北京地区臭氧垂直分布的演变趋势与特征的研究——卫星SBUV资料与地面遥感对比分析

利用地面遥感O₃垂直分布的逆转方法〈C〉测量出的北京上空O₃剖面资料,对雨云7号卫星的SBUV系统测量的同地区的O₃垂直分布数据进行了订正.对订正后的长达8年（1979-1986年）的完整的SBUV资料进行了较为仔细的分析,得出了这一时期内的O₃垂直分布长期演变呈下降趋势.并在上层O₃含量的季节变化特征和周期振荡等方面,有新的发现,得出一些有意义的结果.     

北半球中高纬度对流层顶转换层中O3/H2O 混合关系的结构形态

利用北半球40°N～50°N纬度带上HALOE实验测量的O₃和H₂O廓线资料,根据示踪成分O₃和H₂O空间分布的化学寿命以及输运特征时间常数等性质,在等熵坐标中构建了对流层顶附近及最低平流层300～390 K等熵面间,O₃/H₂O混合关系的结构形态和季节特征.结果表明: (1) 在对流层顶转换层的320～380 K等熵面间O₃混合比廓线的斜率具有空间转折"突变",而H₂O混合比廓线的斜率则出现空间渐变转折.在对流层顶附近O₃和H₂O的源分别是平流层与对流层,使O₃混合比和H₂O混合比在320～380 K等熵面的两侧显现出截然不同的垂直分布梯度.(2) 在对流层顶附近O₃/H₂O达到最小二乘意义上的最佳拟合时,两者参考关系的对流层支与平流层支呈现出非规则"L"结构形态的季节与季节内变化,其中对流层支的斜率为负,而平流层支的斜率可随季节出现正负变化.同时,由"L"形态的转角处可确定随季节变化的化学对流层顶(chemopause)特征.(3) 由O₃/H₂O混合关系反映出对流层不同区域空气携带的物质成分分别与平流层空气混合而形成混合层,而且可使混合层的混合线不恒定.混合层的表现在2003年、2005年1月和2003年4月的混合程度相当,混合的等熵厚度大约是30 K,即在320～350 K等熵面间.2005年11月的混合高度有所增高,进入平流层的H₂O混合比要比2003年和2005年1月的小,混合的等熵厚度大约为30 K,在330～360 K等熵面间.不同季节混合的等熵厚度变化较小,但高度可随季节而变化.O₃/H₂O混合关系的平流层支随季节的变化很明显,1月最低平流层空气脱水是引起平流层支季节变化的重要原因.     

N2O增加对大气环境影响的模拟及其与甲烷和平流层水汽影响的比较

本文利用美国国家大气环境中心(NCAR)的二维化学、辐射和动力相互作用的模式(SOCRATES),模拟了大气中N₂O增加对O₃和温度的影响,并从化学、辐射和动力过程讨论了影响原因,此外还与大气甲烷和平流层水汽增加对大气环境的影响进行了对比.分析表明:大气中N₂O浓度增加以后,将通过化学过程引起30 km以上O₃损耗,30~40 km损耗较多;30 km以上降温明显,下平流层中低纬度地区以及对流层O₃增加并有微弱升温;30~40 km附近,北半球中高纬地区O₃减少以及降温幅度都大于南半球.对流层升温主要是N₂O和O₃增加所致,而平流层温度变化主要受O₃控制.北半球中高纬地区动力过程对温度变化的反馈较其它地区明显,这种反馈对平流层中高层北半球中高纬地区温度和O₃的变化都有明显影响.大气中甲烷增加引起的O₃损耗在45 km以上,45 km以下O₃增加.平流层水汽增加会引起40 km以上O₃减少,20~40 km大部分地区O₃增加.N₂O增加造成的O₃损耗正好位于臭氧层附近,其排放对未来O₃层恢复至关重要.N₂O增加引起下平流层15~25 km中低纬度地区有弱的升温,这与其它温室气体增加对该地区温度的影响不同,CO₂,CH₄和H₂O等增加后下平流层通常是降温.     

