Identification and occurrence of novel C36–C54 3,4-dialkylthiophenes with an unusual carbon skeleton in immature sediments

A series of novel long-chain 3,4-dialkylthiophenes (C₃₆–C₅₄) was identified in a number of sediments ranging from Pleistocene to Cretaceous. The identifications were based on mass spectral characterisation, desulphurisation and mass spectral data of synthesised model compounds. These organic sulphur compounds are probably formed by sulphur incorporation into mid-chain dimethylalkadienes with two methylenic double bonds. These putative precursor lipids are unprecedented and may be considered rather unusual. The distribution of 3,4-dialkylthiophenes in sediments varies considerably with the depositional palaeoenvironment, indicating that these compounds have a potential as molecular markers reflecting changes in palaeoenvironment.     

太阳紫外光谱及NO2光解系数的观测

本文讨论了利用自动太阳光谱仪测量地面的紫外辐射光谱,并进一步计算了NO_2的光分解系数.光谱测量范围为310—375nm.测量结果表明,在北京地区秋季NO_2的光解系数变化在(1—4)×10~(-3)S~(-1),有明显的日变化.     

Beeinflussung der Enzymaktivität einer Protease durch Huminstoffe Influence of Humic Substances on the Activity of a Protease

This paper deals with the influence of different humic substances (HS) on the enzyme activity (EA) of the proteolytic enzyme pronase E. The EA was determined by analyzing the concentration of the amino acid valine hydrolyzed from caseine. For amino acid analysis, a flourescence detector was used after precolumn derivatization and HPLC-separation of the hydrolysis products. The data show that the presence of HS has no adverse effects on amino acid analysis. Based on this result, a decrease of EA was observed in the presence of HS acting as enzyme inhibitors. Clear inhibition effects could be seen for different fulvic acids (HO3 FA, FBR FA and FBR 1.0 FA) at concentrations of 150 mg/L. In case of FBI-2 FA, higher concentrations were necessary to decrease the EA significantly. At an inhibitor concentration of 1500 mg/L the EA was mostly found to be less than 50%. The standard deviations of the results don't allow a differentiation between the HS of different origin and treatment. Specifying HS according to their influence on EA has to remain uncertain. As shown in a kinetic study of the hydrolysis of L-Leucine-2-naphthylamide-hydrochloride, the inhibitor HO3 FA decreases the maximum velocity of the reaction but has no effect on the Michaelis constant. These results indicate that this HS acts as a noncompetitive inhibitor.     

Field measurements of NO and NO2 emissions from fertilized and unfertilized soils

Field measurements of NO and NO₂ emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO _x detector allowing the determination of minimum flux rates of 2 g N m^-2 h^-1 for NO and 3 g m^-2 h^-1 for NO₂.The NO and NO₂ flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO₂, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO₂. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO₂ emission rates were positively correlated with soil moisture in the upper soil layer.The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO₂ equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO₂. The soil acted as a net sink for ambient air NO and NO₂ mixing ratios higher than the equilibrium values and a net source for NO and NO₂ mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO₂ are formed and destroyed concurrently in the soil.Average flux rates measured on bare unfertilized soils were about 10 g N m^-2 h^-1 for NO₂ and 8 g N m^-2 h^-1 for NO. The NO and NO₂ flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO₂.Application of mineral fertilizers increased the NO and NO₂ emission rates. Highest emission rates were observed for urea followed by NH₄Cl, NH₄NO₃ and NaNO₃. The fertilizer loss rates ranged from 0.1% for NaNO₃ to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.The total NO _x emission from soil is estimated to be 11 Tg N yr^-1. This figure is an upper limit and includes the emission of 7 Tg N yr^-1 from natural unfertilized soils, 2 Tg N yr^-1 from fertilized soils as well as 2 Tg N yr^-1 from animal excreta. Despite its speculative character, this estimation indicates that NO _x emission by soil is important for tropospheric chemistry especially in remote areas where the NO _x production by other sources is comparatively small.     

