Products and Mechanism of the Gas Phase Reaction of Ozone with β-Pinene

Gas phase ozonolysis of -pinene was performedin a 570 l static reactor at 730 Torr and 296 K insynthetic air and the products were analysed by acombination of gas phase FTIR spectroscopy, HPLC andIC analyses of gas phase and aerosol samples,respectively. The reaction mechanism was investigatedby adding HCHO, HCOOH and H₂O as Criegeeintermediate scavenger and cyclohexane as OH radicalscavenger. Main identified products (yields inparentheses) in the presence of cyclohexane as OHradical scavenger were HCHO (0.65 ± 0.04),nopinone (0.16 ± 0.04), 3-hydroxy-nopinone (0.15± 0.05), CO₂ (0.20 ± 0.04), CO (0.030± 0.002), HCOOH (0.020 ± 0.002), the secondaryozonide of -pinene (0.16 ± 0.05), andcis-pinic acid (0.02 ± 0.01). The decompositionof the primary ozonide was found to yieldpredominantly the excited C₉-Criegee intermediateand HCHO (0.84 ± 0.04) and to a minor extent theexcited CH₂OO intermediate and nopinone (0.16± 0.04). Roughly 40% of the excitedC₉-Criegee intermediate becomes stabilised andcould be shown to react with HCHO, HCOOH and H₂O. The atmospherically important reaction of thestabilised C₉-Criegee intermediate with H₂Owas found to result in a nopinone increase of (0.35± 0.05) and in the formation of H₂O₂(0.24 ± 0.03). Based on the observed products,the unimolecular decomposition/isomerisationchannels of the C₉-Criegee intermediate arediscussed in terms of the hydroperoxide and esterchannels. Subsequent reactions of the nopinonylradical, formed in the hydroperoxide channel, lead tomajor products like 3-hydroxy-nopinone but also tominor products like cis-pinic acid. A mechanismfor the formation of this dicarboxylic acid isproposed and its possible role in aerosol formationprocesses discussed.     

The influence of aerosol particle composition on cloud droplet formation

A difference in partitioning between cloud droplets and interstitial air for two chemical species (elemental carbon and sulphur) with different expected behaviour in nucleation scavenging was observed in clouds at Mt. Kleiner Feldberg (825 m asl), near Frankfurt, Germany. The fraction of sulphur incorporated in cloud droplets was always higher than the fraction of elemental carbon. This difference in partitioning has also been observed in fog but under different pollution conditions in the Po Valley, Italy. Both these studies were based on bulk samples. In the present study at Kleiner Feldberg, impactor samples of the particles in the interstitial air and the cloud droplet residuals were taken and a single particle analysis was done on the samples. It was found that, for a given particle size, the majority of particles forming cloud droplets were soluble and that insoluble particles preferentially remained in the interstitial air.     

Gradient theory of nucleation in polar fluids

Gradient theory (GT), a form of density functional theory (DFT), was applied to water, methanol, and ethanol using the cubic perturbed hard body (CPHB) equation of state (EOS). Compared to the standard form of classical nucleation theory (CNT), the GT results for water showed an improved temperature dependence, but the supersaturation dependence was slightly poorer. GT and several forms of CNT were also found to be in good agreement with a single high T molecular dynamics rate for TIP4P water. The rates predicted by GT for methanol and ethanol were improved by several orders of magnitude compared to CNT, but no improvement in the predicted temperature dependence of the rates was found.     

河北大茂山碘化银地面发生器增雪作业影响分析

利用常规气象资料、MICAPS资料和NECP/NCAR再分析资料,结合高斯模拟,分析了2012年11月10日唐县大茂山地基碘化银发生器增雪作业的作业条件。结果发现,此次天气背景为自西南向东北移动的冷涡云系,根据帕斯奎尔(Pasquill)稳定度分类法得出作业时间段大气处于中性层结状态;高斯模式模拟得出,有效的AgI浓度向上扩散范围高达3.0 km;作业点作业时段上空至3.2 km均处于上升气流区,计算出作业点发生器出口温度1.0℃。因冬季人工观测云底高度多为2.5~3.0 km,综合分析认为,该作业点的选址是合适的,此次作业条件较好,可以将催化剂输送到云中,起到催化作用。     

The Characteristics of Atmospheric Ice Nuclei Measured at Different Altitudes in the Huangshan Mountains in Southeast China简

