Constraints of authigenic carbonates on trace elements (Sr, Mg) of lacustrine ostracod shells in paleoenvironment reconstruction and its mechanism

Molar ratios of Mg/Ca and Sr/Ca were measured in two species of ostracod shells preserved in the upper core (15-55 m) of the Heqing Basin in Yunnan Province, southwest China. By correlating the molar ratios between Mg/Ca and Sr/Ca and comparing them with Sr concentrations of the sediments, we suggested that: (1) the molar Mg/Ca and Sr/Ca ratio variations in respective ostracod primo re- flected the changes in its ambient water composition and ecology; (2) the molar Sr/Ca ratios responded better to the salinity change linearly than Mg/Ca without aragonite precipitation in the system, and otherwise there was no linear relation between them; and (3) the molar Sr/Ca ratios were mainly con- trolled by salinity and authigenic carbonate precipitation, whereas the molar Mg/Ca ratios were related to both salinity and temperature. In fact, the rate of ostracod growth owing to temperature controls the fluctuation of Mg/Ca in shells. Here, more attentions should be paid to the constraint of authigenic mineral precipitation processes on the trace elements in ostracod shells and to the correlation between these trace elements in biogenic carbonates and compositions of the sediments in systems and in fu- ture in vitro experiments.     

南海神狐海域Site 4B沉积物地球化学特征及其对甲烷渗漏的指示意义

前人对Site 4B站位海底浅表层沉积物的研究显示该站位历史上可能存在甲烷渗漏事件。为研究该站位的甲烷渗漏历史,分析了Site 4B站位柱状沉积物的元素地球化学特征,及沉积物中Mg/Ca和Sr/Ca比随深度的变化规律以及自生碳酸盐矿物的分布特征。元素相关性分析表明:研究区Ca、Sr等碳酸盐相关的元素极有可能来自于与甲烷渗漏有关的自生碳酸盐。结合沉积物的粒度特征,认为Site 4B站位在15.78 ka B.P.之前泥火山活动造成甲烷渗漏,且甲烷渗漏速率具有增大—减小的周期性变化特点。研究站位在24.15 ka B.P.、27.47 ka B.P.、31.05 ka B.P.具有相对较高的甲烷渗漏速率,且在31.05 ka B.P.达到最大值。研究结果对探明南海北部的甲烷渗漏历史具有重要的意义。     

万年尺度下钙华的古环境重建检验——以青海冰凌山为例

采用钙华中微量元素进行古气候环境重建为近年来国内外研究热点。前人研究成果主要为小时间尺度古气候环境重建,因微量元素的影响机制及地区间差异性问题,可能存在未知因素影响稀土元素含量及Mg/Ca、Mg/Sr比值,从而导致解译的古气候环境意义失真。以位于青海省格尔木地区的达布逊湖达1井孢粉谱图与青藏高原湖区变化谱图为参照对象,对青海省平安县三合镇东北冰凌山万年尺度下钙华的古环境重建方法进行了检验,结果表明:1)冰凌山泉华台地沉积环境相对稳定,提供冰凌山钙华物质来源的地下水长期处于接受来自地壳深部CO2补给的偏酸性条件下;2)所采集钙华样品除P04点外,均具有相同的物质来源和形成过程;3)万年尺度下,用钙华中的稀有元素总量重建古气温方法可行,且稀有元素总量与古气温呈负相关关系;4)采用Mg/Ca、Mg/Sr比值重建古降水环境应区分钙华成因类型,表生钙华Mg/Ca、Mg/Sr比值与古降水呈现负相关,而内生钙华Mg/Ca、Mg/Sr比值与古降水呈现正相关.     

Calcium Isotope Ratio (δ44/40Ca) Measurements of Ca‐Dominated Minerals and Rocks without Column Chemistry Using the Double‐Spike Technique and Thermal Ionisation Mass Spectrometry

In this study, to evaluate whether bias free Ca isotope ratios can be properly achieved by thermal ionisation mass spectrometry (TIMS) using the ⁴²Ca–⁴³Ca double‐spike technique without chemical purification, a series of comparable experiments (with or without column chemistry) were made on Ca‐dominated minerals and rocks. Minerals, including fluorite, calcite, titanite and apatite, displayed similar Ca isotope ratios with Δ^44/40Ca_{with‐without} ranging from ?0.02 to +0.07‰. For Ca‐rich rocks, we mainly focused on the carbonates since they are the main repositories of Ca at the surface of the Earth. Coral, stalagmite, carbonatite, dolomite, marble and limestone are studied here. Interestingly, δ^44/40Ca_{SRM 915a} of these minerals and rocks without chemical purification displayed little drift compared with that of rocks with chemical purification, with Δ^44/40Ca_{with‐without} merely spanning from ?0.04 to +0.04‰. This implies that Ca isotope ratios can be achieved without column chemistry, possibly due to a property of TIMS in which Ca ions are only ionised at a target temperature and with a specific activator without ionising other ions. Therefore, for Ca‐dominated minerals or rocks, we suggest that column chemistry is unnecessary if they are totally dissolved and mixed in proper proportion with the ⁴²Ca–⁴³Ca double spike for TIMS measurement.     