Biological marker compounds as indicators of the depositions! history of the Maoming oil shale

The Eocene Maoming oil shale from Guangdong Province occurs as a laterally uniform stratigraphic section, typically 20–25 m thick, from which the aliphatic hydrocarbon constituents of six representative samples were investigated using GC and C-GC-MS. The sediments evaluated included the basal lignite, a vitrinite lens from the overlying claystone, and four intervals from the massive oil shale bed. As expected, the lignite and vitrinite differ markedly from the oil shales. The lignite is dominated by bacterial hopanoids and components of higher plant origin, including C₂₉ steroids and triterpenoids such as oleanenes. Visually, the oil shale samples show corroded and degraded phytoclasts, spores, wispy particles of fluorescent organic material attributable to dinoflagellates and, especially in the uppermost sample, colonial algal bodies. The distributions of biological markers in the oil shales show many features in common, notably a dominance of dinoflagellate-derived 4-methylsteroids, and a significant proportion of higher-plant derived n-alkanes with marked odd-over-even carbon number predominance. Overall, they exhibit several features that resemble characteristics of the Messel shale. The hydrocarbons of the lowest shale horizon suggest that there may have been a gradual transition between deposition of the original peat and the subsequent oil shales. The aliphatic hydrocarbons of the uppermost shale are dominated by a number of C₃₁ and C₃₃ botryococcane homologues and other unusual branched alkanes possibly derived from green algae. All of the samples are immature. Overall, molecular and microscopic examination of the stratigraphic succession of the Maoming oil shale suggests a shallow, lacustrine environment within which peats were deposited. This lake subsequently deepened to support abundant algal populations, especially dinoflagellates, culminating in a dominance of botryococcoid algae.     

北部湾盆地不同凹陷原油生物标志物分布与组成特征

通过对取自北部湾盆地不同凹陷典型原油样品中各类生物标志物的分布与组成特征的系统分析，发现盆地北部的涠西南凹陷和乌石凹陷所产原油具有姥植比低和奥利烷与各类重排构型生物标志物含量低，而C26+长链三环萜烷系列和C304 甲基甾烷含量高的特点，且其三环萜烷系列呈现以C23为主峰的正态分布，指示了该类原油的烃源岩沉积时水体较深，还原性相对较强，且原始生烃母质以藻类为主；而南部福山凹陷和迈陈凹陷所产的原油则具有姥植比高和奥利烷与各类重排构型生物标志物含量高的特征，而C26+长链三环萜烷系列和C304 甲基甾烷含量低，且其三环萜烷系列呈现C19—C26阶梯状依次降低，表明这类原油的烃源岩沉积时水体较浅，还原性相对较弱，且原始生烃母质中被子植物来源的陆源有机质贡献较大。由此表明北部湾盆地南北不同凹陷第三纪的沉积特征和有机质生源构成存在显著差异。     

Heat capacity of γ-Fe2SiO4 between 5 and 303 K and derived thermodynamic properties

A multi-anvil device was used to synthesize 24 mg of pure γ-Fe₂SiO₄ crystals at 8.5 GPa and 1,273 K. The low-temperature heat capacity (C _p) of γ-Fe₂SiO₄ was measured between 5 and 303 K using the heat capacity option of a physical properties measurement system. The measured heat capacity data show a broad λ-transition at 11.8 K. The difference in the C _p between fayalite and γ-Fe₂SiO₄ is reduced as the temperature increases in the range of 50–300 K. The gap in C _p data between 300 and 350 K of γ-Fe₂SiO₄ is an impediment to calculation of a precise C _p equation above 298 K that can be used for phase equilibrium calculations at high temperatures and high pressures. The C _p and entropy of γ-Fe₂SiO₄ at standard temperature and pressure (S°₂₉₈) are 131.1 ± 0.6 and 140.2 ± 0.4 J mol⁻¹ K⁻¹, respectively. The Gibbs free energy at standard pressure and temperature (ΔG° _f,298) is calculated to be −1,369.3 ± 2.7 J mol⁻¹ based on the new entropy data. The phase boundary for the fayalite–γ-Fe₂SiO₄ transition at 298 K based on current thermodynamic data is located at 2.4 ± 0.6 GPa with a slope of 25.4 bars/K, consistent with extrapolated results of previous experimental studies.     

