北半球大气中CCl3F和CCl2FCClF2随纬度变化的特征和趋势研究

从1999年7月到9月作者与中国极地考察队合作，从北半球中纬度到北极圈地区进行了大规模的气体样品采样.运用气相色谱电子捕获检测器得到了随纬度变化的CFCs的特征浓度，并从地理位置和气象条件对所有样品的趋势进行了分析.研究结果有助于更好的理解北半球发达国家与发展中国家逐步取消卤化碳类化合物的现状和趋势.     

CCl2体系的结构和性质研究

采用组态相互作用法QClSD在6-311＋＋G^＊＊基组下对分子体系CCl2进行abinitio计算,得到该体系的两个平衡结构：Cl-CCl（X1A1）角型结构和C-ClCl（X^1∑^＋）线性结构,并计算出它们的结构、能量和力常数.Cl-CCl（X1A1）角型结构为体系的最稳定结构,属于C2v点群;线性C-ClCl（X^1∑^＋）结构为体系的另一稳定结构,属于亚稳态,其分子点群为C∞v.     

电子激发态CCl2自由基被H2O猝灭的研究

对CCl4/Ar混合气体直流脉冲放电产生CCl2自由基,再用541．52nm激光将电子基态CCl2激励到激发态A1B21（0,4,0）振动态的K＝0能级上,通过检测激发态CCl2时间分辨荧光信号,测得室温下CCl2（A1B1和a^3B1)被H2O分子猝灭的实验结果,用三能级模型分析处理实验数据,获得态分辨速率常数KA和Ka值,利用UMP2（Full）／6－31G（d,p）方法计算了该反应的势能面,揭示了反应的插入和加成－消除机理。     

N2，NO，N2O，NH3及胺类分子对电子激发状态CCl2（A^ ～1B1）自由基猝灭的动力学

对CCl4/Ar混合气体直流脉冲放电产生CCl2自由基，再用541．52nm激光将电子基态CCl2激励到激发态A^ ～1B1（0，4，0）振动态的k=0能级上，通过检测激发态CCl2时间分辨荧光信号，该信号呈双指数衰减，测得室温下CCl2(A^ ～1B1）被N2，NO，N2O，NH3及胺类分子猝灭的实验结果，用三能级模型分析处理实验数据，获得态分辨率常数KA和Ka值，并对实验结果进行了讨论。     

CO2浓度和太阳活动对北半球夏季平流层中部气温异常变化的影响

通过逐次滤波法和对比分析可知,北半球夏季7月高空10hPa持续增暖过程是以CO2为主的温室气体增加、火山活动和太阳活动共同引起的,具体表现为：（1）CO2浓度增加趋势与北半球7月平流层10hPa升温趋势基本一致．但是北半球7月10hPa升温过程不像CO2浓度一样线性增加,其中还伴随几次降温波动,最显著的一次是20世纪60年代末至70年代末,90年代中期以前的降温过程也比较清楚．分析认为,这是火山活动和太阳活动引起的．（2）太阳磁场磁性指数曲线与滤除CO2影响的北半球10hPa大气温度距平曲线变化趋势也基本一致,波峰波谷基本对应并且超前一些,就是说太阳北半球黑子群N极前导时期,即太阳磁场南向时期与北半球平流层增温时期对应．太阳北半球黑子群S极前导时期,即太阳磁场北向时期与北半球平流层降温时期对应,显示出太阳磁场方向变化对北半球平流层气温变化的重要影响．（3）谱分析结果表明,滤除趋势变化和准22年周期的7月北半球平流层中层10hPa大气温度具有显著的准11年周期,其方差贡献率1．5％．（4）分析表明CO2浓度变化与太阳磁场强度和磁场方向变化对于平流层中层10hPa温度变化的影响方差贡献率达到58％,是10hPa温度变化的决定性因素．其中CO2影响方差贡献率37％,太阳磁场强度和磁场方向变化方差贡献率21％．     

