Use of dithionite to extend the reactive lifetime of nanoscale zero-valent iron treatment systems. Environ Sci Technol 44:8649–8655

    Article  CAS  Google Scholar 

  • Xie Y, Cwiertny DM (2012) Influence of anionic cosolutes and pH on nanoscale zerovalent iron longevity: time scales and mechanisms of reactivity loss toward 1, 1, 1, 2-tetrachloroethane and Cr (VI). Environ Sci Technol 46:8365–8373

    Article  CAS  Google Scholar 

  • Xin J, Han J, Zheng X, Shao H, Kolditz O (2015) Mechanism insights into enhanced trichloroethylene removal using xanthan gum-modified microscale zero-valent iron particles. J Environ Mang 150:420–426

    Article  CAS  Google Scholar 

  • Yamashita T, Hayes P (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl Surf Sci 254:2441–2449

    Article  CAS  Google Scholar 

  • Yuan X, Shi X, Zhang P, Wei Y, Guo R, Wang L (2011) Anaerobic biohydrogen production from wheat stalk by mixed microflora: kinetic model and particle size influence. Bioresour Technol 102:9007–9012

    Article  CAS  Google Scholar 

  • Zeng YM, Luo JL, Norton PR (2004) A study of semiconducting properties of hydrogen containing passive films. Thin Solid Films 460:116–124

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors thank the National Natural Science Foundation of China (51408571), the China Postdoctoral Science Special Foundation (2017T100517), and the Key Program of National Natural Science Foundation of China (41731280) for their generous financial support.

Author information

Authors and Affiliations

  1. Key Laboratory of Marine Environmental Science and Ecology, Ministry of Education; Shandong Provincial Key Laboratory of Marine Environment and Geological Engineering; College of Environmental Science and Engineering, Ocean University of China, Qingdao, 266100, China

    Fenglin Tang, Jia Xin & Xilai Zheng

  2. College of Chemistry and Chemical Engineering, China West Normal University, Nanchong, 637002, China

    Fenglin Tang

  3. Helmholtz Center for Environmental Research UFZ/TU Dresden, 034202, Leipzig, Germany

    Tianyuan Zheng & Olaf Kolditz

  4. Shandong Provincial Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, Jinan, 250100, China

    Xianzheng Yuan

Authors
  1. Fenglin Tang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jia Xin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xilai Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tianyuan Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xianzheng Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Olaf Kolditz
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jia Xin or Xilai Zheng.

Additional information

Responsible editor: Philippe Garrigues

Electronic supplementary material

ESM 1

(DOCX 10059 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tang, F., Xin, J., Zheng, X. et al. Effect of solution pH on aging dynamics and surface structural evolution of mZVI particles: H2 production and spectroscopic/microscopic evidence. Environ Sci Pollut Res 24, 23538–23548 (2017). https://doi.org/10.1007/s11356-017-9976-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-017-9976-3

Keywords

Search

Navigation