平流层O3、O动力系统的平衡性质及南极平流层O3季节变化规律的研究

本文首次利用常微分方程定性理论对平流层O₃、O动力系统的平衡性质进行了讨论.结果表明,如果在平流层O₃的主要分布高度内,大气扩散作用小于光化学作用,那么平流层的O₃层处于稳定状态;反之,平流层的O₃层将遭到破坏.利用这一机制,我们可以解释南极平流层O₃的季度变化规律和每年9-10月份出现的南极O₃洞.     

探测与2014年新疆于田MS7.3地震相关的大气CO和O3异常变化

基于AQUA AIRS传感器提取了2014年2月12日新疆于田M_S7.3地震前后CO和O₃数据, 讨论了数据变化与地震活动的关系。 差值法和异常指数法结果表明, 于田地震后CO和O₃在3月份达到最大异常, 且气体柱浓度异常沿NE向发震构造呈线性分布; 不同高度的CO和O₃的VMR值变化与差值法和异常指数法得到的结果相吻合; 地震前后短时间内CO和O₃气体柱浓度出现下降, 且地震当月最低。 初步推断可能是阿尔金断裂尾部在SW向运动过程中使得震区断裂带在弹性挤压状态下出现闭锁, 气体不流通导致; CO和O₃异常更多的可能是由于田地震引起地下气体大量释放, 其次可能是与地下气体逸散在大气圈中发生的一系列化学反应有关。 研究表明, 卫星高光谱遥感数据获得的CO和O₃的地球化学信息与地震有密切联系, 在地震监测及预测领域具有重要的应用价值。     

北京及周边气溶胶区域影响与大雾相关特征的研究进展

针对2011年12月初北京及华北持续近一周的严重大雾天气这一热点事件,从城市群大雾过程气溶胶区域影响的视角,基于"973"项目"北京及周边地区大气-水-土环境污染机理与调控原理"的研究工作,就北京及周边地区大雾天气与大气气溶胶区域影响的关系等方面进行了讨论.研究表明,北京城市大雾前低空SO₂和NO₂浓度存在"积聚"与"突增"现象.北京及周边地区冬季雾日数和气溶胶光学厚度则呈正相关,并具有"同位相"的年际变化趋势.研究同时发现北京及其南部周边的冬季气溶胶高值区呈南北向带状分布,其与北京周边居民户数高值区有所吻合,反映了冬季北京城市气溶胶颗粒物的远距离影响源区及大尺度输送效应.统计分析指出,冬季北京气溶胶颗粒物PM₁₀、PM_2.5主要影响成分是SO₂和NO_X,且有关研究也表明,电厂、采暖和工业面源是SO₂的三大本地排放源,而机动车、电厂、工业为NO_X的三大本地排放源,上述大气PM₁₀、PM_2.5主成分污染源亦与雾水样本化学分析结果相吻合,即冬季由于燃煤在生活能源中的比例较大,北京雾水中硫元素和碳元素的含量都较高.因此,北京冬季大雾不仅与北京城区气溶胶及其污染排放影响存在相关关系,而且与北京周边天津、河北、山东等地气溶胶及大气污染物的远距离输送和气溶胶区域影响效应有着重要的联系.因此,北京雾霾天气及相关大气污染的治理工作首先要着眼于局地污染物的减排,但同时如何做好区域大气污染的协同治理也是不容忽视的问题.     

关于O3层垂直剖面遥感的逆转曲线的数学拟合模式

逆转遥感是当前获得大气O₃层垂直剖面资料的重要方法之一，而逆转曲线的质量对遥感结果的精度至关重要．本文在最小二乘法的基础上，结合逆转曲线的特征，加以适当处理，建立了逆转曲线的拟合数学模式．其性能良好，对研究O₃层垂直剖面的长期演变趋势具有重要意义．     

气象条件对京津冀地区O3和PM2.5双高污染的影响及对减排的启示作用

近年来,京津冀地区频繁发生O₃和PM_2.5同时超标的双高污染(CP)过程,给大气污染协同控制带来了严峻挑战.京津冀地区50%以上的CP事件发生在4～5月,并且在2018年达到了最高的11天. CP事件期间的O₃和PM_2.5浓度略低于但接近仅发生O₃和PM_2.5污染时的浓度,这表明双高污染会造成更为严重的危害.由斯堪的纳维亚遥相关型的两个中心与华北上空的异常反气旋环流中心组成的Rossby波波列导致京津冀地区出现高温、潮湿和静稳的气象条件,这同时增加了O₃和PM_2.5的浓度,有利于CP事件的发生.在2018年之后CP日数急剧减少,而气象条件并没有明显的趋势变化.因此,气象条件的变化并没有真正促成2019年和2020年CP日数的下降.这其中隐含着是PM_2.5相关排放的减少导致了CP日数的减少(2019年和2020年共减少约11天).本文所揭示的不同污染事件之间大气条件的差异有助于在日-周的时间尺...     

