天然锰钾矿氧化降解水体中苯酚机理研究

根据锰的溶出、氧气不参与反应、酸度是影响苯酚降解的主要因素等实验结果，推测天然锰钾矿与苯酚的作用机制。研究表明：反应8h，总有机碳去除率达88．7％；锰钾矿在硝酸存在时产生的氧自由基与苯酚发生氧化还原反应，使苯酚降解。根据检出的对苯醌、联苯二酚、2-羟基-苯并呋喃等中间物质推测出苯酚降解的反应途径。     

抽水试验和长观水位联合模拟确定含水层参数

为了更加准确地确定含水层参数,提出了利用地下水流数值模拟软件Modflow耦合大型抽水试验和长观孔水位两个模型的方法,对含水层参数进行了识别与校验。该方法求得的含水层参数避免了只利用抽水试验模型校验所带来的不确定性,同时利用抽水实验数据进行抽水与恢复的全过程曲线拟合,水位降深模拟相对误差小于6%,提高了含水层参数的准确性。     

Matrix rheology effects on reaction rim growth I: evidence from orthopyroxene rim growth experiments

The rim-forming reaction quartz + olivine = orthopyroxene is used to investigate the effect of matrix rheology on rim growth rates. Orthopyroxene rim growth around olivine grains in quartz matrix is compared to rim growth around quartz grains in an olivine matrix. At constant P–T , within one single capsule, orthopyroxene rims grow faster around quartz clasts in olivine matrix than around olivine clasts in quartz matrix. Fourier transform infra-red spectra indicate that the entire samples are water saturated because of water adsorption on the reactant grain surfaces. The increased orthopyroxene growth rates in olivine matrix as opposed to quartz matrix are interpreted in terms of matrix rheology, where in the two different matrix-inclusion arrangements the olivine matrix behaves 'softer' and the quartz matrix 'more rigid'. The strain energy associated with accommodation of the negative reaction volume is higher for the quartz than the olivine matrix and reduces the free energy that drives orthopyroxene rim growth. Growth textures in both kinds of orthopyroxene rims indicate that the diffusivity of MgO slightly exceeds the diffusivity of SiO₂. The relative mobility of MgO and SiO₂ at given P , T , f H₂O seems to be controlled by energy minimization during orthopyroxene growth at the compressive Ol/Opx interface. Our experiments provide evidence for two previously overlooked effects relevant to rim growth reactions in metamorphic rocks: (i) diffusivity along chemical potential gradients to reaction sites is a function of rheology and (ii) the relative diffusivity of components during reaction rim or corona growth is a function of local volume changes at the rim's interfaces.     

长期浸泡作用下灌浆加固裂隙岩体劣化效应

为分析灌浆加固裂隙岩体在压力水长期浸泡作用下力学性能的劣化效应,在前期碳纤维水泥基复合灌浆材料加固裂隙岩体研究基础上开展了考虑水压力影响的灌浆加固裂隙岩体长期浸泡试验和在不同浸泡周进行直剪试验。研究结果表明,(1) 压力水长期浸泡作用下灌浆加固裂隙岩样的剪应力?剪切位移曲线形态变化趋势明显,剪切刚度逐渐减小,达到峰值抗剪强度时的剪切位移逐渐增大;(2) 随着浸泡周期增加,灌浆加固裂隙岩体的抗剪强度呈先陡后缓的劣化趋势,6个浸泡周期（150 d）后不同法向应力下峰值抗剪强度的劣化幅度为32.6%～39.9%,对应内摩擦角和黏聚力分别降低了19.3%、39.4%,其中前4个浸泡周期（0～90 d）抗剪强度参数劣化幅度占总劣化幅度的90%左右;(3) 水压力作用下裂隙岩样发生溶解、溶蚀、润滑、软化等物理化学作用,浆体中的凝胶体被进入浆体内部的水分子软化,导致裂隙岩体和灌浆体本身的力学性质逐渐劣化,浆体与裂隙面之间的胶结作用、浆体与碳纤维之间粘结性能逐渐减弱,使得灌浆加固裂隙岩体抗剪性能逐渐劣化,剪切破坏面逐渐发展到浆体与裂隙面之间的胶结面。相关研究成果可为灌浆加固裂隙岩体的长期稳定性分析评价提供参考。     

Calcite Dissolution in Deionized Water from 50℃ to 250℃ at I0 MPa:Rate Equation and Reaction Order

Carbonate minerals and water (or geofiuids) reactions are important for modeling of geochemical processes and have received considerable attention over the past decades. The calcite dissolution rates from 50℃ to 250℃ at 10 Mpa in deionized water with a flow rate varying from 0.2 to 5 mL/min were experimentally measured in a continuous flow column pressure vessel reactor. The dissolution began near the equilibrium with clceq > 0.3 and finally reached the equilibrium at 100℃-250℃, so the corresponding solubility was also determined as 1.87, 2.02, 2.02 and 1.88×10-4"mol/L at 100℃, 150℃, 200~C and 2500C respectively, which was first increasing and then switching to decreasing with temperature and the maximum value might occur between 150℃ and 200℃. The experimental dissolution rate not only increased with temperature, but also had a rapid increase between 150℃ and 200℃ at a constant flow rate of 4 mL/min. The measured dissolution rates can be described using rate equations of R = k(1-c/c<,eq>)<'n> or R = kc<'-n>. In these equations the reaction order n changed with temperature, which indicates that n was a variable rather than a constant, and the activation energy was 13.4 kJ/mol calculated with R = k(1-c/c<,eq>)<'n> or 18.0 kJ/mol with R = kc<'-n>, which is a little lower than the surface controlled values. The varied reaction order and lower activation energy indicates that calcite dissolution in this study is a complex interplay of diffusion controlled and surface controlled processes.     

