Skip to main content

Chlorophenols Dechlorination Water Treatment Using Ni-Iron Bimetallic Systems: Implications of the Degree of Chlorination, Nickel Coating, and Iron Oxide Phases

  • Chapter
  • First Online:
Contaminants in Drinking and Wastewater Sources

Abstract

Chlorophenols (CPs) have been detected as contaminants causing groundwater and potable water pollution. Toxicity of CPs increases with the increase in the degree of chlorination. This study aimed at investigating the efficiency of Nickel coated iron (Ni/Fe) bimetal for CP dechlorination water treatment. The emphasis was on the effect of degree of chlorination, Nickel coating, and iron oxide films on possible removal mechanisms of CPs such as dechlorination and sorption, co-precipitation, physical entrapment with iron oxides (i.e. incorporation). Batch experiments were conducted with Ni/Fe and four CPs [pentachlorophenol (PCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,4-dichlorophenol (2,4-DCP)], single CP at a time, under identical, and anoxic conditions. Reactivity of CPs with Ni/Fe was PCP > 2,3,4,6-TeCP > 2,4,6-TCP ≈ 2,4-DCP with 55, 46, 34, and 30% of the respective compounds initially introduced to each system removed from the solution after 25 days. Dechlorination of PCP and 2,3,4,6-TeCP resulted in accumulation of lower CPs and trace amounts of phenol with 93–96% mass balance. The 2,4,6-TCP and 2,4-DCP concentrations decreased over time, but a noticeable increase in the corresponding dechlorination products was not observed. Furthermore, the reaction of 2,4,6-TCP and 2,4-DCP resulted in the formation of iron oxides (akaganeite, hematite, lepidocrocite, goethite, and wustite) causing Ni/Fe surface passivation. Incorporation with such iron oxides was a significant removal process of 2,4,6-TCP and 2,4-DCP by Ni/Fe. The higher pKa of 2,4,6-TCP (5.97-7.42) and 2,4-DCP (7.68) and passive oxides could lead to 2,4,6-TCP and 2,4-DCP and their degradation products towards a greater affinity for incorporation with the iron oxides. In conclusion, dechlorination potential of Ni/Fe was greater for CPs with a high number of chlorine (PCP, TeCP). The CPs with a low number of chlorine (TCP, DCP), when reacted with Ni/Fe, demonstrated a low preference for dechlorination but a greater affinity for removal by incorporation with the iron oxides.

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

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 84.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 129.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 109.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  • Arning MD, Minteer SD (2007) Electrode potentials. In: Handbook of electrochemistry. In: Zoski CG (ed). Elsevier Science, p 934

    Google Scholar 

  • ATSDR (Agency for Toxic Substances and Disease Registry) (1999) Toxicological profile for chlorophenols. Agency for toxic substances and disease registry. U.S Department of Health and Human Services, p 260

    Google Scholar 

  • Cheng R, Wang Jl, Zhang W-x (2007) Comparison of reductive dechlorination of p-chlorophenol using Fe0 and nanosized Fe0. J Hazard Mater 144:334–339

    Article  CAS  Google Scholar 

  • Cheng R, Zhou W, Wang J-L, Qi D, Guo L, Zhang W-X, Qian Y (2010) Dechlorination of pentachlorophenol using nanoscale Fe/Ni particles: Role of nano-Ni and its size effect. J Hazard Mater 180:79–85

    Article  CAS  Google Scholar 

  • Choi JH, Choi SJ, Kim YH (2008) Hydrodechlorination of 2,4,6-trichlorophenol for a permeable reactive barrier using zero-valent iron and catalyzed iron. Korean J Chem Eng 25:493–500

    Article  CAS  Google Scholar 

  • Chun CL, Baer DR, Matson DW, Amonette JE, Penn RL (2010) Characterization and reactivity of iron nanoparticles prepared with added Cu, Pd, and Ni. Environ Sci Technol 44:5079–5085

    Article  CAS  Google Scholar 

  • Cornell RM, Schwertmann U (2003) The iron oxides structure, properties, reactions, occurrences, and uses. Wiley-VCH, Weinheim, p 659

    Google Scholar 

  • Cwiertny DM, Bransfield SJ, Roberts AL (2007) Influence of the oxidizing species on the reactivity of iron-based bimetallic reductants. Environ Sci Technol 41(10):3734–3740

