洞穴沉积物氧同位素计温及古气候记录研究

在人类的生存与发展中，气候变化因素的影响尤其重要，为了预测未来气候状况，就必须了解过去气候的变化历史，研究各种尺度的气候变化规律。本项工作是在桂林盘龙洞大型石笋详细沉积学研究的基础上，对其现今滴水与相应的沉积碳酸盐及洞穴环境条件进行两年以上的观测，为检验同位素平衡沉积及＾１４Ｃ的充分交换程度提出依据，与此同时，还沿石笋轴心进行系统的ＡＭＳ－＾１４Ｃ，Ｕ系及稳定同位素综合研究，提出了桂林地区３．６万     

石笋氧碳同位素古气候代用指标研究进展

洞穴石笋以其独立的绝对年龄和稳定的古气候代用指标而成为很好的陆地古气候研究材料。应用U 系定年,可以获得独立精确的日历年时间序列,结合年纹层统计,可以获得年际甚至是季节性变化古气候记录。作为古气候代用指标,石笋氧同位素具有全球可对比性,现已建立了氧同位素的全球气候变化曲线,显示了比深海氧同位素及极地冰芯氧同位素记录更多的优势。石笋δ18O 的影响因素很多,在东亚季风控制区和其它季风控制区,石笋的δ18O 反映了夏季风的强度或者是季风降雨的变化。这些全球可对比的具有高精度绝对定年的石笋δ18O 记录,突破了早期的单一温度控制机理,不仅为古气候学家提供了坚实的古气候变化时间序列,而且使古气候研究能从机理上探讨其变化规律。δ13C不如δ18O 具有全球可对比性,在同位素平衡的开放体系,石笋δ13C 主要反映了洞穴上覆土壤CO2 的同位素特征。因此,一般认为石笋δ13C可直接反映当地植被的特征,包括植被类型C3/C4 比率的变化及植被的茂盛与衰退,在一些地区也可作为大气降水和温度变化的指标。石笋δ13C 很易受到蒸发作用、滴水的快速去气、动力分馏、碳酸盐的先期沉积等影响而使得其数值偏正,应该予以重视。通过介绍石笋氧碳同位素的研究现状,使得读者对石笋的稳定同位素指标有一个初步认识。同时,对今后的研究方向给与一定的探讨。     

湖北清江石笋的碳氧同位素组成及其古气候意义

测定经铀系法和1 4 C法精确定年的石笋 (Z 2 )的碳氧同位素组成 ,探讨它们对古气候的指示意义。研究结果表明 ,研究区石笋碳酸盐氧同位素主要组成反映了地表水的氧同位素组成 ,受气候的两要素———气温和湿度控制 ;碳同位素组成则反映当地的植被面貌 ,即C3和C4植物的比例 ,间接指示古湿度。洞穴石笋稳定同位素的定量解译尚需进一步研究。     

湖北崇阳狮泉洞第四纪石笋的碳氧同位素特征及古气候研究

本文通过对湖北崇阳狮泉洞石笋的碳氧同位素分析,获得湖北地区古气候的若干变化规律:(1)16520a.(B.P.)气候相对温暖;(2)10950a.(B.P.)左右气候寒冷,之后逐渐转暖;(3)7960a.(B.P.)～5270a.(B.P.)气候温和,是人类生存最宜环境期;(4)2980a.(B.P.)左右有过一次寒冷期,之后气温又逐渐转暖。     

石笋高精度高分辨率年代学和古气候研究

古气候变化突变事件的发现和对未来环境变化的预测，提出了取得高分辨率古环境记录的要求。本文介绍了中国洞穴石笋年代学和古气候最新研究的进展以及目前我们用MAT－262质谱仪对洞穴石笋的TIMS铀系定年法对贵州荔波董歌洞、龙泉洞、衙门洞、贵州都匀七星洞洞穴次生碳酸盐石笋进行年代学研究的一些成果。     

