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

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 (SiO2) 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 NH3, (NH4)(2)SO4, NH4HSO4, Na2SO4 and NaOH, with solute concentrations corresponding to water activities a(w) = 0.9-1.0, 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 T-het and the heterogeneously frozen water volume fraction F-het. Quartz particles, which originate from milling coarse samples, show a strong heterogeneous freezing peak in pure water with T-het equal to 247-251 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 (NH4)(2)SO4, NH4HSO4 or Na2SO4, T-het approximately follows T-het(Delta awhet) (a(w)), the heterogeneous freezing onset temperatures that obey Delta a(w)(het)criterion,i.e., T-het(Delta awhet) (a(w)) = T-melt (a(w) + Delta a(w)(het)) with Delta a(w)(het) 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 F-het in the presence of these solutes, implying that the compliance with the Delta a(w)(het) criterion does not necessarily imply constant F-het. In contrast to the sulfates, dilute solutions of NH3 or NaOH (molality >= 5 x 10(-4) mol kg(-1)) reveal T-het by 3-8 K lower than T-het(Delta awhet) (a(w)) , indicating a significant impact on the mineral surface. The lowering of T-het of quartz suspended in dilute NH3 solutions is opposite to the distinct increase in T-het 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.