胶州湾双壳类壳体中的Ca,Mg,Mn,Sr元素组成及影响因素

探讨影响双壳类元素组成的可能因素,从胶州湾沿岸不同取样点采集黄海近海常见的菲律宾蛤仔(Ruditapesphilippinarum)、褶牡蛎(Oystrea denselamellosa)和紫贻贝(Mytilus galloprovincialis),分别测量了3种壳体的矿物物相类型和壳体中的Ca,Mg,Mn,Sr元素组成。研究表明:3种壳体分别属于文石质、方解石质和混合质壳;Ca,Mn元素含量在菲律宾蛤仔、褶牡蛎和紫贻贝壳体中没有差别,而Mg元素含量在菲律宾蛤仔壳体中含量较低,在褶牡蛎壳体和紫贻贝壳体中含量较高,Sr元素恰好与Mg元素相反。双壳类壳体中元素组成主要受壳体矿物物相类型的制约,而与水体环境要素之间的关系弱。     

南海北部冷泉碳酸盐岩中钙质生物壳体和自生碳酸盐矿物的Mg/Ca、Sr/Ca及其环境指示

南海北部冷泉碳酸盐岩具有包裹结构和孔洞结构,并且含有丰富的生物遗迹。利用电子探针对位于不同结构单元(包裹结构和基质)的自生碳酸盐矿物和钙质生物壳体进行了Mg/Ca和Sr/Ca分析,结果显示:自生碳酸盐矿物Mg/Ca变化范围为0.50~39.19mmol/mol,平均为12.50mmol/mol,Sr/Ca变化范围为0.06~2.90mmol/mol,平均为0.53mmol/mol;钙质生物壳体Mg/Ca变化范围为1.14~84.57mmol/mol,平均为24.57mmol/mol,Sr/Ca变化范围为0.77~1.84mmol/mol,平均为1.08mmol/mol。Mg/Ca和Sr/Ca的关系显示自生碳酸盐矿物均具有低到中等的Mg/Ca、低Sr/Ca的特征,没有明显分组现象;但是钙质生物壳体却根据其在岩石中的结构位置呈现明显的分组现象,基质钙质生物壳体具有高Mg/Ca、中等Sr/Ca的特征,包裹的钙质生物壳体具有低Mg/Ca、中等Sr/Ca的特征。根据碳酸盐矿物和钙质生物壳体的Mg/Ca特征,认为基质钙质生物壳体是在甲烷渗漏环境下钙化的,无机碳酸盐矿物的出现影响了其Mg/Ca;而包裹的钙质生物壳体是在非甲烷渗漏环境下钙化的,由于生物扰动、灌洗等作用以包裹团块的形式保存在碳酸盐岩中。依据Sr/Ca在成岩过程中的变化特点推测最初形成的基质钙质生物壳体可能具有较现在高的Sr/Ca。研究结果在甲烷渗漏信息地球化学指标提取方面具有一定意义。     

湖相介形类壳体微量元素在古环境重建中的应用

湖相介形类壳体微量元素(本文主要指Mg和Sr)是重建古环境的重要指标之一,可以定性或定量地反映湖水信息。自20世纪80年开始应用以来,经过30余年的发展取得了很大进展。在古环境重建过程中主要存在两类影响因素:(1)其宿生水体中M/Ca比值(M主要指Mg和Sr)的影响因素:季节变化、微环境差异和湖泊演化过程,这类因素通过对宿生水体中M/Ca比值来影响介形虫壳体中的M/Ca比值,进而造成古环境重建结果的误差增大或可靠性降低;(2)介形类壳体微量元素分配系数的影响因素:宿生水体中M/Ca比值、温度、碱度等,这类因素能够直接影响介形类壳体分泌、钙化的生命-化学过程的因素,是定量重建的重要影响因素。加强现代介形类生活习性和微量元素组成变化过程的研究可以消除或减小以上影响因素对古环境重建的影响,提高介形类壳体化石中微量元素组成在古环境重建研究中的精度和可靠性。     