湖北清江和尚洞石笋的高分辨率碳氧同位素及古气候研究

通过对湖北清江和尚洞HS - 2号石笋的沉积特征及碳、氧同位素特征分析, 利用U系法定年, 获取了湖北地区19.0~6.9ka的古气候、古环境信息(平均分辨率为17a, 局部分辨率达到7a).得出如下结论: (1) 19.0~16.6ka, C, O同位素偏轻, 气候冷湿; (2) 16.6~11.1ka, C, O同位素偏重, 气候干热; (3) 11.1~10.3ka干热时期中的突然回冷事件对应于新仙女木事件; (4) 10.3~6.9ka气候温和, 雨量较丰, 后期逐渐变冷.反映了历史时期湿冷、干热、温暖交替变化的气候趋势, 得出了千年级和百年级的一些气候变化趋势      

内蒙古伊克昭盟盐湖晚第四纪氧碳同位素记录及古气候研究

根据内蒙古伊克昭盟５个盐湖中６个钻孔岩心的３４０件氧碳稳定同位素样品测试数据，分析了该区的古气候变化特征。氧碳同位素记录的研究表明，盐湖水体的δ＾１３Ｃ值的湖动主要受湖泊水体中ＴＤＩＣ变化以及湖泊水体与大气间碳交换的制约。盐湖的水体环境在过去２３ｋａ之中经历了１７次明显的波动变化，提示了晚更新世冷湿－早全新世暖湿－中晚全新世暖干的晚第四纪气候变化规律及３个重要的气候事件，并预测未来全球长周期气候演     

内陆封闭湖泊自生碳酸盐氧同位素剖面的古气候意义

根据水体蒸发过程的同位素分馏方程，详细讨论了内陆封闭湖泊自主碳酸盐氧同位素剖面的古气候意义。计算结果表明，封闭湖泊水在蒸发过程中达到同位素组成稳定状态的时间小于二倍湖水平均滞留时间。因此，湖水同位素组成一般很快就达到与当时的气候环境相平衡的稳定状态，对气候环境的变化极其灵敏。湖泊自生碳酸盐的氧同位素组成则是湖泊汇水区气温、湿度和雨水同位素组成三者的函数。我国大部分地区夏季风盛行时期气候转暖，降水量     

祁连山敦德冰芯氧同位素剖面的古气候信息探究

冰芯δ~（１８）Ｏ剖面的古气候研究一直是基于大气降水同位素组成的温度效应，即冰芯δ~（１８）Ｏ值与气温呈正相关关系。我国大气降水的同位素组成研究结果表明，在亚洲季风区，由于夏季风带来贫重同位素的暖湿气团，使得季风气候区夏季雨水的δｓ值低于冬季的δｗ值，δｓ－δｗ＜０，正好和温度效应预测的相反。因此，我国季风气候区冰芯的δ~（１８）Ｏ曲线主要反映古季风的盛衰进退，即冰芯的低δ~（１８）Ｏ值对应的是夏季风盛行，气候转暖，降水量增加，夏季风前锋北移；冰芯的高δ~（１８）Ｏ值则对应夏季风强度减弱，气候转冷，降水量减少，夏季风前锋南移。用上述季风气候模式解释敦德冰芯的百年、千年、万年三个不同时间尺度的δ~（１８）Ｏ剖面，所得结果与已知的全新世古气候事件吻合。根据敦德冰芯δ~（１８）Ｏ剖面提供的古气候信息，全新世大致可分成三段四期：１０６００－７１００ａＢ．Ｐ．为早全新世，与末次冰期相比，夏季风逐渐增强，气候转暖；７１００－４０００ａＢ．Ｐ．为中全新世的前期，夏季风盛行，气候暖湿；４０００－１７００ａＢ．Ｐ．为中全新世的后期，此时夏季风退缩，气候偏干冷；１７００ａＢ．Ｐ．至今为晚全新世，其间１７００－７００ａＢ．Ｐ．夏季风强度     

矿物氧同位素模式温度计算

根据对现遥氧扩散模型的解析分析,通过模拟矿物之间的氧同位素交换轨迹进行模式温度计算,改进了常规矿物对氧同位素地质温度计方法。将模式温度计算与矿物氧－扩散封闭次上结合,建立了一个系统独立的同位素温度计算方法,因此所得到的同位素温度能够更好地反映矿物在高温岩石冷却过程中,的氧同位素交换行为;模式温度计算有如下优点：（１）考虑到了矿物之间扩散引起的同位素交换;（２）遵循质量守恒原理,更严格地适用于有限封     