    Google Scholar 

  • Czaplicka M (2004) Sources and transformations of chlorophenols in the natural environment. Sci Total Environ 322:21–39

    Article  CAS  Google Scholar 

  • Davenport AJ, Oblonsky LJ, Ryan MP, Toney MF (2000) The structure of the passive film that forms on iron in aqueous environments. J Electrochem Soc 147:2162–2173

    Article  CAS  Google Scholar 

  • EC (2016) List of priority substances in the field of water policy. European Commission. http://eceuropaeu/environment/water/waterframework/priority_substances.htm. Accessed 12 July 2017

    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 

  • Feng J, Lim T-T (2005) Pathways and kinetics of carbon tetrachloride and chloroform reductions by nano-scale Fe and Fe/Ni particles: comparison with commercial micro-scale Fe and Zn. Chemosphere 59:1267–1277

    Article  CAS  Google Scholar 

  • Fu F, Dionysiou DD, Liu H (2014) The use of zero-valent iron for groundwater remediation and wastewater treatment: a review. J Hazard Mater 267:194–205

    Article  CAS  Google Scholar 

  • Furukawa Y, Kim J-w, Watkins J, Wilkin RT (2002) Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron. Environ Sci Technol 36:5469–5475

    Article  CAS  Google Scholar 

  • Gillham RW, Ohannesin SF (1994) Enhanced degradation of halogenated aliphatics by zero valent iron. Ground Water 32:958–967

    Article  CAS  Google Scholar 

  • Gotpagar J, Lyuksyutov S, Cohn R, Grulke E, Bhattacharyya D (1999) Reductive dehalogenation of trichloroethylene with zero-valent iron: surface profiling microscopy and rate enhancement studies. Langmuir 15:8412–8420

    Article  CAS  Google Scholar 

  • Gunawardana B, Singhal N, Swedlund P (2011) Degradation of chlorinated phenols by zero valent iron and bimetals of iron: a review. Environ. Eng. Res. 16:187–203

    Article  Google Scholar 

  • Gunawardana B, Swedlund PJ, Singhal N, Nieuwoudt MK (2018) Pentachlorophenol dechlorination with zero valent iron: a Raman and GCMS study of the complex role of surficial iron oxides. Environ Sci Pollut Res 25:17797–17806

    Article  CAS  Google Scholar 

  • Gunawardana B, Swedlund PJ, Singhal N (2019) Effect of O2, Ni0 coatings, and iron oxide phases on pentachlorophenol dechlorination by zero-valent iron. Environ Sci Pollut Res 26:27687–27698

    Article  CAS  Google Scholar 

  • Henderson AD, Demond AH (2007) Long-term performance of zero-valent iron permeable reactive barriers: a critical review. Environ Eng Sci 24:401–423

    Article  CAS  Google Scholar 

  • Henderson AD, Demond AH (2011) Impact of solids formation and gas production on the permeability of ZVI PRBs. J Environ Eng 137:689–696

    Article  CAS  Google Scholar 

  • Hou M, Wan H, Zhou Q, Liu X, Luo W, Fan Y (2009) The dechlorination of pentachlorophenol by zerovalent iron in presence of carboxylic acids. Bull Environ Contam Toxicol 82:137–144

    Article  CAS  Google Scholar 

  • Hu R, Cui X, Gwenzi W, Wu S, Noubactep C (2018) Fe0/H2O systems for environmental remediation: the scientific history and future research directions. Water 10:1739

    Article  CAS  Google Scholar 

  • IARC (2019) Monographs on the evaluation of carcinogenic risks to humans: pentachlorophenol and some related compounds, Vol 117. International Agency for Research on Cancer, World Health Organization, Lyon, France

    Google Scholar 

  • Jaumot J, Gargallo R, De Juan A, Tauler R (2005) A graphical user-friendly interface for MCR-ALS: a new tool for multivariate curve resolution in MATLAB. Chemometr Intell Lab Syst 76:101–110

    Article  CAS  Google Scholar 

  • Jeen S-W (2005) Effects of mineral precipitation on long-term performance of granular iron permeable reactive barriers: column experiments and numerical simulation. Ph.D., University of Waterloo (Canada)

