Sourcing sedimentary cherts with archaeological use through the combination of chromatographic and spectroscopic techniques

The nature and distribution of organic matter in geological cherts of archaeological use can serve to estimate the sources and origins of some remains of lithic industry. For example, organic and biomarker analysis can provide information to allow a deeper insight into source catchment areas, artefact displacement or the way in which the artefacts were employed. In this work, soluble (bitumen) and insoluble (kerogen) organic matter were isolated from several chert samples with different depositional history and analysed by means of gas chromatography–mass spectrometry (GC–MS) and spectroscopic techniques such as infrared and Raman spectroscopy. Chemometric treatment of the results allowed observation of differences between organic matter content on the basis of the depositional setting of the cherts. Samples with a continental deposition seemed to preserve more organic matter with little alteration. The hydrocarbon profiles of these samples were dominated by high molecular weight n-alkanes, alkylcyclohexanes and isoprenoid groups which allowed distinguishing them from the rest of the analysed samples.     

Geochemical and petrographic characterization of organic matter in the Upper Jurassic Madbi shale succession (Masila Basin,Yemen): Origin,type and preservation

The Upper Jurassic Madbi Formation, located in the Masila Basin, eastern Yemen, represents the major source rock in this basin. Organic rich shales from two oilfields (Kharir and Wadi Taribah) were analysed to evaluate the type and origin of the organic matter and to determine the factors controlling its deposition. This study is based on geochemical analyses of whole rock (total organic carbon content, Rock-Eval pyrolysis and carbon isotope data) and petrographic analyses on organic matter (kerogen maceral composition and palynofacies) by optical and scanning electron microscopy. Organic petrographic composition of kerogen shows that the Madbi shale is characterized by high amounts of organic matter, consisting predominantly of yellow fluorescing amorphous organic matter and alginite of marine origin. Terrigenous organic materials such as vitrinite, spores and pollen are present in low quantities. The predominance of marine plankton, as indicated by visual kerogen analysis, is consistent with reported carbon isotopic values. It appears that the high amounts of organic matter in the Madbi shale succession might be mainly due to good preservation under suboxic–anoxic conditions. Consequently the Madbi shales possess very good petroleum generative potential, owing to high content of hydrogen rich Type II and I oil prone kerogen.     

Depositional environments of the Senonian chert, phosphorite and oil shale sequence in Israel as deduced from their organic matter composition

In the Upper Cretaceous sequence of the Negev (southern Israel) the organic matter in phosphorites and cherts differs from that associated with oil shales in its higher content of humic substances and lower kerogen content, and in its more intensive microbial alteration. The n-alkane distribution pattern of the oil shales, phosphorites and cherts indicates that marine biota, probably algae, are the main organic precursors of their organic matter. In some of the oil shales, however, some contribution of terrestrial organic matter is also evident. Similar high phytane/pristane ratios indicate that the organic matter in the oil shales as well as in the phosphorites and cherts accumulated under reducing conditions. The main differences in the organic matter composition are attributed to early diagenetic processes rather than to different biotic precursors or to late modifications due to temperature-induced maturation. The depositional model suggested for the sequence involves upwelling conditions at the boundary between the deep Tethys and the shallow shelf, which induced high organic productivity deep into the inner shelf. Bottom water circulation enabled intensive microbial alteration of the organic matter, followed by a winnowing process leading to phosphorite formation. Since humification is considered an oxygen-consuming reaction, these processes favoured the formation of oxygen-enriched humic substances and the oxidation of humic substances already present. These humic substances are relatively resistant to further alteration and their conversion into kerogen is thus retarded. Subsequently, syndepositional tectonic activity resulted in the introduction of less saline water, restriction of bottom-water circulation and the establishment of a density stratification in the water body. Consequently, aeration of the bottom layer and the sediments was inhibited, microbial alteration was reduced and later winnowing processes were prevented. Such conditions favoured the formation of kerogen directly, rather than through humic substances, and also favoured the preservation of most of the organic matter in the form of oil shale deposits instead of phosphorites.     

