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硝酸三水合物在粘土矿物上的异质成核:与I a型极地平流层云的相关性。

Heterogeneous nucleation of nitric acid trihydrate on clay minerals: relevance to type ia polar stratospheric clouds.

作者信息

Hatch Courtney D, Gough Raina V, Toon Owen B, Tolbert Margaret A

机构信息

CIRES and the Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.

出版信息

J Phys Chem B. 2008 Jan 17;112(2):612-20. doi: 10.1021/jp075828n. Epub 2007 Dec 4.

Abstract

Although critical to atmospheric modeling of stratospheric ozone depletion, selective heterogeneous nuclei that promote the formation of Type Ia polar stratospheric clouds (PSCs) are largely unknown. While mineral particles are known to be good ice nuclei, it is currently not clear whether they are also good nuclei for PSCs. In the present study, a high-vacuum chamber equipped with transmission Fourier transform infrared spectroscopy and a quadrupole mass spectrometer was used to study heterogeneous nucleation of nitric acid trihydrate (NAT) on two clay minerals-Na-montmorillonite and kaolinite-as analogs of atmospheric terrestrial and extraterrestrial minerals. The minerals are first coated with a 3:1 supercooled H2O/HNO3 solution prior to the observed nucleation of crystalline NAT. At 220 K, NAT formation was observed at low SNAT values of 12 and 7 on kaolinite and montmorillonite clays, respectively. These are the lowest SNAT values reported in the literature on any substrate. However, NAT nucleation exhibited significant temperature dependence. At lower temperatures, representative of typical polar stratospheric conditions, much higher supersaturations were required before nucleation was observed. Our results suggest that NAT nucleation on mineral particles, not previously treated with sulfuric acid, may not be an important nucleation platform for Type Ia PSCs under normal polar stratospheric conditions.

摘要

尽管对平流层臭氧消耗的大气建模至关重要,但促进Ia型极地平流层云(PSC)形成的选择性异质核在很大程度上尚不清楚。虽然已知矿物颗粒是良好的冰核,但目前尚不清楚它们是否也是PSC的良好核。在本研究中,使用配备有透射傅里叶变换红外光谱仪和四极杆质谱仪的高真空室,研究三水合硝酸(NAT)在两种粘土矿物——钠蒙脱石和高岭土(作为大气中陆地和外星矿物的类似物)上的异质成核。在观察到结晶NAT成核之前,先将矿物用3:1的过冷H2O/HNO3溶液包覆。在220 K时,在高岭土和蒙脱石粘土上分别在低至12和7的SNAT值下观察到NAT形成。这些是文献中报道的任何基质上最低的SNAT值。然而,NAT成核表现出显著的温度依赖性。在代表典型极地平流层条件的较低温度下,在观察到成核之前需要更高的过饱和度。我们的结果表明,在正常极地平流层条件下,未经硫酸处理的矿物颗粒上的NAT成核可能不是Ia型PSC的重要成核平台。

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