Proposal for International Agreement on Ca Notation Resulting from Discussions at Workshops on Stable Isotope Measurements Held in Davos (Goldschmidt 2002) and Nice (EGS-AGU-EUG 2003)

A proposal is made to standardise the reporting of Ca isotope data to the δ⁴⁴Ca/⁴⁰Ca notation (or δ⁴⁴Ca/42Ca) and to adopt NIST SRM 915a as the reference standard.     

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℃。     

利用碳酸盐矿物成分研究沉积-成岩过程中流体盐度演化──以东营凹陷沙四段低熟油烃源岩为例

以东营凹陷沙四段上部烃源岩为研究对象,利用电子探针微区测试技术,对同生、成岩及成岩期后不同阶段碳酸盐矿物进行了系统分析,揭示出不同古地理位置碳酸盐成分的三种变化情况,即Mg／Ca比值①由高到低,②一直保持很高,成岩期后降低,和③由低到高,反映了不同层段从沉积到成岩直至成岩期后水体或孔隙流体盐度的三种变化历程,进而确定了该凹陷中心区域烃源岩成岩过程中处于高盐度介质环境中,对于分析该区油气生成条件具有重要意义。本文的研究思路和方法对于其它地区的类似工作也有一定借鉴意义。     

连续光源原子吸收光谱法测定土壤水溶性盐中钙镁

使用连续光源原子吸收光谱仪在不更换元素灯情况下,一次进样测定土壤水溶盐组成中钙、镁离子含量,测定值与标准值的相对偏差小于5%,测定速度显著提高。连续光源原子吸收光谱法可选择元素任一谱线测定,对比30个土壤样品Mg次灵敏线202 nm与主灵敏线285 nm两条谱线测定结果,两者基本一致。高浓度时Mg次灵敏线202 nm的标准曲线相关性好于主灵敏线285 nm。与传统线光源原子吸收光谱仪相比,连续光源原子吸收光谱仪测试灵敏度显著提高。     

Two modes of climatic control in the Holocene stalagmite record from the Japan Sea side of the Japanese islands

The Holocene stalagmite FG01 collected at the Fukugaguchi Cave in Itoigawa, central Japan provides a unique high‐resolution record of the East Asian winter monsoon. Because of the climate conditions on the Japan Sea side of the Japanese islands, the volume of precipitation during the winter is strongly reflected in the stalagmite δ¹⁸O signal. Examination of the carbon isotopes and the Mg/Ca ratio of FG01 provided additional information on the Holocene climate in Itoigawa, which is characterized by two different modes separated at 6.4 ka. Dripwater composition and the correlation between the δ¹³C and Mg/Ca data of FG01 indicate the importance of prior calcite precipitation (PCP), a process that selectively eliminated ¹²C and calcium ions from infiltrating water from CO₂ degassing and calcite precipitation. In an earlier period (10.0–6.4 ka), an increase in soil pCO₂ associated with warming and wetting climate trends was a critical factor that enhanced PCP, and resulted in an increasing trend in the Mg/Ca and δ¹³C data and a negative correlation between the δ¹³C and δ¹⁸O profiles. A distinct peak in the δ¹³C age profile at 6.8 ka could be a response to an increase of approximately 10% in C4 plants in the recharge area. At 6.4 ka, the climate mode changed to another, and correlation between δ¹⁸O and δ¹³C became positive. In addition, a millennial‐scale variation in δ¹⁸O and pulsed changes in δ¹³C and Mg/Ca became distinct. Assuming that δ¹⁸O and PCP were controlled by moisture in the later period, the volume of precipitation was high during 6.0–5.2, 4.4–4.0, and 3.0–2.0 ka. In contrast, the driest interval in Itoigawa was during 0.2–0.4 ka, and broadly corresponds to the Little Ice Age.     

Controls on shell Mg/Ca and Sr/Ca in cultured planktonic foraminiferan, Globigerinoides ruber (white)

Mg/Ca and Sr/Ca ratios were determined on a single species of planktonic foraminiferan, Globigerinoides ruber (white), collected from the Gulf of Eilat and cultured in seawater at five different salinities (32 to 44), five temperatures (18 to 30 °C) and four pH values (7.9 to 8.4). The Mg/Ca-temperature calibration of cultured G. ruber (with an exponential slope of 8 ± 3%/°C) agrees well with previously published calibrations from core-tops and sediment traps. However, the dependence of Mg/Ca on salinity (with an exponential slope of 5 ± 3%/psu) is also significant and should be included in the calibration equation. With this purpose, we calculated a calibration equation for G. ruber dependent on both temperature and salinity within the 95% confidence limits:

Mg/Ca(mmol/mol)=exp[0.06(±0.02)*S(psu)+0.08(±0.02)*T(°C)−2.8(±1.0)],R²=0.95