Heterogeneous electron-transfer kinetics with synchrotron Fe Mössbauer spectroscopy

In the first known kinetic application of the technique, synchrotron ⁵⁷Fe-Mössbauer spectroscopy was used to follow the rate of heterogeneous electron transfer between aqueous reagents and a solid phase containing Fe. The solid, a synthetic ⁵⁷Fe-enriched Fe(III)-bearing pyroaurite-like phase having terephthalate (TA) in the interlayer [Mg₃Fe(OH)₈(TA)_0.5 · 2H₂O], was reduced by Na₂S₂O₄ and then reoxidized by K₂Cr₂O₇ by means of a novel flow-through cell. Synchrotron Mössbauer spectra were collected in the time domain at 30-s intervals. Integration of the intensity obtained during a selected time interval in the spectra allowed sensitive determination of Fe(II) content as a function of reaction time. Analysis of reaction end member specimens by both the synchrotron technique and conventional Mössbauer spectroscopy yielded comparable values for Mössbauer parameters such as center shift and Fe(II)/Fe(III) area ratios. Slight differences in quadrupole splitting values were observed, however. A reactive diffusion model was developed that fit the experimental Fe(II) kinetic data well and allowed the extraction of second-order rate constants for each reaction. Thus, in addition to rapidly collecting high quality Mössbauer data, the synchrotron technique seems well suited for aqueous rate experiments as a result of the penetrating power of 14.4 keV X-rays and high sensitivity to Fe valence state.     

Geochemistry of eucrites: genesis of basaltic eucrites, and Hf and Ta as petrogenetic indicators for altered antarctic eucrites

We performed instrumental neutron activation analysis on a large suite of antarctic and nonantarctic eucrites, including unbrecciated, brecciated, and polymict eucrites and cumulate and noncumulate eucrites. We evaluate the use of Hf and Ta, two highly incompatible elements, as sensitive indicators of partial melting or fractional crystallization processes. Comparison with rare earth element (REE) data from nonantarctic and antarctic eucrites shows that Hf and Ta are unaffected by the terrestrial alteration that has modified the REE contents and patterns of some antarctic eucrites. The major host phases for Hf and Ta—zircon, baddeleyite, ilmenite, and titanite—are much less susceptible to terrestrial alteration than the phosphate hosts of REEs. The host phases for Hf and Ta are minor or trace phases, so sample heterogeneity is a serious concern for obtaining representative compositions. The trace lithophile and siderophile element contents of noncumulate eucrites do not allow for a single, simple model for the petrogenesis of the howardite-eucrite-diogenite suite. Fractional crystallization models cannot reproduce the compositional relationship between eucrites of the main group-Nuevo Laredo trend and those of the Stannern trend. Equilibrium crystallization models cannot explain the trace element diversity observed among diogenites. Partial melting models cannot explain the W variations among eucrites, unless source regions had different metal contents. We suggest that slight variations in oxygen fugacity of eucrite source regions during partial melting can explain the W variations without requiring different metal contents. This hypothesis may fail to account for eucrite Co contents, however.     

Fluxes of Sr into the headwaters of the Ganges

Himalayan weathering is recognized as an important agent in modifying sea water chemistry, but there are significant uncertainties in our understanding of Himalayan riverine fluxes. This paper examines causes of the variability, including that of the seasons, by analysis of downstream variations in Sr, ⁸⁷Sr, and major ions in the mainstream, in relation to the composition of tributary streams from subcatchments with differing geologic substrates.Water samples were collected over four periods spanning the premonsoon, monsoon, and postmonsoon seasons. Uncertainties in the relative fluxes have been estimated, using Monte Carlo techniques, from the short-term variability of mainstream chemistry and the scatter of tributary compositions. The results show marked seasonal variations in the relative inputs related to high monsoon rainfall in the High and Lesser Himalaya, contrasting with the major contribution from glacial melt waters from the Tibetan Sedimentary Series (TSS) at times of low rainfall. Much of the spread in previously published estimates of the sources of Sr in Himalayan rivers may result from these seasonal variations in Sr fluxes.The annual fluxes of Sr into the headwaters of the Ganges are derived from the three main tectonic units in the proportions 35 ± 1% from the TSS, 27 ± 3% from the High Himalayan Crystalline Series (HHCS), and 38 ± 8% from the Lesser Himalaya. The particularly elevated ⁸⁷Sr/⁸⁶Sr ratios characteristic of the HHCS and the Lesser Himalaya enhance their influence on seawater Sr-isotope composition. The TSS contributes 13 ± 1%, the HHCS 30 ± 3%, and the Lesser Himalaya 57 ± 11% of the ⁸⁷Sr flux in excess of the seawater ⁸⁷Sr/⁸⁶Sr ratio of 0.709.     

