ICP-OES测定浮游有孔虫的Mg/Ca���值及其在SST分析中的应用

海洋是驱动大气环流的主要“引擎”，海表温度（SST）又是揭示海洋环境变化的重要参数。利用有孔虫Mg/Ca���值恢复SST具有较高精密度，是目前恢复SST较成功的方法之一。本论文旨在建立一套有效的有孔虫清洗方法和ICP-OES测试有孔虫Mg/Ca���值的分析方法。 文中分析了53份西菲律宾海区(N18°40.23′，E135°37.11′；水深3225m)表层沉积物中浮游有孔虫Globigerinoides ruber（白色）Mg/Ca���值。结合本研究区的特点，文中使用的清洗方法是有孔虫Mg/Ca���值测试常用的“Mg”清洗方法，主要是由以下步骤构成：①用超纯水和甲醇在超声波水浴中清洗，②显微镜下剔除深色硅酸盐颗粒，③用氧化试剂去除有机质(加入30%H2O2和0.1M NaOH溶液在90℃左右的沸水浴中加热)，④酸洗(250μl 0.001N HNO3 超声波水浴中清洗10S)。清洗干净的样品经超纯硝酸溶解成溶液后，利用电感耦合等离子体发射光谱(ICP-OES)对其进行Mg/Ca���值的分析测试。仪器操作条件如下：辅助气流量（Ar）为0.5L/min（0.5L/min-1.5L/min），雾化器压力为0.2Mpa（0-0.4Mpa），泵速为20rpm（0-125rpm），高频输出功率（RF）为1150W（750W-1500W），火焰高度为15.5mm（8-21mm），通过多次重复测量一组Mg/Ca=3.333mmol/mol的标准溶液，其Mg/Ca���期精密度<0.5%,长期精密度为1%。53份样品之间Mg/Ca���值的RSD为2.7%，利用Lea(2000)建立的太平洋地区浮游有孔虫G. ruber(白色)的Mg/Ca���SST的校正公式:Mg/Ca(mmol/mol) ＝0.30exp[0.089×SST(℃)]，得到本研究区的SST为28℃±0.3℃。

INVOLVEMENT OF CA(2+) SIGNALING PATHWAY DURING OOCYTE MATURATION OF THE NORTHERN QUAHOG MERCENARIA MERCENARIA

In many molluses, it has been found that Ca2+ signaling pathway is involved in the resumption of meiotic maturation in oocytes. To better understand the possible role of Ca2+ signaling pathway in regulating meiotic maturation in oocytes of the northern quahog Mercenaria mercenaria, free extracellular Ca2+, A23187 (calcium ionophore), verapamil (calcium channel blocker), and trifluoperazin (calmodulin antagonist) were used to incubate oocytes or serotonin-induced oocytes by pharmacological methods. Results show that extracellular Ca2+ (50 similar to 200 mM) and A23187 (1 similar to 10 mu M) can stimulate the meiotic maturation. In addition, verapamil (1 similar to 100 mu M) and trifluoperazin (10 similar to 1,000 mu M) could inhibit serotonin-induced oocyte maturation. Therefore, Ca2+ is essential for the reinitiation of meiotic maturation in oocytes of the northern quahog. Moreover, an increase i [Ca2+]i can promote meiotic maturation.

低氧对高原鼠兔肝细胞内质网和心肌肌浆网Ca~(2+)泵的影响

模拟高原低氧条件研究高原鼠兔肝细胞内质网(Endoplasmic reticulum , ER ) 和心肌肌浆网(Sarcoplasmic reticulum , SR) 钙泵功能变化。实验设对照组(海拔2 300 m ) 和两个低氧实验组(模拟海拔5 000m 和7 000m )。24 h 急性低氧时, 海拔5 000 m 组高原鼠兔ER 的Ca2+ 泵活性无变化, 海拔7 000 m 组高原鼠兔ER Ca2+泵活性下降29102%。7 d 亚急性低氧时高原鼠兔SR 的Ca2+泵活性无显著变化。高原鼠兔ER 的Ca2+泵活性在海拔5 000 m 组和7 000 m 组分别升高32.50% 和33.33%。25 d 慢性低氧时高原鼠兔ER , SR 的Ca2+ 泵活性均无显著变化.表明: 急性低氧对Ca2+泵功能有抑制作用, 低氧7 d 后抑制缓解, 至25 d 低氧时趋于恢复。