CO2浓度和太阳活动对北半球夏季平流层中部气温异常变化的影响

通过逐次滤波法和对比分析可知,北半球夏季7月高空10 hPa持续增暖过程是以CO2为主的温室气体增加、火山活动和太阳活动共同引起的,具体表现为:(1)CO2浓度增加趋势与北半球7月平流层10hPa升温趋势基本一致.但是北半球7月10 hPa升温过程不像CO2浓度一样线性增加,其中还伴随几次降温波动,最显著的一次是20世纪60年代末至70年代末,90年代中期以前的降温过程也比较清楚.分析认为,这是火山活动和太阳活动引起的. (2)太阳磁场磁性指数曲线与滤除CO2影响的北半球10 hPa大气温度距平曲线变化趋势也基本一致,波峰波谷基本对应并且超前一些,就是说太阳北半球黑子群N极前导时期,即太阳磁场南向时期与北半球平流层增温时期对应.太阳北半球黑子群S极前导时期,即太阳磁场北向时期与北半球平流层降温时期对应,显示出太阳磁场方向变化对北半球平流层气温变化的重要影响. (3)谱分析结果表明,滤除趋势变化和准22年周期的7月北半球平流层中层10 hPa大气温度具有显著的准11年周期,其方差贡献率1.5%. (4)分析表明CO2浓度变化与太阳磁场强度和磁场方向变化对于平流层中层10 hPa温度变化的影响方差贡献率达到58%,是10 hPa温度变化的决定性因素.其中CO2影响方差贡献率37%,太阳磁场强度和磁场方向变化方差贡献率21%.     

TiO2表面掺杂CeO2和NiO及光催化活性研究

以硫酸镍、硝酸铈为掺杂剂,在TiCl4水解过程中,以沉淀包覆或机械混合的掺杂方法制备了改性TiO2粉体,进行了X射线衍射表征和光催化活性评价。晶粒的长大受到了抑制,在450℃焙烧下,掺镍样品的平均粒径由未掺杂纯样品的38.2 nm减小到11.5 nm（机械混合）和8.4 nm（沉淀包覆）,掺铈样品的平均粒径则分别减小到30.5 nm和14nm;镍掺杂导致了样品在焙烧温度450℃时便有金红石相析出,而铈掺杂的样品和纯样品在相同温度下没有金红石相;通过甲苯在样品上的光催化氧化过程,证实了掺杂对样品的光催化性能有影响。在纯样品和掺镍、掺铈的样品上,130 min后甲苯的质量浓度由初始的80 mg/m3分别下降到20、2.5和8.6 mg/m3。     

CCl自由基的氧化反应机理

在UB3LYP/6-311Gd,p水平上研究了CCl自由基与O2反应的微观机理.优化得到了反应路径上各驻点的构型.研究发现,CCl+O2反应有Cl+CO2、ClO+CO和ClCO+O3种产物通道,其中Cl+CO2可能为主要反应通道.     

TiO_2表面掺杂CeO_2和NiO及光催化活性研究

以硫酸镍、硝酸铈为掺杂剂,在TiCl4水解过程中,以沉淀包覆或机械混合的掺杂方法制备了改性TiO2粉体,进行了X射线衍射表征和光催化活性评价。晶粒的长大受到了抑制,在450℃焙烧下,掺镍样品的平均粒径由未掺杂纯样品的38.2 nm减小到11.5 nm(机械混合)和8.4 nm(沉淀包覆),掺铈样品的平均粒径则分别减小到30.5 nm和14nm;镍掺杂导致了样品在焙烧温度450℃时便有金红石相析出,而铈掺杂的样品和纯样品在相同温度下没有金红石相;通过甲苯在样品上的光催化氧化过程,证实了掺杂对样品的光催化性能有影响。在纯样品和掺镍、掺铈的样品上,130 min后甲苯的质量浓度由初始的80 mg/m3分别下降到20、2.5和8.6 mg/m3。     

CH_3CCl_2与NO_2反应机理的理论研究

运用密度泛函方法BMK/6-311+G(d,p)和组合能量算法BMC-CCSD,研究了CH_3CCl_2与NO_2的反应机理,得到了体系的势能面信息和详细的反应机理.反应物发生碰撞后,其中NO_2中的N原子和O原子可以分别进攻CH_3CCl_2中-CCl_2基团上的C原子而首先形成络合物,然后从络合物开始经历一个或者多个过渡态生成产物或者直接分解成产物.共找到了11条反应通道,计算结果表明CH_3CClO和CH_3CCl_2O是反应的主要产物.     

