Constraining the colouration mechanisms of Cretaceous Oceanic Red Beds using diffuse reflectance spectroscopy

We have used diffuse reflectance spectroscopy to investigate the colouration mechanisms of hematite in Cretaceous Oceanic Red Beds (CORBs). Data for samples of CORBs from the Chuangde section in Tibet, Vispi Quarry section in Italy, and Core 12X of Ocean Drilling Program Hole 1049C in the North Atlantic were compared with calibration datasets obtained for hematite in different crystalline forms (kidney and specular hematite) and calcite matrix. Spectra for hematite in either pure form or in calibration datasets show that the centre of the reflection peak shifts to a longer wavelength and depth (D) decreases as the crystallinity of the hematite increases. Compared with specular hematite, the presence of just 0.5% of kidney hematite can cause a much deeper absorption peak and greater redness value, which indicates that kidney hematite has a higher colouration capacity than specular hematite. However, both kidney and specular hematite exhibit a good correlation between the redness value for each calibration dataset and the absorption peak depth. In all three studied sections, hematite is the main iron oxide mineral responsible for colouration. Spectral features such as absorption peak depth and peak centre reveal that hematite crystallinity gradually decreases from red shale to limestone to marl. Based on a spectral comparison of red shale in the Chuangde section before and after citrate–bicarbonate–dithionite (CBD) treatment, we found that two forms of hematite are present: a fine-grained and dispersed form, and a detrital form. The former is relatively poorly crystalline hematite, which has a much stronger colouration capacity than the detrital form. In the Vispi Quarry section and Core 12X of ODP Hole 1049C, a good correlation between the absorption peak depth of hematite and redness value indicates that the red colouration is caused by hematite of similar crystallinity in each section.     

Planktic Foraminiferal Biostratigraphy of the Cretaceous Oceanic Red Beds in Kangmar,Southern Tibet,China

The planktic foraminifera of the Chuangde Formation (Upper Cretaceous Oceanic Red Beds, CORBs) as exposed at Tianbadong section, Kangmar, southern Tibet has been firstly studied for a detailed for a detailed biostratigraphy elaboration. A rich and well-preserved planktic foraminifera were recovered from the Chuangde Formation of the Tianbadong section and the Globotruncanita elevata, Globotruncana ventricosa, Radotruncana calcarata, Globotruncanella havanensis, Globotruncana aegyptiaca, Gansserina gansseri and Abathomphalus mayaroensis zones have been recognized. The planktic foraminiferal assemblage points to an early Campanian to Maastrichitian age for the CORBs of the eastern North Tethyan Himalayan sub-belt, which also provides a better understanding of the shifting progress of the Indian Plate to the north and the evolution of the Neotethyan ocean. The lithostratigraphy of the Chuangde Formation of the Tianbadong section comprises two lithological sequences observed in ascending succession: a lower unit (the Shale Member) mainly composed of purple (cherry-red, violet-red) shales with interbedded siltstones and siliceous rocks; and an upper unit (the Limestone Member) of variegated limestones. The strata of the Chuangde Formation in the Tianbadong section are similar to CORBs in other parts of the northern Tethyan Himalaya area of Asia (Gyangze, Sa’gya, Sangdanlin, northern Zanskar, etc.). The fossil contents of the Chuangde Formation in the sections (CORBs) studied provide a means of correlation with the zonation schemes for those of the northern Tethyan Himalayan sub-belt and the Upper Cretaceous of the southern Tethyan Himalayan sub-belt. Paleogeographic reconstruction for the Late Cretaceous indicates that the Upper Cretaceous Chuangde Formation (CORBs) and correlatable strata in northern Zanskar were representative of slope to basinal deposits, which were situated in the northern Tethyan Belt. Correlatable Cretaceous strata in Spiti and Gamba situated in the southern Tethyan Belt in contrast were deposited in shelf environments along the Tethyan Himalayan passive margin. CORBs are most likely formed by the oxidation of Fe(II)-enriched, anoxic deep ocean water near the chemocline that separated the oxic oceanic surface from the anoxic.     

