Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Towards a molecular-scale theory for the removal of natural organic matter by coagulation with trivalent metals

Nature Water volume 2, pages 285–294 (2024)Cite this article

Subjects

Abstract

Coagulation is one of the most common treatment processes for the removal of contaminants from water, representing ‘the first line of defence’ for drinking water safety. However, the macroscopic and descriptive theories of trivalent metal-based coagulation have limited the optimization of its performance in the removal of natural organic matter species, which are major precursors of hazardous disinfection by-products. In this study, we have extended the coagulation theory to the functional group level, highlighting the fundamental importance of η-H2O and η-OH groups on aluminium precipitates, and finding that the selectivity for natural organic matter during coagulation is determined by their functional groups. Drawing upon the fundamental characteristics of coagulants and organic substances, this study has elucidated their behaviour during the coagulation process and offers valuable theoretical insights to guide future applications of coagulation in practical settings.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Hydrolysis of aluminium.
Fig. 2: Irreversibility of floc breakage and its interpretation.
Fig. 3: Removal of organic matter by coagulation.
Fig. 4: Variation in the coagulation indices with the adsorption of organic compounds.
Fig. 5: Reaction between aluminium hydroxide precipitates and functional groups.

Similar content being viewed by others

Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information.

References

  1. Gan, Y., Zhang, L. & Zhang, S. The suitability of titanium salts in coagulation removal of micropollutants and in alleviation of membrane fouling. Water Res. 205, 117692 (2021).

    Article  CAS  PubMed  Google Scholar 

  2. Cheng, X. et al. Coupling sodium percarbonate (SPC) oxidation and coagulation for membrane fouling mitigation in algae-laden water treatment. Water Res. 204, 117622 (2021).

    Article  CAS  PubMed  Google Scholar 

  3. Cai, G. et al. Control for chlorine resistant spore forming bacteria by the coupling of pre-oxidation and coagulation sedimentation, and UV-AOPs enhanced inactivation in drinking water treatment. Water Res. 219, 118540 (2022).

    Article  CAS  PubMed  Google Scholar 

  4. Du, P. et al. Regulated-biofilms enhance the permeate flux and quality of gravity-driven membrane (GDM) by in situ coagulation combined with activated alumina filtration. Water Res. 209, 117947 (2022).

    Article  CAS  PubMed  Google Scholar 

  5. Yu, W., Graham, N. J. D. & Fowler, G. D. Coagulation and oxidation for controlling ultrafiltration membrane fouling in drinking water treatment: application of ozone at low dose in submerged membrane tank. Water Res. 95, 1–10 (2016).

    Article  PubMed  Google Scholar 

  6. Jiang, J.-Q. The role of coagulation in water treatment. Curr. Opin. Chem. Eng. 8, 36–44 (2015).

    Article  Google Scholar 

  7. Zhang, X., Graham, N., Xu, L., Yu, W. & Gregory, J. The influence of small organic molecules on coagulation from the perspective of hydrolysis competition and crystallization. Environ. Sci. Technol. 55, 7456–7465 (2021).

    Article  CAS  PubMed  Google Scholar 

  8. Su, Z. et al. Discovery of welcome biopolymers in surface water: improvements in drinking water production. Environ. Sci. Technol. 55, 2076–2086 (2021).

    Article  CAS  PubMed  Google Scholar 

  9. An, G. et al. Deprotonation and aggregation of Al13 under alkaline titration: a simulating study related to coagulation process. Water Res. 203, 117562 (2021).

    Article  CAS  PubMed  Google Scholar 

  10. Li, M. et al. Effects of pre-oxidation on residual dissolved aluminum in coagulated water: a pilot-scale study. Water Res. 190, 116682 (2021).

    Article  CAS  PubMed  Google Scholar 

  11. Liu, B. et al. Coagulation behavior of polyaluminum–titanium chloride composite coagulant with humic acid: a mechanism analysis. Water Res. 220, 118633 (2022).

    Article  CAS  PubMed  Google Scholar 

  12. Jarvis, P. et al. Comparison of coagulation performance and floc properties using a novel zirconium coagulant against traditional ferric and alum coagulants. Water Res. 46, 4179–4187 (2012).

