Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH,HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript>   总被引：1，自引：0，他引：1  

K.?M.?Emmerson  N.?CarslawEmail author  M.?J.?Pilling 《Journal of Atmospheric Chemistry》2005,52(2):165-183

A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO₂ and RO₂ radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO₂, in both summer and winter. RO₂ initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO₂ (OH and RCO₃). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.  相似文献   

Ca-H-Al exchanges and aluminium mobility in two Chinese acidic forest soils: a batch experiment     

J.?GuoEmail author  R.?D.?Vogt  X.?Zhang  Y.?Zhang  H.?M.?Seip  H.?Tang 《Environmental Geology》2004,45(8):1148-1153

Exchange reactions between Ca²⁺, H⁺ and Al species and their effects on the aluminium mobility in two Chinese acidic forest soils were studied. The study was based on a batch experiment using extractant solutions with different base cation (calcium) concentrations and pH. The experimental data showed that increased Ca²⁺ concentrations increased the release of soil hydrogen—and aluminium ions, especially from the more acid soil. In agreement with a cation exchange process, the treatment with Ca²⁺ extracts gave significantly decreased soil aluminium saturation (AlS) and increased calcium saturation (CaS) on the ion exchanger. Geochemical calculation using AlCHEMI program showed that activities of Al³⁺ in the extracts were all strongly under-saturated with respect to any gibbsite mineral in the studied pH region (i.e. below 4.1). There were instead apparently two different mechanisms controlling the activities of Al³⁺ in extracts. At pH between about 4.1 and 3.7, the Al³⁺ activity did not change significantly with pH. This is especially the case in the more acid soil. Apparently there are no sizeable pools available to release Al in this pH region. At pH below 3.7 (induced by higher Ca²⁺concentration) the activity of Al³⁺ increased with H⁺ though not in a pattern that complies with a gibbsite solubility control. An increase of base cation deposition would therefore mainly enhance the release of hydrogen ions between pH 4.1 and 3.7 and aluminium ions below pH 3.7 from Chinese mature acidic soils. This will cause an increased acidity of soil water in the short term and a decrease in the soil acidity in the long term. More attention should be paid to this fact in Chinese acid rain studies and control options.  相似文献   

WHCORS的技术拓展与应用现状     

黄兵杰  严小平  林科  刘传逢  郭启幼 《地理空间信息》2012,10(4):79-82

介绍了武汉市连续运行卫星定位服务系统(WHCORS)的基本情况和发展现状;对基于WHCORS技术拓展研究的相关情况和WHCORS的应用推广进行了详述,针对具体的关键技术问题提出了较详细的解决方案,对用户有一定的参考和借鉴作用。  相似文献   

区县级多源异构空间数据共享平台研究及应用     

余应刚  葛爱霞 《测绘与空间地理信息》2012,35(11):53-55,59

针对区县级空间数据凌乱、共享程度低、应用效率不高等现状,充分考虑区县级政府部门对多源异构地理空间数据资源共建共享的需求,基于Web Service和ArcGIS Server技术,构建了包含数据管理、运维管理、共享交换、公共服务等四大子系统为核心的多源异构空间数据共享服务平台框架,并在佛山市顺德区成功应用,实现了区县级多源异构空间数据的集成与共享。  相似文献   

应用通量方差法估算戈壁绿洲下垫面湍流通量的研究   总被引：3，自引：0，他引：3  

王少影  张宇  吕世华 《大气科学》2010,34(6):1214-1222

利用“绿洲系统能量与水分循环过程观测试验” 2005年绿洲、戈壁点的观测资料, 分析与讨论了温度、水汽的归一化标准差随稳定度变化的通量方差关系, 应用通量方差法对感热、 潜热通量进行了计算, 并同涡动相关系统的观测结果进行了比较。不稳定条件下, 戈壁点温度归一化标准差随稳定度变化的通量方差关系优于下垫面非均匀性更强的绿洲点, 绿洲点水汽的归一化标准差随稳定度变化的通量方差关系较温度量表现得更好。对同一站点, 归一化温度标准差的通量方差关系并不总是优于水汽的通量方差关系, 其取决于该站点的温度以及水汽的源汇分布情况; 通量方差法对两个站点的感热、 潜热通量均有较好的再现, 但戈壁点感热通量的计算效果优于非均匀性更强的绿洲点。应用通量方差法对潜热通量计算时若采用直接观测的感热通量, 则潜热通量的计算效果具有一定程度的改善。  相似文献   

