利用富钴结壳碳酸盐基岩有孔虫矿物标型重建古海洋温度

重建古海洋海表温度(SST),是研究地质历史时期气候变化控制过程的关键。组成有孔虫化石的矿物Mg/Ca值是海水温度的可靠代用指标,是重建古海洋SST的一个非常好的手段。麦哲伦海山区的富钴结壳和基岩中普遍存在有孔虫化石,这对重建该区的SST有重要意义。利用LA-ICP-MS测得西太平洋麦哲伦海山区富钴结壳碳酸盐基岩中8颗浮游有孔虫化石Globigerinoides sacculifer的Mg/Ca值为3.84±0.36(mmol/mol),通过线性公式:T(℃)=2.898Mg/Ca(mmol/mol)+13.76及已有的定年数据,得到0.91Ma±西太平洋麦哲伦海山区海表温度为24.9+1.1/-1.0℃,未能检索到前人关于该区0.91Ma±前海表温度数据。     

基于等转化法及多元非线性拟合的高岭石非等温脱羟基动力学分析

采用Netzsch STA409PC同步热分析仪研究了苏州高岭石(KW125)在30℃~1 200℃间的热分解过程。采用"Netzsch Thermokinetics software"软件对其脱羟基机理进行了非等温动力学研究。基于等转化法评价了反应活化能及反应进程的依存关系。基于多元非线性拟合确定了最可能反应机理及动力学参数。研究结果表明:苏州高岭石在30℃~1200℃温度范围的热分解为脱羟基与相转变等两个阶段。其脱羟基(30℃~800℃)过程中活化能呈现三个变化:197.68 kJ/mol±12.95 kJ/mol→181.04kJ/mol±18.98kJ/mol→269.7kJ/mol±14.64kJ/mol。脱羟基反应遵循三步连续反应模型t:f,f;(D3-Fn-Fn),一个三维扩散(D3)反应,然后是两个n序列(Fn)反应。第一步,f(α)=3(1-α)^2/3/(2(1-(1-α)^1/3),E1=185.27 kJ/mol,logA=10.83s^-1;第二步,f(α)=(1-α)^n,n=1.75,E2=187.81 kJ/mol,logA=10.32s^-1;第三步,f(α)=(1-α)^n,n=4.4,E3=262.70 kJ/mol,logA=13.26s^-1。     

南海北部甲烷渗漏的沉积地球化学指标(Sr/Ca和Mg/Ca)识别

自生碳酸盐矿物是揭示甲烷渗漏过程及其周期性变化的重要指标。为了方便、快速地识别出自生碳酸盐矿物,在探讨了前人建立的端元组分模型(文石、高镁方解石、生物成因方解石和碎屑)在我国南海北部适用性的基础上,利用沉积物全样中Sr/Ca和Mg/Ca值计算了南海北部神狐海域两支沉积物柱状样中自生碳酸盐矿物的质量分数,计算结果表明,在不同沉积深度均有含量不等的自生碳酸盐矿物。这一结果被X射线衍射结果和沉积物中存在晶形完好的自生高镁方解石和文石矿物所验证,表明利用前人建立的端元组分模型计算的结果具有可靠性。自生碳酸盐矿物的出现显示该海域深受甲烷渗漏作用影响。利用地球化学指标(Sr/Ca和Mg/Ca)获得的自生碳酸盐矿物含量垂向变化显示该区域甲烷渗漏具有强弱交替的周期变化。运用端元组分模型来获取沉积物柱状样中自生碳酸盐矿物的高分辨率剖面,从而识别甲烷渗漏信息非常方便,在大范围寻找甲烷渗漏和天然气水合物方面具有较大潜力。     

同位素测定样品中钙和锶的分离

与样品中基体和Rb分离了的Ca和Sr,在0.08mol/L柠檬酸-1.5mol/L NH_4OH介质中流经Dowex50×8阳离子树脂柱,并用此溶液淋洗Ca,用4mol/L HCI洗脱Sr。收集的含Sr溶液用于同位素年龄测定,消除了质谱测定过程中Ca的干扰。     