大别-苏鲁造山带大理岩碳氧同位素地球化学研究

大别-苏鲁造山带的大理岩分布非常广泛,在三叠纪的陆-陆碰撞中,经受了不同程度的变质作用。本文对分布在大别地区北淮阳、苏家河、桐柏、宿松和苏鲁地区张八岭、五莲和坪上等地区的浅变质大理岩进行了碳氧同位素分析。结果发现,除了张八岭大理岩δ~(13)C值出现明显正异常(1‰～8‰)外,其他地区大理岩的δ~(13)C值均处于0±2‰(PDB)范围之内。所有地区大理岩的δ~(18)O值都有不同程度的降低,最低的δ~(18)O值达到4.5‰(SMOW)。与前人对大别-苏鲁超高压大理岩碳氧同位素研究结果相对比,我们发现大理岩δ~(13)C值分布与岩石是否经过超高压没有联系,而主要反映了其原岩沉积的时代和环境,并且其特征可以与发生在新元古代的冰川事件相关联。区域性的δ~(18)O值降低则说明,大部分岩石都经过了流体交换,并且流体的主要成分是水,含碳很少或者不舍碳,因此流体的来源是大气降水,可能与新元古代冰川溶融有关。     

硅酸盐岩中微量碳酸盐的碳氧同位素分析及其地球化学应用

硅酸盐岩中总是或多或少地含有一些微量碳酸盐，但是至今尚未对其碳氧同位素地球化学开展研究。本文建立了对硅酸盐岩中微量碳酸盐的碳氧同位素分析方法，并以大别山双河地区两种片麻岩为例，讨论了其地球化学应用。通过对比实验证明，微量法通常可将碳含量检出限降低至5μg/g。对大别山双河两种片麻岩中微量碳酸盐的碳氧同位素测量发现，黑云母副片麻与花岗质正片麻岩具有明显不同的特征。副片麻岩的碳含量较高，δ^13值为－4．5‰－0‰，批示其原岩为正常海相沉积环境，并与邻近大理岩原岩的灰岩沉积环境不同。正片麻岩的碳含量较低，δ^13值为－23．4‰－－2．1‰，反映出地表有机碳对岩浆岩原岩的混染。两种片麻岩中碳酸盐与硅酸盐全岩之间的氧同位素分馏既仍处于平衡状态，也有处于不平衡状态。不平衡分馏指示其受到过后期退变质流体的影响。不过，变质岩中微量碳酸盐的碳含量和碳机位素比值分析能够对原岩类型提供有效的区别。     

A new protocol for oxygen isotope analysis of authigenic and biogenic fine silica grains using laser-extraction technique

We report here a 30 W CO₂ laser heating protocol for analyzing oxygen isotope composition (δ¹⁸O in ‰ vs. V-SMOW) of quartz and amorphous silica grains lower than 50 and 2 μm with a good external precision (1σ < 0.15‰). This technique is used to investigate δ¹⁸O composition of macro-, micro- and crypto-crystalline quartz cements of quartzite levels occurring in a sand sequence from the South of France (Apt Series), after a physical separation of the quartz cements. δ¹⁸O data obtained from this technique are compared with δ¹⁸O data obtained from in situ ion microprobe analyses. This study also presents promising results on δ¹⁸O analysis of phytoliths obtained with the laser heating protocol (1σ < 0.1‰).     