菲律宾蛤仔壳体生长过程中Ca, Mg, Sr, Mn和Fe元素富集规律研究

为了解壳体的生长过程中内部元素含量的变化规律,结合现场养殖实验探讨了菲律宾蛤仔 ( Ruditapes philippinarum ) 壳体元素组成的"生命效应"问题.结果显示:菲律宾蛤仔壳体生长过程中 Ca, Mg, Sr, Mn, Fe 五种元素含量的绝对变化量不是很明显,均在同一数量级范围内波动;根据 5 种元素在壳体生长过程中的相对含量变化规律,可分为两类:①与壳体生长率不相关的 Ca, Mn, Sr, Mg 元素;②大致与壳体生长率呈负相关的 Fe 元素.Fe 元素与壳体生长率的负相关性主要受环境因子和蛤仔壳体生命过程因素的影响,其中温度是最主要的影响因素.     

底栖有孔虫(Florilus decors)壳体微量元素/钙比值的LA-ICP-MS原位微区分析方法及应用——以长江口外海域为例

深海沉积物中有孔虫壳体的微量元素、同位素测试技术已较为成熟，而河口近海沉积物中有孔虫壳体元素微区测试却鲜有报道。本文报道了一种利用激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）分析法测试取自长江口外沉积物中的有孔虫壳体元素/钙比值的技术，研究了氦气载气流量、能量密度、束斑大小、激光剥蚀频率等参数对测试结果的影响，优化了活体有孔虫原位分析方法。应用确定的测试条件对2016年7月取自长江口外的底栖有孔虫优美花朵虫样品（Florilus decors）进行测试，发现Mg、Sr等元素/钙比值在壳体不同位置上无显著差异，而Mn的数据较为离散，可能与有孔虫生长过程中经历的水环境及其变化有关。     

渤、黄海大泷六线鱼耳石微化学特征与群体判别

为探究中国近海大泷六线鱼(Hexagrammosotakii)耳石微化学成分特征及群体分化状况,采集了连云港、青岛、威海、烟台、秦皇岛、大连、丹东7个野生群体和1个威海养殖群体的大泷六线鱼样本。利用LA-ICPMS技术测定耳石中的微量元素,以微量元素与钙的比值进行了分析,结果显示大泷六线鱼耳石中, Na/Ca、Sr/Ca、Fe/Ca、Mg/Ca较高,而Mn/Ca、Ba/Ca、Zn/Ca、Li/Ca较低。耳石1龄前元素比值的组间比较(S-N-K检验)结果显示:Na/Ca、Sr/Ca、Fe/Ca在群体间具显著性差异(P<0.05)。耳石边缘区元素与环境中元素比较发现,Li、Mn元素在耳石中富集程度较大,Sr在耳石的中元素含量远远大于水环境中的浓度,说明耳石中的元素沉积与海水中元素并不是简单的线性关系。判别分析结果显示:耳石1龄前元素指纹的判别分析结果表明,大泷六线鱼群体的判别成功率为63.0%,判别正确范围为30.0%～80.0%,耳石边缘区元素的判别正确率为57.1%,判别正确范围20.0%～80.0%,秦皇岛群体有高的判别成功率80.0%。耳石元素指纹可以用于不同大泷六线鱼群体的...     

渤海西岸介形虫壳体元素地球化学及古海洋学意义

生物地球化学在海洋地质方面的应用已引起人们的重视,尤其是用生物骨骼化学组成进行古环境解释已成为古海洋学研究的重要内容。本文对取自渤海西岸434m一钻孔中21个层位的45个介形虫壳体,利用扫描电镜和能谱仪分析了壳体的Ca,Mg,K,Mn,Ti,Al,Fe,Ba,Sr,Si和Ga‰11种元素成分含量,并进行了两次分析对照检验,其标准误差小于2‰。分析结果表明,介形虫壳的元素成分主要是Ca,平均含量83.86％,其次是Si(4.34％),Al(4.38％),Mg(2.71％),Fe(1.53％);K     

