Geochemistry of a chert breccia

A complex history of diagenetic interactions between a siliceous sediment, seawater and fresh water is revealed by intraformational chert breccias. Chert breccias were formed in the Campanian Mishash Formation in Israel, by “practically contemporaneous” fracturing of lithified cherty layers followed by silicification and lithification of the matrix. Pairs of fragments and matrix were compared with respect to their chemical (Ca, Sr, Na, K, Mg, Li, B, SO₄, Ba) and isotopic (δ¹⁸O, δD, δ¹¹B) composition. δ¹¹B was analyzed by ion-probe and includes a profile across a fragment-matrix contact. The epicontinental cherts of the Mishash Fm. are enriched by a factor of 10 to 50 in all elements other than O and Si in comparison with Deep-Sea cherts. All results are compatible with the proposition that the lithification of the matrix occurred in contact with fresh-water, as opposed to seawater in which the fragments, as well as most of the Mishash sediments were formed. The strongest evidence for this difference is in the higher concentration of B in the fragments (27-70 ppm vs. 11-21ppm in the matrix) and higher δ¹⁸O (29 to 35‰ vs. 21 to 33‰). δD is a less efficient discriminator, though compatible with fresher water diagenesis of the matrix: −115‰ to −76‰ for hydrogen in the chert of the fragments, compared to −141 to −85‰ for the matrix. δ¹¹B in the matrix shows some of the lowest values recorded in sediments (δ¹¹B = −33‰), but varies strongly, suggesting that the source of boron in the matrix is a mixture of a freshwater and a marine component. Both seawater and the freshwater that has equilibrated with the cherts underwent varying degrees of evaporation. Ca, Sr and SO₄ are carried by apatite, trapped as detritus in the matrix. The concentration of lithium in the matrix is high (11-16 ppm), whereas in the adjacent fragments it is mostly only within 1-2 ppm. Li probably enters the matrix from the interstitial solution, during the opal → quartz transformation. The second, prolonged, transformation takes place in a (freshwater) flow-through, open system. This allows a much larger mass of Li to be scavenged by the transforming silica despite its low concentration in freshwater.     

Boron in chert and Precambrian siliceous iron formations

In order to assess the importance of siliceous sediments as a sink for oceanic B and to determine the effect of diagenesis on the mobilization of B, samples were analysed from chert nodules, bedded cherts, and siliceous banded iron formations from a variety of sedimentary environments and geologic ages. Boron analyses on bulk samples were made by prompt gamma neutron activation analysis. The distribution of B in rocks was mapped using α-track methods.Nodular Phanerozoic cherts typically contain 50–150 ppm B, and bedded cherts somewhat less. The B is initially concentrated in tests of silica-secreting organisms, but some is lost in early diagenesis as silica progressively recrystallises to quartz.Banded iron formation silica of Archean and Proterozoic age usually contains < 2 ppm B. This conforms with the view that such silica is not of biogenic origin but, since many iron formations are undoubtedly of marine origin, raises the question whether Precambrian oceans were impoverished in B. Analyses of Precambrian marine argillaceous sediments, averaging 70 ppm B, do not resolve this question.     

Antiphase hydrogen and oxygen isotope periodicity in chert nodules

Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ¹⁸O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ¹⁸O line with δD values that are almost 50‰ lower. The δD-δ¹⁸O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.     

吉林省中部红帘石硅质岩的特征及意义

吉林省中部磐石县境内烟筒山地区的红帘石硅质岩存在于古生代地层之中。地球化学研究发现,该硅质岩具有较低的SiO2(80%左右)和较高的Al2O3(10％左右)。微量元素中V的含量也较低,稀土元素中不出现明显的Ce负异常,表明其形成于与陆源物质关系密切的大陆边缘环境。岩石的强烈变形和无层序特点暗示该区的古生代地层可能大多为构造混杂岩,不具备传统的地层划分和对比意义。矿物温压计算结果显示,该硅质岩经历了约430℃、大于6．OGPa的中压相系变质作用。不存在其他高压变质作用矿物,可能反映了本区为兴蒙造山带中古亚洲洋最后闭合的地点所在,并推测其最后闭合的时间应在古生代末一中生代初期。     