中国火山温泉气体地球化学特征及其在火山监测中的应用

中国火山温泉主要分布在吉林长白山、云南腾冲和黑龙江五大连池等火山区。这些火山虽然处于休眠状态,但大面积的温泉分布指示着岩浆房存在的可能性。本文总结了前人研究成果,分析了中国主要火山区温泉气体地球化学特征,并探讨了温泉气体在火山监测中的应用。长白山、腾冲和五大连池火山区温泉气体地球化学性质类似,都以CO₂为主要气体,含量在80%以上,最高可达99%以上,其它气体组分包括CH₄、N₂、O₂、SO₂、H₂S、He和H₂等。长白山火山温泉气体中氦同位素比值（3He/4He）最高,约为4—6R_A,CO₂中碳同位素比值（δ13C）为-7.9‰—-1.3‰,CH₄中碳同位素为-48.0‰—-28.7‰;腾冲火山温泉气体氦同位素比值为3—5.5R_A,CO₂中的碳同位素为-6.49‰—-2.07‰,CH₄中碳同位素为-23.5‰—-9.3‰;五大连池火山温泉气体氦同位素比值约为3R_A,CO₂中的碳同位素比值为-9.6‰—-3.1‰,CH₄中碳同位素为-47.2‰—-44.4‰。3个火山区的温泉气体均显示地幔来源的岩浆气体特征,并在上升运移过程中受地壳或古俯冲物质的影响。     

f0F2 半年变化的特征和一种可能机制

利用东亚和澳大利亚扇区不同地磁纬度台站和两个极区台站1974-1986 年电离层垂直探测数据, 分析了f₀F₂ 半年变化的主要特征. 提出了产生f₀F₂ 半年变化的一种新的物理机制: 低热层日潮的半年变化, 引起赤道电急流幅度的半年变化, 通过 喷泉效应! 使得赤道电离层异常幅度产生半年变化, 从而形成f₀F₂ 的半年变化.     

Plate motions and the viscosity structure of the mantle — Insights from numerical modelling

We use sulfur (S) isotope signatures within ancient sediments and a photochemical model of sulfur dioxide (SO₂) photolysis to interpret the evolution of the atmosphere over the first half of Earth's history. A decrease in mass-independent sulfur isotope fractionation has been reported in Archean rocks deposited between ~ 2.7 Ga and ~ 3.2 Ga, and is reinforced by new S isotope data that we report here. This pattern has been interpreted by some as evidence that atmospheric oxygen (O₂) was elevated during this time. In this paper, we argue against that conclusion, and show that it is inconsistent with other geochemical data. In its place, we propose a new model that can explain the sulfur isotope record that can also avoid conflicts with independent constraints on O₂ and account for concurrent glacial deposits. Specifically, we suggest that prior to the rise of O₂ excursions in the sulfur isotope record were modulated by the thickness of an organic haze. This haze would have blocked the lower atmosphere from the UV fluxes responsible for the anomalous sulfur photochemistry and would have caused an anti-greenhouse effect that triggered the glaciations. We used a photochemical model to verify that a haze could have affected the isotopic signal in this manner, and to examine how changes in atmospheric methane (CH₄) and carbon dioxide (CO₂) concentrations could have controlled haze thickness. Finally, we combined the resulting relationships with climate models and sulfur isotope and glacial records to deduce a new evolutionary sequence for Archean climate, surface chemistry, and biology.     

