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。     

茎柔鱼眼睛晶体微量元素地理差异及其与水温关系

本研究以2015年和2017年我国远洋鱿钓渔船在东南太平洋的厄瓜多尔、秘鲁和智利公海生产时采集的茎柔鱼眼睛晶体为研究材料,采用LA-ICPMS测定了眼睛晶体外缘的微量元素,比较微量元素地理区域间差异,分析微量元素浓度与茎柔鱼栖息水温的关系。结果显示,厄瓜多尔、秘鲁和智利公海的茎柔鱼眼睛晶体外缘Mg25、Ni60 、Cu63、Sr88和Ba137等元素在3个海区之间存在显著差异(p<0.05),Na23、Al27、Si29、P31、Ca43、Mn55、Zn66和Pb等元素在两两海区之间均不存在显著差异(p>0.05)。除了Sr88、Ba137、Fe57和Ni60与海表面温度呈显著的线性负相关,其他元素与海表面温度均无显著的相关关系。分析认为,Sr88、Ba137、Fe57和Ni60均可以看作茎柔鱼生活水温的指示元素,Ba137元素还可以看作茎柔鱼生活水深以及上升流的指示元素。研究认为,眼睛晶体微量元素可用于头足类栖息环境的重建。     

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。     

Cementation in cold-water bryozoan sand, Tasmania, Australia

Cold-water (<3–11°C) carbonate is the predominant sediment on the Tasmanian shelf. Calcitic skeletal grains (bryozoa, foraminifera, echinoderms, etc.) predominate over aragonitic (gastropods, etc.) ones. Non-skeletal grains are mostly micritic intraclasts with some pellets.

Fibrous spherulitic and rhombohedral calcite submarine cements range up to 90% in the bryozoan sand. X-ray analyses show that the bryozoan sand is characterized by a spectrum of calcites (low to high magnesian) and some aragonite.

A uniform spread of Mg concentrations from 0.06 to 2.48 wt.% indicates <3–10°C ambient water temperatures. The Mn (10–360 ppm) and Fe (176–2499 ppm) concentrations increase with increasing Mg values due to the formation of impure CaCO₃ phases. The Sr content in bryozoan sand (bryozoa = 3200 ppm Sr) decreases with increasing rhombohedral calcite cement, as low Mg-calcite precipitating from 3° C sea water would have 1350 ppm Sr. The bryozoan sand grains with fibrous spherulitic calcite cements have high Sr concentrations (4470–7000 ppm), in the same range as in aragonitic (detected only by X-ray analyses) bryozoan sand grains. The spherulitic calcite cements are either pseudomorphs after original aragonite cements or these calcite cements and aragonite were inverted from fibrous spherulitic vaterite, a predominant CaCO₃ polymorph at temperatures <10°C.     

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。     

Geochemical variation in ferromanganese nodules and associated sediments from the Pacific Ocean

The major and minor element compositions of a suite of abyssal sea-floor ferromanganese nodules and associated sediments from the eastern central Pacific have been used to examine inter-element relationships and the mineralogy of the nodules, the relationship between the composition of nodules and their associated sediments and regional variations in composition with respect to likely modes of formation of such deposits. Apart from Mn and Fe, significant proportions of the total Ti, Ca, Mg, K, Ba, Sr, Th and Y and almost all the P, As, Ce, Co, Cu, Mo, Ni, Pb, Zn and Zr are present in the oxide fractions of the nodules. The Mg, Ba, Cu, Mo, Ni and Zn contents are significantly correlated with the Mn content, while Ti, P, As, Pb, Sr, Y and Zr are similarly correlated with the total Fe content.Nodules from the northeastern tropical Pacific have Mn/Fe ratios higher than those in the oxide fractions of their associated sediments, todorokite as the principal Mn phase and relatively high concentrations of minor elements associated with Mn. Nodules from the south central Pacific have Mn/Fe ratios similar to those in the oxide fractions of the associated sediments, δ-MnO₂ as the only Mn-phase, and relatively high concentrations of minor elements associated with Fe. There appears to be a smooth gradation in composition in the tropical Pacific between these two end members.The regional compositional variation is interpreted as a reflection of different sources of metals for, and different growth mechanisms of, sea-floor nodules. The oxide precipitate from sea water consists of δ-MnO₂, has a relatively low Mn/Fe ratio and minor element contents related to the total Fe and Mn(δ-MnO₂) content. The oxide precipitate forming in areas of very low sedimentation as a result of diagenetic remobilisation in the surface sediment consists of todorokite, and has a high Mn/Fe ratio and enhanced metal content in the Mn-(todorokite)phase. Available information on the morphology and compositional variation of individual nodules from the tropical Pacific corroborates these contrasting metal sources and suggests that they can be resolved on the scale of an individual oxide concretion.     