中-新元古代海洋的硫和碳同位素的演化

Data on seawater carbon isotope in the Mesoproterozoic and Neoproterozoic is abundant. However, the sulfur isotopic age curve of seawater sulfates determined through the analysis of sulfur isotopic composition of marine evaporite is uncertain in the Mesoproterozoic and Neoproterozoic since evaporites are generally rare in Precambrian. The Mesoproterozoic and Neoproterozoic Carbonate Formations preserve not only the carbon isotopic records, but also the sulfur isotopic records of coeval seawater in the Huabei Platform and the Yangtze Platform, China. Sulfur isotopic composition can be determined by the extraction of trace sulfate from carbonate samples. Successive measurements of sulfur and carbon isotopic compositions of carbonate samples from the Mesoproterozoic and Neoproterozoic strata in the Huabei Platform and the Yangtze Platform was accomplished through the extracting of trace sulfate from carbonates. Sulfur and carbon isotopic compositions of coeval seawater were obtained from analytical results of sulfur and carbon isotopes of the same sample without diagenetic alteration. The high-resolution age curve of sulfur isotope given in this paper may reflect the trend of variations in sulfur isotope composition of seawater sulfates during the Mesoproterozoic and Neoproterozoic. It can be correlated with the characteristics of variation in age curve of carbon isotope of coeval seawater carbonates. The δ34S values of seawater varied from +10.3-37.0‰ during the Mesoproterozoic, which took on oscillated variation on the whole. The δ34S values took on high values in the Mesoproterozoic Chuanlinggou stage, Tuanshanzi stage Tieling stage and in Neoproterozoic Jing'eryu stage. The average of those was about +30‰. The sulfates have low δ34S values in the Mesoproterozoic Yangzhuang stage and Hongshuizhuang stage, The average of those was all lower than +20‰. There occured large-amplitude changs in δ34S values of seawater during the Mesoproterozoic. Large-amplitude oscillate of 534S values occured in the intervals of 1600~1400Ma and 1300~1200Ma. The δ13C values of seawater are mostly negative in Changcheng stage of late Paleoproterozoic, -0 ± 1‰ range in Jixian stage of Mesoproterozoic , and the positive 2±2‰ commonly in early Neoproterozoic Jing'eryu stage. From 1000 Ma to 900 Ma, about 108 years interval of oceanic 513C record is shortage. At the end of Paleoproterozoic (1700 - 1600 Ma), the oceanic 813C values change from -3‰ to 0‰, but strongly oscillate near 1600 Ma. Two larger variations of seawater 513C values occur in the Mesoproterozoic: one is a cycle of about 4%o happens at ca. 1400 Ma; another is rise from >2‰ to>5‰ at ca. 1250 Ma and then become stable at the near 1000 Ma. There appears a large positive excursion over +20‰ in 534S value of ancient seawater sulfates in the early Doushantuo stage. Simultaneously, 8 C values of ancient seawater occur a positive excursion reaching 10‰. These allow δ4S values and 513C values to reach high values of+51.7‰ and +6.9‰, respectively. The range of variation in 834S values of seawater is relatively narrow and 513C values are quite high in the middle Doushantuo stage. Then, δ34S values of seawater become oscillating, the same happens in δ13C values. Negative excursions in 834S values and 813C values