Evolution of Earth's redox state during upwelling of carbon-bearing mantle

The oxygen fugacity (f(O₂)) values recorded by diamondiferous peridotite and eclogite xenoliths from Siberia indicate that the redox state of the ancient lithosphere is heterogeneous on a scale of at least four log units, mainly in the range between the wüstite-magnetite (WM) and iron-wüstite (IW) oxygen buffers. Highly reduced peridotites can be interpreted as relict from earlier lower f(O₂). The f(O₂) values recorded by ‘fertile’ and less modified spinel peridotites from Mongolia, Baikal and Tien-Shan show that the redox state of the lithosphere beneath central Asia and Tien-Shan is heterogeneous on a scale of 2–3 log units, mainly in the range between the WM and IW + 1 oxygen buffers. These data provide evidence for the presence of a lower-f(O₂) regime of carbon-bearing mantle beneath the Baikal rift zone and Tien-Shan, and the oxidation of diapirs ascending from the asthenosphere. The ‘dry’ xenoliths from Mongolia primarily reflect closed system behavior in the upper mantle, the f(O₂) of which is buffered by ferric-ferrous redox equilibrium. The observed evolution of f(O₂) values is closely linked to the distribution of volatile species in the mantle. H₂O and CO₂ are the dominant volatiles for the more depleted and oxidized part of peridotites, and CH₄ for the more reduced and less modified part. It is proposed that the upper mantle was originally more reduced and has become progressively more oxidized, resulting perhaps largely from the preferential loss of hydrogen and carbon during melting. The oxygen budget of the upper mantle results from the opposing contributions of crustal recycling and transfer of carbon-bearing material from the deep mantle.     

A new high-pressure phase of Ca2Al2SiO7 and implications for the earth''s interior

Gehlenite (Ca₂Al₂SiO₇) has been found to transform to a new phase at pressures greater than 100 kbar and at about 1000°C, using a diamond-anvil pressure cell coupled with laser heating. The atoms of the new phase appear to be arranged in a perovskite-related structure similar to that described for Na₂Ti₃O₇. The structure probably consists of layers of (Al₂SiO₇)⁴⁻, which are built up from blocks of edge-sharing (Al, Si)O₆ octahedra and these blocks are joined by common octahedra corners. A small cubic unit cell with a = 3.719 ± 0.004 Å indexes completely the strong lines of the powder diffraction pattern, and a superlattice with a = 14.88 ± 0.02 Å satisfies all the observed weak lines in addition to the strong ones. However, the cell may be pseudocubic. The small cell contains a half of the gehlenite formula while the large cell contains 32 gehlenite formulae. Hence the molar volume for the new phase of Ca₂Al₂SiO₇ is calculated to be 61.96 ± 0.20 cm³ at atmospheric pressure and room temperature. The new sodium titanate-type structure is probably more closely packed than an ordinary perovskite-type structure in which all octahedral corners are shared. This view is strongly supported by the very great density of this new phase, which is about 8% denser than the equivalent mixture of CaAl₂O₄ (calcium ferrite type) plus CaSiO₃ (cubic perovskite type). The new phase is probably the most closely packed silicate known. Mg₂SiO₄ (spinel) was found to transform to an assemblage containing MgSiO₃ (perovskite) plus MgO (periclase) at P-T conditions equivalent to the upper part of the lower mantle. By reacting with MgO, the perovskite modification of both MgSiO₃ and MgSiO₃ · xAl₂O₃ may adopt the sodium titanate structure at the still greater depths of the lower mantle. If the sodium titanate structures of Mg₂(Al₂Si)O₇ and Mg₂(MgSi₂)O₇ are present in the deep part of the lower mantle, MgO does not exist as a separate phase at the mantle-core boundary. This might be an obstacle to the possibility of dissolving these oxides (specifically the FeO component) in the molten Fe in the outer core as suggested by geophysical and geochemical studies of the earth's interior. The mechanism for developing the chemical plumes in the deep mantle proposed by Anderson does not appear to be consistent with studies of phase transformations in Ca-Al-rich compounds as outlined in this paper.     

辽宁省地震监测站地下水化学类型及成因分析

通过测试辽宁省15个地震监测站泉水或井水的氢、氧同位素组成及主要离子组分含量,讨论了泉水或井水的化学类型及其成因.测得泉水或井水的δD和δ~(18)O值范围分别为-82.5‰--54.4‰和-11.4‰—-7.3‰,表明所测泉水和井水的主要来源为大气降水.研究区低温泉水为低矿化度的Ca-SO_4·HCO_3型或Ca-HCO_3·SO_4型;而较高温度的花岗岩裂隙水中溶解了较多的钠硅酸盐矿物,水化学类型主要为Na-HCO_3·SO_4型;碳酸盐岩及含砾砂岩含水层分别分布于辽宁省西部及中部地区,水温略低于高温花岗岩裂隙水,水化学类型为Na·Ca-HCO_3型.水中F~-含量较高,且F~-含量与温度、pH值、Na~+和HCO_3~-的浓度呈正相关,表明泉水或井水的化学类型是深部富CO_2流体及大气降水与花岗岩反应的结果.     