Regional insolation forcing of late Quaternary climate change in the Southern Hemisphere

In agreement with the Milankovitch orbital forcing hypothesis it is often assumed that glacial-interglacial climate transitions occurred synchronously in the Northern and Southern hemispheres of the Earth. It is difficult to test this assumption, because of the paucity of long, continuous climate records from the Southern Hemisphere that have not been dated by tuning them to the presumed Northern Hemisphere signals. Here we present an independently dated terrestrial pollen record from a peat bog on South Island, New Zealand, to investigate global and local factors in Southern Hemisphere climate changes during the last two glacial-interglacial cycles. Our record largely corroborates the Milankovitch model of orbital forcing but also exhibits some differences: in particular, an earlier onset and longer duration of the Last Glacial Maximum. Our results suggest that Southern Hemisphere insolation may have been responsible for these differences in timing. Our findings question the validity of applying orbital tuning to Southern Hemisphere records and suggest an alternative mechanism to the bipolar seesaw for generating interhemispheric asynchrony in climate change.     

Millennial-scale climate change since the last glaciation recorded by grain sizes of loess deposits on the northeastern Tibetan Plateau

Whether climatic changes in high latitudes of the Northern Hemisphere since the last glaciation have effects on the Tibetan Plateau monsoon, and the variation characteristics of the Plateau monsoon itself are still not solved but of great significance. The 22-m high-resolution Ioess-paleosol sequence in the Hezuo Basin on the northeastern Tibetan Plateau demonstrates that the Plateau winter monsoon experienced a millennial variation similar to high latitude Northern Hemisphere, with cold events clearly correlated with Heinrich events but less for the warm events (Dansgarrd-Oeschger events). It may indicate that the climate system at high latitudes in the Northern Hemisphere had played an important role in both the Plateau monsoon and the high-level westerlies. On 10^4 year scale, there are two distinct anomalous changes, which are not found in the records from high latitude northern hemisphere, revealed by the loess grain size in the Hezuo Basin. One is that there was a considerable grain size increase at -36 kaBP, suggesting an abrupt enhancement of the Plateau winter monsoon at that time; the other is that, during 43--36 kaBP, the grain size decreased distinctly, indicating a notable weakening of the Plateau winter monsoon around that period. Both of the two anomalies suggest that the Tibetan climate may have been controlled by some other factors, besides the high latitude climatic changes in the Northern Hemisphere.     

North Pacific seasonality and the glaciation of North America 2.7 million years ago

In the context of gradual Cenozoic cooling, the timing of the onset of significant Northern Hemisphere glaciation 2.7 million years ago is consistent with Milankovitch's orbital theory, which posited that ice sheets grow when polar summertime insolation and temperature are low. However, the role of moisture supply in the initiation of large Northern Hemisphere ice sheets has remained unclear. The subarctic Pacific Ocean represents a significant source of water vapour to boreal North America, but it has been largely overlooked in efforts to explain Northern Hemisphere glaciation. Here we present alkenone unsaturation ratios and diatom oxygen isotope ratios from a sediment core in the western subarctic Pacific Ocean, indicating that 2.7 million years ago late-summer sea surface temperatures in this ocean region rose in response to an increase in stratification. At the same time, winter sea surface temperatures cooled, winter floating ice became more abundant and global climate descended into glacial conditions. We suggest that the observed summer warming extended into the autumn, providing water vapour to northern North America, where it precipitated and accumulated as snow, and thus allowed the initiation of Northern Hemisphere glaciation.     