南海北部珊瑚Sr/Ca和Mg/Ca温度计及高分辨率SST记录重建尝试

利用全谱直读等离子体光谱(ICPAES)的分析方法精确分析了南海珊瑚的SrCa和MgCa比值,结合实测表层海水温度(SST),标定了海南岛南部三亚海域和西沙海域两个滨珊瑚的SrCa和MgCa温度计。在此基础上,尝试对两个南海北部全新世时期的珊瑚进行SST记录重建。结果显示约540aB.P.(小冰期)西沙海域夏季月均SST较现代低约1℃,而约6500aB.P.(大暖期)海南岛三亚海域夏季月均SST则高出现代1.0～1.5℃。     

浮游有孔虫壳体Mg/Ca值--SST的替代性指标

通过对东北印度洋区MD77181和MD81349两支岩心中Globigerinoides sacculifer壳体极为精细的清洗和溶样后,由ICP—MS测试获得了近260ka以来Mg／Ca值．结果表明Mg／Ca值与δ^18O值变化趋势较为吻合,随温度的增加而升高,浮游有孔虫G．sacculifer壳体Mg／Ca值是海洋表层水温(SST)良好的替代性指标．运用函数式Mg／Ca=0．4717exp(0．0825*SST)计算表明,包括印度洋在内的中、低纬地区,LGM时期的SST与全新世的温差大于最初CLIMAP推测的2℃,很可能达到4℃．     

电气石—水体系中D／H交换动力学研究

本文对电气石-水体系氢同位素动力分馏进行了实验研究。研究表明,电气石-水体系氢同位素交换以扩散交换为主。在温度为800～450℃范围内,该体系的氢扩散动力学方程为:logD=-5.96-6.68×10~3/T(圆柱模式),logD=-5.64-6.42×10~3/T(薄板模式),扩散活化能为128.0 kJ/mol(圆柱模式)和123.1 kJ/mol(薄板模式)。     

珊瑚中微量铀的ID-ICP-MS高精度测定及其在珊瑚U/Ca温度计研究中的应用

建立了同位素稀释技术与ICP-MS相结合的ID-ICP-MS分析方法,成功测量了取自南海北部的滨珊瑚样品中的微量铀,获得0．5％左右的精度。并以此建立南海北部近岸海域的珊瑚U／Ca温度计,其温度精度可达±0．5℃。     

扬子东部冶山和山里陈埃达克质侵入岩年代学与地球化学:岩石成因和动力学意义

冶山和山里陈岩体构造上属于扬子地块东部,毗邻郯庐断裂带东侧,主要岩石类型为石英闪长玢岩。它们的单矿物(角闪石,黑云母)40Ar/39Ar坪年龄分别为131.22±0.77 Ma和130.07±0.48 Ma。冶山和山里陈岩体具有与埃达克岩类似的地球化学特征,如w(SiO2)>56%,高Al2O3[w(Al2O3)=14.95%～17.67%]、Sr[w(Sr)=495×10-6～2086×10-6]、Sr/Y(44～159)和La/Yb(26～68),低重稀土元素,如w(Yb)=0.82×10-6～1.56×10-6),w(Y)=9.14×10-6～20.32×10-6,无明显-正Eu异常(δEu=0.90～1.11)。另外,样品普遍具有较高的MgO[w(MgO)=2.01%～4.98%]、IMg(45～71)和Cr[w(Cr)=19.2×10-6～199×10-6]、Ni[w(Ni)=13.8×10-6～58.8×10-6]。它们的Sr-Nd-Pb同位素特征为:(87 Sr/86 Sr)i=0.7059～0.7062,εNd(t)=-14.75～-12.15,(206 Pb/204 Pb)t=16.082～16.847,(207 Pb/204 Pb)t=15.303～15.461,(208Pb/204Pb)t=35.889～36.919。冶山和山里陈埃达克质侵入岩可能是由于扬子与华北地块在三叠纪的碰撞及扬子地块东部的地壳拆离作用,导致下地壳增厚并发生拆沉熔融,岩浆在上升过程中与地幔橄榄岩发生了反应。郯庐断裂带两侧早白垩世时期的埃达克(质)岩可能形成于断裂带早白垩世时期由左行平移向伸展活动转变的阶段,其源动力很可能是受到滨太平洋板块构造的影响。     