High-resolution trace element profiles in shells of the mangrove bivalve Isognomon ephippium: a record of environmental spatio-temporal variations?

The shell chemistry of Isognomon ephippium from three Kenyan sites (Tudor, Gazi and Mida) has been investigated to determine whether these bivalves record environmental parameters. The Mg, Sr, Ba and Mn distributions in the calcite shell layer were determined by using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). In addition, whole-shell analyses were made to evaluate inter-site differences. While some variability is observed for mean Mg concentrations, the mean Sr concentrations were similar for the three sites. The decreasing mean Ba and Mn concentrations, following the order Tudor > Gazi > Mida, are related to distinct regimes of freshwater and nutrient supply. The Mg profiles, determined by LA-ICP-MS, displayed a close to regular sinusoidal pattern, depending on specimen and sample site. For the Tudor shells, an arbitrary fitting of the Mg profiles to sea-surface temperature (SST) variations emphasised the good relationship between these two parameters and allowed for the calculation of mean annual growth rates. In most of the shells, Sr partly co-varied with Mg and Ba, highlighting the complexity of Sr incorporation. The Ba and Mn profiles of the Tudor shells displayed several sharp maxima. With a time scale deduced from the Mg–SST relationship, the Ba and Mn maxima of the Tudor shells closely followed periods of maximal rainfall associated with the southeast monsoon. These Ba and Mn maxima were tentatively associated with algal bloom events known to succeed these periods of high rainfall. The less clearly marked seasonality of the Ba and Mn maxima for the Gazi and Mida specimens is thought to result from weaker seasonal variations in nutrient supply and reduced nutrients inputs. This study highlights the potential of I. ephippium as a recorder of spatio-temporal environmental variations in tropical coastal ecosystems.     

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.     

Distribution patterns of Recent planktonic foraminifera in surface sediments of the western continental margin of India

Study of Recent planktonic foraminifera from the surface sediment samples of western continental margin of India reveals the ecological preferences of the different planktonic foraminifer species in the area. Higher absolute abundance of planktonic foraminifera in the offshore associated with the lower frequencies of the productivity indicator Globigerinoides bulloides and lower absolute abundance in the nearshore with higher frequencies of G. bulloides appears to suggest that productivity does not control the absolute abundance of planktonic foraminifera in this area. In general, the difference in absolute abundance between offshore and nearshore indicates that the dilution by terrigenous and other biogenic (benthic foraminifera and diatoms) material governs the absolute abundance of planktonic foraminifera.

Globigerinoides sacculifer shows a significant positive correlation with salinity and a negative correlation with temperature, which reflects its preference for higher salinity and lower temperature of the surface water. Globigerinoides ruber abundances are related to a distinct highly saline Persian Gulf water mass in the eastern Arabian Sea. Neogloboquadrina butertrei shows a strong inverse relationship with surface water salinity in the eastern Arabian Sea. Therefore, the relative abundance variations of N. dutertrei in sediment cores of the southeastern Arabian Sea can be used to reconstruct the past surface water salinity, which varies according to the strength of the northeastern monsoon.

The high diversity of planktonic foraminifera in the offshore is attributable to equitable environmental conditions. The high-salinity surface waters ( > 36‰) and terrigenous dilution in the northeastern Arabian Sea limit the diversification of species in this region.     

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.     