黄河上游河南县地面大气冰核观测分析

用Bigg型混合云室对2001年8月黄河上游青海省河南县的地面大气冰核浓度进行了观测,分析发现(1)青海省河南县冰核浓度低于北京20世纪90年代的测值,但高于大连、西安和兰州(20世纪60年代)等地的测值,同时也高于黄河上游的玛曲(2000年)、西宁(1989年)两地的测值,高温核尤其偏高.(2)降水时大气冰核浓度减少,降水的冲刷可能是其主要原因.(3)当地冰核浓度和气压成正相关.(4)大气冰核浓度受风向的影响,无风时测值较小,偏东风时测值较大,高温核浓度增加明显.     

江西省夏季干旱特征分析

根据1951～2000年江西省降雨量、降雨日数、降雨变率等资料,统计和分析江西省夏季干旱期间降雨量、降雨日数、降雨变率等变化与地理分布客观特征.文章还对江西干旱标准、干旱指数与伏、秋干旱时空分布客观特征等进行分析.分析结果为江西人工增雨抗旱作业提供依据.     

中国气象科学研究院深化科技体制改革

2003年，是中国气象科学研究院深化科技体制改革关键的一年，也是我院通过改革，全院职工奋发向上，精神面貌发生重大变化，各项工作取得可喜成绩的重要一年。《中国气象科学研究院深化改革实施方案》经2002年12月1117t中国气象局党组通过后，于2003年开始全面实施。领导班子明确分工，责任到人，抓好组织落实，积极稳妥地推进了我院的深化改革。     

荒漠戈壁下垫面表面动量和感热湍流通量参数化研究

用合理筛选以后的野外观测资料，研究了荒漠戈壁地表湍流通量参数化的问题。首先，分析了Monin-obukhov相似函数的特征，并拟台出了其经验公式。结果表明，风速和温度相似性函数随稳定度参数的变化曲线与典型经验曲线差异较小，并且在经验曲线分布范围以内，但中性时的值有所不同。同时，还用该资料给出了动量和标量粗糙度(感热粗糙度)长度的平均值及其标量粗糙度随摩擦速度的变化关系。发现标量粗糙度的平均值大约比动量粗糙度的小一个量级，并且随摩擦速度的增大而减小，但明显比其理论预测值要大。     

全球观测应力场的短波分量分析

世界应力图(WSM，World Stress Map)计划的应力指标，目前已累积数据共计10 920个，这些应力指标代表了该地区最大水平主应力的实际观测方向；与此同时，可以假定全球各个板块的绝对运动方向表征了相应各板块的最大水平主应力方向的长波分量．根据应力场的叠加原理，得到由该地区局部构造运动等因素贡献的短波分量的相对大小和方向．将全球划分成2.52.5的基本单元，对每个单元的WSM数据进行加权统计分析，得到其平均应力观测取向，利用HS2-NUVEL1全球绝对板块运动模型计算应力场的长波分量；平均观测应力取向和长波分量取向之间的夹角，决定了相应短波分量相对于观测应力场的大小及其取向的范围，并反映了特定研究地区局部应力场对总应力场的贡献程度．本文的计算结果表明，全球板块的绝大部分地区及各板块的平均效果，长波分量与短波分量对观测应力场的贡献程度相当．对于某些大陆板块内部，局部构造活动对观测应力场的贡献起到重要作用，因而控制着地震的孕育与发生．      

Characteristics of the atmospheric heat source and moisture sink over the Qinghai-Tibetan Plateau during the second TIPEX of summer 1998 and their impact on surrounding monsoon

Summary ?Using the data of 6 automatic heat balance observation (AWS) stations and a data set of 52 surface observation stations over the Qinghai-Tibetan Plateau (“the Plateau”) and surroundings, the horizontal distribution is studied of “apparent atmospheric heat sources” 〈Q ₁〉 and of “apparent atmospheric moisture sinks” 〈Q ₂〉. The AWS stations were established during the period May to August 1998 of the Tibetan Plateau Meteorological Experiment (second TIPEX) by a cooperation of China and Japan. For this period the Plateau mean of 〈Q ₁〉 is positive. Its value of 74 W/m² is a little greater than a climate value and than values from MONEX and the first TIPEX in 1979, respectively. Also the corresponding 〈Q ₂〉 is positive. Hence during that time the Plateau is a heat source and a moisture sink. A day-to-day change of 〈Q ₁〉 and 〈Q ₂〉 is more pronounced over the middle and east part of the Plateau than over the west part. Diagnostics accompanied by numerical simulations are used to study the daily relationship between 〈Q ₁〉 over the Plateau and the weather over China and Asia for this summer. The results suggest that 〈Q ₁〉 may affect precipitation over northern China and position of the west Pacific subtropical high. Abnormal southward retreat of this Pacific high seems to have caused the second flood over the middle and lower Yangtse river basin in July. Received May 20, 2001; revised February 2, 2002