闽西南地区早侏罗世梨山组海平面相对升降及构造背景的元素地球化学证据

福建闽西南地区中生代受特提斯和太平洋构造域共同影响,晚三叠—中侏罗世经历了一次大规模的海侵-海退旋回,最大海侵发生在早侏罗世。对漳平西园剖面和漳平高明坑剖面梨山组泥岩样品进行常量元素分析和ICP-MS微量元素分析,常量、微量元素迁移与富集记录了古盐度高低和古水深深浅变化。古盐度变化随海水深度的增加而增加,海平面的升降变化直接影响着古水深的深浅。所以,元素地球化学特征反映的古盐度高低和古水深的深浅,可以指示海平面相对升降。梨山组的B/Ga、Sr/Ba和Ca/Mg值对古盐度和古水深反映较m值敏感。B/Ga、Sr/Ba和Ca/Mg值曲线在梨山组均出现一次波谷和两次波峰,波峰和波谷在剖面上的位置基本对应。m值在剖面上部出现的波峰与B/Ga、Sr/Ba和Ca/Mg三条比值曲线上部的波峰对应。根据m值、B/Ga、Sr/Ba和Ca/Mg值反映的古盐度、古水深曲线绘制了下侏罗统梨山组的海平面相对升降曲线,早侏罗世梨山组经历了海退—海侵—海退的海平面波动。对样品进行ICP-MS稀土元素分析和砂岩矿物成分分析,梨山组沉积物源岩是来自被动大陆边缘物源区和酸性岛弧源区的沉积岩和花岗岩(Rb100;K2O1;Hf=5.48~14.17;La/Th=2.66~4.94)。砂岩骨架成分研究表明,梨山组物源来自火山弧造山带和岩浆弧物源区,这与泥岩地球化学特征显示的物源区吻合。根据Dickinson图解、K2O/Na2O-Si O2、Zr-Th、La-Th-Sc、Th-Co-Zr/10判别图解和稀土元素特征值(表1)综合分析,梨山组沉积物沉积于靠近大陆岛弧的活动大陆边缘(w(∑REE)=140.4×10-6~335.5×10-6;LREE/HREE=9.52~19.90;δEu=0.48~0.62;La/Yb=11.04~21.13;(La/Yb)N=7.17~13.72),同时具有被动大陆边缘(w(∑REE)=115.4×10-6~383.4×10-6;LREE/HREE=8.30~20.27;δEu=0.55~0.67;La/Yb=8.42~30.12;(La/Yb)N=5.47~19.56)特性的弧后挤压盆地。     

Effects of diagenesis on paleoclimate reconstructions from modern and young fossil corals

