Interaction of Sodium Ions with Feldspar Surfaces and Its Effect on the Selective Separation of Na- and K-Feldspars

Gülgönül, İlhan; Karagüzel, Cengiz; Çınar, Mehmet Ulaş; Çelik, M.S.

doi:10.1080/08827508.2011.562952

Cited by 18 publications

(13 citation statements)

References 19 publications

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“…During this slow dissolution, a surface layer is considered to form on the feldspar particles (Busenberg and Clemency, 1976;Alekseyev et al, 1997;Zhu, 2005;Zhu and Lu, 2009). Interestingly, this slow dissolution of microcline is accompanied with only a slight reduction in IN efficiency even after several months as shown in experiments by Peckhaus et al (2016) and Harrison et al (2016). In order to assess the effect of solutes on IN efficiency over time, aging experiments were performed over a period of 1 week with microcline (2 wt %) suspended in ammonia (0.05 molal) and ammonium sulfate (0.1 and 10 wt %) solutions as well as in pure water (Fig.…”

Section: Aging Effectmentioning

confidence: 95%

“…The −OH groups could also hold the answer to the variability in IN efficiency of various feldspars as they could be affected by weathering processes, chemical aging, microtexture, Al : Si order, etc. (Yang et al, 2014;Harrison et al, 2016;Peckhaus et al, 2016;Tang et al, 2016). Using molecular dynamics simulations, and have recently shown that even non-mineral graphitic surfaces can promote IN due to surface-induced ordered layering of interfacial water.…”

Section: Role Of Adsorbed Nhmentioning

confidence: 99%

“…The decrease in IN efficiency of microcline in suspensions with high solute concentrations shows two specific dependencies on the nature of the salt, namely (i) the sulfate decreases the IN efficiency more strongly than chloride and nitrate and (ii) K + and Na + decreases the IN efficiency when compared with the pure water case and even more so compared with NH + 4 . The microcline surface has a negative charge at neutral pH arising from dissociated silanol groups (Demir et al, 2001(Demir et al, , 2003Karagüzel et al, 2005;Gülgönül et al, 2012). While at low concentrations, cations predominantly participate in ion exchange, increasing the solute concentration leads to adsorption of cations on the negatively charged feldspar surface.…”

Section: Augustinmentioning

confidence: 99%

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Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 1: The K-feldspar microcline

et al. 2018

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Abstract. Potassium-containing feldspars (K-feldspars) have been considered as key mineral dusts for ice nucleation (IN) in mixed-phase clouds. To investigate the effect of solutes on their IN efficiency, we performed immersion freezing experiments with the K-feldspar microcline, which is highly IN active. Freezing of emulsified droplets with microcline suspended in aqueous solutions of NH3, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl, with solute concentrations corresponding to water activities aw = 0.9–1.0, were investigated by means of a differential scanning calorimeter (DSC). The measured heterogeneous IN onset temperatures, Thet(aw), deviate strongly from ThetΔawhet(aw), the values calculated from the water-activity-based approach (where ThetΔawhet(aw)=Tmelt(aw+Δawhet) with a constant offset Δawhet with respect to the ice melting point curve). Surprisingly, for very dilute solutions of NH3 and NH4+ salts (molalities ≲1 mol kg−1 corresponding to aw ≳ 0.96), we find IN temperatures raised by up to 4.5 K above the onset freezing temperature of microcline in pure water (Thet(aw=1)) and 5.5 K above ThetΔawhet(aw), revealing NH3 and NH4+ to significantly enhance the IN of the microcline surface. Conversely, more concentrated NH3 and NH4+ solutions show a depression of the onset temperature below ThetΔawhet(aw) by as much as 13.5 K caused by a decline in IN ability accompanied with a reduction in the volume fraction of water frozen heterogeneously. All salt solutions not containing NH4+ as cation exhibit nucleation temperatures Thet(aw)<ThetΔawhet(aw) even at very small solute concentrations. In all these cases, the heterogeneous freezing peak displays a decrease as solute concentration increases. This deviation from Δawhet = const. indicates specific chemical interactions between particular solutes and the microcline surface not captured by the water-activity-based approach. One such interaction is the exchange of K+ available on the microcline surface with externally added cations (e.g., NH4+). However, the presence of a similar increase in IN efficiency in dilute ammonia solutions indicates that the cation exchange cannot explain the increase in IN temperatures. Instead, we hypothesize that NH3 molecules hydrogen bonded on the microcline surface form an ice-like overlayer, which provides hydrogen bonding favorable for ice to nucleate on, thus enhancing both the freezing temperatures and the heterogeneously frozen fraction in dilute NH3 and NH4+ solutions. Moreover, we show that aging of microcline in concentrated solutions over several days does not impair IN efficiency permanently in case of near-neutral solutions since most of it recovers when aged particles are resuspended in pure water. In contrast, exposure to severe acidity (pH ≲1.2) or alkalinity (pH ≳11.7) damages the microcline surface, hampering or even destroying the IN efficiency irreversibly. Implications for IN in airborne dust containing microcline might be multifold, ranging from a reduction of immersion freezing when exposed to dry, cold and acidic conditions to a 5 K enhancement during condensation freezing when microcline particles experience high humidity (aw≳0.96) at warm (252–257 K) and NH3/NH4+-rich conditions.

