Zeta potential of artificial and natural calcite in aqueous solution

Dawoud Al Mahrouqi, Jan Vinogradov, Matthew D. Jackson

Research output: Contribution to journalArticle

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Abstract

Despite the broad range of interest and applications, controls on calcite surface charge in aqueous solution, especially at conditions relevant to natural systems, remain poorly understood. The primary data source to understand calcite surface charge comprises measurements of zeta potential. Here we collate and review previous measurements of zeta potential on natural and artificial calcite and carbonate as a resource for future studies, compare and contrast the results of these studies to determine key controls on zeta potential and where uncertainties remain, and report new measurements of zeta potential relevant to natural subsurface systems.

The results show that the potential determining ions (PDIs) for the carbonate mineral surface are the lattice ions Ca2 +, Mg2 + and CO32 −. The zeta potential is controlled by the concentration-dependent adsorption of these ions within the Stern layer, primarily at the Outer Helmholtz Plane (OHP). Given this, the Iso-Electric Point (IEP) at which the zeta potential is zero should be expressed as pCa (or pMg). It should not be reported as pH, similar to most metal oxides.

The pH does not directly control the zeta potential. Varying the pH whilst holding pCa constant yields constant zeta potential. The pH affects the zeta potential only by moderating the equilibrium pCa for a given CO2 partial pressure (pCO2). Experimental studies that appear to yield a systematic relationship between pH and zeta potential are most likely observing the relationship between pCa and zeta potential, with pCa responding to the change in pH. New data presented here show a consistent linear relationship between equilibrium pH and equilibrium pCa or pMg irrespective of sample used or solution ionic strength. The surface charge of calcite is weakly dependent on pH, through protonation and deprotonation reactions that occur within a hydrolysis layer immediately adjacent to the mineral surface. The Point of Zero Charge (PZC) at which the surface charge is zero could be expressed as pH, but surface complexation models suggest the surface is negatively charged over the pH range 5.5–11.

Several studies have suggested that SO42 − is also a PDI for the calcite surface, but new data presented here indicate that the value of pSO4 may affect zeta potential only by moderating the equilibrium pCa. Natural carbonate typically yields a more negative zeta potential than synthetic calcite, most likely due to the presence of impurities including clays, organic matter, apatite, anhydrite or quartz, that yield a more negative zeta potential than pure calcite. New data presented here show that apparently identical natural carbonates display differing zeta potential behaviour, most likely due to the presence of small volumes of these impurities. It is important to ensure equilibrium, defined in terms of the concentration of PDIs, has been reached prior to taking measurements. Inconsistent values of zeta potential obtained in some studies may reflect a lack of equilibration.

The data collated and reported here have broad application in engineering processes including the manufacture of paper and cement, the geologic storage of nuclear waste and CO2, and the production of oil and gas.

Original languageEnglish
Pages (from-to)60–76
Number of pages17
JournalAdvances in Colloid and Interface Science
Volume240
Early online date26 Dec 2016
DOIs
Publication statusPublished - 1 Feb 2017

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Calcium Carbonate
Calcite
Zeta potential
calcite
aqueous solutions
Surface charge
Ions
Carbonates
carbonates
ions
Carbonate minerals
Impurities
Radioactive Waste
Apatites
minerals
Deprotonation
Quartz
Protonation
Apatite
impurities

Keywords

  • Zeta potential
  • Streaming potential
  • Calcite
  • Carbonate
  • Wettability alteration
  • Controlled salinity waterflooding

Cite this

Zeta potential of artificial and natural calcite in aqueous solution. / Al Mahrouqi, Dawoud; Vinogradov, Jan; Jackson, Matthew D.

In: Advances in Colloid and Interface Science, Vol. 240, 01.02.2017, p. 60–76.

Research output: Contribution to journalArticle

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AU - Jackson, Matthew D.

