Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 2: Quartz and amorphous silica

• Main Authors: A. Kumar, C. Marcolli, T. Peter
• Format: Article
• Language: English
• Published: Copernicus Publications 2019-05-01
• Series: Atmospheric Chemistry and Physics
• Online Access: https://www.atmos-chem-phys.net/19/6035/2019/acp-19-6035-2019.pdf

<p>Divergent ice nucleation (IN) efficiencies of quartz, an important component of atmospheric mineral dust, have been reported in previous studies. We show here that quartz particles obtain their IN activity from milling and that quartz aged in water loses most of its IN efficiency relative to freshly milled quartz. Since most studies so far reported IN activities of commercial quartz dusts that were milled already by the manufacturer, IN active samples prevailed. Also, the quartz surface – much in contrast to that of feldspars – is not prone to ammonia-induced IN enhancement. In detail we investigate the influence of solutes on the IN efficiency of various silica (<span class="inline-formula">SiO₂</span>) particles (crystalline and amorphous) with special focus on quartz. We performed immersion freezing experiments and relate the observed variability in IN activity to the influence of milling, the aging time and to the exposure conditions since milling. Immersion freezing with silica particles suspended in pure water or aqueous solutions of <span class="inline-formula">NH₃</span>, <span class="inline-formula">(NH₄)₂SO₄</span>, <span class="inline-formula">NH₄HSO₄</span>, <span class="inline-formula">Na₂SO₄</span> and NaOH, with solute concentrations corresponding to water activities <span class="inline-formula"><i>a</i>_w=0.9</span>–1.0, were investigated in emulsified droplets by means of differential scanning calorimetry (DSC) and analyzed in terms of the onset temperature of the heterogeneous freezing signal <span class="inline-formula"><i>T</i>_het</span> and the heterogeneously frozen water volume fraction <span class="inline-formula"><i>F</i>_het</span>. Quartz particles, which originate from milling coarse samples, show a strong heterogeneous freezing peak in pure water with <span class="inline-formula"><i>T</i>_het</span> equal to 247–251&thinsp;K. This IN activity disappears almost completely after aging for 7 months in pure water in a glass vial. During this time quartz slowly grew by incorporating silicic acid leached from the glass vial. Conversely, the synthesized amorphous silica samples show no discernable heterogeneous freezing signal unless they were milled. This implies that defects provide IN activity to silica surfaces, whereas the IN activity of a natural quartz surface is negligible, when it grew under near-equilibrium conditions. For suspensions containing milled quartz and the solutes <span class="inline-formula">(NH₄)₂SO₄</span>, <span class="inline-formula">NH₄HSO₄</span> or <span class="inline-formula">Na₂SO₄</span>, <span class="inline-formula"><i>T</i>_het</span> approximately follows <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M14" display="inline" overflow="scroll" dspmath="mathml"><mrow><msubsup><mi>T</mi><mi mathvariant="normal">het</mi><mrow><mi mathvariant="normal">Δ</mi><msubsup><mi>a</mi><mi mathvariant="normal">w</mi><mi mathvariant="normal">het</mi></msubsup></mrow></msubsup><mo>(</mo><msub><mi>a</mi><mi mathvariant="normal">w</mi></msub><mo>)</mo></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="49pt" height="21pt" class="svg-formula" dspmath="mathimg" md5hash="1d8fcd7e9a681df856ae697114c01ebf"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-19-6035-2019-ie00001.svg" width="49pt" height="21pt" src="acp-19-6035-2019-ie00001.png"/></svg:svg></span></span>, the heterogeneous freezing onset temperatures that obey <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M15" display="inline" overflow="scroll" dspmath="mathml"><mrow><mi mathvariant="normal">Δ</mi><msubsup><mi>a</mi><mi mathvariant="normal">w</mi><mi mathvariant="normal">het</mi></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="28pt" height="16pt" class="svg-formula" dspmath="mathimg" md5hash="95b5e80a0a3574ef6190a18aa5d5488f"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-19-6035-2019-ie00002.svg" width="28pt" height="16pt" src="acp-19-6035-2019-ie00002.png"/></svg:svg></span></span> criterion, i.e., <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M16" display="inline" overflow="scroll" dspmath="mathml"><mrow><msubsup><mi>T</mi><mi mathvariant="normal">het</mi><mrow><mi mathvariant="normal">Δ</mi><msubsup><mi>a</mi><mi