occur simultaneously at the end of the Doushantuo stage, and the minimum of δ34S values and δ13C values dropped to -11.3‰ and -5.7‰, respectively. The ancient seawater in the Dengying stage has high δS values and δ13C values. Most of the δ34S values of the trace sulfate samples varied between +23.6‰ and +37.9‰ except two boundaries of the Dengying Formation, and the S13C values of the carbonate samples of the Dengying Formation varied between +0.5‰ and +5.0‰. There appeared large negative excursion in 834S values and δ13C values of ancient seawater at the bounder of Precambrian-Cambrian. The isotopic characteristics of sulfur and carbon implicated that the organic productivity and isotopic fractionation caused by biology were low and the palaeoceanic environment was quite unstable during the Mesoproterozoic. The increase and subsequent oscillation of seawater δ13C value occurred from 1700 to 1600 Ma and near 1300 Ma may be responsible to the two global tectonic events happened at coeval time. The characteristics of variation in sulfur and carbon isotopes of ancient seawater imply strong changes in oceanic environment, which became beneficial to inhabitation and propagation of organism. The organic production and the burial rate of organic carbon once reached a quite high level during the Doushantuo stage. However, the state of environment became unstable that means the global climate and the environment possibly were fluctuating and reiterating after the global glaciation. The negative excursions of S34S values and δ13C values occurring at the end of the Doushantuo stage represent a global event, which might be relative to the oxidation of deep seawater. The isotopic characteristics of sulfur and carbon implicated that there were a high organic productivity and a high burial rate of organic carbon in the Dengying stage. It is obvious that the palaeoceanic environment in Dengying stage was stable corresponding and beneficial for biology to inhabit and propagate except for the two boundaries. The tendency of sulfur and carbon isotopic variations maybe resulted from the gradual oxygenation of ocean environment during the Dengying stage. It has been reported that the secular variations of the sulfur isotopic compositions in seawater was negative correlated with that of carbon isotopic compositions. However, our results show that it is not the case. They were negatively correlated in some intervals and positively in some other intervals of the Mesoproterozoic and Neoproterozoic. The difference in correlation may be associated with the changes in conditions of redox in oceanic environment, e.g. sharp change of the oxidation-reduction interface. The strong changes in global environment may induce the abnormality to occur in the biogeo chemical S and C cycles in the ocean and accordingly sharp Variations in isotopic composition of seawater sulfur and carbon during the Mesoproterozoic and Neoproterozoic. Simultaneously, the global tectonism caused large changes of 87Sr/86Sr ratios. The leading factor that causes the variation in isotopic composition is different in the different intervals of the Mesoproterozoic and Neoproterozoic. Thus, there may exist different models of the biogeochemical S and C cycles in the ocean during the Mesoproterozoic and Neoproterozoic.