沉积物中铁氧化物的定量方法及其 在白垩纪大洋红层中的应用

赤铁矿和针铁矿是自然界中最稳定的两种铁氧化物,广泛存在于地球的各个圈层。很多沉积物的颜色都是由它们引 起的,它们的形成和保存具有重要的环境指示意义。实验室中赤铁矿和针铁矿的表征和鉴定手段很多,但受其含量低、结 晶差、颗粒细小难分离等因素的困扰以及某些测试方法自身的限制,能用于铁氧化物定量分析的方法很少。文中就常用的 基于X射线衍射（XRD） 和漫反射光谱（DRS） 的铁氧化物定量方法进行了系统评价。在定性分析的基础上,采用基于 XRD的K值法获得西藏床得剖面红色页岩中赤铁矿的含量为3.81％~8.11％,采用DRS与多元线性回归相结合的方法获得北 大西洋ODP1049C孔12X岩芯段棕色层中赤铁矿和针铁矿的含量分别为0.13％~0.82％和0.22%~0.81％,橙色层中赤铁矿和 针铁矿的含量分别为0.19%~0.46％和0.29%~0.67％。与其它分析结果的比较表明,这两种定量方法在白垩纪大洋红层中的 应用是可行的。但在实际应用时,首先要通过XRD和DRS相结合来提高定性分析的准确性,然后通过综合分析铁氧化物的 预判含量范围和结晶程度来选择合适的定量方法。     

白垩纪大洋红层：特征、分布与成因

“白垩纪大洋红层”（CORB）自20世纪末正式提出后已经迅速成为白垩纪新的研究方向之一。本文在参考国外CORB的学术研究成果基础上,重点对我们在西藏南部和意大利中部两个研究程度较高地区所获得的立典研究成果予以详细介绍,同时对CORB的全球性对比进行总结和归纳,对大洋红层蕴涵的古海洋、古气候信息进行详细评述。我们认为,CORB是沉积物在原地氧化条件下的产物,导致该氧化条件出现的主要因素是底层水高含量的溶解氧,而深层古洋流的发育很可能是导致高溶解氧含量的主要原因。     

Distribution,Compositions and Significance of Oceanic Red Beds

Oceanic red beds are widely distributed in the global oceans and across the entire Phanerozoic period, which mostly appeared after oceanic anoxic events. They represent typical oxygen-rich sedimentary environment and play a significant role on ocean science research. Numerous studies have been carried out since the oceanic red beds were discovered. However, previous studies mainly focused on the Cretaceous oceanic red beds, and the understanding of the characteristics and scientific significance of oceanic red beds are not comprehensive. Therefore, we here summarized the global distribution characteristics and compared mineral and element compositions of various lithological oceanic red beds, including marly, clayey and cherty oceanic red beds. The main mineral and element components of oceanic red beds have no direct relationship with the color of the sediments, and mainly are affected by the regional environment and provenances. Therefore, the mineralogical and geochemical characteristics of oceanic red beds should be analyzed in combination with the regional background. The red coloration of oceanic red beds is controlled mainly by hematite, goethite and manganese-bearing calcite, which have two main mechanisms: ① Colored minerals formed in oxic conditions; ② Colored minerals formed due to low deposition rates. These two mechanisms are not completely independent, but complement one another with either dominance in most oceanic red beds. Lithological characteristics of oceanic red beds are controlled by three factors, including water depth, productivity and nutrients. Therefore, the formation of oceanic red beds should be considered with global changes and regional events. The unique origin mechanism and global distribution characteristics of long time-scale oceanic red beds can be used to indicate sedimentary paleoenvironment, paleo-oceanic current, and paleoclimate change. In addition, hydrothermal or magmatic activities on the ocean floor could also produce red-color deposits that are strongly different from sedimentary oceanic red beds. Based on the existing research, we also put forward the future in-depth studies on the oceanic red beds from multidisciplinary perspectives.     