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N2 - Despite the broad range of interest and applications, controls on calcite surface charge in aqueous solution, especially at conditions relevant to natural systems, remain poorly understood. The primary data source to understand calcite surface charge comprises measurements of zeta potential. Here we collate and review previous measurements of zeta potential on natural and artificial calcite and carbonate as a resource for future studies, compare and contrast the results of these studies to determine key controls on zeta potential and where uncertainties remain, and report new measurements of zeta potential relevant to natural subsurface systems.The results show that the potential determining ions (PDIs) for the carbonate mineral surface are the lattice ions Ca2 +, Mg2 + and CO32 −. The zeta potential is controlled by the concentration-dependent adsorption of these ions within the Stern layer, primarily at the Outer Helmholtz Plane (OHP). Given this, the Iso-Electric Point (IEP) at which the zeta potential is zero should be expressed as pCa (or pMg). It should not be reported as pH, similar to most metal oxides.The pH does not directly control the zeta potential. Varying the pH whilst holding pCa constant yields constant zeta potential. The pH affects the zeta potential only by moderating the equilibrium pCa for a given CO2 partial pressure (pCO2). Experimental studies that appear to yield a systematic relationship between pH and zeta potential are most likely observing the relationship between pCa and zeta potential, with pCa responding to the change in pH. New data presented here show a consistent linear relationship between equilibrium pH and equilibrium pCa or pMg irrespective of sample used or solution ionic strength. The surface charge of calcite is weakly dependent on pH, through protonation and deprotonation reactions that occur within a hydrolysis layer immediately adjacent to the mineral surface. The Point of Zero Charge (PZC) at which the surface charge is zero could be expressed as pH, but surface complexation models suggest the surface is negatively charged over the pH range 5.5–11.Several studies have suggested that SO42 − is also a PDI for the calcite surface, but new data presented here indicate that the value of pSO4 may affect zeta potential only by moderating the equilibrium pCa. Natural carbonate typically yields a more negative zeta potential than synthetic calcite, most likely due to the presence of impurities including clays, organic matter, apatite, anhydrite or quartz, that yield a more negative zeta potential than pure calcite. New data presented here show that apparently identical natural carbonates display differing zeta potential behaviour, most likely due to the presence of small volumes of these impurities. It is important to ensure equilibrium, defined in terms of the concentration of PDIs, has been reached prior to taking measurements. Inconsistent values of zeta potential obtained in some studies may reflect a lack of equilibration.The data collated and reported here have broad application in engineering processes including the manufacture of paper and cement, the geologic storage of nuclear waste and CO2, and the production of oil and gas.

AB - Despite the broad range of interest and applications, controls on calcite surface charge in aqueous solution, especially at conditions relevant to natural systems, remain poorly understood. The primary data source to understand calcite surface charge comprises measurements of zeta potential. Here we collate and review previous measurements of zeta potential on natural and artificial calcite and carbonate as a resource for future studies, compare and contrast the results of these studies to determine key controls on zeta potential and where uncertainties remain, and report new measurements of zeta potential relevant to natural subsurface systems.The results show that the potential determining ions (PDIs) for the carbonate mineral surface are the lattice ions Ca2 +, Mg2 + and CO32 −. The zeta potential is controlled by the concentration-dependent adsorption of these ions within the Stern layer, primarily at the Outer Helmholtz Plane (OHP). Given this, the Iso-Electric Point (IEP) at which the zeta potential is zero should be expressed as pCa (or pMg). It should not be reported as pH, similar to most metal oxides.The pH does not directly control the zeta potential. Varying the pH whilst holding pCa constant yields constant zeta potential. The pH affects the zeta potential only by moderating the equilibrium pCa for a given CO2 partial pressure (pCO2). Experimental studies that appear to yield a systematic relationship between pH and zeta potential are most likely observing the relationship between pCa and zeta potential, with pCa responding to the change in pH. New data presented here show a consistent linear relationship between equilibrium pH and equilibrium pCa or pMg irrespective of sample used or solution ionic strength. The surface charge of calcite is weakly dependent on pH, through protonation and deprotonation reactions that occur within a hydrolysis layer immediately adjacent to the mineral surface. The Point of Zero Charge (PZC) at which the surface charge is zero could be expressed as pH, but surface complexation models suggest the surface is negatively charged over the pH range 5.5–11.Several studies have suggested that SO42 − is also a PDI for the calcite surface, but new data presented here indicate that the value of pSO4 may affect zeta potential only by moderating the equilibrium pCa. Natural carbonate typically yields a more negative zeta potential than synthetic calcite, most likely due to the presence of impurities including clays, organic matter, apatite, anhydrite or quartz, that yield a more negative zeta potential than pure calcite. New data presented here show that apparently identical natural carbonates display differing zeta potential behaviour, most likely due to the presence of small volumes of these impurities. It is important to ensure equilibrium, defined in terms of the concentration of PDIs, has been reached prior to taking measurements. Inconsistent values of zeta potential obtained in some studies may reflect a lack of equilibration.The data collated and reported here have broad application in engineering processes including the manufacture of paper and cement, the geologic storage of nuclear waste and CO2, and the production of oil and gas.

KW - Zeta potential

KW - Streaming potential

KW - Calcite

KW - Carbonate

KW - Wettability alteration

KW - Controlled salinity waterflooding

U2 - 10.1016/j.cis.2016.12.006

DO - 10.1016/j.cis.2016.12.006

M3 - Article

VL - 240

SP - 60

EP - 76

JO - Advances in Colloid and Interface Science

JF - Advances in Colloid and Interface Science

SN - 0001-8686

ER -