内蒙古岱海DH99a岩芯沉积物碳含量变化与湖区全新世气候变迁

Daihai Lake, a graben-type closed lake, lies ca. 10 km east of Liangcheng County, Inner Mongolia, north-central China. For its location at the transition of semi-humid and semi-arid areas, and in the north edge of the East Asian monsoon, the lake is sensitive to changes in climate and environment. Based on analyses of total inorganic carbon (TIC), total organic carbon (TOC) and the ratio of total organic carbon to total nitrogen (C/N ratio) of DH99a core sediments recovered in the central part of Daihai Lake, the data suggest Holocene climatic history of the lake region is reconstructed. In this paper, the TIC and TOC contents of the lake sediments are closely related to climate changes. 1) Changes in TIC content of the lake sediments is closely related to climate, which directly reflect changes of temperature in the lake region, i.e., higher TIC content is linked with warmer temperature and stronger evaporation; 2) Changes in TOC and C/N ratio reflect the regional precipitation, i.e., relatively higher TOC content and C/N ratio indicate higher rainfall which results in stronger river flow and more organic matter entering into the lake. Data of the TIC content, TOC content and C/N ratio of DH99a core sediments suggest that climatic history of the Daihai Lake region is characterized by 4 stages. During the interval of ca. 11200-7500 a BP, higher TIC content, relatively lower TOC content and C/N ratio value indicate a warmer and slight dry condition over the lake area. From ca. 7500 to 4500 a BP, high values of TIC content, with an increase in TOC content and C/N ratio suggest the climate was warm and humid. Changes of TIC content, TOC content show that both temperature and precipitation displayed obvious fluctuations during the period, i.e., slightly cool and humid ca. 7500-6700 a BP, warm and moist ca. 6700-5300a BP, mild and comparatively humid ca. 5300-4500a BP. Between ca. 4500 and 2900 a BP, TIC content and TOC content decreased gradually while fluctuating, C/N ratio displayed a decreasing trend. These data imply that the climate generally became cooler and drier than the preceding period. The lowest values of TIC content, TOC content and C/N ratio during the interval of ca. 2900-0 a BP, demonstrate that the climate was severe, and became cool and dry. However the relative higher values of TIC content, TOC content and C/N ratio between ca. 1700 and 1300 a BP may denote an increase both in temperature and in precipitation. Data of TIC content, TOC content and C/N ratio in Daihai DH99a core sediments indicate that the warm period was asynchronous with the humid time, the warm interval began in ca. 11200 a BP, and ended in ca. 2900 a BP. The humid period was ca. 7500-2900 a BP. During ca. 7500^500 a BP, the climate was warm and humid, which was the climatic optimum of the Holocene Epoch in the Daihai Lake region. Data of TIC content, TOC content and C/N ratio in Daihai DH99a core sediments imply that the Holocene climate was unstable, the fluctuating events happened occasionally. Such as the cold and dry climate in ca. 4400-4200a BP, the warm and humid climatic condition in the period between ca.1700 and 1300a BP.

生物壳体Sr／Ca���Mg／Ca���^87Sr／^86Sr比值在恢复古气候、古环境中的应用—以小渡口剖面为例

生物壳体的Sr/Ca���Mg/Ca���值能反映其沉积水体的Sr/Ca���Mg/Ca���值，在一定条件下反映水体的盐度、温度，并分别与宿生水体的盐度、温度呈正比关系。生物壳体的^87Sr/^86Sr比值是恢复盆地古水文条件的一种重要手段。本文以著名的泥河湾盆地小渡口剖面的第28层为实例，力图通过对有孔虫、介形虫、腹足类生物壳体Sr/Ca���Mg/Ca���值与^87Sr/^86Sr比值的对比研究，并结合前人所作的中更新世古地理特征研究，来恢复生物壳体沉积时泥河古湖水的温度、盐度，进而进行古气候、古环境的恢复。研究结果表明：在0.97-0.94Ma间，古泥河湾湖为一陆相湖泊，湖水的温度、盐度变化趋势相吻合，均呈低－高－低的演化特征，可能对应着盆地水体的扩展－退缩－扩展变化。其中，在0.96-0.95Ma间，古泥河湾湖具有较高的温度、盐度特征。生物壳体的Sr/Ca���Mg/Ca���值能反映其沉积水体的Sr/Ca���Mg/Ca���值，在一定条件下反映水体的盐度、温度，并分别与宿生水体的盐度、温度呈正比关系。生物壳体的^87Sr/^86Sr比值是恢复盆地古水文条件的一种重要手段。本文以著名的泥河湾盆地小渡口剖面的第28层为实例，力图通过对有孔虫、介形虫、腹足类生物壳体Sr/Ca���Mg/Ca���值与^87Sr/^86Sr比值的对比研究，并结合前人所作的中更新世古地理特征研究，来恢复生物壳体沉积时泥河古湖水的温度、盐度，进而进行古气候、古环境的恢复。研究结果表明：在0.97-0.94Ma间，古泥河湾湖为一陆相湖泊，湖水的温度、盐度变化趋势相吻合，均呈低－高－低的演化特征，可能对应着盆地水体的扩展－退缩－扩展变化。其中，在0.96-0.95Ma间，古泥河湾湖具有较高的温度、盐度特征。