The integrity of coral-based reconstructions of past climate variability depends on a comprehensive knowledge of the effects of post-depositional alteration on coral skeletal geochemistry. Here we combine millimeter-scale and micro-scale coral Sr/Ca data, scanning electron microscopy (SEM) images, and X-ray diffraction with previously published δ¹⁸O records to investigate the effects of submarine and subaerial diagenesis on paleoclimate reconstructions in modern and young sub-fossil corals from the central tropical Pacific. In a 40-year-old modern coral, we find secondary aragonite is associated with relatively high coral δ¹⁸O and Sr/Ca, equivalent to sea-surface temperature (SST) artifacts as large as −3 and −5 °C, respectively. Secondary aragonite observed in a 350-year-old fossil coral is associated with relatively high δ¹⁸O and Sr/Ca, resulting in apparent paleo-SST offsets of up to −2 and −4 °C, respectively. Secondary Ion Mass Spectrometry (SIMS) analyses of secondary aragonite yield Sr/Ca ratios ranging from 10.78 to 12.39 mmol/mol, significantly higher compared to 9.15 ± 0.37 mmol/mol measured in more pristine sections of the same fossil coral. Widespread dissolution and secondary calcite observed in a 750-year-old fossil coral is associated with relatively low δ¹⁸O and Sr/Ca. SIMS Sr/Ca measurements of the secondary calcite (1.96-9.74 mmol/mol) are significantly lower and more variable than Sr/Ca values from more pristine portions of the same fossil coral (8.22 ± 0.13 mmol/mol). Our results indicate that while diagenesis has a much larger impact on Sr/Ca-based paleoclimate reconstructions than δ¹⁸O-based reconstructions at our site, SIMS analyses of relatively pristine skeletal elements in an altered coral may provide robust estimates of Sr/Ca which can be used to derive paleo-SSTs.     

GEOCHEMICAL CHARACTERISTICS OF THE EARLY MESOZOIC GRANODIORITES AND THEIR TECTONIC IMPLICATIONS

The early Mesozoic granodiorites (ca. 165 Ma) in the northeastern Hunan Province (NEH) have SiO2=65.4-69.65%, K2O/Na2O=0.95-1.38 and K2O Na2O＞6%, A/CNK=0.96-1.13 and belong to metaluminous high-K calc-alkaline series. They are characterized by LREE and LILEs enrichment, and HFSE depletion with slightly negative Eu anomalies (Eu/Eu*=0.62-0.90). The initial 87Sr/86Sr ratios are in range from 0.711458 to0.717461, and εNd values vary from -9.4 to -12.3, distinct from those of the contemporaneous granodiorites mantle-derived from the Southeastern Hunan Province (SEH) (87Sr/86Sr(i)=0.707962～0.710396, εNd(t)=-6.98～-2.30).By contrast, such signatures are roughly similar to those of the neighboring other Mesozoic granitic plutons (Eu/Eu*=0.30-0.70; 87Sr/86Sr ＞0.710; εNd = -12 to -16) in South China Block (SCB), which have been interpreted as the remelting products of Precambrian basement. The Proterozoic lower-middle crust is an important contributor to the petrogenesis of these early Mesozoic granodiorites in the NEH. An intracontinental extension setting is present in the northeastern Hunan Province at that time due to the demand of enough thermal transfer.     

湘东北早中生代花岗闪长岩地球化学特征及其构造意义

湘东北早中生代花岗闪长岩 (约 16 5Ma)SiO2 =6 5 .4 %～ 6 9.6 5 % ,K2 O +Na2 O =6 .0 %～ 7.17% ,K2 O≈Na2 O ,A/NKC =0 .96～ 1.13,为弱过铝质钙碱性岩石。该花岗闪长岩 (La/Yb) CN=12 .75～ 37.5 0 ,(Gd/Yb) CN =1.2 8～ 2 .90 ,Eu/Eu =0 .6 2～ 0 .90 ,以富集LILE和亏损Nb Ta、Ti、P为特征。初始87Sr/ 86Sr =0 .7114 5 8～ 0 .7174 6 1,εNd=- 9.0～ - 12 .3,其同位素组成明显有别于被认为其成因与地幔派生岩浆有关的湘东南高钾花岗闪长质岩石。暗示湘东北早中生代花岗闪长岩可能是在华南早中生代伸展构造背景下中 /下地壳物质深熔作用的产物。湘东北早中生代代表性花岗闪长质岩石不能与湘东南同期花岗闪长质岩石一起构成一条连续的高εNd、低TDM钾质岩石带。     

