Stratospheric meteorological conditions in the arctic polar vortex, 1991 to 1992

Stratospheric meteorological conditions during the Airborne Arctic Stratospheric Expedition II (AASE II) presented excellent observational opportunities from Bangor, Maine, because the polar vortex was located over southeastern Canada for significant periods during the 1991-1992 winter. Temperature analyses showed that nitric acid trihydrates (NAT temperatures below 195 k) should have formed over small regions in early December. The temperatures in the polar vortex warmed beyond NAT temperatures by late January (earlier than normal). Perturbed chemistry was found to be associated with these cold temperatures.     

Physical Chemistry of the H2SO4/HNO3/H2O System: Implications for Polar Stratospheric Clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.     

Role of the stratospheric polar freezing belt in denitrification

Homogeneous freezing of nitric acid hydrate particles can produce a polar freezing belt in either hemisphere that can cause denitrification. Computed denitrification profiles for one Antarctic and two Arctic cold winters are presented. The vertical range over which denitrification occurs is normally quite deep in the Antarctic but limited in the Arctic. A 4 kelvin decrease in the temperature of the Arctic stratosphere due to anthropogenic and/or natural effects can trigger the occurrence of widespread severe denitrification. Ozone loss is amplified in a denitrified stratosphere, so the effects of falling temperatures in promoting denitrification must be considered in assessment studies of ozone recovery trends.     

Metastable phases in polar stratospheric aerosols

Phase changes in stratospheric aerosols were studied by cooling a droplet of sulfuric acid (H(2)SO(4)) in the presence of nitric acid (HNO(3)) and water vapor. A sequence of solid phases was observed to form that followed Ostwald's rule for phase nucleation. For stratospheric partial pressures at temperatures between 193 and 195 kelvin, a metastable ternary H(2)SO(4)-HNO(3) hydrate, H(2)SO(4) . HNO(3) . 5H(2)O, formed in coexistence with binary H(2)SO(4) . kH(2)O hydrates (k = 2, 3, and 4) and then transformed to nitric acid dihydrate, HNO(3) . 2H(2)O, within a few hours. Metastable HNO(3) . 2H(2)O always formed before stable nitric acid trihydrate, HNO(3).3H(2)O, under stratospheric conditions and persisted for long periods. The formation of metastable phases provides a mechanism for differential particle growth and sedimentation of HNO(3) from the polar winter stratosphere.     

The seasonal evolution of reactive chlorine in the northern hemisphere stratosphere

In situ measurements of chlorine monoxide (ClO) at mid- and high northern latitudes are reported for the period October 1991 to February 1992. As early as mid-December and throughout the winter, significant enhancements of this ozone-destroying radical were observed within the polar vortex shortly after temperatures dropped below 195 k. Decreases in ClO observed in February were consistent with the rapid formation of chlorine nitrate (ClONO(2)) by recombination of ClO with nitrogen dioxide (NO(2)) released photochemically from nitric acid (HNO(3)). Outside the vortex, ClO abundances were higher than in previous years as a result of NOx suppression by heterogeneous reactions on sulfate aerosols enhanced by the eruption of Mount Pinatubo.     

Chlorine chemistry on polar stratospheric cloud particles in the arctic winter

Simultaneous in situ measurements of hydrochloric acid (HCl) and chlorine monoxide (ClO) in the Arctic winter vortex showed large HCl losses, of up to 1 part per billion by volume (ppbv), which were correlated with high ClO levels of up to 1.4 ppbv. Air parcel trajectory analysis identified that this conversion of inorganic chlorine occurred at air temperatures of less than 196 +/- 4 kelvin. High ClO was always accompanied by loss of HCI mixing ratios equal to (1/2)(ClO + 2Cl(2)O(2)). These data indicate that the heterogeneous reaction HCl + ClONO(2) --> Cl(2) + HNO(3) on particles of polar stratospheric clouds establishes the chlorine partitioning, which, contrary to earlier notions, begins with an excess of ClONO(2), not HCl.     