    Google Scholar 

  • Jin suk O, Jeen S-W, Gillham RW, Gui L (2009) Effects of initial iron corrosion rate on long-term performance of iron permeable reactive barriers: Column experiments and numerical simulation. J Contam Hydrol 103:145–156

    Google Scholar 

  • Kim YH (1999) Reductive dechlorination of chlorinated aliphatic and aromatic compounds using zero valent metals: modified metals and electron mediators. PhD, Texas A & M University

    Google Scholar 

  • Kim YH, Carraway ER (2000) Dechlorination of pentachlorophenol by zero valent iron and modified zero valent irons. Environ Sci Technol 34:2014–2017

    Article  CAS  Google Scholar 

  • Klausen J, Vikesland PJ, Kohn T, Burris DR, Ball WP, Roberts AL (2003) Longevity of granular iron in groundwater treatment processes: solution composition effects on reduction of organohalides and nitroaromatic compounds. Environ Sci Technol 37:1208–1218

    Article  CAS  Google Scholar 

  • Ko SO, Lee DH, Kim YH (2007) Kinetic studies of reductive dechlorination of chlorophenols with Ni/Fe bimetallic particles. Environ Technol 28:583–593

    Article  CAS  Google Scholar 

  • Lan Q, Liu H, Li FB, Zeng F, Liu CS (2011) Effect of pH on pentachlorophenol degradation in irradiated iron/oxalate systems. Chem Eng J 168:1209–1216

    Article  CAS  Google Scholar 

  • Li L, Benson CH (2010) Evaluation of five strategies to limit the impact of fouling in permeable reactive barriers. J Hazard Mater 181:170–180

    Article  CAS  Google Scholar 

  • Li Y, Niu J, Yin L, Wang W, Bao Y, Chen J, Duan Y (2011) Photocatalytic degradation kinetics and mechanism of pentachlorophenol based on Superoxide radicals. J Environ Sci 23:1911–1918

    Article  CAS  Google Scholar 

  • Liu Y, Yang F, Yue PL, Chen G (2001) Catalytic dechlorination of chlorophenols in water by palladium/iron. Water Res 35:1887–1890

    Article  CAS  Google Scholar 

  • Liu CC, Tseng DH, Wang CY (2006) Effects of ferrous ions on the reductive dechlorination of trichloroethylene by zero-valent iron. J Hazard Mater 136:706–713

    Article  CAS  Google Scholar 

  • Long M, Ilhan ZE, Xia S, Zhou C, Rittmann BE (2018) Complete dechlorination and mineralization of pentachlorophenol (PCP) in a hydrogen-based membrane biofilm reactor (MBfR). Water Res 144:134–144

    Article  CAS  Google Scholar 

  • Ma H-Y, Zhao L, Guo L-H, Zhang H, Chen F-J, Yu W-C (2019) Roles of reactive oxygen species (ROS) in the photocatalytic degradation of pentachlorophenol and its main toxic intermediates by TiO2/UV. J Hazard Mater 369:719–726

    Article  CAS  Google Scholar 

  • Matheson LJ, Tratnyek PG (1994) Reductive dehalogenation of chlorinated methanes by iron metal. Environ Sci Technol 28:2045–2053

    Article  CAS  Google Scholar 

  • Morales J, Hutcheson R, Cheng IF (2002) Dechlorination of chlorinated phenols by catalyzed and uncatalyzed Fe(0) and Mg(0) particles. J Hazard Mater 90:97–108

    Article  CAS  Google Scholar 

  • Nadoll P, Mauk JL (2011) Wüstite in a hydrothermal silver-lead-zinc vein, Lucky Friday mine, Coeur d'Alene mining district, U.S.A. Am Mineral 96(2–3):261–267

    Google Scholar 

  • Nardo AD, Natale, MD, Erto A, Musmarra D, Bortonea I (2010) Permeable reactive barrier for groundwater PCE remediation: the case study of a solid waste landfill pollution. In: Pierucci S, Ferraris GB (eds) Computer aided chemical engineering, Vol 28. Elsevier, pp 1015–1020

    Google Scholar 

  • Noubactep C (2007) Processes of contaminant removal in “Fe0-H2O” systems revisited: the importance of co-precipitation. Open Environ J 1:9–13