北淮阳庐镇关岩浆岩锆石U-Pb年龄和氧同位素组成

对大别造山带北麓的北淮阳庐镇关浅变质岩浆杂岩进行了锆石阴极发光显微结构观察、激光剥蚀等离子质谱锆石U-Pb定年以及单矿物激光氟化氧同位素分析。锆石阴极发光图像显示,这些样品中的锆石具有明显的振荡环带或片状分带,为典型的岩浆锆石。少数样品的锆石具有窄的蚀变边。锆石U-Pb定年结果表明,这些岩浆岩有较一致的形成年龄,变化范围为739±8Ma～754±5Ma。岩浆岩单矿物的氧同位素组成具有较大的变化范围,其中锆石δ~(18)O为1.39‰～6.81‰,石英为3.12‰～12.47‰,斜长石为0.71‰～8.38‰。锆石的δ~(18)O值在不同岩体和/或同一岩体的不同样品之间具有明显差别,反应了其初始岩浆在氧同位素组成上的不均一性。锆石与其它矿物之间表现出显著的氧同位素不平衡,说明它们经历了岩浆期后的扰动,其中部分样品受到了亚固相条件下高温热液蚀变作用的影响,还有部分样品在岩浆后期演化过程中可能同化混染了高δ~(18)O值的围岩。大多数锆石具有低于典型地慢锆石的δ~(18)O值,表现出~(18)O亏损特征。低δ~(18)O锆石的内部结构和化学组成表现出典型岩浆锆石的特征,表明这些低δ~(18)O锆石是从亏损~(18)O的岩浆中结晶出来的,而非热液蚀变成因。这一结果证明,扬子板块北缘新元古代低δ~(18)O锆石形成于热液蚀变岩石经部分熔融所形成的低δ~(18)O岩浆。结合这些样品的形成年龄,我们认为这些低δ~(18)O岩浆的形成与Rodinia超大陆裂解有关的地幔柱裂谷岩浆活动有关,并对应于全球性的雪球地球事件。此外,这些岩石中锆石U-Pb年龄与矿物δ~(18)O分布与大别造山带高压-超高压变火成岩原岩相似,指示北淮阳单元属于俯冲的扬子板块北缘     

Two types of gneisses associated with eclogite at Shuanghe in the Dabie terrane: carbon isotope, zircon U–Pb dating and oxygen isotope

There are two types of gneisses, biotite paragneiss and granitic orthogneiss, to be closely associated with UHP eclogite at Shuanghe in the Dabie terrane. Both concentration and isotope composition of bulk carbon in apatite and host gneisses were determined by the EA-MS online technique. Structural carbonate within the apatite was detected by the XRD and FTIR techniques. Significant ¹³C-depletion was observed in the apatite with δ¹³C values of −28.6‰ to −22.3‰ and the carbon concentrations of 0.70–4.98 wt.% CO₂ despite a large variation in δ¹⁸O from −4.3‰ to +10.6‰ for these gneisses. There is significant heterogeneity in both δ¹³C and δ¹⁸O within the gneisses on the scale of several tens meters, pointing to the presence of secondary processes after the UHP metamorphism. Considerable amounts of carbonate carbon occur in some of the gneisses that were also depleted in ¹³C primarily, but subjected to overprint of ¹³C-rich CO₂-bearing fluid after the UHP metamorphism. The ¹³C-depleted carbon in the gneisses is interpreted to be inherited from their precursors that suffered meteoric–hydrothermal alteration before plate subduction. Both low δ¹³C values and structural carbonate in the apatite suggest the presence of ¹³C-poor CO₂ in the UHP metamorphic fluid. The ¹³C-poor CO₂ is undoubtedly derived from oxidation of organic matter in the subsurface fluid during the prograde UHP metamorphism.

Zircons from two samples of the granitic orthogneiss exhibit low δ¹⁸O values of −4.1‰ to −1.1‰, demonstrating that its protolith was significantly depleted in ¹⁸O prior to magma crystallization. U–Pb discordia datings for the ¹⁸O-depleted zircons yield Neoproterozoic ages of 724–768 Ma for the protolith of the granitic orthogneiss, consistent with protolith ages of most eclogites and orthogneisses from the other regions in the Dabie–Sulu orogen. Therefore, the meteoric–hydrothermal alteration is directly dated to occur at mid-Neoproterozoic, and may be correlated with the Rodinia supercontinental breakup and the snowball Earth event. It is thus deduced that the igneous protolith of the granitic orthogneiss and some eclogites would intrude into the older sequences composing the sedimentary protoliths of the biotite paragneiss and some eclogites along the northern margin of the Yangtze plate at mid-Neoproterozoic, and drove local meteoric–hydrothermal circulation systems in which both ¹³C- and ¹⁸O-depleted fluid interacted with the protoliths of these UHP rocks now exposed in the Dabie terrane.     