Reaction of chlorine nitrate with hydrogen chloride and water at antarctic stratospheric temperatures

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO(2)) with H(2)0 and hydrogen chloride (HCl) on surfaces that simulate polar stratospheric clouds [ice and nitric acid (HNO(3))-ice and sulfuric acid] are studied at temperatures relevant to the Antarctic stratosphere. The reaction of ClONO(2) on ice and certain mixtures of HNO(3) and ice proceeded readily. The sticking coefficient of ClONO(2) on ice of 0.009 +/- 0.002 was observed. A reaction produced gas-phase hypochlorous acid (HOCl) and condensed-phase HNO(3); HOC1 underwent a secondary reaction on ice producing dichlorine monoxide (Cl(2)O). In addition to the reaction with H(2)0, ClONO(2) reacted with HCl on ice to form gas-phase chlorine (Cl(2)) and condensed-phase HNO(3.) Essentially all of the HCl in the bulk of the ice can react with ClONO(2) on the ice surface. The gaseous products of the above reactions, HOCl, Cl(2)0, and Cl(2), could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the formation of condensed-phase HNO(3) could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.     

Evidence that nitric acid increases relative humidity in low-temperature cirrus clouds

In situ measurements of the relative humidity with respect to ice (RHi) and of nitric acid (HNO3) were made in both natural and contrail cirrus clouds in the upper troposphere. At temperatures lower than 202 kelvin, RHi values show a sharp increase to average values of over 130% in both cloud types. These enhanced RHi values are attributed to the presence of a new class of HNO3-containing ice particles (Delta-ice). We propose that surface HNO3 molecules prevent the ice/vapor system from reaching equilibrium by a mechanism similar to that of freezing point depression by antifreeze proteins. Delta-ice represents a new link between global climate and natural and anthropogenic nitrogen oxide emissions. Including Delta-ice in climate models will alter simulated cirrus properties and the distribution of upper tropospheric water vapor.     

Interhemispheric Differences in Polar Stratospheric HNO3, H2O, CIO, and O3

Simultaneous global measurements of nitric acid (HNO(3)), water (H(2)O), chlorine monoxide (CIO), and ozone (O(3)) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO(3) was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H(2)O after mid-July. By mid-August, near the time of peak CIO, abundances of gas-phase HNO(3) and H(2)O were extremely low. The concentrations of HNO(3) and H(2)O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO(3) or H(2)O were observed in the 1992-1993 Arctic winter vortex. Although CIO was enhanced over the Arctic as it was over the Antarctic, Arctic O(3) depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone "hole" is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.     

The detection of large HNO3-containing particles in the winter Arctic stratosphere

Large particles containing nitric acid (HNO3) were observed in the 1999/2000 Arctic winter stratosphere. These in situ observations were made over a large altitude range (16 to 21 kilometers) and horizontal extent (1800 kilometers) on several airborne sampling flights during a period of several weeks. With diameters of 10 to 20 micrometers, these sedimenting particles have significant potential to denitrify the lower stratosphere. A microphysical model of nitric acid trihydrate particles is able to simulate the growth and sedimentation of these large sizes in the lower stratosphere, but the nucleation process is not yet known. Accurate modeling of the formation of these large particles is essential for understanding Arctic denitrification and predicting future Arctic ozone abundances.     

Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice: release of active chlorine

The reaction rate between atmospheric hydrogen chloride (HCl) and chlorine nitrate (ClONO(2)) is greatly enhanced in the presence of ice particles; HCl dissolves readily into ice, and the collisional reaction probability for ClONO(2) on the surface of ice with HCl in the mole fraction range from approximately 0.003 to 0.010 is in the range from approximately 0.05 to 0.1 for temperatures near 200 K. Chlorine (Cl(2)) is released into the gas phase on a time scale of at most a few milliseconds, whereas nitric acid (HNO(3)), the other product, remains in the condensed phase. This reaction could play an important role in explaining the observed depletion of ozone over Antarctica; it releases photolytically active chlorine from its most abundant reservoir species, and it promotes the formation of HNO(3) and thus removes nitrogen dioxide (NO(2)) from the gas phase. Hence it establishes the necessary conditions for the efficient catalytic destruction of ozone by halogenated free radicals. In the absence of HCl, ClONO(2) also reacts irreversibly with ice with a collision efficiency of approximately 0.02 at 200 K; the product hypochlorous acid (HOCI) is released to the gas phase on a time scale of minutes.     