喀斯特石灰土-灌丛系统主要养分含量分布特征研究---以贵阳花溪杨中石灰土-灌丛系统Ca���Mg、 K 、P为例

本论文通过对贵州贵阳花溪杨中喀斯特山区的植被调查与土壤样品分析, 研究土壤-植被中Ca���Mg、 K、P分布特征、变化规律及其影响因素，并在此基础上尝试Ca���位素的预处理研究，以期为喀斯特地区土壤-植被中Ca���Mg、 K、P（尤其是Ca���的生物地球化学循环研究奠定基础，同时为植被演替、物质循环研究和退耕还林还草的人工恢复提供植物自身的营养依据。本次研究取得如下认识： 1.受石灰岩母岩控制，土壤样品元素含量的特征为：CaO>MgO>K2O> P2O5。同一元素沿海拔变化有一定的相关性，并且相关性随元素的不同存在差异：随海拔高度的增加CaO含量有升高的趋势，而MgO 、K2O、Na2O含量都有所降低。表层土壤中K2O-Na2O含量正相关变化，CaO-K2O含量负相关变化。并且从土壤表层到底层在剖面-1中随深度增加，CaO、MgO、K2O含量升高，而P2O5的含量则有上升的趋势。土壤中元素的上述分布特征主要与石灰岩的风化成土作用过程中不同分化程度土壤Ca���淋失和来自高处的富钙雨水输入有关。 2.喀斯特生态环境富钙的这一特点对喀斯特灌丛植物的种类成分和营养元素含量有很大影响。地貌部位、海拔高度对植物Ca���Mg 、K、P含量也有不同程度的影响。植物Ca���Mg 、K、P含量由高到低依次为：Ca > K > Mg >P。苔藓与其它植物比较， Ca���Mg、 K、P的含量都小于其它三类较高等的植物，这一现象与其自身的生物学特性有关：苔藓植物组织结构简单，不具备发达的输导组织，不具备真正的根系，不利于从土壤等基质中吸收营养。在、灌草、灌木、藤本三类植物营养元素之间Ca –P含量具有负相关变化，Mg –P含量具有正相关变化；在所分析的植物种，P- K含量变化呈正相关，并且植物叶片Ca/K比值随着P含量的增加而显著地以指数形式减小。这是因为植物体内的K和P对于Ca���说起着平衡离子（counter ion）的作用。 3. 生境中基岩裸露和土体浅薄的特点，极大地制约了喀斯特灌丛的发育，喀斯特生境的富含钙的特点对喀斯特灌丛植物的种类成分和元素含量有很大的影响。但是杨中灌丛群落植物Ca���Mg、K、P含量和对应土壤CaO、MgO、K2O和P2O5含量相关性不明显。植物Ca���Mg、K、P元素虽主要来源于土壤，但因其含量受元素地球化学性质、植物种类、土壤元素对植物有效态的含量等因素的制约，而使植物元素含量和土壤元素的含量没有明显的相关性． 4.从Ca���位素的预处理研究来看，离子交换分离法对去除样品中的杂质效果较好。在以后测定过程中，有利于增强离子流稳定性和强度, 提高测量精度和准确度，与沉淀法相比较，此法适宜作为钙同位素样品的前处理方法。 关键词： 喀斯特 石灰土-灌丛系统 Ca���Mg、K、P含量分布 钙同位素 环境地球化学