东北太平洋中国合同区悬浮颗粒物元素地球化学

利用ICP-MS对东北太平洋中国合同区3个测站分层采集的悬浮颗粒物的元素组成进行了测试,对Na、Mg、Al、Ca、Ti、Mn、Fe、Co、Cu、Sr、Ba和Pb等12种元素的含量分布及其地球化学特征进行了研究和对比。结果表明,水体中悬浮体总量(TSM)一般低于0.3mg/dm3,12种元素含量从几百到不足0.01μg/dm3。其分布以500和5000m为界可分为3层。元素中Al和Ti可作为陆源元素指标,Sr和Ba可作为生源元素指标,Pb主要来源于人类活动。在西区,Na、Mg和Ca主要为生源元素,Mn、Fe、Co和Cu主要为陆源元素。在东区,Na、Mg和Cu为多源元素,Ca、Mn、Fe和Co以陆源为主。颗粒物物源及供应量是颗粒物和元素含量分布的控制因素。西小区海底火山活动强烈是影响两区元素组分差异的直接因素之一。     

黔北石膏洞9.9～4.2 kaBP石笋微量元素记录及环境意义

通过对黔北石膏洞一石笋(编号SG-1)进行碳氧稳定同位素测试和XRF元素扫描分析,结果表明研究时段内Mg/Ca、Sr/Ca和Ba/Ca比值都表现了较明显的阶段性变化:Mg/Ca比值在9.9~6.6kaBP偏低,6.6~4.2kaBP期间逐渐升高,整体变化趋势与石笋δ18 O变化趋势较为一致,呈正相关关系,表明石膏洞石笋Mg/Ca比值主要受降水的影响,即降水增多(δ18 O偏负),岩溶水在母岩中滞留时间短,Mg/Ca比值降低;反之则升高。Sr/Ca和Ba/Ca比值在8.7~4.2kaBP的变化与石笋δ13 C变化趋势一致,呈反相关关系,植被和土壤微生物活动有可能是影响石膏洞石笋Sr/Ca和Ba/Ca的主要因素。但是在9.9~8.7kaBP,Sr/Ca和Ba/Ca比值与石笋δ13 C关系复杂,有可能同时受到温度、降水、地表植被和上覆土壤等众多因素的影响。因此,运用Ba/Ca和Sr/Ca进行古气候研究时需要慎重,要注重多指标对比研究。     

珊瑚礁的成岩作用:来自南海永兴岛珊瑚礁的原位地球化学研究

珊瑚礁的地球化学特征记录了其形成时周围海水的状况,能够反映古海洋、古气候和古环境变化;然而珊瑚礁形成过程中及其形成后,容易受到成岩作用的影响,导致其矿物组成和地球化学特征发生变化;因此,在对珊瑚礁的研究中,首先要识别出保存原始沉积特征的组分,并排除后期成岩改造的影响。以西沙群岛永兴岛的SSZK1珊瑚礁钻孔岩心为研究对象,通过矿物学、岩相学和地球化学相结合的研究方法,对不同层位的生物化石、碳酸盐胶结物进行原位地球化学分析,探索成岩作用对不同形成阶段矿物的改造。SSZK1井岩心的岩石类型主要为骨架灰岩和生物碎屑灰岩两大类;岩心礁相碳酸盐岩沉积后主要受控于早期大气成岩作用,成岩层段揭示的主要成岩作用类型有胶结作用、新生变形作用和溶解作用。电子探针和LA-ICP-MS的原位分析结果表明,不同阶段的珊瑚礁碳酸盐岩的矿物成分较为单一,主要是由方解石组成,仅在局部的生物化石中保存了原始形成的文石。后期形成的碳酸盐胶结物(低Sr/Ca、低Sr、高Mg/Ca)和原始的生物化石(高Sr/Ca、高Sr、低Mg/Ca)具有明显不同的地球化学特征,表明不同阶段的碳酸盐矿物受不同来源流体的制约。     

Experimentally determined Mg/Ca and Sr/Ca ratios in juvenile bivalve calcite for Mytilus edulis: implications for paleotemperature reconstructions