The Clacton Flint industry: A supplementary note

In my Henry Stopes Lecture I recorded an abraded group of artifacts as ‘Derivative?’; reasons will now be given for removing the question mark and dividing the Clacton industry into two phases, Primitive and Advanced, the latter having been the subject of the lecture. The present improved definition of the Primitive phase has brought out the superior quality of the retouch in the trimmed flakes of the Advanced phase, which is nearer to the High Lodge industry, the main difference between the two phases being in the trimmed flakes.The opinion is confirmed that the Clactonian industries are probably rooted in the ancient traditions of the great Pebble Tool cultures.     

藏南地区中生代硅质岩的地球化学特征及其成因意义

藏南地区中生代硅质岩包括蛇绿岩套硅质岩(与蛇绿岩共生)和非蛇绿岩套硅质岩两大类.本文重点分析日喀则地区彭错林、夏鲁以及泽当地区的罗布莎、江孜盆地宗卓组及四个剖面的硅质岩.其中,彭错林、夏鲁和罗布莎硅质岩与蛇绿岩共生,江孜盆地宗卓组为非蛇绿岩套硅质岩.分析表明:(1)藏南地区硅质岩剖面地球化学特征鲜明,具有一致性和多样性特点;(2)与蛇绿岩共生的彭错林、夏鲁、罗布莎硅质岩普遍具有高Si、高Fe、低Al特征,大部分微量元素相对于克拉克值亏损,稀土元素总量低,经北美页岩标准化后,Ce异常明显或不明显,重稀土相对轻稀土富集.硅质泥岩的∑REE要明显高于硅质岩;(3)非蛇绿岩套宗卓组硅质岩SiO2含量稍低,Al2O3、TiO2则相反.V、Th、Hf、Ta等不相容元素上亏损程度较小,部分样品含量可接近克拉克值.稀土总量相对较高,页岩标准化配分模式上体现为弱Ce正异常,负Eu异常,轻重稀土分异不明显的平坦型曲线图;(4)地球化学特征指示了,藏南地区硅质岩多数具有明显的热水沉积成因属性,同时有正常陆源组分的加入.其中,夏鲁硅质岩的热水沉积地球化学特征较为典型,而宗卓组硅质岩则表现出受陆源物质加入的影响显著的地球化学特点.     

西藏西南部与蛇绿岩伴生的硅质岩特征及地质意义

西藏西南部达巴—休古嘎布存在一条蛇绿岩带,与蛇绿岩伴生的中生界硅质岩分布广泛。其中与拉昂错蛇绿岩体伴生的硅质岩,常量元素和稀土元素地球化学特征参数,以及地球化学环境判别图,显示其沉积于大陆边缘盆地的构造环境,其形成包括生物作用和热液作用两种因素。含硅质岩的地层剖面自下而上岩性为石英砂岩→含岩屑石英砂岩、杂砂岩→放射虫硅质岩,形成环境是从三角洲或浅海过渡到大陆边缘,再到边缘盆地。硅质岩中含有大量放射虫,放射虫组合显示硅质岩的沉积时代为晚侏罗世晚期。含硅质岩地层和蛇绿岩都是印度大陆北缘小洋盆的组成部分,两者因洋盆碰撞闭合而汇聚在一起。硅质岩的形成环境反映了该陆缘小洋盆在晚侏罗世所处的构造背景。     