Determination of Dominant Pathways in Chemical Reaction Systems: An Algorithm and Its Application to Stratospheric Chemistry

The analysis of complex chemical reaction systems is frequently complicatedbecause of the coexistence of fast cyclic reaction sequences and slower pathways that yield a net production or destruction of a certain species of interest.An algorithm for the determination of both these types of reaction sequences (in a given reaction system) is presented. Under the assumption that reaction rates are known, it finds the mostimportant pathways by solving a linear optimization problem for each of them.This algorithm may be used as a tool for the interpretation of chemical model runs.For illustration, it is applied to examples in stratospheric chemistry, including the determination of catalytic ozone destruction cycles.     

我国江淮地区5-7月降水异常的区域特征

采用旋转经验正交展开(REOF)方法，对我国江淮地区50a5—7月降水标准化距平场进行客观分区，并分析了南北两区5—7月降水异常的长期变化趋势及其周期的变化。结果表明，江淮地区5—7月降水方差场可以分为2个区域，各区降水量异常有明显的季节变化，降水异常峰值出现在6月和7月，基本呈单峰型分布；南部区变化趋势比北部区明显，均具有显著的年际和年代际变化特征：南北两区都存在3a的主周期，南部和北部分别有21a和15a的年代际周期；江淮南、北区的降水在降水偏多、偏少年都与全国大部分地区呈同位相分布，但江淮北区的降水始终都与华南地区呈反位相分布；副热带季风系统的强弱及副高南北位置的变化直接影响江淮5—7月降水。     

ANALYSIS OF SPHERICAL FUNCTION SPECTRAL STRUCTURE OF THE NORTHERN HEMISPHERE 500 HPA MONTHLY MEAN HEIGHT

Study is undertaken of spherical function spectral structures of long-term mean and anomaly patterns of theNorthern Hemisphere 500 hPa monthly mean geopotential height together with the seasonal and interannual variationsinvestigated.Results show that they are marked by low dimensions and low orders,and the mean and anomaly fields canbe described in terms of 20 and 50 spherical function components,respectively.     

Modeling Study of the Impact of Heterogeneous Reactions on Dust Surfaces on Aerosol Optical Depth and Direct Radiative Forcing over East Asia in Springtime

The spatial distributions and interannual variations of aerosol concentrations,aerosol optical depth(AOD) ,aerosol direct radiative forcings,and their responses to heterogeneous reactions on dust surfaces over East Asia in March 2006-10 were investigated by utilizing a regional coupled climate-chemistry/aerosol model. Anthropogenic aerosol concentrations(inorganic+carbonaceous) were higher in March 2006 and 2008,whereas soil dust reached its highest levels in March 2006 and 2010,resulting in stronger aerosol radiative forcings in these periods.The domain and five-year(2006-10) monthly mean concentrations of anthropogenic and dust aerosols,AOD,and radiative forcings at the surface(SURF) and at the top of the atmosphere(TOA) in March were 2.4μg m-3,13.1μg m-3,0.18,-19.0 W m-2,and-7.4 W m-2,respectively.Heterogeneous reactions led to an increase of total inorganic aerosol concentration;however,the ambient inorganic aerosol concentration decreased,resulting in a smaller AOD and weaker aerosol radiative forcings.In March 2006 and 2010,the changes in ambient inorganic aerosols,AOD,and aerosol radiative forcings were more evident.In terms of the domain and five-year averages,the total inorganic aerosol concentrations increased by 13.7%(0.17μg m-3) due to heterogeneous reactions,but the ambient inorganic aerosol concentrations were reduced by 10.5%(0.13μg m-3) .As a result,the changes in AOD,SURF and TOA radiative forcings were estimated to be-3.9%(-0.007) ,-1.7%(0.34 W m-2) ,and-4.3%(0.34 W m-2) ,respectively,in March over East Asia.     

内蒙古春季久旱转雨大气环流系统特征

利用1960-2009年春季内蒙古104个测站逐日降水量资料,统计出春季第一次有效降水作为久旱转雨天气过程,分析了近50年春季久旱转雨降水特征和年代变化,利用NCEP/NCAR再分析资料分析了久旱转雨的大气环流型.结果表明,20世纪60-80年代内蒙古春季久旱转雨天气过程平均为1～2次,90年代有3次,表明1998年以后出现的频次明显增多.60-80年代500hPa高度场在高纬度欧亚大陆地区为一脊一槽的环流形势,乌拉尔山为高压脊,西伯利亚地区维持一稳定的低涡槽系统,西风急流位于50°-60°N之间,内蒙古受强西风控制;中低纬度地区的西风槽成为久旱转雨的主要影响系统. 1990-2007年500hPa高度场上,在高纬度地区东亚大槽位置偏北,欧亚大陆50°-60°N西风急流北抬至70°-80N,中高纬度地区贝加尔湖到东北地区和蒙古高原为低涡,中低纬度地区多短波槽、脊活动.2008年和2009年又出现了60-80年代的环流特征.对500hPa环流系统进行了分型,得到3种类型:A型(蒙古冷槽(涡))、B型(贝加尔湖低涡)和C型(东北低涡).这3种类型是造成内蒙古春季久旱转雨的主要环流系统.