To further evaluate the potential use of Mg/Ca and Sr/Ca ratios as a paleothermometer in the shell carbonate of the blue mussel Mytilus edulis, we grew juvenile mussels (～15 mm shell height; <2 years old) collected from Maine, USA, in controlled environments for 4 months. The four-by-three factorial design consisted of four circulating temperature baths (7, 11, 15 and 19°C), and three salinity ranges (23, 28, and 32). During the experiment, water Mg/Ca and Sr/Ca molar ratios were monitored weekly, and showed little variation across all salinity and temperature ranges. Data from sampled shells including all salinity treatments yielded relatively poor relationships between shell elemental chemistry and water temperatures. However, if only the low salinity treatment data (23) are used, the relationships between shell elemental chemistry and water temperature improve moderately. Based on the data presented here, it may be possible to use Mg/Ca and Sr/Ca ratios from the shell carbonate of juvenile M. edulis to reconstruct paleotemperatures in estuarine settings (salinity below 24) with a corresponding RMSE (root mean squared error; 95% confidence interval) of ±2.4°C and ±2.8°C, respectively. In order for this methodology to be statistically meaningful, water temperature changes must be rather large, as the errors associated with using Mg/Ca and Sr/Ca ratios from the shell material of M. edulis are substantial. Further work is required to determine if the findings presented here can be duplicated, and if the potential salinity effect is pervasive.     

Stock Identification of Chum Salmon (<Emphasis Type="Italic">Oncorhynchus keta</Emphasis>) Using Trace Elements in Otoliths

The relationship between trace elements in chum salmon otoliths and in their rearing water was investigated to develop ways to distinguish chum salmon stocks in Korea. Rearing water and otoliths of hatchery-reared chum salmon fry were collected from three major hatcheries (Yangyang, Samchuk, and Uljin) on the east coast of Korea in spring 2001 and 2002. Trace elements in the otoliths and rearing water were analyzed using inductively coupled plasma mass spectrometry (ICP-MS) at the Korea Basic Science Institute. The chemical composition of rearing water and otoliths of the salmon fry at specific sites did not vary significantly through the study period. The ratios of some trace elements to Ca in rearing water, such as Sr/Ca and Ba/Ca, was clearly reflected in the chemical composition of otoliths, although the absolute concentrations were different. These two elements may be useful in distinguishing between salmon hatcheries, which have different chemical environments. Discriminant analysis with the ratios of eight elements to Ca (Na/Ca, Mg/Ca, Al/Ca, Cu/Ca, Sr/Ca, Ba/ Ca, Mn/Ca, and Zn/Ca) revealed a distinct separation of natal area in stocks. The analysis of otolith chemistry may be an effective technique for identifying the origins of wild salmon caught at sea.     

Shell architecture,element composition,and stable isotope signature of the giant deep-sea oyster Neopycnodonte zibrowii sp. n. from the NE Atlantic

