甲烷氧化偶联La-Mn-Li系复合氧化物催化剂的研究

用XRD、IR、XPS和SEM等方法研究了混合氧化物LiLa_(1-x)Mn_xO_2的结构和它们对甲烷氧化偶联的催化性能。结果表明,随着MnO_2的变化,可形成一系列复合氧化物,其中三元复合氧化物La_2Mn_(1-y)Li_yO_4是甲烷氧化偶联的活性相,由于Li~+部分取代Mn~(2+)形成Li~+-O~--Mn(2+)缺陷簇,增加了活性氧种的浓度和再生速度是这种氧化物具有较高甲烷偶联活性的主要原因。脉冲实验证明,CH_4脱氢生成CH_3·偶联生成C_2H_6,进一步氧化脱氢生成C_2H_4都可在催化剂表面完成,而CO和CO_2是在气相反应中生成的。在780℃C_2收率可达23.9%。

非加热TiO_2气敏元件

本文首次报道了非加热SnO_2—TiO_2气敏元件。该元件不掺任何贵金属,不加热,对 H_2、煤气、LPG有较高灵敏度,响应时间7秒左右,恢复时间小于19秒,老化实验11个月,气敏性不变,低功耗,0.1瓦左右。对CO和CH_4不敏感,有一定选择性。通过IR、BET、以及温度与元件电阻的关系,探讨了元件的机理。

芳香聚酰亚胺气体分离膜

芳香聚酰亚胺一直在电子、复合材料及粘接剂等领域广泛地应用。最近,聚酰亚胺膜已用于气体的分离过程。这是因为芳香聚酰亚胺是具有高玻璃化温度的玻璃态聚合物,它对小分子比大分子有更大的选择透过性,高选择性是与玻璃态聚合物的僵硬主链,对不同尺寸的分子提供筛分作用相连系的。新开发的芳香聚酰亚胺膜是用联苯四甲酸二酐与芳香二胺缩聚制备的聚酰亚胺溶液制造的。这种中空纤维状的膜是由一个多孔结构支撑的一个很薄的外表面组成的。它可通过聚合物溶液采用干——湿法过程纺丝而成,经溶剂交换干燥,外层的致密部分由计算可知厚度低于0.1μm。它对H_2与CO、CH_4.N_2及其它气体的分离有高度的选择性。由于它具有聚酰亚胺特有的耐高温性能,所以可以在很广的气体加工条件下使用。这种膜对水蒸气有很高的透过性,因而也可用于有机蒸气的脱水,或空气干燥。此膜对水蒸气的透过速度为乙醇的100～200倍。30%的乙醇水溶液,经一次膜分离,浓度可提高到99%。空气干燥系统可产出达到-50℃露点的空气。

舍饲绵羊甲烷和二氧化碳的日排放动态

运用密闭呼吸代谢箱系统,对3只舍饲绵羊24h（有间断）甲烷（CH_4）和二氧化碳（CO_2）日排放特征进行了研究。供试3只甘肃细毛羊体况相近（平均体重为（25±5）kg）,其基础日粮为燕麦干草和玉米精料,粗精比为6∶4。结果表明：供试绵羊CH_4和CO_2的平均排放量分别为11g/d和147g/d,CH_4排放的峰值分别出现在17：00和22：00左右,达0.4217g/h和0.8082g/h,直到0：00降至最小为0.2993g/h;之后趋于平稳,次日8：00左右再次达到排放高峰,排放量为0.6587 g/h。而CO_2在各个测定时间段内差异不显著（p〉0.05）。因此,舍饲条件下绵羊CH_4和CO_2排放量动态（g/m in）变化不同步。由此,推算出舍饲绵羊（25±5）kg年排放CH_4和CO_2总量分别约为4.38 kg和53.66 kg。

