高分辨率古海水温度记录──珊瑚Sr／Ca比值

高分辨率古海水温度记录──珊瑚Ｓｒ／Ｃａ比值韦刚健，李献华（中国科学院广州地球化学研究所，广州５１０６４０）关键词ＳＳＴ记录Ｓｒ／Ｃａ比值，珊瑚礁１弓】言研究第四纪古气候古环境变化，了解过去的气候演变规律，对预测未来气候变化趋势有重要意义，而依据地质...     

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℃。     

灵台风尘堆积中钙质结核的地球化学研究

通过对甘肃灵台风成黄土－古土壤－红粘土序列中钙质结核的野外分布及形态特征观察,并对主元素和微量元素进行化学分析,发现结核中氧化物活动给分和惰性组分含量的比值在剖面中自下而上逐渐变大,反映了结核形成时其上覆土层所经历的淋溶程度逐渐增强;而ＭｇＯ含量校正后的ＭｇＯ／Ｃａｏ比值则逐渐减小,批示结核形成时环境温度逐渐降低。灵台剖面自下而上不同层位结核中Ｓｒ／Ｂａ比值及ＣａＣＯ３含量的变化同氧化物含量及比值     

海南岛中元古代花岗岩地球化学及成因研究

海南岛中元古代花岗岩岩体主要由二长花岗岩、花岗冈长岩等岩石组成，构成一个明显的 自花岗岩向花岗闪长岩和英云闪长岩的岩浆演化系列及钙碱性演化趋势。该岩体为一套板块碰撞 后隆起期原地一半原地过铝质花岗岩。是板块碰撞引起的地壳增厚升温和随之的玄武岩浆底侵加 热联合作用下，主要由抱板群变质沉积岩及斜长角闪片麻岩部分融熔、并在幔源物质的参与下形 成的，所形成的花岗质岩浆在“走滑扩容泵吸”机制驱动下沿戈枕剪切带上升、固结就位，因而具壳 幔二元混合成因特点。化学成分以高 ＳｉＯ２、Ｋ２Ｏ、Ｒｂ、Ｂａ、Ｔａ、Ｃｅ和贫Ｐ、Ｔｉ、Ｚｒ、Ｓｒ、Ｆｅ２Ｏ３＋ＦｅＯ、 ＭｇＯ、ＣａＯ为特征；元素比值Ｚｒ／Ｎｂ、Ｌａ／Ｎｂ、Ｂａ／Ｎｂ、Ｒｂ／Ｎｂ、Ｋ／Ｎｂ、Ｂａ／Ｌａ及Ｃｒ、Ｃｏ、Ｎｉ、Ｖ均接近 大陆中下地壳成分，Ｒｂ、Ｓｒ、Ｂａ、Ｔａ、Ｚｒ及比值Ｋ／Ｓｒ、Ｒｂ／Ｓｒ石ｒ／Ｂａ变化范围小，反映岩浆源区成分 或熔融方式上的一致性；轻重稀土较强分馏，负铕异常明显，稀土配分模式总体相似，呈左高右低 型，和抱板群变质沉积岩稀上元素组成基本一致；εＮｄ（ｔ）值普遍高于抱板群地层，（８７Ｓｒ／８６Ｓｒ）ｉ值变化 大，暗示幔源参与信息。结合抱板群变基性火山岩的     

古边缘海的识别——其物质组成特征

通过沉积作用及岩浆活动产物的特征，可以识别古边缘海的存在，沉积作用形成的沉积物主要为火山碎屑岩，深海浊积岩 岩浆活动的产物主要是玄武岩，其特征是具有高挥发组分，高气孔率，Ｋ，Ｒ和Ｂａ含量较高，Ｆｅ，Ｍｇ，Ｃｒ，Ｚｒ和Ｎｉ含量较低，ＬＩＬ／ＨＦＳ比值较高，Ｋ／Ｒｂ，Ｋ／Ｂａ和Ｚｒ／Ｎｂ比值较你，轻稀土富集中等偏高等。     