平流层爆发性增温的时空分布特征

利用1950～2003年逐日平均NCEP资料,对平流层爆发性增温（SSW）的特征进行了统计分析,得到如下结果：北半球SSW具有多发性,在这53年里共发现了69次增温事件,平均每年一次以上,有些年份甚至出现2～3次;SSW中心位置随高度变化,在较低层（16 km附近）中心位置大部分偏于西半球的北美北部到北极地区,高层（30 km附近）附近其中心多偏于东半球欧亚大陆的北边到北极地区;北半球SSW最先发生在30 km附近的欧亚大陆以北地区,然后由上向下延伸和传递,同时中心位置也逐渐转到西半球的北美大陆北端;在北半球发生SSW期间,平流层温度场和环流场的变化也会影响到对流层,引起对流层温度场和环流场的变化.对2002年9月发生在南半球平流层的一次强爆发性增温进行分析表明,南半球的这次SSW发生时表现出的特征与北半球稍有不同,在较低层（16 km附近）SSW中心出现在东半球的南端,在较高层（25～30 km）SSW中心位于西半球的南端.     

Evidence from U-Th dating against Northern Hemisphere forcing of the penultimate deglaciation

Milankovitch proposed that summer insolation at mid-latitudes in the Northern Hemisphere directly causes the ice-age climate cycles. This would imply that times of ice-sheet collapse should correspond to peaks in Northern Hemisphere June insolation. But the penultimate deglaciation has proved controversial because June insolation peaks 127 kyr ago whereas several records of past climate suggest that change may have occurred up to 15 kyr earlier. There is a clear signature of the penultimate deglaciation in marine oxygen-isotope records. But dating this event, which is significantly before the 14C age range, has not been possible. Here we date the penultimate deglaciation in a record from the Bahamas using a new U-Th isochron technique. After the necessary corrections for alpha-recoil mobility of 234U and 230Th and a small age correction for sediment mixing, the midpoint age for the penultimate deglaciation is determined to be 135 +/- 2.5 kyr ago. This age is consistent with some coral-based sea-level estimates, but it is difficult to reconcile with June Northern Hemisphere insolation as the trigger for the ice-age cycles. Potential alternative driving mechanisms for the ice-age cycles that are consistent with such an early date for the penultimate deglaciation are either the variability of the tropical ocean-atmosphere system or changes in atmospheric CO2 concentration controlled by a process in the Southern Hemisphere.     

Northern Hemisphere forcing of climatic cycles in Antarctica over the past 360,000 years

The Milankovitch theory of climate change proposes that glacial-interglacial cycles are driven by changes in summer insolation at high northern latitudes. The timing of climate change in the Southern Hemisphere at glacial-interglacial transitions (which are known as terminations) relative to variations in summer insolation in the Northern Hemisphere is an important test of this hypothesis. So far, it has only been possible to apply this test to the most recent termination, because the dating uncertainty associated with older terminations is too large to allow phase relationships to be determined. Here we present a new chronology of Antarctic climate change over the past 360,000 years that is based on the ratio of oxygen to nitrogen molecules in air trapped in the Dome Fuji and Vostok ice cores. This ratio is a proxy for local summer insolation, and thus allows the chronology to be constructed by orbital tuning without the need to assume a lag between a climate record and an orbital parameter. The accuracy of the chronology allows us to examine the phase relationships between climate records from the ice cores and changes in insolation. Our results indicate that orbital-scale Antarctic climate change lags Northern Hemisphere insolation by a few millennia, and that the increases in Antarctic temperature and atmospheric carbon dioxide concentration during the last four terminations occurred within the rising phase of Northern Hemisphere summer insolation. These results support the Milankovitch theory that Northern Hemisphere summer insolation triggered the last four deglaciations.     