黄土中主要温室气体组分特征

Scientists have paid much attention to the greenhouse effects and the greenhouse gases for the fact of global warming. There are many uncertainties in the prediction of future climatic change. One of the important reasons causing the uncertainties is insufficient researches of the sources and sinks of greenhouse gases, especially, there is a missing sink in the global carbon cycle. The recent researches proposal that there may be an important carbon sink in the middle-latitude terrestrial ecosystems (vegetation and soil) in the North Hemisphere, despite that there is much disputation about its position and amplitude. Chinese loess is located in the middle latitude area in the North Hemisphere, what kind of role does it play in and how does it influence on the balance of the global greenhouse gases budget? For this reason, many samples were taken and analyzed from wide range and multi-stratum of Chinese loess to understand characteristics of major greenhouse gases in loess and loess possible effect on global greenhouse gas budget. Using self-made spiral corer, we totally took 81 gas samples and 65 soil samples from 7 loess profiles in China such as Zhaitang loess section of Beijing, Pianguan, Xingxian, Lishi, Puxian, Jishan loess section of Shanxi Province, and Luochuan loess section of Shaanxi Province. The gas concentrations for CO_2, CH_4 and N_2O, the contents of N_2, O_2 and carbonate, and the carbon isotopic compositions of CO_2 and carbonate in loess strata sequences are observed and measured. In addition, 19 gas samples data of the Weinan loess section, Shaanxi Province are combination with this research to study characteristics of greenhouse gases in loess. This research indicates that (1) the free gases in loess are neither paleo-atmospheric gases nor modern atmospheric gases; (2) the concentrations of CO_2, CH_4 and N_2O in loess are higher than atmospheric level; (3) the δ~(13)C of loess CO_2 shows that the CO_2 in loess mainly comes from the oxygenolysis of organic matters, but because of isotopic exchange with carbonate in loess, the carbon isotopic exchange with carbonate in loess, the carbon isotopic compositions of loess CO_2 are much more heavier than organic original CO_2; (4) the concentration of CH_4 in Malan loess is lower because it is not favorable for the decomposition of anaerobic bacteria in the Malan Loess; (5) estimation of the total amount of the carbonate in loess reveals that loess is a huge carbon reservoir (about 850PgC). In addition, the impact of the deuterogenic carbonatization during the loess accumulation on the global carbon cycle was discussed, and the preliminary conclusion is that the research work is still not enough to evaluate the effect of loess on the sources and sinks of the anthropogenic CO_2.

新疆萨瓦亚尔顿（穆龙套型）金矿床物质来源与成矿机制

萨瓦亚尔顿金矿床是我国90年代金矿地质工作者在新疆西南天山地区寻找穆龙套型金矿床的一个突破。本文通过对新疆萨瓦亚尔顿金矿床的矿石矿物组成、稀土元素地球化学、同位素地球化学以及流体包裹体特征等方面的研究，探讨了萨瓦亚尔顿金矿床地质地球化学特征、金的赋存状态及成矿流体特征、成矿流体来源，提出了该矿床的成矿机制，取得如下认识：1．流体包裹体岩相学研究表明，萨瓦亚尔顿金矿床的流体包裹体主要为V＋L相和富CO_2相包裹体，前者为NaCl-H_2O体系，后者主要有L_(CO2)、L_(CO2)+L、V_(CO2)+L、V_(CO2)＋L_(CO2)＋L相包裹体；并发现极少量含子晶流体包裹体。2．通过流体包裹体显微测温学研究，表明金矿床的均一温度成矿早阶段为270～320 ℃，成矿主阶段为170～250 ℃，成矿晚阶段为110-250 ℃，呈逐渐降低的趋势，低温成矿作用明显。3．单个流体包裹体的激光拉曼分析表明，流体包裹体中除含有CO2之外，还含有一定量的N_2和CH_4。4.成矿物质来源的复杂性。萨瓦亚尔顿金矿床矿石中微量元素组成、稀土配分模式大都反映了成矿金属物质主要来自赋矿地层本身。金属硫化物的6345：-3.4‰～+2.6‰，西南天山地区下古生界地层中广泛存在各类火山岩可能是该矿床的主要硫源，部分可能有深部物质的参与。矿石中主要脉石矿物石英和菱铁矿 中包裹体水的氢氧同位素组成为δD = -72％～-62‰，δ~(18)O ＝ -11.6‰～＋5.4‰。成矿流体主要为大气降水补给的地下卤水，并有少量岩浆水的混合。5．Ar-Ar同位素地球化学研究表明，萨瓦亚尔顿金矿床的主要成矿时代为印支晚期，210 Ma。6. 对矿石中的流体包裹体进行了温度、压力、成分、pH、含盐度等的分要的，并系统的进行了矿床形成时的物理化学条件的理论计算，基中包括EH、PH、f_(O_2)、f_(S_2)等及金在矿液运移中的搬运形式。指出减压过程或伴生沸腾的减压过程，是矿床形成过程中矿质卸载的基本机制，此外，酸蚀变过程（如绢云母化等）中由于H~+的消耗促进了溶液中pH值的升高；含高炭质的围岩，降低了矿液的氧逸度以及含矿热液与地表下渗冷水的混合等诸多因素，则是矿订形成的辅助机制。