青藏高原崇测冰芯氯离子、硫酸根离子记录

通过对青藏高原崇测冰帽一支18．70m冰芯中Cl^-、SO4^2-离子含量变化的分析表明，20世纪90年来Cl^-、SO4^2-离子含量在波动中呈下降趋势，两种离子的周期性波动变化相似，20世纪晚期比早期和中期的波动幅度小，总体上离子含量逐渐减少与温度在波动中上升相一致，但每一次温度的升高与离子含量的下降并非一一对应。陆源物质和青藏高原上的盐湖是冰芯中Cl^-、SO4^2-离子的主要贡献者。揭示了研究地区大气成分和环境变化与气候变化的关系及亚洲粉尘在全球环境变化中的源区地位。     

海南三亚地区S4指数与C/N、ROTI的比较分析

本文通过利用海南三亚站（1834°N, 10962°E）GPS闪烁/TEC接收机2004年8月到2005年7月间观测数据，在对三亚地区闪烁初步统计分析的基础上，比较分析了观测数据中S₄（幅度闪烁指数）和C/N（载噪比），S₄和ROTI（TEC变化率标准差）的关系，同时对2004年11月7日的闪烁事件进行了具体的分析. 通过比较分析得出：（1）三亚地区全年的闪烁强度具有明显的半年变化，在春秋季出现全年闪烁强度的最大值；（2）S₄与C/N具有很好的负相关性；（3）ROTI可以作为由小尺度不规则结构引起闪烁出现的指示剂.     

High-resolution climate variability of southwest China during 57-70 ka reflected in a stalagmite δ18O record from Xinya Cave

A 26-cm-long stalagmite (XY2) from Xinya Cave in northeastern Chongqing of China has been ICP-MS ²³⁰Th/U dated, showing a depositional hiatus at 2.3 cm depth from the top. The growth of the 2.3–26 cm interval determined by four dates was between 57 ka and 70 ka, with a linear growth rate of 0.023 mm/a. We have analyzed 190 samples for δ ¹⁸O and δ ¹³C, mostly in the 2.3–26 cm part. The δ ¹⁸O and δ ¹³C values between 57 ka and 70 ka reveal decadal-to-centennial climatic variability during the glacial interval of Marine Isotope Stage 4 (MIS4), exhibiting much higher resolution than that of the published Hulu and Dongge records during this interval. Speleothem δ ¹⁸O in eastern China, including our study area can be used as a proxy of summer monsoon strength, with lighter values pointing to stronger summer monsoon and higher precipitation, and vice versa. Two decreases in the δ ¹⁸O signature of XY2 record around 59.5 and 64.5 Ka are argued to correspond to the Dansgaard-Oeschger (D-O) events 17 and 18 respectively. The Heinrich event 6 (H6) can be identified in the record as a heavy δ ¹⁸O peak around 60 ka, indicating significant weakening of the monsoon in Chongqing during the cold period. The XY2 δ ¹⁸O record shows very rapid change toward to the interstadial condition of the D-O event, but more gradual change toward to the cold stadial condition. This phenomenon found in the Greenland ice core records is rarely observed so clearly in previously published speleothem records. According to SPECMAP δ ¹⁸O record, the glacial maximum of MIS 4 was around 64.5 ka with the boundary of MIS 3/4 around 60 ka. Unlike the marine record, the speleothem record of XY2, China, exhibits much high frequency variations without an apparent glacial maximum during MIS 4. However, the timing of MIS 3/4 boundary seems to be around 60 ka when the H6 terminated, in agreement with the marine chronology. The growth period of sample XY2 during glacial times probably reflects a local karstic routing of water, rather than having climatic significance. Supported by the National Natural Science Foundation of China (Grant Nos. 40672165, 90511004, 40672202) and the Academician Special Project of Chongqing Science Committee (Grant No. 2003-7835)