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。     

Environmental influences on the shell mineralogy ofMytilus edulis

The shells ofMytilus edulis in the Tay estuary, Scotland, show mean aragonite contents of 55%, but in one zone the average aragonite proportion is only 45%. Comparison with data forMytilus edulis from other regions indicates the temperature and salinity are not the only significant determinants of the aragonite/calcite ratio. Elimination of other variables suggests that sewage discharges may influence the mineralogy of the shell secreted byMytilus edulis in the relatively nutrient-enriched areas.     

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。     

Geochemistry of eastern Mediterranean sediments: Primary sediment composition and diagenetic alterations

Two cores recovered in the eastern Mediterranean were analysed for major, minor and trace elements. The primary chemical composition of the sediment is different at each location, probably because the lithological sources and the relative biogenic contributions differ.

Carbonates are important for the concentration of Ca, Mg and Sr, whereas aluminosilicates determine the concentration of Si, Al, K, Li, Y and Be, and to a lesser extent that of Fe, Cr, Ti, Mg, Zn and Zr. In sapropels, organic carbon and sulphur seem to be closely related. Bromine, Mo, P, Fe, V, Cu, Zn, Co, Ni and Cr are closely associated with organic and sulphidic compounds. The concentration versus depth profile for organic carbon in two sapropels points to a rapid establishment of conditions that gave rise to sapropel formation, followed by a gradual transition back to “normal” conditions.

The primary composition is overprinted by diagenetic processes. Sulphate-reducing conditions occurred during and just after sapropel deposition. A progressive oxidation front mechanism, which became active after sapropel deposition, is responsible for additional major geochemical changes. This diagenetic phenomenon has strong implications for the chemistry of Fe, Mn, Ni, Co, Zn, Cu, Cr, V, U, As and Sb.     

Cerium anomaly variations in ferromanganese nodules and crusts from the Indian Ocean

Fifty analyses of rare earth elements as well as mineralogical studies have been carried out on a suite of manganese nodules and crusts from the Central Indian Basin and the Western Indian Ocean. The aim was to identify the processes controlling the REE patterns of the phases hosting the REE in the manganese nodules, with an emphasis on an understanding of the Ce anomaly. This has involved separating the encrusting layers and nuclei physically as well as Fe-Mn oxides from the aluminosilicate phase chemically (using a 2 M HCl leach) prior to analysis.

The presence of nodule nuclei seems to have little influence (mostly <5% to a maximum of 30%) on the overall magnitude of the Ce anomalies in these nodules. The ratios of concentrations of elements in the acid leachates and the corresponding bulk values yield flat REE patterns indicating that the aluminosilicate phase contributes very little to the Ce anomalies. Interelement relations indicate that the Ce anomalies are largely controlled by the amorphous mineral phase FeOOH.xH₂O. The relationship of Fe, Ce anomaly and δ-MnO₂ further suggests that Ce is chemisorbed onto iron oxyhydroxides which are epitaxially intergrown with δ-MnO₂.

The regional distribution of the Ce anomaly values appears to depend on many of the factors responsible for the uptake of other minor metals in nodules and crusts.     

Concentrations of the elements Ag,Al, Ca,Cd, Cu,Fe, Mg,Mn, Pb and Zn,and the radionuclides 210Pb and 210Po in the digestive gland of the squid Nototodarus gouldi

Ag, Al, Ca, Cd, Cu, Fe, Mg, Mn, Pb and Zn concentrations and ²¹⁰Po and ²¹⁰Pb activities were measured in 26 specimens of the squid Nototodarus gouldi taken from the waters of Bass Strait in one jigging operation. All the elements show wide ranges in concentrations in specimens apparently subject to the same environmental conditions. Copper concentration was 27-1 200 μg/g, and ²¹⁰Po activity 4·8–24·2 Bq/g. The animal wet weights, the elements Ag, Al, Cd, Fe and Zn, and the radionuclide ²¹⁰Po have coefficients of variation in the range 40–60%; Ca, Mg and Mn show the smallest variability (CV = < 30%), and Cu the greatest (CV = 12%). Significant correlations (p < 0·001) were found between the following pairs of elements: Cd-Zn, Cd-Cu, Zn-Cu, Mg-Mn, Fe-Mn, Ca-Mg and Fe-²¹⁰Po.     