    Article  CAS  PubMed  Google Scholar 

  13. Mattson, S. Cataphoresis and the electrical neutralization of colloidal material. J. Phys. Chem. 32, 1532–1552 (1928).

    Article  CAS  Google Scholar 

  14. Abeysinghe, S., Unruh, D. K. & Forbes, T. Z. Crystallization of Keggin-type polyaluminum species by supramolecular interactions with disulfonate anions. Cryst. Growth Des. 12, 2044–2051 (2012).

    Article  CAS  Google Scholar 

  15. Bi, S., Wang, C., Cao, Q. & Zhang, C. Studies on the mechanism of hydrolysis and polymerization of aluminum salts in aqueous solution: correlations between the ‘core-links’ model and ‘cage-like’ Keggin-Al13 model. Coord. Chem. Rev. 248, 441–455 (2004).

    Article  CAS  Google Scholar 

  16. Tang, H., Xiao, F. & Wang, D. Speciation, stability, and coagulation mechanisms of hydroxyl aluminum clusters formed by PACl and alum: a critical review. Adv. Colloid Interface Sci. 226, 78–85 (2015).

    Article  CAS  PubMed  Google Scholar 

  17. Banfield, J. F., Welch, S. A., Zhang, H. Z., Ebert, T. T. & Penn, R. L. Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. Science 289, 751–754 (2000).

    Article  CAS  PubMed  Google Scholar 

  18. Yukselen, M. A. & Gregory, J. The reversibility of floc breakage. Int. J. Miner. Process. 73, 251–259 (2004).

    Article  CAS  Google Scholar 

  19. Jin, X., Liao, R., Zhang, T. & Li, H. Theoretical insights into the dimerization mechanism of aluminum species at two different pH conditions. Inorg. Chim. Acta 520, 120311 (2021).

    Article  CAS  Google Scholar 

  20. Yu, W., Gregory, J. & Campos, L. C. Breakage and re-growth of flocs: effect of additional doses of coagulant species. Water Res. 45, 6718–6724 (2011).

    Article  CAS  PubMed  Google Scholar 

  21. Han, Q. et al. Trihalomethanes (THMs) precursor fractions removal by coagulation and adsorption for bio-treated municipal wastewater: molecular weight, hydrophobicity/hydrophily and fluorescence. J. Hazard. Mater. 297, 119–126 (2015).

    Article  CAS  PubMed  Google Scholar 

  22. Kim, H.-C. & Yu, M.-J. Characterization of natural organic matter in conventional water treatment processes for selection of treatment processes focused on DBPs control. Water Res. 39, 4779–4789 (2005).

    Article  CAS  PubMed  Google Scholar 

  23. Mecozzi, S., West, A. P. & Dougherty, D. A. Cation−π Interactions in simple aromatics: electrostatics provide a predictive tool. J. Am. Chem. Soc. 118, 2307–2308 (1996).

    Article  CAS  Google Scholar 

  24. Ma, J. C. & Dougherty, D. A. The cation−π interaction. Chem. Rev. 97, 1303–1324 (1997).

    Article  CAS  PubMed  Google Scholar 

  25. Casey, W. H. Large aqueous aluminum hydroxide molecules. Chem. Rev. 106, 1–16 (2006).

    Article  CAS  PubMed  Google Scholar 

  26. Guo, K. et al. Highly efficient Al–Ti gel as a coagulant for surface water treatment: insights into the hydrolysate transformation and coagulation mechanism. Water Res. 221, 118826 (2022).

    Article  CAS  PubMed  Google Scholar 

  27. Yu, W.-Z. et al. Aggregation of nano-sized alum–humic primary particles. Sep. Purif. Technol. 99, 44–49 (2012).

    Article  CAS  Google Scholar 

  28. Hopkins, D. C. & Ducoste, J. J. Characterizing flocculation under heterogeneous turbulence. J. Colloid Interface Sci. 264, 184–194 (2003).

    Article  CAS  PubMed  Google Scholar 

  29. Xiao, F., Ma, J., Yi, P. & Huang, J. C. H. Effects of low temperature on coagulation of kaolinite suspensions. Water Res. 42, 2983–2992 (2008).