西沙珊瑚锶温度计：便捷高精度海洋古水温代用指标

西沙群岛现代滨珊瑚1976－1994年生长期间Sr含量的高精度热电离质谱测定结果表明，Sr含量随季节发生周期性的变化，并与当地同期实测海水月平均温度变化相吻合，其Sr含量与实测海水温度相关系数为－0．94。这18年冬夏极端Sr含量与同期月温的相关系数可高达－0．98。Sr温度计误差小于0．5℃。     

塔里木盆地巴楚隆起寒武系及奥陶系白云岩类型及形成机理

采用染色薄片鉴定、阴极发光显微镜观察、微量元素分析、碳氧稳定同位素测定及包体侧温等手段，对塔里木盆地巴楚断隆区寒武系和奥陶系白云岩的特征及成因进行了研究，共划分出四种类型的白云岩：①泥粉晶白云岩，其m(Ca)/m(Mg)平均为3-10，Sr含量高（>300×10-6 ），m(Sr)/m(Ba)>>1，?13C值较高（-1‰-+1‰），₁₈O值较低（-5‰--8‰），沉积环境为潮上带云坪，为准同生作用阶段潮上萨布哈白云化作用形成。②含雾心亮边白云石的细晶白云岩，其m(Ca)/m(Mg)较低（1-2），Sr含量中等（100×10-6-200×10-6），m(Sr)/m(Ba) >1，?13C值在-2‰左右，₁₈O值低，在-7‰左右，沉积环境为开阔台地浅滩，为准同生或早期成岩作用阶段回流渗透白云化作用形成。③含明亮白云石晶体及钙质残余的钙质白云岩，其m(Ca)/m(Mg)较低（1左右），Sr含量最低（100×10-6左右），m(Sr)/m(Ba) < 1，?13C值最低（-1‰--3‰），?18O值较低（-6‰左右），沉积环境为灰坪、云坪及开阔台地，为准同生或早期成岩作用阶段混合水白云化作用形成。④砂糖状白云岩，其m(Ca)/m(Mg)较低（1-2），Sr含量低（<100×10-6），m(Sr)/m(Ba)<1，?13C值较高（-1‰-+3‰），₁₈O值较低（-5‰--8‰），沉积环境多为浅滩，为晚期成岩作用阶段埋藏白云化作用形成。     

汝城地区晚中生代火山岩地球化学特征及其对源区属性的指示

湘东南汝城地区发育一套由基性玄武岩和中酸性安山质-英安质岩石组成的火山岩建造,属于低钾拉斑系列,该火山岩系中两个玄武岩的K-Ar年龄分别为124.5±2.5Ma和127.6±1.9Ma,属晚侏罗—早白垩世产物。在主、微量元素上两者成分存在明显差异。其中安山质-英安质岩石具有高MgO特征,属高MgO岩石,LILE富集、Nb-Ta、Sr-P亏损强烈,(La/Yb)N=6.7～7.9,Eu*/Eu=0.74～0.85,具岛弧型微量元素配分型式,87Sr/86Sr(t)=0.71079～0.71118,εNd(t)=-7.64～-8.16,与adakites高Mg岩石有着明显的差别,可能是富集岩石圈地幔熔融后直接分异的产物;玄武岩LILE富集,Nb-Ta富集,(La/Yb)cn=4.0～4.3,Eu*/Eu=1.00～1.16,具OIB型微量元素配分型式,87Sr/86Sr(t)=0.70812～0.70832,εNd(t)=0.48～1.03,其源区具二元混合趋势,其源区可能是富集型岩石圈地幔端员与亏损的软流圈地幔端员的混合产物。汝城地区晚中生代玄武岩和高Mg安山质-英安质岩石源区属性的限定及其相互的空间依存关系表明该区晚中生代时有着较薄的岩石圈厚度,处于岩石圈伸展减薄的大地构造背景。     