No extreme bipolar glaciation during the main Eocene calcite compensation shift

Major ice sheets were permanently established on Antarctica approximately 34 million years ago, close to the Eocene/Oligocene boundary, at the same time as a permanent deepening of the calcite compensation depth in the world's oceans. Until recently, it was thought that Northern Hemisphere glaciation began much later, between 11 and 5 million years ago. This view has been challenged, however, by records of ice rafting at high northern latitudes during the Eocene epoch and by estimates of global ice volume that exceed the storage capacity of Antarctica at the same time as a temporary deepening of the calcite compensation depth approximately 41.6 million years ago. Here we test the hypothesis that large ice sheets were present in both hemispheres approximately 41.6 million years ago using marine sediment records of oxygen and carbon isotope values and of calcium carbonate content from the equatorial Atlantic Ocean. These records allow, at most, an ice budget that can easily be accommodated on Antarctica, indicating that large ice sheets were not present in the Northern Hemisphere. The records also reveal a brief interval shortly before the temporary deepening of the calcite compensation depth during which the calcite compensation depth shoaled, ocean temperatures increased and carbon isotope values decreased in the equatorial Atlantic. The nature of these changes around 41.6 million years ago implies common links, in terms of carbon cycling, with events at the Eocene/Oligocene boundary and with the 'hyperthermals' of the Early Eocene climate optimum. Our findings help to resolve the apparent discrepancy between the geological records of Northern Hemisphere glaciation and model results that indicate that the threshold for continental glaciation was crossed earlier in the Southern Hemisphere than in the Northern Hemisphere.     

Late Pliocene Greenland glaciation controlled by a decline in atmospheric CO2 levels

It is thought that the Northern Hemisphere experienced only ephemeral glaciations from the Late Eocene to the Early Pliocene epochs (about 38 to 4 million years ago), and that the onset of extensive glaciations did not occur until about 3 million years ago. Several hypotheses have been proposed to explain this increase in Northern Hemisphere glaciation during the Late Pliocene. Here we use a fully coupled atmosphere-ocean general circulation model and an ice-sheet model to assess the impact of the proposed driving mechanisms for glaciation and the influence of orbital variations on the development of the Greenland ice sheet in particular. We find that Greenland glaciation is mainly controlled by a decrease in atmospheric carbon dioxide during the Late Pliocene. By contrast, our model results suggest that climatic shifts associated with the tectonically driven closure of the Panama seaway, with the termination of a permanent El Ni?o state or with tectonic uplift are not large enough to contribute significantly to the growth of the Greenland ice sheet; moreover, we find that none of these processes acted as a priming mechanism for glacial inception triggered by variations in the Earth's orbit.     

Surface ozone observations during voyages to the Arctic and Antarctic regions

Surface ozone concentration and UV-B data between 75° N and 70° S were obtained aboard the Chinese polar scientific vessel “Xue -long” (Snow-Dragon) during the first voyage to the Arctic and the 16th to the Antarctic in 1999–2000. Analysis of these data presents that variations of the surface ozone concentration have small amplitude during voyages except the mid-latitude in the Northern Hemisphere. As a whole, average surface ozone concentration in the Northern Hemisphere is higher than that in the Southern, and high value occurred when the ship sailed close to the continents. The average diurnal variations of the surface ozone in the Northern Hemisphere are also higher compared to the southern counterparts, and high diurnal variations were found at low latitudes, and relative low level in the polar region.     

Recent Northern Hemisphere tropical expansion primarily driven by black carbon and tropospheric ozone

Observational analyses have shown the width of the tropical belt increasing in recent decades as the world has warmed. This expansion is important because it is associated with shifts in large-scale atmospheric circulation and major climate zones. Although recent studies have attributed tropical expansion in the Southern Hemisphere to ozone depletion, the drivers of Northern Hemisphere expansion are not well known and the expansion has not so far been reproduced by climate models. Here we use a climate model with detailed aerosol physics to show that increases in heterogeneous warming agents--including black carbon aerosols and tropospheric ozone--are noticeably better than greenhouse gases at driving expansion, and can account for the observed summertime maximum in tropical expansion. Mechanistically, atmospheric heating from black carbon and tropospheric ozone has occurred at the mid-latitudes, generating a poleward shift of the tropospheric jet, thereby relocating the main division between tropical and temperate air masses. Although we still underestimate tropical expansion, the true aerosol forcing is poorly known and could also be underestimated. Thus, although the insensitivity of models needs further investigation, black carbon and tropospheric ozone, both of which are strongly influenced by human activities, are the most likely causes of observed Northern Hemisphere tropical expansion.