湖泊沉积物碳氧同位素和介形虫Li/Ca���值与古环境重建

了解过去是认识现在和预测未来的基础。晚全新世是PAGES研究的目标时段之一。寻找和解译最近2000年连续、高分辨率自然记录是古气候研究的热点与难点。本项研究有针对性地选择程海、草海和青海湖开展湖泊沉积物环境记录的精细研究，结合14C、210Pb和137Cs定年，系统探讨了碳酸盐碳氧同位素、纤维素碳氧同位素、有机质碳同位素以及介形虫壳体Li/Ca���值指标的古环境指示意义。 通过研究，本论文取得了如下成果和新的认识： 1. 建立了一套有效的四阶段湖泊沉积物有机质纤维素提取方法（5%NaOH碱洗、5%HCl酸洗、亚氯酸钠和冰醋酸混合溶液漂白以及17.5%NaOH碱洗），红外光谱鉴定提取物为纯的α-纤维素，表明该实验方法是可行的，为今后广泛开展湖泊沉积物纤维素稳定同位素研究打下了坚实基础。 2. 多指标综合辨识了程海和草海沉积物碳酸盐主要是自生碳酸盐。程海和草海沉积物有机质C/N比值结合有机质碳同位素结果表明两湖的有机质分别源于水生植物藻类和大型水草。程海和草海沉积物碳酸盐含量主要反映了湖区温度的变化。 3. 程海、草海沉积物碳酸盐与青海湖沉积物介形虫壳体氧同位素组成均反映了湖区降水/蒸发比。降水/蒸发比大的湿润期，碳酸盐δ18O值小；降水/蒸发比小的干旱期，碳酸盐δ18O值大。程海沉积物碳酸盐碳同位素组成影响因素复杂，除了受大气与湖水之间的CO2交换影响外，还受水生植物光合/吸收作用的影响；草海沉积物碳酸盐碳同位素组成更大的变化范围，反映了湖区水生植物光合/吸收作用的影响，其异常的正值可能指示了湖区细菌参与有机质碳同位素分馏过程。 4. 利用草海沉积物有机质纤维素氧同位素定量恢复了湖水氧同位素组成变化。在此基础上，结合碳酸盐氧同位素组成初步恢复了草海地区过去500年来温度变化历史：草海地区在过去500年明显存在四个冷期，包括1550－1610年，1670－1730年，1770－1870年和1890－1920年冷期，其中前三个发生在传统意义上的现代小冰期时段。与其它记录研究结果的一致性表明纤维素氧同位素结合碳酸盐氧同位素是恢复古温度变化的最有效途径之一，同时也为现代小冰期在中国西南地区的存在提供了湖泊沉积学方面的证据。 5. 不同类型水生植物湖泊，湖泊沉积物有机质δ13C值对湖泊初级生产力变化的响应过程不同。大型水草为主的湖泊（草海），其沉积物有机质δ13C值随湖泊生产力的增大呈现增加的变化趋势；藻类为主的湖泊（程海），其沉积物有机质δ13C随湖泊生产力的增大呈现减小的变化趋势，藻类易降解是导致δ13C值随湖泊生产力的增大呈现减小变化趋势的主要原因。 6. 程海沉积物碳酸盐和有机质碳同位素组成的正相关变化以及草海沉积物碳酸盐和有机质碳同位素组成的负相关变化.表明湖泊生产力变化并不是导致碳酸盐和有机质碳同位素正相关变化的主要原因，湖泊水生植物类型以及湖泊大小均起着重要作用。湖泊沉积物碳酸盐与有机质之间的碳同位素分馏（△δ13C）是一种有效的湖泊生产力指示剂，即使是在有微生物参与有机质碳同位素分馏过程的草海，△δ13C值也反映了湖泊生产力的变化过程。 7. 青海湖沉积物单一种属介形虫壳体胖真星介（Eucypris inflata）Li/Ca���值与气象记录以及邻近地区都兰和祁连山树轮宽度指数恢复的古温度变化序列的对比研究揭示，介形虫壳体Li/Ca���值与温度呈明显的负相关变化（Li/Ca���值高，温度低；Li/Ca���值低，温度高），表明介形虫壳体Li/Ca���值是一种有效的古温度代用指标。 8. 青海湖沉积物单一种属介形虫壳体胖真星介（Eucypris inflata）Li/Ca���值、氧同位素与反映太阳活动的大气14C含量和冰芯10Be含量的一致性变化表明青海湖地区温度和降雨量的同步变化主要受太阳活动控制。