A conspicuous new deep-sea oyster, Neopycnodonte zibrowii sp. n., is described from the Azores Archipelago, where it thrives in 420 to >500 m water depth in high densities concealed underneath overhangs. The new species reaches a relatively large size, which may exceed 20 cm, and is characterised by a very unusual hinge line morphology, straight without a bulge of the resilium. It is compared to the extant Indo-Pacific Empressostrea kostini Huber and Lorenz, 2007 and to the cosmopolitan Neopycnodonte cochlear (Poli, 1791), which has a broadly sympatric distribution at shallower depths in the Azores and Bay of Biscay. Radiocarbon dating reveals that individuals reach an impressive lifespan of one to more than five centuries, placing them among the longest-lived molluscs known to date. They often grow on top of each other, forming stacks that resemble dish piles—an effective measure to optimise shell stability with minimal biomineralisation effort, but with the drawback of increased bioerosion ultimately leading to detachment.Three microstructure types are developed in N. zibrowii: (1) the cross-foliated, calcitic, dorsal to central endostracum and aragonitic ligostracum, (2) the porous vesicular structure of the calcitic ventral endostracum, and (3) the simple prismatic aragonitic myostracum. Foliated and vesicular shell portions show sub-millimetre-scale first-order increments delineated by conchiolin-rich growth breaks (interpreted as reproductive cyclicity), and less distinct second-order increments (interpreted as annual in nature). This pattern is clearly reflected by the elemental composition with the primary growth breaks lacking Ca and Sr but including Mg and S as organic matrix constituents. The second-order increments within the calcite are mirrored by moderately co-varying Mg/Ca and S/Ca fluctuations at stable Sr concentrations, reflecting varying proportions of organic matrix. Dorsal and central endostracum transects reveal a low inter-valve, but considerable inter-specimen variability with high Mg/Ca molar ratios and fluctuations (22.5±17.6 mmol/mol), low Sr/Ca values (0.2±0.1 mmol/mol), and a typical to high S/Ca content (6.9±2.2 mmol/mol), when compared to other calcitic bivalves.Unlike short-lived, shallow-water oysters, N. zibrowii thrives under very stable environmental conditions. Minimal temperature fluctuations and stable open marine salinity provide an optimal basis to recognise biological fractionation processes. Strong Mg/Ca fluctuations indicate a physiological control related to metabolism and biomineralisation, prohibiting the use of this ratio as a temperature or ocean chemistry proxy. Low Sr/Ca ratios indicate rather constant and low long-term accretion rates, while short-scale fluctuations may be attributed to short-term variations in growth rate and Mg incorporation. Oxygen isotopes yield a considerable spread of 1.8‰ with a mean of 2.0±0.3‰ δ¹⁸O V-PDB, and low correlation between different contemporaneous parts of the shell and between specimens. These values surprisingly exceed expected equilibrium conditions, calculated from in situ temperature data (annual mean 12.3±0.3 °C) and seawater isotopic composition (0.5±0.1‰ δ¹⁸O SMOW), by 0.5‰ on average. Such positively shifting vital effects, previously reported for limpets and barnacles, are often overlooked in high-temperature and high-amplitude settings and may be more common than is currently believed. Carbon isotopes range from 0.2 to 3.5‰ δ¹³C V-PDB (mean 1.8±0.7‰) and show an ontogenetic decrease, but may incorporate an environmental signal in adult portions, indicated by a strong correspondence of peaks between specimens. This signal is likely driven by a complex interplay of different factors, such as primary production, current-based food supply and metabolism.     

Pristine or altered: low-Mg calcite shells survived from massive dolomitization? A case study from Miocene carbonates

Low-Mg calcite shells have been widely used to reconstruct the chemistry of ancient seawater. There is always a question: are the shells chemically pristine? This paper presents the isotope and elemental geochemistry of low-Mg calcite bivalve shells in late Miocene platform carbonates, SE Spain. The platform carbonates were extensively dolomitized, and limestone is restricted to older stratal units, and to units mainly in topographically higher and more landward strata. Low-Mg calcite oyster shells were completely dissolved out in the basinward dolomite, but are well preserved in the limestone. These shells appear to retain the original growth microstructures, based on hand samples. Under the microscope, however, dissolution and recrystallization, as well as pristine growth lines are all present. Sr isotopes in these shells range from that of normal Miocene seawater to radiogenic values. δ¹⁸O and δ¹³C values, and Mg, Sr, and Na concentrations in these shells are rather variable. The high end members are consistent with the typical values of modern/late Miocene normal-seawater low-Mg calcite shells, whereas the low end members are close to those of diagenetic calcite cements, which have low δ¹⁸O, δ¹³C, Sr and Na values, and radiogenic Sr. The Nijar shells were altered physically and chemically to different degrees by diagenesis, although these shells are consistent with some “criteria” of unalteration. The isotopic and trace-element data collected in altered and pristine (or less altered) portions coexisting in the same shells are clearly differentiable. Quantitative simulation of covariations of geochemical pairs indicates that solid mixing of unaltered and altered portions by sampling is consistent with the variations in isotopic and elemental data recorded in the Nijar shells. The geological significance of this study is that ancient fabric-retentive calcite shells may have been altered geochemically although they may appear pristine. Calcite shells that underwent intensive diagenesis should be examined rigorously under the microscope, coupled with investigations of multiple geochemical proxies to assess chemical alteration. Only the data of unaltered shells can be used to reconstruct the chemistry of ancient seawater.     