东海钙质生物骨屑的矿物学特征

通过电镜、电子探针和X射线等项分析,对东海沉积物中的有孔虫、腹足类、双壳类、苔藓、珊瑚、海胆等骨屑进行了矿物学研究,确定了矿物成分与生物属种的关系,并基于有孔虫壳体化学成分将壳体分为均质壳和异质壳,生物碳酸盐中镁主要富集在方解石及镁方解石中,锶在方解石和镁方解石中的分配系数(D)相似,为0.11—0.14;在文石质骨屑中D=1.09-1.20。碳氧同位素组成与生物属种有明显关系。据一些有孔虫壳体氧同位素偏差值计算的水温来看,本次测定的有孔虫属种的骨屑不能作为理想的骨屑温度计。     

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...     

Hardground formation in the Bannock Basin, Eastern Mediterranean

Twenty kilogrammes of crusts and slabs of indurated carbonate sediment, usually referred to as hardgrounds, were dredged along the eastern steep wall of the Bannock Basin during the 1984 cruise of R.V. Bannock.

The crusts range in thickness from one to a few centimetres and the fragments of these crusts are irregular in shape. Their surface is always uneven and their colour ranges from white to brownish dark grey. Some slabs are impregnated along one side by ferromanganese sesquioxides, and borings occur in several samples. Serpulid tubes have been observed in one instance. The borings and serpulids suggest formation of the hardgrounds at or close to the sediment/water interface and exposure at the seafloor.

The degree of lithification is generally different on the inferred upper and lower sides of the slabs. An upward increase of lithification across the slabs is reflected by mineralogy, ultrastructure and stable isotope composition of the carbonate. X-ray diffraction analyses indicate high-magnesian calcite as the predominant carbonate with minor amounts of low-magnesian calcite and dolomite. Occasionally, large gypsum crystals are attached to the hardgrounds and sometimes smaller ones are dispersed through the carbonate matrix.

An increase in diagenesis is reflected by the passage from friable, nodular nannofossil chalk to nannofossil limestone and hard xenotopic calcite micrite. Overgrowth of coccoliths and internal cementation of the tests of planktonic foraminifera by high-Mg calcite increase from chalk to limestone. In the hard, fully cemented micrites, coccoliths can no longer be recognised in the xenotopic fabric. Pteropods occur as dissolution moulds with aragonite preserved as only tiny relics.

Carbon and oxygen isotope analyses were performed on different samples. The progressive lithification to chalk and limestone is marked by a shift in the δ¹⁸O values from +1.2‰ to +5.4‰ (PDB). This change indicates that precipitation of high-Mg calcite and possibly also recrystallisation of the original biogenic carbonate took place within cold and hypersaline brines which were enriched in ¹⁸O. The oxygen isotope data suggest that lithification and gypsum precipitation occurred under identical conditions. The carbon isotope data show progressive diagenetic change from values near +1‰ to values of +3‰. This change may reflect a contribution of methanogenetic CO₂ to the hypersaline brine.     

Riddle of the Nautilus: Specific Structural Features of Its Shell

The shells of the chambered nautilus (Nautilus pompilius) are studied by X-ray structure analysis (XRD) and electron microscopy (SEM and TEM). The shell structure is examined in a nanometer scale using XRD and synchrotron-based small angle X-ray scattering (SAXS). The mineral composition of shells includes 98–99 wt % aragonite, ~1 wt % organic substance (conchiolin), 1 wt % strontianite, and 0.5 wt % calcite. Trace elements comprise Na, Mg, Al, K, Si, Fe, P, S, Zn, Sr, Ba, and Cl. The laminated layers are composed of aragonite crystals with a width of 5–10 μm and a thickness of 0.5–1 μm; the prismatic layers, with a length of 7–12 μm long and a width of 1–3 μm. According to XRD and SAXS assays, the aragonite layers are formed of flawless monocrystals lacking any internal structuring. The shell conchiolin is a polymer formed of a system of parallel fibers folded with a step of approximately 100 nm without longitudinal structuring. Presumably, the unique structure of the nautilus shells has determined the existence of Nautiloidea over 500 Ma and their preservation as fossils for over 100 Ma.