    Article  CAS  Google Scholar 

  • Noubactep C (2008) A critical review on the process of contaminant removal in Fe0-H2O systems. Environ Technol 29:909–920

    Article  CAS  Google Scholar 

  • Noubactep C (2009) An analysis of the evolution of reactive species in Fe0/H2O systems. J Hazard Mater 168:1626–1631

    Article  CAS  Google Scholar 

  • Noubactep C (2013) Metallic Iron for water treatment: a critical review. CLEAN—Soil, Air, Water, pp 1–9

    Google Scholar 

  • Olaniran AO, Igbinosa EO (2011) Chlorophenols and other related derivatives of environmental concern: Properties, distribution and microbial degradation processes. Chemosphere 83:1297–1306

    Article  CAS  Google Scholar 

  • Patel UD, Suresh S (2006) Dechlorination of chlorophenols by magnesium-silver bimetallic system. J Colloid Inter Sci 299:249–259

    Article  CAS  Google Scholar 

  • Patel UD, Suresh S (2007) Dechlorination of chlorophenols using magnesium-palladium bimetallic system. J Hazard Mater 147:431–438

    Article  CAS  Google Scholar 

  • Patterson BM, Lee M, Bastow TP, Wilson JT, Donn MJ, Furness A, Goodwin B, Manefield M (2016) Concentration effects on biotic and abiotic processes in the removal of 1, 1, 2-trichloroethane and vinyl chloride using carbon-amended ZVI. J Contam Hydrol 188:1–11

    Article  CAS  Google Scholar 

  • Phillips DH, Van Nooten T, Bastiaens L, Russell MI, Dickson K, Plant S, Ahad JME, Newton T, Elliot T, Kalin RM (2010) Ten year performance evaluation of a field-scale zero-valent iron permeable reactive barrier installed to remediate trichloroethene contaminated groundwater. Environ Sci Technol 44:3861–3869

    Article  CAS  Google Scholar 

  • Ritter K, Odziemkowski MS, Gillham RW (2002) An in situ study of the role of surface films on granular iron in the permeable iron wall technology. J Contam Hydrol 55:87–111

    Article  CAS  Google Scholar 

  • Scherer MM, Balko BA, Tratnyek PG (1999) The role of oxides in reduction reactions at the metal-water interface In: Mineral-Water Interfacial Reactions, Chapter 15, vol 715. ACS Symposium Series, pp 301–322

    Google Scholar 

  • Schrick B, Blough JL, Jones AD, Mallouk TE (2002) Hydrodechlorination of trichloroethylene to hydrocarbons using bimetallic nickel-iron nanoparticles. Chem Mater 14:5140–5147

    Article  CAS  Google Scholar 

  • Shih Y-h, Chen M-Y, Su Y-F (2011) Pentachlorophenol reduction by Pd/Fe bimetallic nanoparticles: Effects of copper, nickel, and ferric cations. Appl Catal B 105:24–29

    Article  CAS  Google Scholar 

  • Shiu W-Y, Ma K-C, Varhanícková D, Mackay D (1994) Chlorophenols and alkylphenols: a review and correlation of environmentally relevant properties and fate in an evaluative environment. Chemosphere 29:1155–1224

    Article  CAS  Google Scholar 

  • Song Y, Swedlund PJ, Singhal N (2008) Copper(II) and cadmium(II) sorption onto ferrihydrite in the presence of phthalic acid: some properties of the ternary complex. Environ Sci Technol 42:4008–4013

    Article  CAS  Google Scholar 

  • Tanjore S, Viraraghavan T (1994) Pentachlorophenol—Water pollution impacts and removal technologies. Int J Environ Stud 45:155–164

    Article  CAS  Google Scholar 

  • Tian H, Li J, Mu Z, Li L, Hao Z (2009) Effect of pH on DDT degradation in aqueous solution using bimetallic Ni/Fe nanoparticles. Sep Purif Technol 66:84–89

    Article  CAS  Google Scholar 

  • UNEP (2014) Pentachlorophenol and its salts and esters: draft risk management evaluation, UNEP/POPS/POPRC.10/2, persistent organic pollutants review committee, United Nations Stockholm Convention on Persistent Organic Pollutants

    Google Scholar 

  • USEPA (2010) Toxicological review of pentachlorophenol: in support of summary information on the integrated risk information system (IRIS). United States Environmental Protection Agency, Washington, DC