The concentration of ice nuclei （IN） and the relationship with aerosol particles were measured and analyzed using three 5-L mixing cloud chambers and a static diffusion cloud chamber at three altitudes in the Huangshan Mountains in Southeast China from May to September 2011.The results showed that the mean total number concentration of IN on the highest peak of the Huangshan Mountains at an activation temperature （Ta） of-20℃C was 16.6 L-1.When the supersaturation with respect to water （Sw） and with respect to ice （Si） were set to 5％,the average number concentrations of IN measured at an activation temperature of-20℃C by the static diffusion cloud chamber were 0.89 and 0.105 L-1,respectively.A comparison of the concentrations of IN at three different altitudes showed that the concentration of IN at the foot of the mountains was higher than at the peak.A further calculation of the correlation between IN and the concentrations of aerosol particles of different size ranges showed that the IN concentration was well correlated with the concentration of aerosol particles in the size range of 1.2-20 μtm.It was also found that the IN concentration varied with meteorological conditions,such as wind speed,with higher IN concentrations often observed on days with strong wind.An analysis of the backward trajectories of air masses showed that low IN concentrations were often related to air masses travelling along southwest pathways,while higher IN concentrations were usually related to those transported along northeast pathways.     

Experimental solidification of anhydrous latitic and trachytic melts at different cooling rates: The role of nucleation kinetics

Two sets of cooling experiments were run at atmospheric conditions for two anhydrous starting latitic and trachytic melts: 1) five cooling rates (25, 12.5, 3, 0.5, and 0.125 °C/min) between 1300° and 800 °C, and 2) a 0.5 °C/min cooling rate from 1300 °C with quench temperatures at 1200°, 1100°, 1000° and 900 °C. Trachytic run-products are invariably glassy. Nucleation is also suppressed in the latitic run-products at the three highest cooling rates. Conversely, in the 0.5 and 0.125 °C/min runs, latites have a crystal content of  90 vol.%. The phases are: plagioclase, clinopyroxene, glass and iron-bearing oxide (in order of abundance). The variable quench temperatures, investigated by coupling experiments with Pt wire and Pt capsule sample containers in set 2, again did not produce crystallization of trachyte, whereas latitic samples are characterized by  10 vol.% of oxides, pyroxenes and plagioclase (in order of appearance), at temperature < 1000 °C. Effects of (preferential) heterogeneous nucleation on sample holders, of superheating degree, and chemical species loss during cooling are absent for both melt compositions. The difference of solidification paths between these two silicate melts can be ascribed only to their small chemical differences. In comparison with calculated equilibrium conditions all the experimental latitic and trachytic run-products revealed strong kinetic effects, interpretable in the light of the nucleation theory. The glass-forming ability (GFA) of trachyte is higher, whereas their critical cooling rate (Rc) is lower (< 0.125 °C/min), in comparison to latitic melts (Rc > 0.5 °C/min). The experimental results carried out in this study can be applied to lava flows and domes; trachytic lavas are able to flow for longer period with respect to latitic ones in a metastable condition. Glass-rich terrestrial lavas, i.e. obsidians, can be the result of sluggish nucleation kinetics due to the relative high polymerisation of evolved silicate melts.     

地震前低频事件的实验研究

介绍了几种强震前超低频事件的观测证据,并通过实验,研究了产生和传播机理。初步结果表明,微破裂的集结和断层的破裂起始会出现超低频脉冲,并透射到空气中形成次声波。塑性体的冲击或超临界流体的膨胀比脆性破裂更容易激发（超）低频波,且不伴随明显高频辐射成分。这样可以较为合理地解释震前“平衡”背景下的（超）低频事件。对实验中破坏前的低频脉冲给出了断裂力学解释。断裂力学的实验和膨胀－－扩容理论证明了震前会产生断层的张裂隙,从而为超临界流体提供了运移空间。流体在运移过程中突然涨缩会激发（超）低频辐射波。讨论了改进（超）低频事件的观测条件问题。     