Infiltration of river water to a shallow aquifer investigated with H/He, noble gases and CFCs

Noble gas isotopes (³He, ⁴He, Ne, Ar, Kr, Xe), tritium (³H), chlorofluorocarbons (CFCs) and dissolved oxygen (O₂) were seasonally measured in a small groundwater system recharged by infiltration of river water at Linsental, northeastern Switzerland. All Groundwater samples contained an excess of atmospheric noble gases (‘excess air’) usually with an elemental composition equal to air. The concentrations of atmospheric noble gases in the groundwater were used to calculate the excess air component and the water temperature at recharge. The noble gas temperatures (NGTs) in the boreholes close to the river vary seasonally, however, the average NGT of all samples lies close to the mean annual temperature of the river water. Groundwater ages were calculated using the tritium/helium-3 (³H/³He) dating method. The water ages of the samples obtained near the river depend on the amount of recently infiltrated river water and are young during times of active river discharge. In contrast, the mean water age of about 3 years of the deep aquifer remained nearly constant over the sampling period. The observed CFC-11 (CFCl₃) and CFC-12 (CF₂Cl₂) concentrations are significantly higher than the atmospheric equilibrium concentrations and therefore CFCs do not provide any direct information on the residence time of the groundwater. Nevertheless, the CFC excess in the groundwater shows a linear increase with the ³H/³He age. Additionally, both accumulation of radiogenic He (⁴He_rad) and O₂ consumption are strongly correlated with residence time. All these correlations can be interpreted either in terms of mixing of recently infiltrated river water with older groundwater or in terms of accumulation/consumption rates.     

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

The solubility of CO₂CO fluids in a mid-ocean ridge basalt (morb) has been measured at 1200°C, 500–1500 bar, and oxygen fugacities between NNO and NNO-4. High oxygen fugacities, and thus CO₂-rich fluids, were produced by using a starting material equilibrated at NNO, and Ag₂C₂O₄ as the fluid source. Low oxygen fugacities were achieved by using graphite capsules, and MgCO₃ as the fluid source. These graphite-saturated fluids have the lowest possibleC/O₂CO ratio for a given pressure and temperature.

Experiments were run in a rapid-quench internally heated pressure vessel. Fluid compositions were measured using a simple vacuum technique and by Raman spectroscopy of fluid inclusions. The two techniques yielded comparable results. Fourier transform micro-infrared spectroscopy was used to identify and measure concentrations of dissolved volatiles in double-polished wafers of the quenched glasses. Carbonate was the only carbon-bearing species identified. Raman spectroscopic analysis of inclusion-free areas of glass confirmed the absence of dissolved molecular CO₂, CO and carbon. The measured concentrations of dissolved CO₂ in the glasses were proportional to the fugacity of CO₂ during the experiments, calculated from the measured fluid compositions. The data were fit to the equationX_CO2^melt(ppm)= 0.492 fCO₂ (bar).

The insolubility of CO, compared to CO₂, may be related to the fact that dissolution of CO requires reduction of another species in the melt, whereas dissolution of CO₂ does not. Due to the fact that CO will be an important component of natural CO fluids at low pressures and low oxygen fugacities, equilibrium dissolved CO₂ contents will be less than calculated assuming pure CO₂ fluids, but as theC/O₂CO ratio in a pure CO fluid at fixed pressure and temperature is a direct function of oxygen fugacity, measurement of the oxygen fugacity of quenched glasses or trapped fluids in natural samples should allow saturation concentrations to be calculated. Dissolved CO₂ contents of somemorb are less than expected if they were in equilibrium with pure CO₂. These samples must, therefore, have been more reduced than average if they were fluid-saturated. Together with results from other studies of CO₂ and H₂O solubilities in basalt, the results of this study provide a comprehensive framework for modelling CO₂ solution inmorb.