A tale of two minerals: contrasting behaviors and mitigation strategies of gypsum scaling and silica scaling in membrane desalination
Tiezheng Tong1,2(), Shinyun Park1,2, Yiqun Yao1,2
. Department of Civil and Environmental Engineering, Colorado State University, Fort Collins, CO 80523, USA . School of Sustainable Engineering and the Built Environment, Arizona State University, Tempe, AZ 85287, USA
Mineral scaling represents a major constraint that limits the efficiency of membrane desalination, which is becoming increasingly important for achieving sustainable water supplies in the context of a changing climate. Different mineral scales can be formed via distinct mechanisms that lead to a significant variation of scaling behaviors and mitigation strategies. In this article, we present a comprehensive review that thoroughly compares gypsum scaling and silica scaling, which are two common scaling types formed via crystallization and polymerization respectively, in membrane desalination. We show that the differences between scale formation mechanisms greatly affect the thermodynamics, kinetics, and mineral morphology of gypsum scaling and silica scaling. Then we review the literatures on the distinct behaviors of gypsum scaling and silica scaling during various membrane desalination processes, examining their varied damaging effects on desalination efficiency. We further scrutinize the different interactions of gypsum and silica with organic foulants, which result in contrasting consequences of combined scaling and fouling. In addition, the distinctive mitigation strategies tailored to controlling gypsum scaling and silica scaling, including scaling-resistant membrane materials, antiscalants, and pretreatment, are discussed. We conclude this article with the research needs of attaining a better understanding of different mineral scaling types, aiming to inspire researchers to take scale formation mechanism into consideration when developing more effective approaches of scaling control in membrane desalination.
Just Accepted Date: 29 August 2024Issue Date: 29 October 2024
Cite this article:
Tiezheng Tong,Shinyun Park,Yiqun Yao. A tale of two minerals: contrasting behaviors and mitigation strategies of gypsum scaling and silica scaling in membrane desalination[J]. Front. Environ. Sci. Eng.,
2025, 19(1): 3.
Fig.1 (A) Schematic of classical nucleation theory and non-classical nucleation pathway of mineral formation. (B) The change of free energy during mineral nucleation. and refer to the free energy barrier to homogeneous nucleation and heterogeneous nucleation, respectively. (C) Schematic of four stages of gypsum crystal formation, including the formation, aggregation, self-assembly, and coalescence of CaSO4 clusters. (D) Transmission electron microscopic image of bassanite nanorods formed before gypsum crystal formation. The figures are adapted with permission from Meldrum and Sear (2008), copyright American Association for the Advancement of Science; Tong et al. (2019a), copyright Elsevier; Stawski et al. (2016), copyright Nature Portfolio; Van Driessche et al. (2012), copyright American Association for the Advancement of Science.
Fig.2 Schematic of silicic acid polymerization that leads to silica formation.
Fig.3 (A and B) Water vapor flux (red) and feed conductivity (blue) curves during MD desalination in the presence of (A) gypsum scaling and (B) silica scaling. (C and D) Normalized transmembrane impedance (red) and distillate conductivity (blue) during MD desalination in the presence of (C) gypsum scaling and (D) silica scaling. A decrease of normalized impedance and an increase of distillate conductivity indicate the occurrence of pore wetting. (E and F) Top-down SEM images of (E) gypsum and (F) silica scales formed in MD. (G and H) Cross-section energy dispersive X-ray spectroscopy mapping of membranes scaled by (G) gypsum and (H) silica. The figures are adapted with permission from Christie et al. (2020), copyright American Chemical Society.
Fig.4 Representative normalized water flux decline curves for (A and B) gypsum and (C and D) silica scaling in the presence of proteins in RO. Each graph includes water flux curves of individual mineral scaling and organic fouling, the additive curve of individual scaling and fouling, and the actual water flux curve of combined scaling and fouling. (E and F) SEM images of the membrane surface after combined scaling and fouling experiments: gypsum scaling with (E) BSA and (F) lysozyme fouling, and silica scaling with (G) BSA and (H) lysozyme fouling. The figures are adapted with permission from Park et al. (2024) (A, B, E, F), copyright Elsevier; Quay et al. (2018) (C, D, G, H), copyright American Chemical Society.
Fig.5 (A) Water flux curve of RO desalinating feedwater containing supersaturated silica using membranes of different surface properties. (B) The water flux decline ratio of membranes shown in Fig. 5(A) demonstrates a strong correlation with surface charge, manifested by zeta potential, of the membranes. (C) Mechanisms underlying the relationship between membrane surface charge and propensity of silica scaling. (D) Water flux curve of RO desalinating feedwater containing supersaturated gypsum using a pristine polyamide membrane and membranes coated with zwitterionic polymer. (E) The membrane-water and membrane-gypsum interfacial free energies for the pristine polyamide and zwitterion-coated membranes. The figures are adapted with permission from Tong et al. (2017), copyright American Chemical Society; Jaramillo et al. (2021), copyright Elsevier.
Fig.6 (A–F) Three possible mechanisms underlying the resistance of superhydrophobic membranes against gypsum scaling in MD. It is worth mentioning that the mechanism shown by Figures 6E and 6F is unlikely to be the main mechanism because gypsum is described more appropriately by a non-classical pathway. (G) A four-step mechanism of silica scaling in MD. The figures are adapted with permission from Horseman et al. (2021), copyright American Chemical Society; Yin et al. (2019), copyright Royal Society of Chemistry.
Fig.7 (A and B) Normalized water vapor flux as a function of water recovery in MD for (A) gypsum scaling and (B) silica scaling in the presence of different antiscalant candidates. (C and D) Schematic illustration of the mechanisms of antiscalants for mitigating (C) gypsum scaling and (D) silica scaling in MD. (E) Schematic illustration of amino-containing polymers of different conformation hindering silica polymerization through interactions with silicic acid. The figures are adapted with permission from Yin et al. (2021), copyright American Chemical Society; Kaneda et al. (2024), copyright American Chemical Society.
Fig.8 Schematic illustrations of different pretreatment techniques. (A) Ion-ion selective separation process using NF for gypsum scaling mitigation. (B) Magnetic iron-aluminum hybrid nanomaterials for silica removal. (C) Electrocoagulation for removing silica and hardness. The figures are adapted with permission from (Zhang and Zhang, 2021) (copyright Elsevier), (Guan et al., 2019) (copyright American Chemical Society) and (Liu et al., 2022) (copyright American Chemical Society).
Gypsum scaling
Silica scaling
Formation mechanism
Crystallization
Polymerization
Formation kinetics
Fast
Slow
Crystal growth
Anisotropic
Isotropic
Membrane surface property – scaling propensity relationship in RO
Grafting of hydrophilic polymer brushes reduces scaling
More negative charged membrane reduces scaling
Membrane surface property – scaling propensity relationship in MD
Superhydrophobic membranes reduce scaling
Not sensitive to membrane surface wettability
Inducting pore wetting in MD
Yes
No
Interactions with organic foulants
Antagonistic or additive effects (e.g., the presence of BSA reduces scaling)
Amplifying effects (e.g., the presence of BSA facilitates scaling)
Antiscalants in RO
Carboxyl- and phosphonate-based molecules(elimination of water flux decline is achievable)
Poly(ethylene glycol)-based molecules (elimination of water flux decline has not been achieved)
Antiscalants in MD
Carboxyl- and phosphonate-based molecules
Amine-enriched molecules and poly(ethylene glycol)-based molecules
Tab.1 Comparison between gypsum scaling and silica scaling in membrane desalination
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