    Google Scholar 

  • USEPA (2018a) Drinking water contaminants—standards and regulations. National Primary Drinking Water Regulations. https://www.epa.gov/dwstandardsregulations. Accessed 18 March 2019

  • USEPA (2018b) Groundwater & drinking water. National primary drinking water regulations. https://www.epa.gov/ground-water-and-drinking-water/national-primary-drinking-waterregulations#Organic. Accessed 18 Mar 2019

  • USEPA (2019) Priority pollutant list. Toxic and priority pollutants under the clean water act. http://water.epa.gov/scitech/methods/cwa/pollutants.cfm. Accessed 10 July 2019

  • Wang X, Chen C, Liu H, Ma J (2008) Characterization and evaluation of catalytic dechlorination activity of Pd/Fe bimetallic nanoparticles. Ind Eng Chem Res 47:8645–8651

    Article  CAS  Google Scholar 

  • Wei J, Xu X, Liu Y, Wang D (2006) Catalytic hydrodechlorination of 2,4-dichlorophenol over nanoscale Pd/Fe: reaction pathway and some experimental parameters. Water Res 40:348–354

    Article  CAS  Google Scholar 

  • WHO (2003) Chlorophenols in drinking-water. Background document for development of WHO Guidelines for Drinking-water quality. WHO/SDE/WSH/03.04/47. In: Guidelines for drinking-water quality, 2nd ed. Vol. 2. Health criteria and other supporting information. World Health Organization, Geneva, 1996

    Google Scholar 

  • Xu F, Deng S, Xu J, Zhang W, Wu M, Wang B, Huang J, Yu G (2012) Highly active and stable Ni–Fe bimetal prepared by ball milling for catalytic hydrodechlorination of 4-chlorophenol. Environ Sci Technol 46:4576–4582

    Article  CAS  Google Scholar 

  • Xu Y, Xue L, Ye Q, Franks AE, Zhu M, Feng X, Xu J, He Y (2018) Inhibitory effects of sulfate and nitrate reduction on reductive dechlorination of PCP in a flooded paddy soil. Front Microbiol 9:567

    Article  Google Scholar 

  • Yang BR, Chen AH (2016) Effects of pentachlorophenol on the bacterial denitrification process. Chem Speciat Bioavailab 28:163–169

    Article  CAS  Google Scholar 

  • Zhang W, Quan X, Wang J, Zhang Z, Chen S (2006) Rapid and complete dechlorination of PCP in aqueous solution using Ni-Fe nanoparticles under assistance of ultrasound. Chemosphere 65:58–64

    Article  CAS  Google Scholar 

  • Zhou T, Li Y, Lim T-T (2010) Catalytic hydrodechlorination of chlorophenols by Pd/Fe nanoparticles: Comparisons with other bimetallic systems, kinetics and mechanism. Sep Purif Technol 76:206–221

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Authors would like to thank Dr. Michel Nieuwoudt for the technical assistance provided with the Raman spectroscopic analysis. The research funding was provided by the New Zealand International Doctoral Research Scholarship, New Zealand Foundation for Research, Science and Technology and the University of Auckland, New Zealand.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Buddhika Gunawardana .

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2021 Springer Nature Singapore Pte Ltd.

About this chapter

Check for updates. Verify currency and authenticity via CrossMark

Cite this chapter

Gunawardana, B., Singhal, N., Swedlund, P.J. (2021). Chlorophenols Dechlorination Water Treatment Using Ni-Iron Bimetallic Systems: Implications of the Degree of Chlorination, Nickel Coating, and Iron Oxide Phases. In: Kumar, M., Snow, D., Honda, R., Mukherjee, S. (eds) Contaminants in Drinking and Wastewater Sources. Springer Transactions in Civil and Environmental Engineering. Springer, Singapore. https://doi.org/10.1007/978-981-15-4599-3_12

Download citation

  • DOI: https://doi.org/10.1007/978-981-15-4599-3_12

  • Published:

  • Publisher Name: Springer, Singapore

  • Print ISBN: 978-981-15-4598-6

  • Online ISBN: 978-981-15-4599-3

  • eBook Packages: EngineeringEngineering (R0)

Publish with us

Policies and ethics