Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

浙江沐尘岩体与西山头组火山岩的岩浆同源性分析

沐尘岩体与旁侧西山头组火山岩、潜火山岩在空间上密切共生,形成时间相近;岩石类型都属中酸性岩类;具有相近的岩石化学成分,均属弱碱质岩系;各种岩石的稀土配分曲线除Eu外具有基本一致的型式,微量元素配分曲线形态也基本一致,说明它们是同源岩浆演化的产物。其岩石类型、岩石化学和稀土元素、微量元素地球化学方面具有相似性和一致性,岩浆演化均有反序现象,说明它们属同熔型火山-侵入岩组合。根据2004年国际地层委员会公布的侏罗系与白垩系的分界年龄(145.5±4.0Ma),并结合沐尘岩体与旁侧西山头组火山岩的成因关系,沐尘岩体的形成时代确定为早白垩世早期似更合理。     

赣东北前寒武纪港边杂岩体的岩浆混合（和）作用及其地质意义

赣东北地区沿江绍断裂北缘和江南造山带南侧有大量的前寒武纪火山侵入杂岩呈带状分布,主要由大面积的陆相火山岩和若干长英质镁铁质火成杂岩体组成,后者中出露面积最大的港边杂岩体在填图尺度上可划分为长英质岩、镁铁质岩和过渡性岩3大组成部分,长英质岩颗粒锆石U_Pb谐和不一致曲线上交点年龄为822±4Ma,代表杂岩体中岩浆混合作用发生的时间。港边岩体中长英质岩石的Nd模式年龄为1·49~1·68Ga,镁铁质岩中玄武质岩石为1·51~2·21Ga,辉长岩的Nd模式年龄与玄武质岩石基本相同,为1·54~2·13Ga,经计算的过渡性岩石的Nd模式年龄为1·58~1·90Ga,因此认为镁铁质岩石从源区分离的时间要远早于长英质岩石,而过渡性岩石含有前两个端员岩浆相互混合(和)的信息。长英质岩石的εNd(t=822Ma)值为-0·8~-4·4,87Sr/86Sr(822)比值为0·70368~0·70549;玄武质岩石的εNd(822)值为-2·6~+2·3,87Sr/86Sr(822)比值为0·70387~0·70527,这反映了镁铁质岩浆的源区接近总地球,长英质岩浆则来自具壳幔混合性质的EMⅠ型地幔的源区。可以推测,赣东北前寒武纪也曾发生过岩浆底侵作用。底侵作用对港边火成杂岩体岩浆的形成起着重要的作用。底侵于壳幔边界的玄武质岩浆使地壳熔融形成长英质岩浆并聚集于浅部岩浆房。随着长英质岩浆房降温,长英质岩浆的结晶度和粘度增加,其物理状态发生液态→(固+液)混合态→固态的变化;当玄武质岩浆穿透下地壳并不断进入物理状态变化的长英质岩浆房时,持续地发生两种岩浆的化学混合作用或两岩浆的机械混合作用或玄武质岩浆的侵入,其混合作用的时间以长英质岩锆石的U_Pb谐和不一致曲线上交点年龄822±4Ma界定。根据Nd模式年龄(tDM)和Nd富集系数(fSm/Nd)分布特征,可以确定中元古代江南造山带为太古宙扬子古陆核的横向增生体,而新元古代陆相火山侵入杂岩带则横向增生于江南造山带南缘。至此,扬子古陆横向增生作用结束,开始与华夏古陆拼贴,包括港边火成杂岩体在内的新元古代火山侵入杂岩带则成为两古陆连结的纽带。     

Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR

Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower.     

河北西北部熔积岩特征及其地质意义

熔积岩是火山碎屑岩的一种特殊类型，由熔浆和未固结的湿沉积物两种组分掺杂混合而成。熔积岩的形成主要受炽热熔浆与未固结的湿沉积物接触时引起的淬碎或蒸汽爆炸作用以及寄主沉积物流体化作用控制，通常分布于熔岩流底部或前缘，也可分布于超浅成侵人体周围。据熔浆碎屑物的结构特征，冀西北熔积岩可分为流状和块状两种类型。流状熔积岩多是熔浆与细粒沉积物混合的结果，块状熔积岩大多与粗粒沉积物相关。正确鉴别熔积岩对确定沉积作用与岩浆作用的时序、研究盆地发展演化历史具有重要意义。     