A garnet population in Yellowknife schist, Canada

Abstract Data are presented on a garnet population in a specimen of garnet-biotite-plagioclase-quartz schist from the cordierite zone of an Archaean thermal dome in the Southern Slave Province of the Canadian Shield. Garnet crystals are bounded by planar dodecahedral faces and by trapezohedral faces which on the 10-μm scale are corrugated. Crystal distribution, as revealed by dissection of a small cubic volume of rock, is random. The size distribution is normal, with a mean diameter of 0.81 mm and a standard deviation of 0.32 mm. In the largest crystal of the population (mean radius 0.83 mm), [Mn] = 100 Mn/(Fe + Mg + Mn + Ca) decreases from 14.5 at the centre to 7.5 and then increases in the outer margin to 8.5; [Fe] increases continuously from 67 at the centre to 77 at the surface; [Mg] increases from 12.5 to 13.5 and then falls sharply to 11; [Ca] remains unchanged at 4.0 and then drops to 3.3. Progressively smaller crystals have progressively lower [Mn] and higher [Fe] concentrations at their centres, while all crystals have the same margin composition. Growth vectors extending from given concentration contours to crystal surfaces are of equal length regardless of the size of the crystal in which the vector is located. A garnet-forming model is presented in which reaction was initiated by a rise in temperature. Nucleation sites were randomly selected. The nucleation rate increased with time and then declined. Crystal faces advanced at a constant linear rate, which implies an increase in volume proportional to surface area. Initially, the composition of garnet deposited on crystal surfaces was determined by van Laar equations of equilibrium, which demanded the withdrawal of Mn and Fe from within chlorite crystals. This transfer reaction was then accompanied by an ion exchange reaction which moved Mn and Fe to garnet surfaces from biotite, in exchange for Mg. The exchange reaction provides an explanation for the high overall concentration of Mn and Fe in garnet and for the observed Mn and Mg reversals in the margins of crystals. The increase of garnet volume in the garnet population is found to be parabolic, i.e. Vαα⁵.     

Early formed regional antiforms and synforms that fold younger matrix schistosities: their effect on sites of mineral growth

In the metamorphic cores of many orogenic belts, large macroscopic folds in compositional layering also appear to fold one or more pervasive matrix foliations. The latter geometry suggests the folds formed relatively late in the tectonic history, after foliation development. However, microstructural analysis of four examples of such folds suggests this is not the case. The folds formed relatively early in the orogenic history and are the end product of multiple, near orthogonal, overprinting bulk shortening events. Once large macroscopic folds initiate, they may tighten further during successive periods of sub-parallel shortening, folding or reactivation of foliations that develop during intervening periods of near orthogonal shortening. Reactivation of the compositional layering defining the fold limbs causes foliation to be rotated into parallelism with the limbs.Multiple periods of porphyroblast growth accompanied the multiple phases of deformation that postdated the initial development of these folds. Some of these phases of deformation were attended by the development of large numbers of same asymmetry spiral-shaped inclusion trails in porphyroblasts on one limb of the fold and not the other, or larger numbers of opposite asymmetry spirals on the other limb, or similar numbers of the same asymmetry spirals on both limbs. Significantly, the largest disparity in numbers from limb to limb occurred for the first of these cases. For all four regional folds examined, the structural relationships that accompanied these large disparities were identical. In each case the shear sense operating on steeply dipping foliations was opposite to that required to originally develop the fold. Reactivation of the folded compositional layering was not possible for this shear sense. This favoured the development of sites of approximately coaxial shortening early during the deformation history, enhancing microfracture and promoting the growth of porphyroblasts on this limb in comparision to the other. These distributions of inclusion trail geometries from limb to limb cannot be explained by porphyroblast rotation, or folding of pre-existing rotated porphyroblasts within a shear zone, but can be explained by development of the inclusion trails synchronous with successive sub-vertical and sub-horizontal foliations.     

The clustered nucleation and growth processes of garnet in regional metamorphic rocks from north-west Connecticut,USA

Serial sectioning and imaging with a flatbed scanner yielded the three-dimensional size and spatial distribution of garnet porphyroblasts in two garnet schists and one staurolite-bearing schist from the Everett Formation, north-west Connecticut. The dominant garnet-producing reaction in all samples was chlorite+quartz=garnet+H₂O. The appearance of staurolite, and additional garnet growth in the staurolite-bearing sample, was due to the reaction chloritoid=garnet+staurolite+chlorite. Statistical measures of garnet spatial distributions, using the pair correlation function (PCF), indicate that garnet crystals are weakly to strongly clustered at length scales between 2 and 10 mm. Such clustered nucleation may reflect minor bulk compositional variations. Covariance measures between garnet size and nearest-neighbour distance, using the mark covariance function (MCF), suggest a very weak correlation between crystal size and nearest-neighbour distance for length scales of 2 mm or less. These statistical data suggest that if diffusional gradients were present around growing garnet crystals, they did not influence nucleation and growth patterns at length scales greater than c. 2 mm. Compositional maps, through the garnet centres, show that the smaller crystals have lower Mn core compositions relative to larger crystals, consistent with progressive nucleation during pro-grade metamorphism. Radius-rate plots calculated from compositional X-ray maps show similar growth rates for garnet crystals of different size, consistent with an interface-controlled growth model for garnet. The presence of minor diffusional gradients around growing garnet cannot be entirely dismissed, but the lack of observable reaction rims, the clustered spatial distribution and the radius-rate data are most consistent with an interface-controlled garnet growth model.