Effects of salinity on mineralogy and chemical composition of Cerastoderma edule and Monodonta articulata shells

Shells of the mollusks Cerastoderma (Cerastoderma) edule (Linnaeus 1758) and Monodonta (Osilinus) articulata Lamark 1822 from salt evaporate basins in western Sicily are studied and the effect of environmental conditions (particularly salinity and water chemistry) on mineralogy and chemical composition is investigated and discussed.

The elements determined both in seawater and shell carbonate are: Ca, Mg, Mn, Fe, Ni, Co, Cu, Zn, Sr and Pb.

Both species studied discriminate against all the minor and trace elements determined; the degree of such discrimination, for some elements, is inversely related to salinity.

The mineralogical composition of the shells (Monodonta has a mixed mineralogy while Cerastoderma is entirely aragonitic) appears to be controlled neither by temperature nor by salinity.

In Monodonta shells direct correlations have been found between the following parameters: calcite-Sr (in younger shells only), calcite-Fe, calcite-Pb (in older shells only), calcite-Zn, salinity-Mg and salinity-Pb, whereas inverse correlations were observed between calcite and Sr (in older shells only) and calcite and Pb (in younger shells only). In Cerastoderma shells a direct correlation was found between salinity and Fe and Mg.

The thickness of the shells appears, in both species, to be an inverse linear function of salinity.     

Using LA-ICP-MS to analysis elemental composition of statoliths of Scyphozoan jellyfish

Scyphozoan jellyfish outbreak events are drawing increasing attentions during the past decade. Elemental compositions of statoliths are helpful to understand jellyfish life history and blooming mechanisms, but very rare endeavor has been focused on the Scyphozoan class. In this work, we explored the feasibility of element analysis of Aurelia aurita (a representative Scyphozoan jellyfish outbreak species in China) which may be used as proxies of environment parameters during jellyfish living and moving. Statolith crystals of Aurelia aurita were found to be a gathering of hexahedron type trigonal needle with size of 10?50 μm long, and 5?10 μm in diameter. By using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) downhole profiling method, elements such as Ca, Sr, Mg, Na and P were found to be above the limit of detection and limit of quantification. The epidermis of statocyst could significantly impact the element analyses, so the real statolith element signal section needs to be selected based on elements and Ca profiles together with care. By laser ablated a signal spot repeatedly, the analytical uncertainty was about 3%?4% for Sr/Ca content ratio and Mg/Ca content ratio, but above 10% for other element/Ca content ratios (n=3). Based on the analysis of statolith from temperature-control cultured jellyfish, Sr/Ca content ratios among different statoliths of the same jellyfish were about 6% (n=14), demonstrating biological processes/vital effects causing small variations compared with analytical uncertainties. Therefore, Sr/Ca content ratios may be used as a potential proxy to reveal the living environment variations the Scyphozoan jellyfish has experienced, such as temperature history, which is helpful to understand jellyfish bloom mechanisms.     

淡水径流影响下珊瑚温度计(B/Ca、Mg/Ca、Sr/Ca、U/Ca和δ18O)的稳定性测试

对南海北部珠江口采集的滨珊瑚骨骼地球化学温度计指标B/Ca、Mg/Ca、Sr/Ca、U/Ca和δ¹⁸O进行了分析,目的在于测试这些地化指标在径流冲淡水影响下的稳定性.测试方法是将各个地化指标与水温对比并进行相关性分析.结果表明,Sr/Ca比值与当地水温有最好的相关性(r²=0.59),说明Sr/Ca是最稳定的温度计指标.而δ¹⁸O(r²=0.46)、B/Ca(r²=0.43)和U/Ca(r²=0.41)与水温的相关系数相对较低,说明这些指标除受到水温控制以外还受到其他环境因素的影响.在这些指标中,相关性最低的是Mg/Ca(r²=0.27),说明Mg/Ca受到除水温以外的因素影响最为显著,这就限制了Mg/Ca作为有效的温度计指标应用于古气候重建的研究.