一种新类型铜矿床的地球化学研究

本文对云南兰坪－思茅盆地中若干典型脉状铜矿进行了详细的地质地球化学研究。通过野外和镜下观察讨论了矿石组构、矿物组合及其分带特征和生成序列；对作为本区脉状铜矿主要且特征矿石矿物的黝铜矿系列成分进行了分析，据此探讨了其时空分布特征：成矿带由南到北，砷黝铜矿逐渐向锑黝铜矿过渡；富Cu贫Ag的砷黝铜矿主要分布于矿床的深部，而富Ag贫Cu的锑黝铜矿则主要分布矿体的浅部；高Ag高Sb黝铜矿和低Ag低Sb黝铜矿有可能首先从溶液中结晶出来，这主要取决于初始溶液中As与sb的原子比(X_As/X_Sb)。脉石矿物组合、REE及包裹体的研究表明，成矿流体具热卤性质，为一种富重稀土，富含CO_2、CH_4、H_2S等挥发份，中到弱碱性、弱氧化到弱还原、中高盐度的中低温热水溶液。结合矿床的微量、REE及H.O.Pb.Sr.S.C稳定同位素研究，进一步揭示，成矿流体的水主要源自大气降水；成矿金属(Cu.Ag.Pb.Zn.As.Sb.Fe.REE)、有机炭（C）及CO_2.CH_4.H_2S等矿化剂主要源自深部。通过黝铜矿的溶解实验研究，提出了黝铜矿的沉淀机理模式，认识到成矿流体的温度（T）和酸碱度（PH）是Cu.Zn.Fe.As.Sb等成矿组分共同运移和沉淀的主要控制因素。在上述研究的基础上，并通过与海相热水沉积矿床的对比，提出了本区脉铜矿系陆相热水沉积成矿作用形成，为一新类型铜矿。通过本次论文工作还获得了以下两点重要且可能具普遍意义的意认识：1）地下浅部的脉状型矿床可能是陆相热水沉积矿床的一种主要表现形式，这一认识使我们有必要对大量产于陆相环境中的浅成（中）低温热液贵金属矿床及沉积－（强）改造矿床的成因进行重新考虑和统一。2）Cu.Zn.Fe.As.Sb等组分共同迁移所需的狭窄的物化条件（尤其是温度和PH范围）是导致黝铜矿多以次要组分出现在自然界热液矿床中的主要原因。