莺歌海盆地上新统双壳类贝壳的锶含量及其意义

锶（Ｓｒ）是碳酸盐沉积物及软体动物介壳中的重要微量元素之一,Ｓｒ含量和Ｓｒ／Ｃａ比值的变化明显受沉积相的控制。因此,锶作为地球化学指标具有一定的环境意义。通过对南海北部莺歌海盆地莺６井上新统双壳类贝壳中的Ｓｒ含量和Ｓｒ／Ｃａ比值的变化与环境、成岩作用关系的研究,发现莺歌海盆地上新世沉积环境为上陆坡→潮下带→潮间带,所得结论与双壳类的生态环境和地层沉积相的综合分析结果一致。     

应用加速器质谱计测定^41Ca地质年龄的研究进展

综述了４１Ｃａ的起源、加速器质谱计测量的特点以及４１Ｃａ在地质年龄测定中的应用。４１Ｃａ半衰期为１０５ａ,它可用来测定５×１０４～１０６ａ地质样品的年龄。天然样品中ｗ（４１Ｃａ）／ｗ（４０Ｃａ）比值很小,只能用ＡＭＳ测定。目前,检测ｗ（４１Ｃａ）／ｗ（４０Ｃａ）比值的灵敏度可达１０－１５。在全球气候变化、古人类学研究及医学示踪研究中应用４１Ｃａ具有非常重要的意义。     

铊—寻找微细浸染型金矿的指示元素

本文对桂西北几个微细浸染型金矿床研究表明：Ｔｌ在矿石中富集，Ｋ／Ｔｌ、Ｂａ／Ｔｌ比值，矿石中明显低于围岩，Ｔｌ含量、Ｋ／Ｔｌ、Ｂａ／Ｔｌ比值离差小，变化稳定，利用他们作为指示元素及特征比寻找微细浸染型金矿床是一条可行途径。     

高分辨率洞穴石笋中稳定同位素应用——北京元大都建立后对森林资源 …

对采自北京西山石花洞内的石笋进行了δ＾１８Ｏ,δ＾１３Ｃ和Ｍｇ／Ｓｒ分析,获得分辨率为２５ａ的北京地区３０００ａ认来的古气候和古环境信息,以δ＾１８Ｏ和Ｄｍｇ／Ｃａ作为气候变化信息,证实石笋δ＾Ｃ反映了古气候变化对植被的影响,当石笋δ＾１３Ｃ植增大时,表示Ｃ３／Ｃ４植物比值降低,气候变干热,当石笋δ＾１３Ｃ值减小时,表示Ｃ３／Ｃ４植物比值升高,气候变湿冷,同时,笔者也发现了北京元大都建立以来对森林     

南海北部珊瑚高分辨率硼同位素组成及其对珊瑚礁海水pH变化的指示意义

造礁珊瑚是研究热带海洋高分辨率气候环境演变的重要载体。对采自海南岛南部三亚湾的活体滨珊瑚SY10进行了约为月分辨率的碳、氧、硼同位素组成分析,并利用珊瑚δ11B重建了海水pH。结果显示,所测量样品的δ13C变化范围为–3.32‰~–1.76‰,δ18O为–6.13‰~–4.78‰,δ11B为23.51‰~26.23‰,且这些珊瑚样品的碳、氧、硼同位素组成均存在明显的季节性周期波动。其中pH与δ18O之间存在明显的正相关关系,高的pH值更倾向于在低温的季节出现,这意味着短时间尺度该处珊瑚礁海水pH可能主要不是受海水CO2溶解度控制,而是与生物活动有密切的关系。利用SY10珊瑚样品硼同位素组成重建的海水pH值变化范围为7.77~8.37,并呈季节性周期波动,这种大幅度的周期波动与我们对三亚珊瑚礁海水pH进行现场观测所得到的结果以及前人的研究成果相符,说明了利用珊瑚δ11B重建海水pH记录是可靠的。     