非均匀下垫面陆面过程参数化问题研究进展   总被引：3，自引：0，他引：3  

乔娟  张强  张杰 《干旱气象》2008,26(1):73-78

非均匀下垫面对陆面过程模式应用有着重要影响。若将下垫面一概视为均一,在很多情况下会影响模式模拟的准确性。本文详细介绍了目前非均匀地表陆面过程参数化的方法(Mosaic法、统计—动力法和其它方法),初步分析了这些参数化方法的缺陷,并简单探讨了陆面参数尺度转换问题,最后对今后研究的问题给出了建议,其中特别提出要寻找适当方法实现陆面物理量不同尺度间的转换。  相似文献   

Interplay between equilibrium and kinetics in prograde metamorphism of pelites: an example from the Nelson aureole, British Columbia   总被引：2，自引：0，他引：2  

D. R. M. PATTISON  D. K. TINKHAM 《Journal of Metamorphic Geology》2009,27(4):249-279

The distribution of metapelitic mineral assemblages in the Nelson aureole, British Columbia, generally conforms to what is predicted from phase equilibria. However, in detail, the sequence and spacing of isograds, mineral textures and mineral compositions and mineral chemical zoning do not. Two of the main disequilibrium features in the aureole are: (i) delay in the onset and progress of several reactions, i.e. overstepping in temperature; and (ii) unreactivity of staurolite and especially garnet porphyroblasts when they are reactants in prograde reactions. The thermal overstepping is ascribed to difficulty of nucleation of the product porphyroblasts and sluggishness of dissolution of porphyroblasts when they are reactants. The extent to which these kinetic barriers delay the onset of reaction is related to the reaction affinity of each reaction, defined herein as the Gibbs free‐energy difference between the thermodynamically stable, but not‐yet‐crystallized, products and the metastable reactants. For oversteps in temperature (ΔT), reaction affinity is, in turn, related to the difference in entropy (ΔS) between these two states through the relation A = ΔT * ΔS. Mineral reactions which release large quantities of H₂O, such as chlorite‐consuming reactions, have a higher entropy change per unit of temperature overstep, and therefore a higher reaction affinity, than those which release little or no H₂O, such as the chlorite‐free staurolite‐consuming reaction. Thermal overstepping is consequently expected to be less for the former than for the latter, as was estimated in the aureole where 0 to 30 °C overstepping was required for garnet, staurolite and andalusite growth from a muscovite + chlorite‐bearing precursor rock and ～70 °C overstepping was required for the growth of Al₂SiO₅ from a staurolite‐bearing, chlorite‐free precursor. In all cases, reaction progress was strongly influenced by the presence or absence of fluid, with presence of fluid lowering kinetic barriers to nucleation and growth and therefore the degree of thermal overstepping. Textural features of rocks from the nearly coincident garnet, staurolite and andalusite isograds are suggestive of a fluid‐catalysed ‘cascade effect’ in which reaction took place in a narrow temperature interval; several competing muscovite + chlorite‐consuming reactions, some metastable, appear to have occurred in parallel. Metamorphic reaction, fluid release and possibly fluid presence in general in the aureole were episodic rather than continuous, and in several cases well removed from equilibrium conditions. The extent to which these findings apply to regional metamorphism depends on several factors, a major one being enhanced deformation, which is expected to lower kinetic barriers to nucleation and growth.  相似文献   

地球自由振荡弹性简正模研究进展与展望     

栾威  申文斌  丁浩 《地球与行星物理论评》2021,(3):308-325

在构建现代地球模型时,地球内部分层结构主要是根据地震波资料确定的;而地球内部密度及弹性参数,特别是地幔以下大尺度结构的密度分布,则主要是根据地球自由振荡的弹性简正模观测资料确定的.本文概述了地球自由振荡简正模本征值的求解理论和方法,介绍了球型和环型模态位移场表达式,讨论了地球自由振荡模态的衰减、分裂与耦合效应;总结了多线态分裂谱线探测和分裂参数估计的方法,综述了利用弹性简正模开展地震矩张量、地球三维非均匀性结构和内核超速旋转约束与反演研究的主要进展和存在的问题.最后作为展望,本文还讨论了地球自由振荡简正模的未来研究趋势.  相似文献   