非生物成因天然气的稳定同位素地球化学特征与判据

本采自松辽盆地的天然气进行了化学组分和氦、碳同位素分析。经空气校正后的氦同位素组成为 ~3He/~4He＝0.26 * 10~(-6)～7.48 * 10~(-6)，相应的幔源氦的贡献额为 2.3%～63%，显示了明显的幔源氦信息，表明松辽盆地天然气藏中有幔源挥发份加入。烃类气藏甲烷的灿位素组成为 δ~(13)C＝-53.3‰～-16.7‰，δ~(13)C小于-25‰ 的甲烷是生物成因的产物，δ~(13)大于-25‰的甲烷则可能是非生物成因的。甲烷及其同系物的碳同位素组成存在两类不同的分配模式。正序排列的分析模式，即 δ~(13)C_(CH_4) < δ~(13)C_(C_2H_6) < δ~(13)C_(C_3H_8) < δ~(13)C_(C_4H_(10))，表明了生物成因天然气的特征，而反序排列的分配模式，即 δ~(13)C_(CH_4) > δ~(13)C_(C_2H_6) > δ~(13)C_(C_3H_8) > δ~(13)C_(C_4H_(10))的存在则暗示了松辽盆地存在非生物成因的商业天然气藏。模拟原始太阳星云中地球吸积区条件进行了原始宇宙成因烃类的合成实验（费托反应）。对合成气进行了碳同位素组成分析，并结合反应机理讨论了费托反应中碳同位素的分馏和原始宇宙成因烃类的碳同位素分配模式。反应合成气中二氧化碳具有最重的碳同位素组成。甲烷及其同系物的碳同位素分配模式具有与生物成因烃类完全不同的反序排列特征，即 δ~(13)C_(CH_4) > δ~(13)C_(C_2H_6) > δ~(13)C_(C_3H_8) > δ~(13)C_(C_4H_(10))，这表明由原始宇宙成因烃类构成的非生物成因天然气中甲烷及其同系物的碳同位素分配的反序排列的。对非生物成因天然气的判识应依靠多项指标。作为灵敏的幔源挥发份示踪剂的氦同位素是非生物成因天然气有效的间接指示剂，甲烷及其同系物碳同位素的反序排列分配模式加上重的碳同位素组成可作为非生物成因天然气的可靠的内在指标。松辽盆地的区域构造特征，天然气中显著的幔源氦的存在，较重的甲烷同位素组成 (δ~(13)C_(CH_4) > -25‰)和甲烷及其同系物碳同位素的反序排列充分证明了松辽盆地存在非生物成因的商业天然气藏。

Carbon and nitrogen emissions from stored manure and cropped fields in irrigated mountain oases of Oman

Little is known about gaseous carbon (C) and nitrogen (N) emissions from traditional terrace agriculture in irrigated high mountain agroecosystems of the subtropics. In an effort towards filling this knowledge gap measurements of carbon dioxide (CO_2), methane (CH_4), ammonia (NH_3) and dinitrous oxide (N_2O) were taken with a mobile photoacoustic infrared multi-gas monitor on manure-filled PE-fibre storage bags and on flood-irrigated untilled and tilled fields in three mountain oases of the northen Omani Al Jabal al Akhdar mountains. During typical 9-11 day irrigation cycles of March, August and September 2006 soil volumetric moisture contents of fields dominated by fodder wheat, barley, oats and pomegranate ranged from 46-23%. While manure incorporation after application effectively reduced gaseous N losses, prolonged storage of manure in heaps or in PE-fibre bags caused large losses of C and N. Given the large irrigation-related turnover of organic C, sustainable agricultural productivity of oasis agriculture in Oman seems to require the integration of livestock which allows for several applications of manure per year at individual rates of 20 t dry matter ha^−1.

Reconstructing the last interglacial at Summit, Greenland: Insights from GISP2

The Eemian (last interglacial, 130-115 ka) was likely the warmest of all interglacials of the last 800 ka, with summer Arctic temperatures 3-5 degrees C above present. Here, we present improved Eemian climate records from central Greenland, reconstructed from the base of the Greenland Ice Sheet Project 2 (GISP2) ice core. Our record comes from clean, stratigraphically disturbed, and isotopically warm ice from 2,750 to 3,040 m depth. The age of this ice is constrained by measuring CH_4 and delta O^18 of O_2, and comparing with the historical record of these properties from the North Greenland Ice Core Project (NGRIP) and North Greenland Eemian Ice Drilling (NEEM) ice cores. The d^18 O_ice, d^15N of N_2, and total air content for samples dating discontinuously from 128 to 115 ka indicate a warming of similar to 6 degrees C between 127-121 ka, and a similar elevation history between GISP2 and NEEM. The reconstructed climate and elevation histories are compared with an ensemble of coupled climate-ice-sheet model simulations of the Greenland ice sheet. Those most consistent with the reconstructed temperatures indicate that the Greenland ice sheet contributed 5.1 m (4.1-6.2 m, 95% credible interval) to global eustatic sea level toward the end of the Eemian. Greenland likely did not contribute to anomalously high sea levels at ~127 ka, or to a rapid jump in sea level at ~120 ka. However, several unexplained discrepancies remain between the inferred and simulated histories of temperature and accumulation rate at GISP2 and NEEM, as well as between the climatic reconstructions themselves.