Source of trace element variability in Great Barrier Reef corals affected by the Burdekin flood plumes

Massive corals in the Great Barrier Reef, analyzed at high-resolution for Sr/Ca (thermal ionization mass spectrometry) and trace elements such as Ba and Mn (laser ablation inductively coupled plasma mass spectrometry), can provide continuous proxy records of dissolved seawater concentrations, as well as sea surface temperature (SST). A 10-yr record (1989 to 1998) from Pandora Reef, an inshore reef regularly impacted by the freshwater plumes of the Burdekin River, is compared with an overlapping record from a midshelf reef, away from runoff influences. Surface seawater samples, taken away from river plumes, show little variability for Sr/Ca (8484 ± 10 μmol/mol) and Ba (33.7 ± 0.7 nmol/kg). Discrete Ba/Ca peaks in the inshore coral coincide with flood events. The magnitude of this Ba/Ca enrichment is most likely controlled by the amount of suspended sediments delivered to the estuary, which remains difficult to monitor. The maximum flow rate at peak river discharge is used here as a proxy for the sediment load and is shown to be strongly correlated with coral Ba/Ca (r = 0.97). After the wet summer of 1991, the coral Ba/Ca flood peak is followed by a plateau that lingers for several months after dissipation of plume waters, signifying an additional flux of Ba that may originate from submarine groundwater seeps and/or mangrove reservoirs. Both Mn and Y are enriched by a factor of ∼5 in inshore relative to midshelf corals. Mn/Ca ratios show a seasonal cycle that follows SST (r = 0.7), not river discharge, with an additional high variability in summer suggesting a link with biological activity. P and Cd show no significant seasonal variation and are at a low level at both inshore and midreef locations. However, leaching experiments suggest that part of the coral P is not lattice bound.     

海南岛东部海域滨珊瑚Sr/Ca比值温度计 及其影响因素初探*

文章采用全谱直读等离子体原子发射光谱(ICP-AES)的方法测定了1986~1996年海南岛东部海域滨珊瑚的Sr/Ca比值,建立了该海域月分辨率的Sr/Ca海水表面温度计方程:SST(℃)=170-16 (mmol/mol),n = 133,r=0.80,p=0.01, 此与韦刚健等在西沙海域建立的温度计方程:SST(℃)=169-16.7 (mmol/mol)一致,这表明南海中、北部海域也出现有相似的微量元素温度计。此外,文章还分析了在某些年月份SST的实测值和计算值出现的显著差别,探讨了可能造成的海洋气象环境因素。     

海南岛沙老岸礁区滨珊瑚氧、碳同位素对气候的记录

通过对海南岛沙老岸礁中正在连续生长的澄黄滨珊瑚骨骼进行氧，碳同位素的测定，对9年生长的珊瑚骨骼依次分析了352个样品，平均每旬有1－2个控制样品，以此来分析珊瑚生长期间的气候变化。首先分析出每年雨季和旱季的差别，得到雨季和旱季曲线的特征，并得出雨季在每年夏季，旱季在每年的秋冬季，表明海南岛礁区是典型的季风气候区。同时将珊瑚骨骼的氧同位素分析数值与相关记录的气温资料做比较，它们的相关系数为0．97和0．79，并得出以氧同位素分析数值求气温的公式。     

Compositional and morphological features of aragonite precipitated experimentally from seawater and biogenically by corals

