Measurements of tropospheric OH concentrations: A comparison of field data with model predictions

Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×10⁶ to 3.2×10⁶ cm^-3. Simultaneously we measured the concentrations of O₃, H₂O, NO, NO₂, CH₄, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O₃ and NO₂. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO _x concentrations. It is argued that additional, so far unidentified. HO _x loss reactions must be responsible for that discrepancy.     

浙江缙云斜发沸石水的核磁共振分析

本文应用宽线NMR技术,结合红外测定,研究了缙云斜发沸石中水的结构类型、存在状态、运动特征和热稳定性。结果表明:缙云斜发沸石中的沸石水按其运动特性可以分为受阻旋转水、自由旋转水和自扩散运动水三种类型,它们以谱线中分裂的双线和线宽不同的单峰相区别。低温时,受阻旋转运动的水在晶格中转变为刚性配置。其脱水次序决定于各类型水与沸石结构骨架键合的强弱,脱水是连续的。研究显示缙云斜发沸石的结构骨架相当疏宽,骨架对水分子的吸引力没有严格的方向性,这一特性有利于阳离子的交换。     

Infrared estimates of aliphatic kerogen carbon in sedimentary rocks

An infrared routine has been developed to estimate the aliphatic portion of kerogen carbon in sedimentary rocks. The procedure does not require isolation of the organic matter and is based on a computer-assisted determination of global band areas in the region of the aliphatic carbon-hydrogen stretching vibrations around 2900cm⁻¹. From these integrated absorptions the amount of aliphatic carbon C_al (mg of aliphatic carbon per gram of solvent-extracted rock) is calculated by means of a calibration with model rocks. Carbonate overtones which interfere in the case of limestones are eliminated by comparison to a CaCO₃ standard.The method has been applied to rocks containing kerogens of different types and maturities at TOC levels of 0.5 to 12%. The aliphatic carbon concentrations range from 0.5 to 60mg·g⁻¹ and correlate reasonably well with the residual genetic potentials of the rocks as measured by S₂ values from Rock-Eval pyrolysis. The ratio S₂/C_al is found to decrease with burial depth reflecting a maturity enhanced conversion of aliphatic carbon to fixed aromatic carbon under Rock-Eval conditions.     

区域航空γ能谱场地球化学解释及预测方法的探讨

本文以“铀矿区域评价准则”为依据,试用因子分析主成分比值法,铀对钍(钾)的区域相对场法和铀成矿有利指数法,对我国YW-10和YW-10B两个测区的区域航空γ能谱场进行了地球化学解释及预测方法的研究,与已知矿区660测区从宏观上做了对比分析,并研究了γ能谱参数在走向长270km,宽50—70km空间上的分布变化规律。研究结果表明,这些方法对了解成岩时原始铀的分布及后期铀的地球化学活动规律,估计成岩、成矿阶段铀源岩可能提供的生铀量,识别铀成矿有利地区是有用的。     

利用漫反射光谱鉴定红粘土中针铁矿和赤铁矿

针铁矿(Gt)和赤铁矿(Hm)是广泛存在于土壤和沉积物中的重要铁矿物。这两种矿物在土壤和沉积物中含量很低,常规的测试手段很难有效地测定其含量。利用反射光谱联合加热处理的方法,可对土壤及沉积物样品中针铁矿和赤铁矿进行定性或半定量测定。实验结果显示,样品加热到300℃后,针铁矿的反射光谱的一阶导数特征峰发生了变化,赤铁矿的一阶导数特征峰却没有明显的变化。因此加热前后样品反射光谱一阶导数的变化取决于针铁矿和赤铁矿的含量。利用这种方法估计黄土高原第三纪红粘土样品中的赤铁矿含量约为0.3%～0.4%,针铁矿含量约为0.5%～1%。     

Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.     

反射光谱技术:研究南极企鹅古生态演化的一种新方法

为探求快速、廉价、无损和同步的光谱技术在南极生态环境研究中的可能性,本文利用南极阿德雷岛的四根企鹅粪土沉积柱样品的反射光谱,通过逐步多元线性回归和主成分回归两种数学运算方法,建立了反射光谱数据与企鹅粪九种标型元素浓度之间的关系,并探讨了南极企鹅粪土沉积物光谱数据的古生态意义。结果表明:南极粪土沉积样品反射率光谱与企鹅粪九种标型元素(P、Ca、Cu、F、Ba、S、Zn、Sr、Se)含量之间存在良好的相关性,预测值与实测值之间的相关系数R都达到了0.9以上,在深度剖面上预测浓度与实测浓度具有非常一致的变化趋势;南极粪土沉积物光谱数据包含有明确的古生态变化信息,可利用主成分分析快速恢复历史时期企鹅数量演化过程。本研究结果为在偏远的南极地区开展古生态环境研究提供了一种新的快捷方法和技术途径。     

Analysis of Physical and Chemical Parameters for Discrimination of Water Origin in a Hydroelectric Reservoir

Seventeen physical and chemical parameters were obtained from a hydroelectric reservoir located in a tropical region in the south of Brazil. Multivariate Principal Component Analysis (PCA) and Hierarchical Group Analysis (HGA) were used to identify the parameters discriminating the origin of water from the Tibagi and the Primeiro de Maio River, after it has passed the mixing region. The study was conducted during the dry and rainy seasons in July 2002 and February 2003 at three depths and three sampling sites located 0, 5, and 10 km away from the mixing region. The statistical methods showed to be appropriate for identifying the contribution of each tributary in the water mixing site of a complex water system. The most important discriminating parameter was the absorbance relation A(253 nm)/A(203 nm), followed by the concentrations of Fe(III), Mn(III), and Ni(II). An anthropogenic interference was found in the reservoir due to high Ni(II) and orthophosphate concentrations caused by a nearby town sewage discharge. The interference was more important during the dry periods due to the lower dispersion of the pollutants. Urgent initiatives should be taken from the state government to build treatment stations for the wastewater of the small cities around the Capivara hydroelectric reservoir to prevent the drinking water quality from deteriorating.