PETN为基的高聚物粘结炸药(PBX)力学性能的MD模拟

PETN(季戊四醇四硝酸酯,又名太安)是爆炸性能优良的硝酸酯类高能炸药的典型,该研究将其选作高聚物粘结炸药(PBX)中的基炸药。选择聚偏二氟乙烯、聚三氟氯乙烯、F2311和F2314作为粘结剂,对PETN及其与这4种含氟聚合物组成的PBX,用国际上流行的Materials Studio软件中的DISCOV-ER模块,以先进的COMPASS力场,主要模拟研究了PETN基PBX在不同温度下的力学性能。发现随温度升高,PBX的刚性减小,弹塑性增强。     

Vapor pressures of solid hydrates of nitric Acid: implications for polar stratospheric clouds

Thermodynamic data are presented for hydrates of nitric acid: HNO(3).H(2)O, HNO(3).2H(2)O, HNO(3).3H(2)O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO(3).2H(2)O may be favored in polar stratospheric clouds over the slightly more stable HNO(3).3H(2)O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO(3).2H(2)O and HNO(3).3H(2)O. Vapor transfer from HNO(3).2H(2)O to HNO(3).3H(2)O could be a key step in the sedimentation of HNO(3), which plays an important role in the depletion of polar ozone.     

The dynamics of the stratospheric polar vortex and its relation to springtime ozone depletions

Dramatic springtime depletions of ozone in polar regions require that polar stratospheric air has a high degree of dynamical isolation and extremely cold temperatures necessary for the formation of polar stratospheric clouds. Both of these conditions are produced within the stratospheric winter polar vortex. Recent aircraft missions have provided new information about the structure of polar vortices during winter and their relation to polar ozone depletions. The aircraft data show that gradients of potential vorticity and the concentration of conservative trace species are large at the transition from mid-latitude to polar air. The presence of such sharp gradients at the boundary of polar air implies that the inward mixing of heat and constituents is strongly inhibited and that the perturbed polar stratospheric chemistry associated with the ozone hole is isolated from the rest of the stratosphere until the vortex breaks up in late spring. The overall size of the polar vortex thus limits the maximum areal coverage of the annual polar ozone depletions. Because it appears that this limit has not been reached for the Antarctic depletions, the possibility of future increases in the size of the Antarctic ozone hole is left open. In the Northern Hemisphere, the smaller vortex and the more restricted region of cold temperatures suggest that this region has a smaller theoretical maximum for column ozone depletion, about 40 percent of the currently observed change in the Antarctic ozone column in spring.     

国庆1号温州蜜柑果实成熟过程中极性代谢物的变化

【目的】研究不同成熟阶段的国庆1号温州蜜柑（Citrus unshiu Marc.cv.Guoqing No.1）果实极性代谢物的变化,为客观评价柑橘果实成熟度和果实品质提供科学理论依据。【方法】采用气相色谱质谱联用技术（GC-MS）,初步建立柑橘果实初生代谢产物的提取和分析方法,检测绿熟期、转色期和完熟期温州蜜柑果实有色层和果肉组织的极性代谢物,并对其进行主成分分析。【结果】共鉴定出代谢物37种。随温州蜜柑果实不断转黄,其有色层中的果糖、甘露糖和大部分氨基酸（尤其是GABA和脯氨酸）含量逐渐增加,在完熟期达最高。相反地,柠檬酸和一些不饱和脂肪酸的含量则逐渐降低。与有色层相比,果肉中显著变化的初级代谢物较少。其中甘露糖、阿拉伯糖、草酸、磷酸、琥珀酸、2 - 酮戊二酸、十六碳烷酸、9,12-十八碳二烯酸、十八碳烷酸、十四碳烷酸等在绿熟期含量最高,随着果实不断转黄其含量逐渐降低,而蔗糖,GABA以及多种有机酸则大量积累。PCA结果显示,不同组织和不同发育时期的代谢物均很好的分离,且不同发育时期代谢物的差异小于不同组织间代谢物的差异。【结论】找到一些可以作为评价果实成熟度指标的代谢物。此外,发现果实成熟过程中有色层和果肉中多种极性代谢物发生剧烈的变化,且表现出很强的组织特异性,尤其是糖类和有机酸类物质。     

Heterogeneous reaction probabilities, solubilities, and the physical state of cold volcanic aerosols

On 19 January 1992, heterogeneous loss of HNO(3), ClNO(3), and HCl was observed in part of the Mount Pinatubo volcanic cloud that had cooled as a result of forced ascent. Portions of the volcanic cloud froze near 191 kelvin. The reaction probability of ClNO(3) and the solubility of HNO(3) were close to laboratory measurements on liquid sulfuric acid. The magnitude of the observed loss of HCl suggests that it underwent a heterogeneous reaction. Such reactions could lead to substantial loss of HCl on background sulfuric acid particles and so be important for polar ozone loss.     