显生宙碳酸盐岩中燧石结核的几种成因模式

显生宙以来,碳酸盐岩地层中有燧石结核产出的现象十分普遍。现有研究认为,硅质生物壳体是燧石结核最主要的硅质来源,随着地质历史上主要硅质生物类型的演变,燧石结核的产出环境逐渐从浅水变为深水。不同地区不同层位的燧石结核往往具有一些共同特征,包括呈孤立分散的结核状产出、硅质选择性交代方解石颗粒而保留晶形完好的白云石、硅质矿物具有隐晶硅质-微晶石英-粗晶石英的规律性变化等。基于上述主要特征及不同研究实例的特点,前人总结出了有机质氧化模式、半透膜模式、混合水硅化模式、重结晶应力控制交代模式等燧石结核成因模式,从不同角度对燧石结核的典型特征进行了解释。然而由于燧石结核成因的复杂性及其可形成于沉积-成岩的不同阶段,各个成因模式均存在一定的局限性,只可用于解释部分地质特征。鉴于燧石结核对研究区的沉积环境、成岩历史等具有很好的指示作用,对其成因的研究具有重要意义,尽管上述模式的提出时间较早,但针对特定问题的研究非常深入,在以后的研究中应加以借鉴。     

湖南安化留茶坡硅质岩的REE地球化学特征及其意义

湖南安化留茶坡硅质岩沉积在埃迪卡拉纪末期(551～542 Ma)的深水盆地中,它们具有如下REE地球化学特征:和PAAS相比,∑REE含量很低(8.6x10-6~18x10-6,平均13.6x10-4),Y/Ho比值较高(33.6～43.9,平均37.4),接近现代海水的Y/Ho比值(44);正的La异常(LaN/CeN平均为1.46),中等负的Ce异常(平均0.65).弱的正Eu异常(平均1.1),正的Gd异常(平均1.07),正的Y异常(平均1.22),LREE和MREE相对于HREE亏损(LaN/YbN平均为0.17,GdN/YbN平均为0.45),显示出和现代海水相似的REE特征.而与海底热液流体及与热液有关的碧玉的REE特征明显不同.这些表明留茶坡硅质岩受陆源碎屑及热液流体的影响很小.留茶坡硅质岩是由风化作用大量带人海洋的溶解的硅质化学沉积而成的.生物作用促进了海水中溶解硅质的沉淀.     

Diagenetic density inversions and the deformation of shallow marine chert beds in Israel

ABSTRACT Chert folds and 'dyke'-like boudinage in the Senonian Mishash Formation of Israel have orientations consistent with contemporaneous tectonic patterns whereas their amplitudes are anomalously high relative to strains calculated for adjacent layers. We suggest several means by which density inversions associated with chert diagenesis might amplify gentle structures whose wavelengths and orientations were determined by regional stresses.     

Geochemistry of Upper Devonian Hydrothermal Mammilated Chert Guangxi,Southwest China

The mammilated chert (MC) studied in this paper is a kind of silica-rich concretion (SiO₂ 93%) occurring in the Upper Devonian argillaceous silicolites (SiO₂≈88%) in Mugui, Guangxi. Impurity components in the MC are relatively low and show systematic variations as compared with the country rocks. Abundances of Mg, Si, Ti, Fe, Mn, U and Th are characteristically similar to those of recent and fossil hot-water sediments. Moreover, the MC is also characterized by low REE abundance, LREE > HREE, apparent negative Ce anomaly and moderate positive Eu anomaly. Oxygen isotope data show that the formation temperature of the MC is about 20 °C, higher than that of the host rock. The results of geochemical, geological and lithological studies suggest that the MC may have been formed through metasomatism, filling and crystallization beneath the sedimentary basin during the Devonian period.     

Chemical criteria to identify the depositional environment of chert: general principles and applications