mathvariant="normal">w</mi><mi mathvariant="normal">het</mi></msubsup></mrow></msubsup><mo>(</mo><msub><mi>a</mi><mi mathvariant="normal">w</mi></msub><mo>)</mo><mo>=</mo><msub><mi>T</mi><mi mathvariant="normal">melt</mi></msub><mo>(</mo><msub><mi>a</mi><mi mathvariant="normal">w</mi></msub><mo>+</mo><mi mathvariant="normal">Δ</mi><msubsup><mi>a</mi><mi mathvariant="normal">w</mi><mi mathvariant="normal">het</mi></msubsup><mo>)</mo></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="139pt" height="21pt" class="svg-formula" dspmath="mathimg" md5hash="d43ef2ca3c6a0c7e8785a18e6ed91733"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-19-6035-2019-ie00003.svg" width="139pt" height="21pt" src="acp-19-6035-2019-ie00003.png"/></svg:svg></span></span> with <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M17" display="inline" overflow="scroll" dspmath="mathml"><mrow><mi mathvariant="normal">Δ</mi><msubsup><mi>a</mi><mi mathvariant="normal">w</mi><mi mathvariant="normal">het</mi></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="28pt" height="16pt" class="svg-formula" dspmath="mathimg" md5hash="24d0d048df71ca5c23f2acbe6083b91d"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-19-6035-2019-ie00004.svg" width="28pt" height="16pt" src="acp-19-6035-2019-ie00004.png"/></svg:svg></span></span> being a constant offset with respect to the ice melting point curve, similar to homogeneous IN. This water-activity-based description is expected to hold when the mineral surface is not altered by the presence of the solutes. On the other hand, we observe a slight enhancement in <span class="inline-formula"><i>F</i>_het</span> in the presence of these solutes, implying that the compliance with the <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M19" display="inline" overflow="scroll" dspmath="mathml"><mrow><mi mathvariant="normal">Δ</mi><msubsup><mi>a</mi><mi mathvariant="normal">w</mi><mi mathvariant="normal">het</mi></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="28pt" height="16pt" class="svg-formula" dspmath="mathimg" md5hash="aed39b8794244ad8b5a1723f858a4f31"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-19-6035-2019-ie00005.svg" width="28pt" height="16pt" src="acp-19-6035-2019-ie00005.png"/></svg:svg></span></span> criterion does not necessarily imply constant <span class="inline-formula"><i>F</i>_het</span>. In contrast to the sulfates, dilute solutions of <span class="inline-formula">NH₃</span> or NaOH (molality <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M22" display="inline" overflow="scroll" dspmath="mathml"><mrow><mo>≥</mo><mn mathvariant="normal">5</mn><mo>×</mo><msup><mn mathvariant="normal">10</mn><mrow><mo>-</mo><mn mathvariant="normal">4</mn></mrow></msup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="52pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="7da40eebe763b1e39349b261c6f19929"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-19-6035-2019-ie00006.svg" width="52pt" height="14pt" src="acp-19-6035-2019-ie00006.png"/></svg:svg></span></span>&thinsp;mol&thinsp;kg<span class="inline-formula">⁻¹</span>) reveal <span class="inline-formula"><i>T</i>_het</span> by 3–8&thinsp;K lower than <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M25" display="inline" overflow="scroll" dspmath="mathml"><mrow><msubsup><mi>T</mi><mi mathvariant="normal">het</mi><mrow><mi mathvariant="normal">Δ</mi><msubsup><mi>a</mi><mi mathvariant="normal">w</mi><mi mathvariant="normal">het</mi></msubsup></mrow></msubsup><mo>(</mo><msub><mi>a</mi><mi mathvariant="normal">w</mi></msub><mo>)</mo></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="49pt" height="21pt" class="svg-formula" dspmath="mathimg" md5hash="7553570b3707d803d92a0e6fc123316a"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-19-6035-2019-ie00007.svg" width="49pt" height="21pt" src="acp-19-6035-2019-ie00007.png"/></svg:svg></span></span>, indicating a significant impact on the mineral surface. The lowering of <span class="inline-formula"><i>T</i>_het</span> of quartz suspended in dilute <span class="inline-formula">NH₃</span> solutions is opposite to the distinct increase in <span class="inline-formula"><i>T</i>_het</span> that we found in emulsion freezing experiments with aluminosilicates, namely feldspars, kaolinite, gibbsite and micas. We ascribe this decrease in IN activity to the increased dissolution of quartz under alkaline conditions. The defects that constitute the active sites appear to be more susceptible to dissolution and therefore disappear first on a dissolving surface.</p>