皖南新元古代花岗闪长岩体锆石U-Pb定年以及元素和氧同位素地球化学研究

对皖南新元古代花岗闪长岩样品进行了锆石LA-ICPMS微区U-Pb定年、全岩主微量元素分析和Sr-Nd同位素分析以及矿物氧同位素分析。结果表明,皖南花岗闪长岩中存在两个时代的岩浆锆石,在阴极发光结构图像上没有明显区别, 对应的U-Pb年龄分别为821±7Ma和881±9Ma,其中较老年龄的分析点多在锆石核部。这些岩石以富Al2O3为特点,为典型的过铝花岗岩;其全岩δ18O值高达11．1-13．6‰,显示了突出的壳源S型花岗岩的特点。但是,这些岩石具有与地幔相似的 Nd-Sr同位素组成,εNd(t)值为-2．06-0．02,初始87Sr／86Sr比值是0．7033-0．7087,指示其岩浆源区含有显著的初生地壳组分, 类似于Ⅰ型花岗岩的特点。石英、锆石、石榴石等氧同位素封闭温度高的矿物保存了岩浆结晶时的δ18O值,而钾长石、斜长石等矿物在岩浆冷却中经受不同程度地中低温热液蚀变。根据这些岩石的同位素年代学和地球化学特征,我们将U-Pb年龄 881±9Ma左右的锆石解释为继承来源,而年龄821±7Ma的锆石解释为同时代岩浆成因。因此在约900-880Ma,在扬子板块东南缘的皖南地区出现过大规模的幔源岩浆活动。这些新生岩浆岩很快遭受风化沉积作用后,形成低成熟度的沉积岩。大约820Ma热事件(地幔超柱活动?)使岩石圈地幔及其上覆地壳加热,导致拉伸加厚地壳内部的富水沉积岩重熔形成典型S型花岗岩。在花岗岩浆冷却过程中,出现的是中低温热液蚀变而不是高温超固相热液蚀变,指示皖南花岗闪长岩体形成于大陆边缘前裂谷期而不是裂谷活动高峰期。由于前裂谷期阶段没有软流圈地幔物质的直接加入,只有热源引起地壳加厚部位岩石部分熔融,因此由这种年青沉积物重熔所形成的花岗闪长岩兼具S型花岗岩和初生地壳的岩石学和地球化学特点,从而见证了初生地壳的短周期再循环。     

The mechanism of cation and oxygen isotope exchange in alkali feldspars under hydrothermal conditions

The mechanism of re-equilibration of albite in a hydrothermal fluid has been investigated experimentally using natural albite crystals in an aqueous KCl solution enriched in ¹⁸O at 600°C and 2 kbars pressure. The reaction is pseudomorphic and produces a rim of K-feldspar with a sharp interface on a nanoscale which moves into the parent albite with increasing reaction time. Transmission electron microscopy (TEM) diffraction contrast and X-ray powder diffraction (XRD) show that the K-feldspar has a very high defect concentration and a disordered Al, Si distribution, compared to the parent albite. Raman spectroscopy shows a frequency shift of the Si-O-Si bending vibration from ~476 cm⁻¹ in K-feldspar formed in normal ¹⁶O aqueous solution to ~457 cm⁻¹ in the K-feldspar formed in ¹⁸O-enriched solution, reflecting a mass-related frequency shift due to a high enrichment of ¹⁸O in the K-feldspar silicate framework. Raman mapping of the spatial distribution of the frequency shift, and hence ¹⁸O content, compared with major element distribution maps, show a 1:1 correspondence between the reaction rim formed by the replacement of albite by K-feldspar, and the oxygen isotope re-equilibration. The textural and chemical characteristics as well as the kinetics of the replacement of albite by K-feldspar are consistent with an interface-coupled dissolution-reprecipitation mechanism.     