Many chert sequences are located at key stratigraphic intervals or in structurally allochthonous packages, and because such sequences provide critical information regarding the formation of sedimentary basins and tectonic orogens it is important to determine precisely their original depositional position. Chemical methods of delineating environments are becoming increasingly sophisticated and useful, in part because even slight post-depositional recrystallization may obscure primary rock textures. Most chemical criteria have developed only on a case-by-case and local basis, however, with limited broad applicability. Here I synthesize major, trace, and rare earth element (REE) data in bulk chert from 49 sequences from continental margin, pelagic, and ridge-proximal environments, ranging in age from Early Paleozoic to Neogene, and develop a set of depositional chemical criteria applicable to cherts regardless of age, diagenetic history, or tectonic region. The criteria allow for analytical limitations and diagenetic modifications (precluding use of Si, Ca, Mn, Mg, P, Sr, and Ba, and other elements) intrinsic to chert chemistry. Major element ratios, capitalizing on the affiliations of Al₂O₃ and TiO₂ to terrigenous matter and of Fe₂O₃ to metalliferous input, can distinguish continental margin from ridge-proximal sedimentation, but cannot uniquely identify pelagic deposition. Trace element data are too few to interpret rigorously, with substantial overlap occurring between depositional regimes. REE ratios (i.e., La_n/ Ce_n) allow the best resolution of all three depositional regimes and are independent of diagenetic modification. I present new diagrams illustrating the chemical depositional criteria, and apply them to several sequences described in the literature that have historically yielded problematic genetic interpretations.     

Biogenic chert in the Cow Head Group (Cambro-Ordovician), western Newfoundland

Chert in the Cow Head Group is mainly a replacement of limestone and shale and, to a lesser extent, an interparticle cement. Its field occurrences are distinct as: (1) silicified margins on coarse conglomerates and thinly bedded limestones; (2) nodules within limestone and shale; (3) pervasively silicified beds of limestone and shale; and (4) clasts or partial replacement of clasts within conglomerate. Radiolarians and sponge spicules are composed of microquartz or calcite and are particularly common in the Ordovician part of the succession where most chert occurs. In limestone spatially associated with chert, the use of cathodoluminescence demonstrates that calcite-replaced radiolarians and spicules are volumetrically more important than realized through transmitted-light petrography. Petrographic relations between siliceous and rare pyritized radiolarians further indicate that these particles may be dissolved prior to compaction. No trace of their former existence remains, other than indirectly through the presence of silicified limestone and shale. Crushed grains cemented by chalcedony indicate that chert was precipitated during or after compaction. The history of silicification and the replacement or dissolution of siliceous bioclasts is protracted, ranging from near the sediment-water interface, where it is concomitant with early limestone lithification, to deeper burial, postdating mechanical compaction.     

Oxygen and hydrogen isotope ratios in freshwater chert as indicators of ancient climate and hydrologic regime

The oxygen and hydrogen isotopic composition of Eocene and Miocene freshwater cherts in the western United States records regional climatic variation in the Cenozoic. Here, we present isotopic measurements of 47 freshwater cherts of Eocene and Miocene age from the Great Basin of the western United States at two different sites and interpret them in light of regional climatic and tectonic history. The large range of δ¹⁸O of terrestrial cherts measured in this study, from 11.2‰ to 31.2‰ (SMOW: Standard Mean Ocean), is shown to be primarily the result of variations in δ¹⁸O of surface water. The following trends and patterns are recognized within this range of δ¹⁸O values. First, in Cenozoic rocks of northern Nevada, chert δ¹⁸O records the same shift observed in authigenic calcite between the Eocene and Miocene that has been attributed to regional surface uplift. The consistent covariation of proxies suggests that chert reliably records and retains a signal of ancient meteoric water isotopic composition, even though our analyses show that chert formed from warmer waters (40°C) than coexisting calcite (20°C). Second, there is a strong positive correlation between δ¹⁸O and δD in Eocene age chert from Elko, Nevada and Salina, Utah that suggests large changes in lake water isotopic composition due to evaporation. Evaporative effects on lake water isotopic composition, rather than surface temperature, exert the primary control on the isotopic composition of chert, accounting for 10‰ of the 16‰ range in δ¹⁸O measured in Eocene cherts. From authigenic mineral data, we calculate a range in isotopic composition of Eocene precipitation in the north-central Great Basin of −10 to −14‰ for δ¹⁸O and −70 to −100‰ for δD, which is in agreement with previous estimates for Eocene basins of the western United States. Due to its resistance to alteration and record of variations in both δ¹⁸O and δD of water, chert has the potential to corroborate and constrain the cause of variations in isotope stratigraphies.