Burial Records of Reactive Iron in Cretaceous Black Shales and Oceanic Red Beds from Southern Tibet

One of the new directions in the field of Cretaceous research is to elucidate the mechanism of the sedimentary transition from the Cretaceous black shales to oceanic red beds. A chemical sequential extraction method was applied to these two types of rocks from southern Tibet to investigate the burial records of reactive iron. Results indicate that carbonate-associated iron and pyrite are relatively enriched in the black shales, but depleted or absent in red beds. The main feature of the reactive iron in the red beds is relative enrichment of iron oxides （largely hematite）, which occurred during syn-depostion or early diagenesis. The ratio between iron oxides and the total iron indicates an oxygen-enriched environment for red bed deposition. A comparison between the reactive iron burial records and proxies of paleo-productivity suggests that paleo-productivity decreases when the ratio between iron oxides and the total iron increases in the red beds. This phenomenon could imply that the relationship between marine redox and productivity might be one of the reasons for the sedimentary transition from Cretaceous black shale to oceanic red bed deposition.     

阿尔卑斯-喀尔巴阡上白垩统大洋红层特征与对比

在前人研究的基础上,从时代、岩性、古生物、沉积速率、沉积环境等方面对阿尔卑斯—喀尔巴阡地区的上白垩统大洋红层进行了详细对比,发现研究区内上白垩统大洋红层最早出露于Cenomanian期,最晚可延续至古近纪,且在Campanian期出露最为广泛,其岩性以灰岩、泥灰岩和含泥灰岩为主,生物化石以浮游有孔虫为主,沉积速率较低且在各地不尽相似,在CCD面上、下均可以出现,沉积环境一般是大陆边缘盆地、斜坡和大洋盆地等远洋、半远洋环境。通过比较分析,为进一步深入研究上白垩统大洋红层提供较为全面的基础资料。     

白垩纪大洋红层的致色机制及成因研究

为了查明白垩纪大洋红层的致色矿物及其赋存状态,并探讨白垩纪大洋红层可能的制约因素及成因模式,本文以中国西藏床得剖面红色页岩、意大利Vispi Quarry剖面红色灰岩以及北大西洋ODP1049C孔12X岩芯段Aptian-Albian期高频旋回红色泥灰岩为研究对象,对各剖面(或岩芯)中的红色和非红色样品分别进行了X射线衍射和漫反射光谱测试,同时对配制的含赤铁矿的标样进行了同样的测试。测试结果表明,无论是红色页岩、红色灰岩,还是红色泥灰岩,赤铁矿都是主要的致色矿物,其中西藏床得剖面红色页岩由结晶较好的碎屑状赤铁矿和结晶较差的细分散状的赤铁矿共同致色。在意大利Vispi Quarry剖面红色泥岩中,结晶程度相近的赤铁矿是唯一的致色铁氧化物,而在ODP1049C孔红色泥灰岩中,结晶差的赤铁矿和针铁矿的出现是泥灰岩呈红色的矿物学根源。赤铁矿的形成主要受铁的来源、沉积时的氧化还原条件以及成岩作用的影响,这些因素也成为制约红层形成的关键因素。本课题组在多年研究的基础上,结合前人研究成果进一步从矿物学的角度深化了大洋红层的成因模式。     