Mineralogy,petrography, and oxygen and aluminum-magnesium isotope systematics of grossite-bearing refractory inclusions

Grossite (CaAl₄O₇) is one of the one of the first minerals predicted to condense from a gas of solar composition, and therefore could have recorded isotopic compositions of reservoirs during the earliest stages of the Solar System evolution. Grossite-bearing Ca,Al-rich inclusions (CAIs) are a relatively rare type of refractory inclusions in most carbonaceous chondrite groups, except CHs, where they are dominant. We report new and summarize the existing data on the mineralogy, petrography, oxygen and aluminum-magnesium isotope systematics of grossite-bearing CAIs from the CR, CH, CB, CM, CO, and CV carbonaceous chondrites. Grossite-bearing CAIs from unmetamorphosed (petrologic type 2―3.0) carbonaceous chondrites preserved evidence for heterogeneous distribution of ²⁶Al in the protoplanetary disk. The inferred initial ²⁶Al/²⁷Al ratio [(²⁶Al/²⁷Al)₀] in grossite-bearing CAIs is generally bimodal, ˜0 and ˜5×10⁻⁵; the intermediate values are rare. CH and CB chondrites are the only groups where vast majority of grossite-bearing CAIs lacks resolvable excess of radiogenic ²⁶Mg. Grossite-bearing CAIs with approximately the canonical (²⁶Al/²⁷Al)₀ of ˜5×10⁻⁵ are dominant in other chondrite groups. Most grossite-bearing CAIs in type 2–3.0 carbonaceous chondrites have uniform solar-like O-isotope compositions (Δ¹⁷O ˜ ‒24±2‰). Grossite-bearing CAIs surrounded by Wark-Lovering rims in CH chondrites are also isotopically uniform, but show a large range of Δ¹⁷O, from ˜ ‒40‰ to ˜ ‒5‰, suggesting an early generation of gaseous reservoirs with different oxygen-isotope compositions in the protoplanetary disk. Igneous grossite-bearing CAIs surrounded by igneous rims of ±melilite, Al-diopside, and Ca-rich forsterite, found only in CB and CH chondrites, have uniform ¹⁶O-depleted compositions (Δ¹⁷O ˜ ‒14‰ to ‒5‰). These CAIs appear to have experienced complete melting and incomplete O-isotope exchange with a ¹⁶O-poor (Δ¹⁷O ˜ ‒2‰) gas in the CB impact plume generated about 5 Ma after CV CAIs. Grossite-bearing CAIs in metamorphosed (petrologic type >3.0) CO and CV chondrites have heterogeneous Δ¹⁷O resulted from mineralogically-controlled isotope exchange with a ¹⁶O-poor (Δ¹⁷O ˜ ‒2 to 0‰) aqueous fluid on the CO and CV parent asteroids 3–5 Ma after CV CAIs. This exchange affected grossite, krotite, melilite, and perovskite; corundum, hibonite, spinel, diopside, forsterite, and enstatite preserved their initial O-isotope compositions. The internal ²⁶Al-²⁶Mg isochrons in grossite-bearing CAIs from weakly-metamorphosed CO and CV chondrites were not disturbed during this oxygen-isotope exchange.HCCJr is grateful to Klaus Keil for all his sound profession counsel and collegial friendship over the years. He has always been willing to talk and has the generous nature of listening and sharing his thoughts freely and constructively. Professor Klaus Keil has been a mentor to and played a key role in the careers of three of the authors of this paper (ANK, KN, and GRH). He has also influenced the careers of the other authors and most of the people who have worked on meteorites over the past 50+ years. We therefore dedicate this paper to Professor Keil and present it in this Special Issue of Geochemistry.     

Decoupling of stalagmite-derived Asian summer monsoon records from North Atlantic temperature change during marine oxygen isotope stage 5d

The Asian monsoon is an important component of the global climate system. Seasonal variations in wind, rainfall, and temperature associated with the Asian monsoon systems affect a vast expanse of tropical and subtropical Asia. Speleothem-derived summer monsoon variation in East Asia was previously found to be closely associated with millennial-scale change in temperature in the North Atlantic region between 75 and 10 ka. New evidence recovered from East Asia, however, suggests that the teleconnection between summer monsoon in East Asia and temperature change in the North Atlantic region may have significantly reduced during 120 to ~ 110 ka, a period directly after the full last interglaciation and corresponding roughly to marine oxygen isotope stage 5d. This reduction may be due to the low ice volume in the North Hemisphere at that time, which makes the millennial-scale change in temperature in the North Atlantic region less effective in influencing the Asian summer monsoon. This is important for investigating the mechanisms controlling the Asian summer monsoon and the paleoclimatic teleconnection between East Asia and the North Atlantic region, and for predicting monsoon-associated precipitation in East Asia under a global-warming trend.