The morphology and composition of abiogenic (synthetic) aragonites precipitated experimentally from seawater and the aragonite accreted by scleractinian corals were characterized at the micron and nano scale. The synthetic aragonites precipitated from supersaturated seawater solutions as spherulites, typically 20-100 μm in diameter, with aggregates of sub-micron granular materials occupying their centers and elongate (fibrous) needles radiating out to the edge. Using Sr isotope spikes, the formation of the central granular material was shown to be associated with high fluid pH and saturation state whereas needle growth occurred at lower pH and saturation state. The granular aggregates have significantly higher Mg/Ca and Ba/Ca ratios than the surrounding fibers.Two types of crystals are identified in the coral skeleton: aggregates of sub-micron granular material and bundles of elongate (fibrous) crystals that radiate out from the aggregates. The granular materials are found in “centers of calcification” and in fine bands that transect the fiber bundles. They have significantly higher Mg/Ca and Ba/Ca ratios than the surrounding fibers.The observed relationship between seawater saturation state and crystal morphology and composition in the synthetic aragonites was used as a framework to interpret observations of the coral skeleton. We propose that coral skeletal growth can be viewed as a cyclical process driven by changes in the saturation state of the coral’s calcifying fluids. When saturation state is high, granular crystals precipitate at the tips of the existing skeletal elements forming the centers of calcification. As the saturation state decreases, aragonitic fibres grow in bundles that radiate out from the centers of calcification.     

Metal contents of Porites corals from Khang Khao Island,Gulf of Thailand: Anthropogenic input of river runoff into a coral reef from urbanized areas,Bangkok

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been used to assess the impact of metal pollution on Porites skeletons taken from the Gulf of Thailand since the 1980s. The collection period coincided with a series of laws enacted by the Thai government to curb environmental pollution. The extent of metal pollution by riverine input, including aerosol deposits, was assessed by comparing the metal/Ca (Me/Ca) ratios in the Thai corals to the ratios of another colony of corals sampled from Rukan-sho, a relatively unpolluted coral reef located in Okinawa, Japan. In this comparison, high riverine inputs of Ba, V, Cd and Pb were observed in the Thai coral samples. Higher V/Ca ratios found in the Thai corals compared to the Rukan-sho coral suggest anthropogenic V inputs due to fuel oil pollution in the Gulf since the late 1990s. The levels of Cd in the coral suggest a gradual decrease in the Gulf in the late 1990s, with a drastic drop in concentration from the 1980s. The historical variation in Pb/Ca ratios recorded in the coral skeletons suggests that exposure to anthropogenic Pb was a result of discharge from urbanized areas from 1984 to 1998, which has been gradually reduced since Thailand prohibited the use of leaded gasoline in the late 1990s.     

Elemental Geochemistry of a Soil Chronosequence on Basalt onNorthern Hainan Island, China

With increasing soil age, the contents of Sr, Ba and ratios of Sr/Be in soils tend to decrease, whereas the contents of V, Sc, Ni, Cr, Co and ratios of Fe/Ni and Fe/Co tend to increase, as evidenced from a study on soils of different ages, developed on basahs in the northern part of Hainan Island. Ba/Nb, significantly correlative with soil age, can be used to evaluate soil evolution. By using the mass-balance method, the element migration was discussed with Ti as an immobile element. The results showed that element leaching was most intensive in the early pedogenic period. In this period (Primosols) , over 90% of Ca, Mg, K and Na was leached out of soils till Ferrosol formation. The leaching of P occurred mainly at the beginning of soil development. About 60% of Si was mobilized in the stage of Cambosol formation and 80% in the stage of Ferralosol formation.     

High-resolution coral records of rare earth elements in coastal seawater: biogeochemical cycling and a new environmental proxy