湖北武汉地区志留系下红层的古鱼类化石及其生物古地理意义*

依据在湖北武汉古姆山志留系浅海红层中新发现的古鱼类化石,确证了兰多维列统特列奇阶下部红层——志留系下红层在鄂东南地区广泛存在,并在前人工作基础上对武汉地区原坟头组进行了重新厘定,将其一分为二,上部仍为坟头组,下部则称清水组。新厘定后的坟头组以黄绿色、灰绿色、灰黄色泥岩、泥质粉砂岩、粉砂岩为主,富含腕足类、双壳类、腹足类、三叶虫和遗迹化石; 清水组下部以紫红色、红褐色泥岩、泥质粉砂岩为主,夹少量石英砂岩,上部以紫红色、黄绿色石英砂岩为主,夹泥岩、泥质粉砂岩、粉砂岩。在清水组上部新发现的鱼类化石包括盔甲鱼类锅顶山汉阳鱼(Hanyangaspis guodingshanensis)、意外洪山鱼(Hongshanaspis inexpectatus)、后棘江夏鱼(Jiangxialepis retrospina)及软骨鱼类中华棘鱼(Sinacanthus)、新中华棘鱼(Neosinacanthus)。这些新发现的古鱼均为张家界脊椎动物群温塘鱼类化石组合中的成员,其中,后棘江夏鱼可以跟产自江西武宁地区下红层清水组中的九江江夏鱼(J. jiujiangensis)直接对比,二者同属于真盔甲鱼目曙鱼科江夏鱼属,而曙鱼科成员则可以作为志留系下红层的标志性分子。根据鱼群面貌和地层层序,武汉地区的志留系下红层可以与皖、苏地区的侯家塘组、浙西北地区的唐家坞组、赣西北地区的清水组、湘西北地区的溶溪组以及新疆塔里木地区的塔塔埃尔塔格组进行很好的对比,其时代为志留纪兰多维列世特列奇期早期。华南板块志留系下红层的分布特征表明, 在特列奇期早期,上、下扬子海之间存在一狭长的浅海区域,这为盔甲鱼类在湖北武汉和江西武宁两地之间的扩散与交流提供了便利条件和可能。     

Response of Reactive Phosphorus Burial to the Sedimentary Transition from Cretaceous Black Shales to Oceanic Red Beds in Southern Tibet

The mechanism of sedimentary transition from the Cretaceous black shales to the oceanic red beds is a new and important direction of Cretaceous research. Chemical sequential extraction is applied to study the burial records of reactive phosphorus in the black shale of the Gyabula Formation and oceanic red beds of the Chuangde Formation, Southern Tibet. Results indicate that the principal reactive phosphorus species is the authigenic and carbonate-associated phosphorus (CaP) in the Gyabula Formation and iron oxides-associated phosphorus (FeP) in the Chuangde Formation which accounts for more than half of their own total phosphorus content. While the authigenic and carbonate-associated phosphorus (CaP) is almost equal in the two Formations; the iron oxides-associated phosphorus is about 1.6 times higher in the Chuangde Formation than that in the Gyabula Formation resulting in a higher content of the total phosphorus in the Chuangde Formation. According to the observations on the marine phosphorus cycle in Modern Ocean, it is found that preferential burial and regeneration of reactive phosphorus corresponds to highly oxic and reducing conditions, respectively, leading to the different distribution of phosphorus in these two distinct type of marine sediments. It is the redox-sensitive behavior of phosphorus cycle to the different redox conditions in the ocean and the controlling effects of phosphorus to the marine production that stimulate the local sedimentary transition from the Cretaceous black shale to the oceanic red beds.     

北美西部内陆海盆Niobrara组的钙质超微化石及其环境意义——Ⅱ：古环境研究

沉积于北美西部白垩纪内陆海盆的Niobrara组，是一套以白垩，白垩质灰岩，以及钙质页岩为主的海相沉积，其中自垩的主要组分为颗石藻及其它钙质超微化石。通过对Kansas州西部和South Dakota州东部四条剖面中Niobrara组的岩性，沉积物厚度，及钙质超微化石的研究，证明北美西部内陆海盆的沉积环境及水体温度在Niobrara组沉积时期因地而异。在Niobrara组沉积初期，海盆内的水体温度为北冷南暖，其后，至少在位于Kansas西部海域的海水温度呈与时逐渐降低趋势。钙质超微化石有关属种在盆地内的分布差异，进一步说明海水变冷的直接原因源自北极海域水体的缓慢南浸。     

白垩纪特殊沉积的古气候指示及红层定量古温度测量研究

介绍了白垩纪陆相红层研究的现状及前景,特别是其在白垩纪陆相古气候恢复方面所具有的重要意义。系统讨论了白垩纪陆相红层中的特殊沉积及其古气候指示意义,并讨论了碳酸盐岩氧同位素方法定量古温度恢复的可能性及其局限性。指出白垩纪古气候具有时间上和空间上的不均匀性;并结合陆相红层的类型、特殊沉积的分布,参照古生物的地理分区对白垩纪古气候进行初步地理分区。     