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Section: Aging Effectmentioning

confidence: 95%

Section: Role Of Adsorbed Nhmentioning

confidence: 99%

Section: Augustinmentioning

confidence: 99%

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Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 1: The K-feldspar microcline

et al. 2018

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“…The K-rich feldspar sample studied here consists of 85% microcline (KAlSi3O8) and 15% albite (NaAlSi3O8). Since, in general, microcline is a better ice nucleus than albite, microcline is likely responsible for ice nucleation in our experiments (Harrison et al, 2016;Peckhaus et al, 2016b;Zolles et al, 2015;Atkinson et al, 2013;Whale et al, 2017 (Gülgönül et al, 2012;Nash and Marshall, 1957;Stumm and Morgan, 1971;Barker, 1964):…”

Section: Mechanismsmentioning

confidence: 68%

The effect of (NH4)2SO4 on the freezing properties of non-mineral dust ice nucleating substances of atmospheric relevance

Worthy

Kumar

et al. 2021

Preprint

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Abstract. A wide range of materials including mineral dust, soil dust, and bioaerosols have been shown to act as ice nuclei in the atmosphere. During atmospheric transport, these materials can become coated with inorganic and organic solutes which may impact their ability to nucleate ice. While a number of studies have investigated the impact of solutes at low concentrations on ice nucleation by mineral dusts, very few studies have examined their impact on non-mineral dust ice nuclei. We studied the effect of dilute (NH4)2SO4 solutions on immersion freezing of a variety of non-mineral dust ice nucleating substances including bacteria, fungi, sea ice diatom exudates, sea surface microlayer, and humic substances using the droplet freezing technique. We also studied the effect of (NH4)2SO4 on immersion freezing of mineral dust particles for comparison purposes. (NH4)2SO4 had no effect on the median freezing temperature of nine of the ten tested non-mineral dust materials. There was a small but statistically significant decrease in the median freezing temperature of the bacteria X. campestris (change in median freezing temperature ∆T_50 = -0.43 ± 0.19 °C) in the presence of (NH4)2SO4 compared to pure water. Conversely, (NH4)2SO4 increased the median freezing temperature of four different mineral dusts (Potassium-rich feldspar, Arizona Test Dust, Kaolinite, Montmorillonite) by 3 °C to 8 °C. This significant difference in the response of mineral dust and non-mineral dust ice nucleating substances when exposed to (NH4)2SO4 suggests that they nucleate ice and/or interact with (NH4)2SO4 via different mechanisms. This difference suggests that the relative importance of mineral dust to non-mineral dust particles for ice nucleation in mixed-phase clouds could increase as these particles become coated with ammonium sulfate in the atmosphere. This difference also suggests that the addition of (NH4)2SO4 to atmospheric samples of unknown composition could be used as an indicator or assay for the presence of mineral dust ice nuclei.

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“…Similar effects can be observed in the current study. Even the slightest increase in the sulfuric acid The microcline surface has a negative charge at neutral pH arising from dissociated silanol groups (Demir et al, 2001;Demir et 315 al., 2003;Karagüzel et al, 2005;Gülgönül et al, 2012). While at low concentrations, cations predominantly participate in ion exchange, increasing the solute concentration leads to adsorption of cations on the negatively charged feldspar surface.…”

Section: Reduced Ice Nucleation Activity At Higher Solute Concentratimentioning

confidence: 99%

Enhanced ice nucleation efficiency of microcline immersed in dilute NH3 and NH4+-containing solutions

Kumar

Marcolli

Luo

et al. 2018

Preprint

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solutes and the microcline surface not captured by the water-activity-based approach. One such interaction is the exchange of K + available on the microcline surface with externally added cations (e.g.NH ). However, the presence of a similar increase in IN efficiency in dilute ammonia solutions indicates that the cation exchange cannot explain the increase in IN temperatures. Instead, we hypothesize that NH3 molecules hydrogen bonded on the microcline surface form an ice-like overlayer, which provides hydrogen bonding favorable for ice to nucleate on, thus enhancing both the freezing temperatures and the heterogeneously frozen 25 fraction in dilute NH3 and NH solutions. Moreover, we show that aging of microcline in concentrated solutions over several days does not impair IN efficiency permanently in case of near neutral solutions since most of it recovers when aged particles are re-suspended in pure water. In contrast, exposure to severe acidity (pH < 1.2) or alkalinity (pH > 11.7) damages the microcline surface, hampering or even destroying the IN efficiency irreversibly. Implications for ice nucleation on airborne dust containing microcline might be multifold, ranging from a reduction of immersion freezing when exposed to dry, cold and NH3/NH -free 30 conditions, to a 5-K enhancement during condensation freezing when microcline particles experience high humidity ( > 0.96) at warm (252 -257 K) and NH3/NH -rich conditions. Atmos. Chem. Phys. Discuss., https://doi

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Interaction of Sodium Ions with Feldspar Surfaces and Its Effect on the Selective Separation of Na- and K-Feldspars

Cited by 18 publications

References 19 publications

Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 1: The K-feldspar microcline

Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 1: The K-feldspar microcline

The effect of (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> on the freezing properties of non-mineral dust ice nucleating substances of atmospheric relevance

Enhanced ice nucleation efficiency of microcline immersed in dilute NH<sub>3</sub> and NH<sub>4</sub><sup>+</sup>-containing solutions

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Interaction of Sodium Ions with Feldspar Surfaces and Its Effect on the Selective Separation of Na- and K-Feldspars

Cited by 18 publications

References 19 publications

Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 1: The K-feldspar microcline

Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 1: The K-feldspar microcline

The effect of (NH&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; on the freezing properties of non-mineral dust ice nucleating substances of atmospheric relevance

Enhanced ice nucleation efficiency of microcline immersed in dilute NH&lt;sub&gt;3&lt;/sub&gt; and NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;-containing solutions

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The effect of (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> on the freezing properties of non-mineral dust ice nucleating substances of atmospheric relevance

Enhanced ice nucleation efficiency of microcline immersed in dilute NH<sub>3</sub> and NH<sub>4</sub><sup>+</sup>-containing solutions