地下洞室超欠挖问题非线性有限元分析

运用数值分析的方法,采用ANSYS10.0版有限元分析程序对洞室超欠挖进行三维模拟计算,分析了不同超挖位置、超挖深度、超挖数量等对洞室围岩稳定性的影响,得出了超欠挖部位应力集中数值解及塑性区产生的影响范围,为地下工程掘进施工和初期支护设计提供重要的参考依据。     

Impact of climate change on wetland ecosystems: A critical review of experimental wetlands

Climate change is identified as a major threat to wetlands. Altered hydrology and rising temperature can change the biogeochemistry and function of a wetland to the degree that some important services might be turned into disservices. This means that they will, for example, no longer provide a water purification service and adversely they may start to decompose and release nutrients to the surface water. Moreover, a higher rate of decomposition than primary production (photosynthesis) may lead to a shift of their function from being a sink of carbon to a source. This review paper assesses the potential response of natural wetlands (peatlands) and constructed wetlands to climate change in terms of gas emission and nutrients release. In addition, the impact of key climatic factors such as temperature and water availability on wetlands has been reviewed. The authors identified the methodological gaps and weaknesses in the literature and then introduced a new framework for conducting a comprehensive mesocosm experiment to address the existing gaps in literature to support future climate change research on wetland ecosystems. In the future, higher temperatures resulting in drought might shift the role of both constructed wetland and peatland from a sink to a source of carbon. However, higher temperatures accompanied by more precipitation can promote photosynthesis to a degree that might exceed the respiration and maintain the carbon sink role of the wetland. There might be a critical water level at which the wetland can preserve most of its services. In order to find that level, a study of the key factors of climate change and their interactions using an appropriate experimental method is necessary. Some contradictory results of past experiments can be associated with different methodologies, designs, time periods, climates, and natural variability. Hence a long-term simulation of climate change for wetlands according to the proposed framework is recommended. This framework provides relatively more accurate and realistic simulations, valid comparative results, comprehensive understanding and supports coordination between researchers. This can help to find a sustainable management strategy for wetlands to be resilient to climate change.     

金伯利岩中“熔离小球”的特征及其成因

在金伯利岩人工重砂中发现的“熔离小球”,直径多数<1 mm,除个别出现微晶外,均为非晶质,属于熔体淬火冷却产物。提供了29个小球的主元素分析和3件微量元素分析结果。“熔离小球”按成分可分为3种类型:(1)高铁钛小球;(2)硫铁镍小球;(3)浅色硅铝质小球。其中高铁小球w(FeO)高达99.39%,高钛小球w(TiO2)达45.90%,它们含MnO也偏高,最高达23.75%。Fe、Mn、Ti都属于高负电性元素,在熔体中与氧结合的键强度大,容易发生熔离。硫铁镍小球的w(SO3)变化于38.27%~51.95%,w(FeO)为0.31%~23.10%,w(NiO)为25.24%~61.05%。浅色小球w(SiO2)变化范围为24.01%~52.64%,Al2O3、CaO含量高但变化范围大,总体成分接近基性—超基性硅酸盐熔浆。主元素、微量元素特征以及硫铁镍小球中发现了高镁(Fo=0.95)橄榄石捕虏晶表明,小球形成于金伯利岩岩浆的介质环境。此外高铁及硅铝质两种成分呈交生结构的两相小球的发现,暗示二者为熔离作用成因。小球的熔离作用可以应用SiO2-FeS-FeO的液态不混溶相图做出解释。认为小球形成于岩浆结晶的晚期阶段,相对富含CO2、SO3、FeO、MnO、TiO,在岩浆快速上升、快速降温、降压、熔体中出现了多种局部有序区的条件下发生的。     

郭家岭岩体矿物包裹体研究

通过对胶东金成矿区郭家岭岩体中熔融包裹体、含石盐子晶包裹体、ＣＯ２三相包裹体和Ｈ２Ｏ两相包裹体的显微测温,结果表明,该岩体在岩浆结晶晚期发生过高盐度流体与硅酸盐熔体的不混熔过程。根据熔融包裹体均一温度与均一过程的时间,利用相应公式,计算出郭家岭岩体包裹体熔体的粘度和含水量,认为该岩体是从一种高温高粘度的岩浆中结晶成岩的。     

岩浆侵位机制研究综述

岩浆侵位机制是研究地球动力作用的重要依据,综合国内外资料,对岩浆侵位机制提出了按侵位深度,岩浆迁移距离,岩浆结晶程度的分类方案及其联合侵位类型。分别对各类侵位机制 岩浆侵位过程,特点,研究现状进行了综述,并讨论了岩浆定位空间问题和影响岩浆定位的因素。