江西信江盆地上白垩统风成红层的古地磁研究

红层是古地磁学的重要研究对象之一。以往对河湖相红层的古地磁研究较多，而对于风成红层的研究较少。因 此，对于风成红层剩磁记录是否可靠等基本问题仍然缺乏清晰的认识。文章对江西信江盆地上白垩统圭峰群塘边组风成 红层和河口组河流相红层开展了古地磁研究，并通过对比风成红层与河流相红层的古地磁结果，探究风成红层剩磁记录 的可靠性及不同沉积过程对古地磁记录的影响。逐步热退磁实验结果显示仅有19% 的塘边组风成红层分离出稳定的特征 剩磁，而且其强度衰减曲线为凸形，表明特征剩磁为碎屑赤铁矿携带的原生剩磁。其平均方向为Ds=15.6 °, Is=28.9 °, n= 25, κ=13.0, α95=8.3 °；对应的古地磁极为Latitude=70.7 °, Longitude=245.6 °, A95=6.8 °。该古地磁极与赣州地区河湖相红层 的古地磁极及华南晚白垩世的古地磁极位置一致，表明风成红层的剩磁记录是可靠的。河口组河流相红层绝大部分样品 未能分离出稳定的特征剩磁。磁化率各向异性结果显示塘边组和河口组为沉积组构。岩石磁学结果表明，载磁矿物为赤 铁矿和磁铁矿。通过对塘边组风成红层的薄片观察和红度值比较等进一步研究表明，颗粒粒度和胶结程度可能对红层剩 磁记录的稳定性有一定影响。     

Cretaceous Oceanic Redbeds: Implications for Paleoclimatologyand Paleoceanography

The Cretaceous is among the most unusual eras in the geological past. Geoscience communities have been having great concerns with geological phenomena within this period, for example carbonate platforms and black shales in the Early and Middle Cretaceous respectively, during the last decades. But few people have paid any attention to the set of pelagic redbeds lying on the black shales, not to mention the applications to paleoclimatology and paleoceanography. It is shown by the sedimentary records of redbeds, that they were deposited around the CCD, with both a higher content of iron and much lower concentrations of organic carbon, which implies conditions with a     

江西信江盆地上白垩统风成红层的古地磁研究

红层是古地磁学的重要研究对象之一。以往对河湖相红层的古地磁研究较多,而对于风成红层的研究较少。因 此,对于风成红层剩磁记录是否可靠等基本问题仍然缺乏清晰的认识。文章对江西信江盆地上白垩统圭峰群塘边组风成 红层和河口组河流相红层开展了古地磁研究,并通过对比风成红层与河流相红层的古地磁结果,探究风成红层剩磁记录 的可靠性及不同沉积过程对古地磁记录的影响。逐步热退磁实验结果显示仅有19% 的塘边组风成红层分离出稳定的特征 剩磁,而且其强度衰减曲线为凸形,表明特征剩磁为碎屑赤铁矿携带的原生剩磁。其平均方向为Ds=15.6 °, Is=28.9 °, n= 25, κ=13.0, α95=8.3 °;对应的古地磁极为Latitude=70.7 °, Longitude=245.6 °, A95=6.8 °。该古地磁极与赣州地区河湖相红层 的古地磁极及华南晚白垩世的古地磁极位置一致,表明风成红层的剩磁记录是可靠的。河口组河流相红层绝大部分样品 未能分离出稳定的特征剩磁。磁化率各向异性结果显示塘边组和河口组为沉积组构。岩石磁学结果表明,载磁矿物为赤 铁矿和磁铁矿。通过对塘边组风成红层的薄片观察和红度值比较等进一步研究表明,颗粒粒度和胶结程度可能对红层剩 磁记录的稳定性有一定影响。     

藏南白垩系黑-红层沉积岩有机质组成分布特征

对藏南江孜县床得剖面白垩系黑层和红层沉积岩进行的有机地球化学研究表明,黑层有机碳含量高于红层5～10倍,红层和黑层饱和烃主峰碳数分别为nC25和nC23;黑层和红层沉积有机质的母质来源都以水生植物和菌藻类等低等生物为主,陆源有机质的输入非常有限;但饱和烃的分布和主峰碳数的差异可能反映了有机母源物质在种群方面的差异,而这种差异可能主要是水体温度存在差异造成的,即红层发育时期水体温度可能高于黑层沉积时期.而在高温度条件下,水生生物和陆生植物的生长发育受到限制,造成原始有机质产率和有机质沉积保存量低可能是红层沉积岩形成的主要原因.     