Researches on the Internal Molecular Weight Uniformity of Chitosan Biomaterials     

LANG Xuqian  LI Yang  SUN Guohui  ZHOU Zhongzheng  LI Jing  FENG Chao  KONG Ming  LIU Ya  CHENG Xiaojie  CHEN Xiguang 《中国海洋大学学报(英文版)》2020,19(2):459-465

Uniform molecular weight(Mw)chitosan(CS)is highly demanded in medical biomaterial industry.This present article described heterogeneous degradation of CS in aqueous HCl/ethanol solution,in which progress uniform Mw CS was successfully prepared.The Mw distribution of CS was measured by gel permeation chromatography(GPC)analysis.Moreover,the structure and properties of degraded CS were characterized by Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance spectroscopy(^1H NMR),X-ray diffraction(XRD)and thermogravimetric(TG)analysis.In addition,the biocompatibility of degraded CS was also assessed by hemolysis rate(HR)measurement.The Mw of CS dramatically decreased from 246 KDa to 76 k Da at the initial 30 min,and stabilized at 18 kDa after 24 h.GPC analysis results showed that the degraded CS molecular become homogenization.FT-IR and 1 H NMR analysis confirmed the basic structure of CS molecular backbone was not destroyed during this progress.Besides,the water solubility of CS was not significantly influenced by this reaction.Moreover,the XRD analysis revealed that crystallinity of degraded CS increased from 70.32% to 99.25%with time.The TG analysis showed improved thermal stability of degraded CS.HR measurement demonstrated the degraded CS possessed excellent biocompatibility.This simple and efficient heterogeneous degradation would open up a new route to produce uniform Mw CS.  相似文献   

Primary Product Distributions from the Reaction of OH with m-, p-Xylene, 1,2,4- and 1,3,5-Trimethylbenzene     

D. F. Smith  T. E. Kleindienst  C. D. McIver 《Journal of Atmospheric Chemistry》1999,34(3):339-364

A study was conducted to examine the OH-initiated degradation products of the four title compounds in the presence of sub-part-per-million levels of NO_x. The oxidation was conducted in a dynamic reactor to minimize the conversion of the aromatic compounds. The experiments were designed to represent reaction pathways that occur in the atmosphere at ambient NO₂ concentrations. A wide range of ring-retaining and ring-cleavage products having widely varying yields were measured during the study. For m-xylene, the major primary products observed (with molar yields) were methyl glyoxal (0.40), 4-oxo-2-pentenal (0.12), glyoxal (0.079), and m-tolualdehyde (0.049). For p-xylene, the major primary products were p-tolualdehyde (0.103), 2,5-dimethylphenol (0.13), cis-3-hexene-2,5-dione (0.176), trans-3-hexene-2,5-dione (0.045), 2-methyl-butenedial (0.071), glyoxal (0.394), and methylglyoxal (0.217). Several other reaction products were measured at yields less than 3%. The primary products for OH + 1,2,4-trimethylbenzene were found as follows: methylglyoxal (0.44), glyoxal (0.066), cis-3-hexene-2,5-dione (0.13), trans-3-hexene-2,5-dione (0.031), biacetyl (0.114), 3-methyl-3-hexene-2,5-dione (0.079), and 2-methyl-butenedial (0.045). Six other (ring retaining) products were measured at yields less than 3%. The primary products for OH + 1,3,5-trimethylbenzene were methylglyoxal (0.90), 3-methyl-5-methylidene-5(2H)-furanone (0.1), 3,5-dimethyl-3(2H)-2-furanone (0.1), 3,5-dimethyl-5(2H)-2-furanone biacetyl (0.08), and 2-methyl-4-oxo-2- pentenal (0.05). Three other products were detected at molar yields less than 5%. In some cases, the yields for the ring fragmentation products could only be based on calibrations from surrogate compounds. Yields for several of the unsaturated dicarbonyl compounds have not been reported previously while yields for methylglyoxal, glyoxal, and biacetyl are largely consistent with previous reports. Some of the primary furanone products are the identical to those reported as secondary products in aromatic systems.  相似文献