    Article  CAS  PubMed  Google Scholar 

  30. Huguet, A. et al. Properties of fluorescent dissolved organic matter in the Gironde Estuary. Org. Geochem. 40, 706–719 (2009).

    Article  CAS  Google Scholar 

  31. Gregory, J. & Nelson, D. W. Monitoring of aggregates in flowing suspensions. Colloids Surf. 18, 175–188 (1986).

    Article  CAS  Google Scholar 

  32. Su, Z., Li, X. & Yang, Y. Regrowth ability and coagulation behavior by second dose: breakage during the initial flocculation phase. Colloids Surf. A 527, 109–114 (2017).

    Article  CAS  Google Scholar 

  33. Zhang, B., Shan, C., Wang, S., Fang, Z. & Pan, B. Unveiling the transformation of dissolved organic matter during ozonation of municipal secondary effluent based on FT-ICR-MS and spectral analysis. Water Res. 188, 116484 (2021).

    Article  CAS  PubMed  Google Scholar 

  34. Johansson, G. The crystal structures of [Al2(OH)2(H2O)8](SO4)2·2H2O and [Al2(OH)2(H2O)8](SeO4)2·2H2O. Acta Chem. Scand. 16, 403–420 (1962).

    Article  CAS  Google Scholar 

  35. Johansson, G., Lundgren, G., Sillén, L. & Sderquist, R. J. On the crystal structure of a basic aluminum sulfate and the corresponding selenate. Acta Chem. Scand. 14, 769–771 (1960).

    Article  CAS  Google Scholar 

  36. Pascual-Cosp, J., Artiaga, R., Corpas-Iglesias, F. & Benítez-Guerrero, M. Synthesis and characterization of a new aluminium-based compound. Dalton Trans. 28, 6299–6308 (2009).

    Article  Google Scholar 

  37. Wang, W., Wentz, K. M., Hayes, S. E., Johnson, D. W. & Keszler, D. A. Synthesis of the hydroxide cluster [Al13(μ3-OH)6(μ-OH)18(H2O)24]15+ from an aqueous solution.Inorg. Chem. 50, 4683–4685 (2011).

    Article  CAS  PubMed  Google Scholar 

  38. Wu, M., Yu, W., Qu, J. & Gregory, J. The variation of flocs activity during floc breakage and aging, adsorbing phosphate, humic acid and clay particles. Water Res. 155, 131–141 (2019).

    Article  CAS  PubMed  Google Scholar 

  39. Liu, M. & Yu, W. Surface chemical groups of flocs are key factors for the growth of flocs in sweep coagulation: a case study of surface occupation by humic acid. ACS ES T Eng. 2, 2301–2310 (2022).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Key Research and Development Plan of the Chinese Ministry of Science and Technology (grant no. 2019YFC1906501, W.Y.) and Beijing Natural Science Foundation (grant no. JQ21032, W.Y.).

Author information

Authors and Affiliations

  1. State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, People’s Republic of China

    Mengjie Liu & Wenzheng Yu

  2. University of Chinese Academy of Sciences, Beijing, People’s Republic of China

    Mengjie Liu

  3. Department of Civil and Environmental Engineering, Imperial College London, London, UK

    Nigel Graham

  4. Department of Civil, Environmental and Geomatic Engineering, University College London, London, UK

    John Gregory

  5. Department of Chemical and Environmental Engineering, Yale University, New Haven, CT, USA

    Menachem Elimelech

Authors
  1. Mengjie Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Nigel Graham
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. John Gregory
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Menachem Elimelech
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wenzheng Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

W.Y., N.G. and M.E. designed the experiments. M.L. completed the main experiments and wrote the first draft of the paper. W.Y., N.G., J.G. and M.E. made the final revisions to the paper.

Corresponding authors

Correspondence to Menachem Elimelech or Wenzheng Yu.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Water thanks Gregory Korshin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Notes 1–6, Figs. 1–16, and Tables 1 and 2.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, M., Graham, N., Gregory, J. et al. Towards a molecular-scale theory for the removal of natural organic matter by coagulation with trivalent metals. Nat Water 2, 285–294 (2024). https://doi.org/10.1038/s44221-024-00212-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s44221-024-00212-x

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing