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。     

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.     

近2ka以来东海内陆架泥质区记录的高分辨率古气候演化

通过对位于东海内陆架泥质区中部的MZ02柱样岩芯进行粒度、常量元素、AMS14C分析,获得了粒度和常量元素随时间变化的高分辨率曲线.结果表明,近2 ka以来研究区沉积环境稳定,以沿岸流控制的浅海沉积为主,沉积物中CaO/K2O,MgO/Al2 O3和MnO/Na2 O比值的变化与我国东部气候变化序列具有较好的一致性,证...     

Synchronous barium peaks in high-resolution profiles of calcite and aragonite marine bivalve shells

Barium/calcium profiles of bivalve shells are characterized by flat background signals periodically interrupted by sharp peaks, with the background signals correlated with water Ba/Ca. To test if the peaks are an environmental signal related to productivity, we analyzed high-resolution Ba/Ca profiles in bivalve shells that grew adjacent to one another. Two aragonitic Saxidomus giganteus show remarkable similarity over a decade of growth, clearly indicating an environmental forcing. Four calcitic Pecten maximus shells also record synchronous Ba/Ca peaks, again indicating an exogenous control. The Ba/Ca peaks, however, start ~40 days after the crash of a bloom, while sedimentation takes place immediately following the bloom. Barite formation in settling phytoplankton flocs, as has been previously proposed, is clearly not the cause of these peaks. Other possible causes, such as dissolved Ba in ambient water, spawning, shell organic matter content, and kinetic growth rate effects are also discussed, but none provide satisfactory explanations. Background shell Ba partition coefficients (Ba/Ca_carbonate/Ba/Ca_water) for both the calcitic shells (0.18) and aragonitic shells (0.16) are similar to that previously reported for the calcitic Mytilus edulis (~0.1). We suggest that Ba/Ca peaks in bivalve shells are caused by an as yet undetermined environmental forcing, while background Ba/Ca levels are a good indication of dissolved Ba/Ca in the water; both are independent of shell mineralogy.     

Upstream dams and downstream clams: growth rates of bivalve mollusks unveil impact of river management on estuarine ecosystems (Colorado River Delta, Mexico)

We studied how the extensive diversion of Colorado River water, induced by dams and agricultural activities of the last 70 years, affected the growth rates of two abundant bivalve mollusk species (Chione cortezi and Chione fluctifraga) in the northern Gulf of California. Shells alive on the delta today (‘Post-dam’ shells) grow 5.8–27.9% faster than shells alive prior to the construction of dams (‘Pre-dam’ shells). This increase in annual shell production is linked to the currently sharply reduced freshwater influx to the Colorado River estuary. Before the upstream river management, lower salinity retarded growth rates in these bivalves. Intra-annual growth rates were 50% lower during spring and early summer, when river flow was at its maximum. Growth rates in Chione today are largely controlled by temperature and nutrients; prior to the construction of dams and the diversion of the Colorado River flow, seasonal changes in salinity played an important role in regulating calcification rates.Our study employs sclerochronological (growth increment analysis) and geochemical techniques to assess the impact of reduced freshwater influx on bivalve growth rates in the Colorado River estuary. A combination of both techniques provides an excellent tool to evaluate the impact of river management in areas where no pre-impact studies were made.     

尺度重整分析中周期性成分的影响

目前，越来越多的研究者将尺度重整分析(R／S)引入古气候环境研究中。但在这些研究中很少提及周期性成分对尺度重整分析结果的影响。然而实际上，古气候环境演化往往显示出明显的周期性变化，而周期性成分的存在对尺度重整分析具有显著的影响。笔者列举了2个实例对此进行了说明。这些事实表明，在古气候环境研究中，没有考虑周期性成分影响的尺度重整分析的结果需要谨慎使用，有些可能需要做进一步修正。     

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。     

南黄海牡蛎壳元素组成的原位微区分析及环境指示

碳酸盐生物壳体的周期性生长纹层是记录气候环境变化的天然材料。随着原位微区测试技术的快速发展,高分辨率的同位素和化学元素组成的快速分析显著推动了古气候环境变化及生物地球化学研究。应用激光剥蚀等离子体质谱仪(LAICP-MS)对南黄海现代牡蛎Crassostrea gigas壳体韧带部的元素组成进行原位微区测试,利用内标元素43Ca进行元素比值的校正,探讨了牡蛎壳中化学元素特征及其环境意义。研究的长牡蛎壳体中Mg/Ca、Sr/Ca、Na/Ca比值具有显著的季节性周期变化。环境水体物理化学性质的变化对壳体生长速率影响较大,壳中白垩质方解石和叶片方解石生长层分别对应较高和较低的环境温度,白垩方解石层具有较高的Mg/Ca、Sr/Ca和较低的Na/Ca比值。Mg/Ca比值可指示牡蛎壳体生长环境水体温度,利用前人Mg/Ca比值公式计算可以恢复与器测资料相符的近岸海水温度结果。本研究对应用LA-ICP-MS分析技术开展高分辨率的生物壳体元素组成和环境示踪研究具有借鉴意义。     

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.     

Late Holocene marine productivity changes in Northern Patagonia-Chile inferred from a multi-proxy analysis of Jacaf channel sediments

A multi-proxy approach based on organic (organic carbon, alkenones, and C/N) and inorganic geochemical proxies (biogenic opal, inorganic carbon, Fe, Ti, and Ca) preserved in the sediments of the Jacaf channel (CF7-PC33; 44°21′S, 72°58′W, 510 m water depth), Chilean fjords, yields evidence of major past productivity fluctuations in accordance with climatic changes over the last ∼1800 years. The downcore record clearly shows two productivity/climate modes. The first period, prior to 900 cal yr BP, is characterized by decreased marine productivity and a reduced continental signal, pointing to diminished precipitation and runoff. In contrast, the second period between ∼750 cal yr BP and the late 1800s (top of core) is illustrated by elevated productivity and an increased continental signal, suggesting higher precipitation and runoff. Both time intervals are separated by a relatively abrupt transition of ∼150 years which roughly coincides with the beginning of the Little Ice Age. The increased content of freshwater diatoms and Chrysophyte cysts that characterize the last 200 years of the latter mode coincides with a significant decrease in the carbonate content of the sediment; together they further indicate increased terrigenous contributions and decreased marine carbonate productivity at the end of the Little Ice Age. The correspondence between our record and other paleoclimate studies carried out in South America and Antarctica demonstrates that the Chilean fjord area of Northern Patagonia is not just sensitive to local climatic variability but also to regional and possibly global variability.     

Progress in the Study of Coastal Storm Deposits

Numerous studies have been carried out to identify storm deposits and decipher storm-induced sedimentary processes in coastal and shallow-marine areas. This study aims to provide an in-depth review on the study of coastal storm deposits from the following five aspects. 1) The formation of storm deposits is a function of hydrodynamic and sedimentary processes under the constraints of local geological and ecological factors. Many questions remain to demonstrate the genetic links between storm-related processes and a variety of resulting deposits such as overwash deposits, underwater deposits and hummocky cross-stratification (HCS). Future research into the formation of storm deposits should combine flume experiments, field observations and numerical simulations, and make full use of sediment source tracing methods. 2) Recently there has been rapid growth in the number of studies utilizing sediment provenance analysis to investigate the source of storm deposits. The development of source tracing techniques, such as mineral composition, magnetic susceptibility, microfossil and geochemical property, has allowed for better understanding of the depositional processes and environmental changes associated with coastal storms. 3) The role of extreme storms in the sedimentation of low-lying coastal wetlands with diverse ecosystem services has also drawn a great deal of attention. Many investigations have attempted to quantify widespread land loss, vertical marsh sediment accumulation and wetland elevation change induced by major hurricanes. 4) Paleostorm reconstructions based on storm sedimentary proxies have shown many advantages over the instrumental records and historic documents as they allow for the reconstruction of storm activities on millennial or longer time scales. Storm deposits having been used to establish proxies mainly include beach ridges and shelly cheniers, coral reefs, estuary-deltaic storm sequences and overwash deposits. Particularly over the past few decades, the proxies developed from overwash deposits have successfully retrieved many records of storm activities during the mid to late Holocene worldwide. 5) Distinguishing sediments deposited by storms and tsunamis is one of the most difficult issues among the many aspects of storm deposit studies. Comparative studies have investigated numerous diagnostic evidences including hydrodynamic condition, landward extent, grain property, texture and grading, thickness, microfossil assemblage and landscape conformity. Perhaps integrating physical, biological and geochemical evidences will, in the future, allow unambiguous identification of tsunami deposits and storm deposits.     

The curse of physiology—challenges and opportunities in the interpretation of geochemical data from mollusk shells

Physiology corrupts geochemical records of mollusk shells in many ways, e.g., by actively controlling the incorporation of trace elements in the skeleton. However, the effects of variable biomineralization rates and growth cessation have largely remained unconsidered. Mediated by endogenous timekeeping mechanisms, mollusks stop growing skeletal material on a regular basis ranging from ultradian to annual timescales. During growth cessation, the shells do not record environmental conditions. Shell growth also stops when environmental conditions are beyond the physiological tolerance of the organism, e.g., above and below genetically determined, species-specific thermal extremes where shell growth slows and eventually ceases. Such growth disruptions can occur at non-periodic time intervals. Due to growth retardations and halts, proxy records of mollusk shells are thus incomplete, and reconstructed environmental amplitudes prone to truncation. Furthermore, environmental records are biased toward the physiological optimum of the animal. Favorable environmental conditions increase shell growth, whereas adverse environmental conditions result in reduced shell production and lowered overall metabolism. Not least, the duration of the growing season and overall growth rate decrease as the mollusk grows older. Mathematical modeling approaches can significantly improve proxy records obtained from mollusk shells. For example, if the duration of growth cessation is known, it may be possible to model the missing environmental record. It is also fairly easy to account for age-related growth trends, or variable time-averaging in different portions of the shell. However, a major premise for a reliable interpretation of proxy records from a mollusk shell or other organisms secreting biogenic hard parts is a proper understanding of the physiology, and of course, a high-resolution record of the many different environmental factors that may influence physiology and shell growth. The present paper reviews examples from the literature, and unpublished data on how physiology influences geochemical proxy records from mollusk shells, and presents methods how to eliminate such adverse effects.     

古海洋生产力的研究方法

海洋的初级生产力控制了温室气体CO2在海洋和大气中的分配,进而影响着全球气候变迁,只有通过运用不同的生产力标志物才能探讨地质历史上海洋初级生产力的变迁及其对气候的影响。介绍了国内外在古海洋生产力研究领域内使用的主要方法和动态,并分别对生源物质累积率、底栖有孔虫标志物和地球化学标志物等研究方法进行了全面的分析和评述,指出在运用生产力标志物研究古生产力时应充分考虑不同标志物的适用性和局限性。     

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。     

The structure of benthic environments and the paleochemical record of foraminifera

Benthic foraminiferal shell geochemistry has been extensively used to develop paleoceanographic tracers. Many of these proxies are sensitive to the geochemical conditions of the microhabitats selected by particular foraminiferal species. Understanding these microhabitats, then, is essential for proper interpretation of the proxies. A simple, broadly accepted, view is that foraminiferal species’ habitats are vertically stratified in the sediments due to general pore-water chemical gradients, which develop in response to the seabed organic carbon flux. Species are categorized into epifaunal, shallow infaunal and deep infaunal habitats, and are supposed to acquire the geochemical characteristics of these. However, this view is at odds with species’ distributional data and foraminiferal geochemical properties. We present an alternate model in which foraminifera select for habitats within the bio-irrigation system of the sediments created by the activities of macro-/meio-fauna. Our distributional and geochemical data indicate that foraminiferal species seek particular biotic associations and geochemical conditions within the complex bio-architecture of the sediments and are not tied to particular sediment depths, or the general pore-water chemistry of their apparent habitation zone. Instead, foraminifera inhabit micro-environments with steep oxic to anoxic gradients. This might account for disparities among geochemical tracers.     

热带印度-太平洋浮游有孔虫Pulleniatina obliquiloculata的B/Ca和Cd/Ca指标：次表层海水碳化学参数计算的应用

Pulleniatina obliquiloculata shells from 16 core-top samples from the tropical Indo-Pacific Oceans are analyzed for the ratios of boron and cadmium to calcium(B/Ca and Cd/Ca). The B/Ca ratios show a very weak positive relationship with [B(OH)_4~-] and the dissolved carbonate species at the apparent calcification depth of P.obliquiloculata. The boron partition coefficients(K_D) between P. obliquiloculata B/Ca and seawater[B(OH)_4~-]/[HCO_3~-] distribute around 1.1×10~(-3)-1.3×10~(-3) with a mean value of(1.19±0.12)×10~(-3),and are significantly related to the nutrient concentration, especially phosphate. The lack of any clear correlation between the P. obliquiloculata B/Ca and seawater carbonate chemical parameters suggests that the physiochemical controls on boron incorporation are masked by the complexity of natural seawater condition. But the significant dependence of Ku on nutrient may likely be explained by a nutrient related growth-rate effect. Cd/Ca of P.obliquiloculata shows significant correlation with seawater phosphate concentration, and its partition coefficients(D_(cd)) are significantly related to temperature. A first-principle methodology of P. obliquiloculata B/Ca is applied;with the aid of Cd/Ca as a phosphate proxy and a constraint on K_D, to estimating sea water carbonate chemistry(e.g., pH). The results are fairly promising and allow us to propose the possibility to apply the combination of B/Ca and Cd/Ca proxies(and also Mg/Ca and δ~(18)O for estimating temperature and salinity) for the paleoreconstruction of seawater carbonate chemistry.     

全新世泥炭古气候记录研究进展

以年代标尺和古气候代用指标的建立为线索,总结了国内外近年来对全新世泥炭沉积古气候记录研究取得的最新进展,展望了未来泥炭古环境记录研究的前景,指出在建立可靠年代标尺和可靠环境代用指标过程中存在的一些急需解决的问题,如年代标尺与环境代用指标序列的协调问题,提出在泥炭剖面年代标尺建立过程中有必要分析环境代用指标,选取合适的组分进行测年。最后,作者指出用泥炭沉积进行全新世大气环境示踪研究具有较好的前景和重要的意义。     

赤道东经90°海岭活塞柱状心钙同位素曲线特征及其古环境意义

A δ~(44) Ca curve from shells of the planktonic foraminifera Globigerinoides sacculifer in calcareous biogenic oozes has been extracted from the Nintyeast Ridge in the Indian Ocean since 300 ka. By combining terrigenous inputs(e.g., grain size, magnetic susceptibility, and turbidite frequency) with the oceanic productivity(e.g., biogenic content and Neogloboquadrina dutertrei content), it is found that the curve's variations are closely related to the historical evolution of the oceanic calcium cycle. The δ~(44)Ca value is in lower tendency and has small oscillation during Marine Isotope Stage(MIS) 6, when the supply of terrigenous detrital is highest. In contrast, during MIS 3,5 and 7, the δ~(44) Ca values are in higher tendency, and their fluctuations are consistent with the variations of the productivity proxies. These results suggest that the calcium isotopes are mainly influenced by the input of the Himalayan erosion products to the northern Indian Ocean. In addition, the developmental stages of calcareous planktons may have a secondary impact on the fluctuations of the calcium isotope ratio of sea water.     

介形类壳体无机成份的定量分析及其指相意义

本文报道了笔者对四十六枚现生和化石四组介形类标本(现生海洋、现生淡水湖泊、化石海相、化石陆相介形类)壳体的内表皮层(即钙质层)进行能谱无机成份定量分析的结果。初步研究表明:介形类钙质壳体中各微量元素的出现频度、平均含量、钙镁比值等有关指数与它们的生活环境有密切关系。     

Radioecological investigations on the Northern Novaya Zemlya Archipelago

Multidisciplinary investigations carried out in the Cape Zhelaniya area and on the Severny ice dome of Severny Island in the Novaya Zemlya Archipelago during cruise 63 of the R/V Akademik Mstislav Keldysh in September 2015 included a study of the environmental radiation level. The landscape?geochemical and radiation?glaciological data show that the Severny ice dome serves as a secondary source of radionuclides on the surface of the ice sheet; this source originated from past nuclear weapons testing in the atmosphere over the Severnaya Zemlya test site. Some samples taken from the periglacial zone near the edge of the Severny ice dome yielded specific activity levels of radioactive cesium of 450–650 Bq/kg. The study of ice cores obtained by shallow (up to 5.4 m) drilling of three boreholes revealed no significant activity values. At the same time, glaciological investigations made it possible to obtain the first data on the previously unexamined glacier, which indicate that the radioactively contaminated layer is located at a depth of 15?20 m at the boundary of the glacier alimentation zone. No similar investigations had been conducted earlier either by Russian or international scientific teams.