High precision measurements of Mg/Ca and Sr/Ca ratios in carbonates by cold plasma inductively coupled plasma quadrupole mass spectrometry

We present a new high precision analytical method for the determination of Mg/Ca and Sr/Ca ratios in carbonates using an inductively coupled plasma quadrupole mass spectrometer (ICP-QMS) with a 650-W cold plasma technique and a desolvation introduction system. Signal intensities are detected in pulse-counting mode and Mg/Ca and Sr/Ca ratios are calculated directly from intensity ratios of ²⁴Mg/⁴³Ca and ⁸⁶Sr/⁴³Ca using external matrix-matched standards for every 4–5 samples to correct for instrumental mass discrimination and low-frequency ratio drift. Significant matrix effect of Ca content on Mg/Ca determination (− 0.018 Mg/Ca (mmol/mol)/[Ca] (ppm)), can be overcome by diluting [Ca] to 6–8 ppm in the sample solution or using an empirical correction. The Sr/Ca ratio affects the Mg/Ca determination, with a factor of − 0.32% Mg/Ca per mmol/mol. This is mainly caused by the influence of doubly charged ⁸⁶Sr, which biases the intensity measurement of the ⁴³Ca⁺ ion beam. This effect results in a trivial offset of less than 0.1% on Mg/Ca measurements for Quaternary foraminiferal and coral samples. The internal precision of our method ranges from 0.1 to 0.2%. Replicate measurements made on standards and samples show long-term external uncertainties (2σ) of Mg/Ca = 0.84% and Sr/Ca = 0.49%. The minimum sample size requirement is only 3.5 μg of carbonate. The application of this newly developed technique on the planktonic foraminifera Globigerinoides ruber from a core recovered in the southern South China Sea yields a glacial–interglacial difference in sea surface temperature (SST) of 3 °C. Three-year coral Sr/Ca data suggest that the seasonal SST ranged from 22.6–23.8 °C in winter to 26.9–27.9 °C in summer in Nanwan, south Taiwan, during 2000–2002. The coral-Sr/Ca inferred SSTs in 2002 match well with instrumental records, which demonstrates the validity of this ICP-QMS method.     

Oxygen and carbon isotope and Sr/Ca signatures of high-latitude Permian to Jurassic calcite fossils from New Zealand and New Caledonia

Calcite fossils from New Zealand and New Caledonia provide insight into the Permian to Jurassic climatic history of Southern High Latitudes (southern HL) and Triassic Southern Intermediate Latitudes (southern IL). These results permit comparison with widely studied, coeval sections in Low Latitudes (LL) and IL. Oxygen isotope ratios of well-preserved shell materials indicate a partially pronounced Sea Surface Temperature (SST) gradient in the Permian, whereas for the Triassic no indication of cold climates in the southern HL is found. The Late Jurassic of New Zealand is characterized by a slight warming in the Oxfordian–Kimmeridgian and a subsequent cooling trend in the Tithonian. Systematic variations in the δ¹³C values of southern HL samples are in concert with those from LL sections and confirm the global nature of the carbon isotope signature and changes in the long-term carbon cycle reported earlier.Systematic changes of Sr/Ca ratios in Late Triassic brachiopods, falling from 1.19 mmol/mol in the Oretian (early Norian) to 0.67 mmol/mol in the Warepan (late Norian) and subsequently increasing to 1.10 mmol/mol in the Otapirian (~ Rhaetian), are observed. Also Sr/Ca ratios of Late Jurassic belemnite genera Belemnopsis and Hibolithes show synchronous changes in composition that may be attributed to secular variations in the seawater Sr/Ca ratio. For the two belemnite genera an increase from 1.17 mmol/mol in the Middle Heterian (~ Oxfordian) to 1.78 mmol/mol in the Mangaoran (~ late Middle Tithonian) and a subsequent decrease to 1.51 mmol/mol in the Waikatoan (~ Late Tithonian) is documented.