Discovery of Pseudofrenelopsis gansuensis from the Lower Cretaceous of Wangqing, Jilin Province, and Its Significance in Correlation of Cretaceous Red Beds in China

New data from abundant vegetative shoots and cuticular analysis are provided for the Cretaceous cheirolepidiaceous conifer Pseudofrenelopsis gansuensis Deng, Yang et Lu. The material was found from a new locality of the Lower Cretaceous strata in the Luozigou Basin, Wangqing, Jilin Province, northeastern China. Pseudofrenelopsis is a common plant in the Dalazi Formation of the Yanji Basin about 150 km from Wangqing, but there exists different species, Pseudofrenelopsis dalatzensis only. Both P. dalatzensis and P. gansuensis have been recorded from the Lower Cretaceous of Jiuquan, Gansu Province, but they are in different stratigraphic horizons. The Lower Cretaceous plant-bearing strata in Luozigou have used to correlate with the Dalazi Formation of the Yanji Basin. The discovery of P. gansuensis, which is lower in horizon than P. dalatzensis in Jiuquan, may indicate that they are also different in horizon in Jilin. Cheirolepidiaceous conifers are among the few fossils of red beds of the Early Cretaceous in China. The present discovery of Pseudofrenelopsis gansuensis provides important evidence for classification, correlation and determination of geological ages of the Early Cretaceous non-marine red deposits of the two separate basins in remote areas of North China.     

北大西洋ODP1049C孔Aptian-Albian期高频旋回大洋红层的成因:矿物学证据

北大西洋ODP171B航次1049C孔Aptian-Albian期沉积以出现大洋红层与灰色、白色沉积物高频旋回为特征。为了探讨大洋红层的成因,本文进行了矿物学、地球化学、沉积学等方面的研究。漫反射光谱、磁化率和活性铁数据表明,赤铁矿、针铁矿的出现是导致样品由白色向红色转变的矿物学原因。棕色和橙色样品中出现赤铁矿和针铁矿的特征峰,FeR/FeT平均值分别为0.23和0.24,明显区别于其他颜色的样品。磁化率与红层成良好的正相关关系,说明铁氧化物矿物含量的变化是导致磁化率变化的原因。X射线衍射结果表明,不论颜色如何,样品中均含伊利石、高岭石、蒙脱石、绿泥石等粘土矿物,其分布与样品颜色没有直接关系,很可能反映当时物源区气候稳定。ODP1049C孔岩芯沉积物出现橙色、棕色、白色、灰色等颜色的高频变化,颜色过渡接触界线清晰,说明导致红色变化的赤铁矿和针铁矿是沉积期低温氧化的产物。棕色样品中CaCO3含量最低,推测红层所对应的氧化条件是由于较低的有机质堆积速率造成的。     

青海柴达木盆地北缘寒武纪和奥陶纪海相红层的分布与时代

参照青海省柴达木盆地北缘寒武纪和奥陶纪地层相关文献资料,通过野外地质调查和系统样品分析结果,在柴北缘寒武纪—奥陶纪地层中梳理和识别出了19层海相红层。其中,寒武纪地层中识别出了12层海相红层,奥陶纪地层中识别出了7层海相红层。除奥陶纪石灰沟组海相红层(QORB3,QORB4,QORB5及QORB6)为深水大洋红层外,其余15层海相红层均属浅水—半深水陆棚红层。依据海相红层及其上下层位所含化石,本文初步论述了各海相红层的大致时代,并与我国主要块体的同期海相红层进行对比。上述研究对进一步开展全国乃至全球寒武纪、奥陶纪海相红层分布及对比提供了基础数据和资料。此外,通过国内同期红层的对比,本文还讨论了河北唐山寒武纪海相红层的分布及中国南方中奥陶世大坪期—达瑞威尔期早期海相红层广布事件。