In this study we have used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to produce a high resolution coral record of rare earth elements (REE), Mn and Ba from coastal Porites corals from the Great Barrier Reef of Australia. Validation of the LA-ICP-MS technique indicated that the method provides accurate and reproducible (RSD = 13-18%) analysis of low concentration REE in corals (∼1 to 100 ppb). The REE composition in coral samples was found to closely reflect that of the surrounding seawater and distribution coefficients of ∼1-2 indicated minimal fractionation of the series during incorporation into coral carbonate. To explore the idea that coral records of REE can be used to investigate dissolved seawater composition, we analyzed two coastal corals representing a total of ∼30 yr of growth, including a 10-yr overlapping period. Comparable results were obtained from the two samples, particularly in terms of elemental ratios (Nd/Yb) and the Ce anomaly. Based on this evidence and results from the determination of distribution coefficients, we suggest that useful records of seawater REE composition can be obtained from coral carbonates. When compared to the REE composition of a mid shelf coral, coastal corals showed a significant terrestrial influence, characterized by higher REE concentrations (greater than 10 times) and light REE enrichment. The REE composition of coastal seawater inferred from the coral record was dependent on seasonal factors and the influence of flood waters. REE fractionation displayed a strong seasonal cycle that correlated closely with Mn concentration. We suggest that higher Nd/Yb ratios and higher Mn concentrations in summer result from scavenging of heavy REE by particulate organic ligands and Mn reductive dissolution respectively, both processes displaying higher rates during periods of high primary productivity. The Ce anomaly also displayed a strong seasonal cycle showing an enhanced anomaly during summer and during flood events. This is consistent with the Ce anomaly being primarily controlled by the abundance of Ce oxidizing bacteria. Based on these arguments, we suggest that the coral record of dissolved REE and Mn may be regarded as a useful proxy for biological activity in coastal seawater.     

Rayleigh-based, multi-element coral thermometry: A biomineralization approach to developing climate proxies

This study presents a new approach to coral thermometry that deconvolves the influence of water temperature on skeleton composition from that of “vital effects”, and has the potential to provide estimates of growth temperatures that are accurate to within a few tenths of a degree Celsius from both tropical and cold-water corals. Our results provide support for a physico-chemical model of coral biomineralization, and imply that Mg²⁺ substitutes directly for Ca²⁺ in biogenic aragonite. Recent studies have identified Rayleigh fractionation as an important influence on the elemental composition of coral skeletons. Daily, seasonal and interannual variations in the amount of aragonite precipitated by corals from each “batch” of calcifying fluid can explain why the temperature dependencies of elemental ratios in coral skeleton differ from those of abiogenic aragonites, and are highly variable among individual corals. On the basis of this new insight into the origin of “vital effects” in coral skeleton, we developed a Rayleigh-based, multi-element approach to coral thermometry. Temperature is resolved from the Rayleigh fractionation signal by combining information from multiple element ratios (e.g., Mg/Ca, Sr/Ca, Ba/Ca) to produce a mathematically over-constrained system of Rayleigh equations. Unlike conventional coral thermometers, this approach does not rely on an initial calibration of coral skeletal composition to an instrumental temperature record. Rather, considering coral skeletogenesis as a biologically mediated, physico-chemical process provides a means to extract temperature information from the skeleton composition using the Rayleigh equation and a set of experimentally determined partition coefficients. Because this approach is based on a quantitative understanding of the mechanism that produces the “vital effect” it should be possible to apply it both across scleractinian species and to corals growing in vastly different environments. Where instrumental temperature records are available, a Rayleigh-based framework allows the effects of stress on coral calcification to be identified on the basis of anomalies in the skeletal composition.     

海南岛南岸全新世珊瑚礁的发育

海南岛南岸的珊瑚礁,是我国全新世珊瑚岸礁最为发育的地区之一,仅次于台湾岛南端的恒春半岛沿岸。前人从生物学^[1-5]、地貌学^[6-8]和地质学^[9-12]角度对海南岛南岸的珊瑚礁进行过较为广泛的研究。作者报道过崖县鹿回头水尾岭剖面珊瑚礁样品的C¹⁴年代测定结果^[13,14]。1979年底至1980年初,作者在海南岛南岸东起小东海沿岸西至西瑁岛西岸地区进行了野外调查与采样。根据野外和室内分析资料,本文公布了一批新测试的C¹⁴年代数据,并进一步讨论了全新世珊瑚礁的发育历史及其与海岸变迁、海面变化和地壳运动的关系等问题。