Size distribution of fine particles from coal combustion

Measurements of the particle size distribution at the outlets of six coal-fired utility boilers showed a peak at a particle diameter near 0.1 micrometer. This submicrometer mode appears to be a general feature of coal combustion that results from a volatilization-condensation process in the boiler. At the boilers tested, the submicrometer mode contained 0.2 to 2.2 percent of the total fly ash mass. The importance of this mode is greater than its small quantity suggests because particles in the submicrometer size range are often much more difficult to collect with conventional particulate control devices than larger particles. Thus, the submicrometer mode may significantly influence the design and selection of future power plant emission controls. The particle mass in the submicrometer mode was correlated with the nitric oxide concentration in the flue gas. This correlation suggests that control of nitric oxide by modification of the combustion conditions may reduce the generation and emission of submicrometer particles.     

Spontaneous ferroelectric order in a bent-core smectic liquid crystal of fluid orthorhombic layers

Macroscopic polarization density, characteristic of ferroelectric phases, is stabilized by dipolar intermolecular interactions. These are weakened as materials become more fluid and of higher symmetry, limiting ferroelectricity to crystals and to smectic liquid crystal stackings of fluid layers. We report the SmAP(F), the smectic of fluid polar orthorhombic layers that order into a three-dimensional ferroelectric state, the highest-symmetry layered ferroelectric possible and the highest-symmetry ferroelectric material found to date. Its bent-core molecular design employs a single flexible tail that stabilizes layers with untilted molecules and in-plane polar ordering, evident in monolayer-thick freely suspended films. Electro-optic response reveals the three-dimensional orthorhombic ferroelectric structure, stabilized by silane molecular terminations that promote parallel alignment of the molecular dipoles in adjacent layers.     

基于EOS/MODIS数据的裸土多层土温遥感反演研究——以陕西省为例

以EOS/MODIS为数据源,采用地表温度(LST)遥感信息模型耦合土壤温度CERES模型反演多层裸土土温。结果表明:土壤温度的模拟值与实测值的变化趋势比较一致,不同土层反演值和地面观察值的相关性均达极显著水平;5~60 cm土层土壤温度的平均绝对误差随土层加深逐渐降低,40~60 cm土层土壤温度的平均绝对误差降至1℃以内,但80、160 cm两层的反演精度误差则相对较大,说明结合其他模型,遥感能够反演一定深度土层的土壤温度,并达到一定精度。     

预热温度对层状压缩木材力学性能的影响

不同预热温度下形成的层状压缩木材,因压缩层位置差异形成的不同结构及预热温度本身的变化均会引起力学性能变化。以毛白杨Populus tomentosa弦向板为材料,采用水热控制方法,通过改变预热温度获得了压缩层位于表层至中心层的不同结构的层状压缩木材。对其表面硬度、木材硬度、抗弯弹性模量与抗弯强度进行对比研究。结果表明:①随着预热温度的升高,木材表面硬度显著升高（P < 0.01）,较对照的增加率为3.9%~57.2%,而木材硬度则极显著降低（P < 0.001）,较对照的增加率为8.6%~38.5%。这个结果与压缩层随着预热温度升高,逐渐由表层向中心层移动形成的表层下0.32和2.82 mm厚度范围内木材的平均密度变化以及高温的作用密切相关。②随着预热温度的升高,弦向弯曲弹性模量逐渐增大,径向弯曲弹性模量逐渐减小;抗弯强度先增大,150℃后逐渐减小;但抗弯性能无显著差异（P>0.05）。不同预热温度下形成的层状压缩木材的力学性主要受其结构的影响,其次是温度的影响。控制压缩层的位置出现于木材表层,同时提高压缩层的密度,可获得力学性能更好的层状压缩木材。