扬子地块西北缘及西南缘卡林型金矿的有机质地质地球化学

扬子地块西北缘，西南缘卡林型金矿床的有机碳含量为０．０５％－８．７３％。含金建造形成的环境不同，其改造成的金矿床的有机碳含量不同；矿化主岩的岩性不同，基有机碳的含量不同。由浊积岩型含金建筑改造成的卡林型金矿床，其干酪根属Ⅱ型酪根，原始有机母质属还原环境沉积的海相菌藻类生物演化成的腐泥型有机质。     

Limits in pyrolysis–GC–MS analysis of kerogen isolated from Archean cherts

Pyrolysis–GC–MS was recently proposed as an emerging technique for establishing biogenicity of 3.5 Gyr old insoluble organic matter in cherts (Derenne et al., 2008. Earth and Planetary Science Letters 272, 476–480). When applied to four kerogens isolated from Archean chert samples for biogenicity determination, this method highlights the importance of having a significant aliphatic component remaining in the kerogen. If not, fatty acid decarboxylation may bias the n-alkane distribution. However, in most cases, mature samples such as Archean cherts usually do not have such an aliphatic fraction. This shows the limits of the technique and the need for a new biogenicity marker.     

阿拉善右旗杭乌拉地区下二叠统埋汗哈达组烃源岩特征

通过对阿拉善右旗杭乌拉地区下二叠统埋汗哈达组岩性特征、暗色泥页岩油气地球化学特征研究,总结了烃源岩纵向分布、有机质丰度、干酪根类型和热演化特征。下二叠统埋汗哈达组烃源岩分布层段集中,暗色泥页岩累计厚度160.1 m,占碎屑岩厚度的33.3%。有样品控制的暗色泥页岩厚度94.1 m,w（TOC）平均为0.75%,大于0.3%的样品占93.5%。其中:w（TOC）大于1.0%的好烃源岩厚度22.2 m,占样品控制厚度的23.6%;w（TOC）为0.5%~1.0%的中等烃源岩厚度45.5 m,占48.3%;w（TOC）为0.3%~0.5%的差烃源岩厚度16.5 m,占17.5%。甾烷相对含量具有明显的C₂₇优势,族组分饱和烃含量显著高于芳烃含量,干酪根类型为II型。R_c平均为0.77%,表明干酪根演化进入成熟阶段,最高热解温度（T_max）分布范围为350~550 ℃,属成熟-高成熟阶段。综合评价认为,下二叠统埋汗哈达组具有较好的生烃条件,以生气为主。     

西藏北羌塘盆地光明湖地区上侏罗统白龙冰河组烃源岩有机质特征

通过对研究区露头烃源岩样品进行Rock-Eval热解模拟实验、干酪根镜鉴、镜质体反射率、族组分分离、单体烃碳同位素等分析,对北羌塘盆地光明湖地区侏罗系白龙冰河组烃源岩有机质特征进行研究。结果表明,该区白龙冰河组烃源岩以碳酸盐岩为主,有机碳含量0.01%~1.21%,平均值为0.39%,有机质丰度较高;干酪根显微组分以腐泥组为主,含量70%~92%,平均值为80%,以Ⅱ₁型为主,主峰碳、(nC_21-/ nC₂₂₊)轻/重比及Pr/nC₁₇-Ph/nC₁₈的相关图均表明有机质来自低等水生生物,有机质类型较好;镜质体反射率最小值1.409%,最大值2.423%,平均值为1.909%,有机质的热演化程度总体较高,达到高成熟-过成熟阶段。     

Source rock potential of selected Cretaceous shales,Orange Basin,South Africa

Twenty Cretaceous shale samples from two wells in the Orange Basin of South Africa were evaluated for their source rock potential. They were sampled from within a 1400 m-thick sequence in boreholes drilled through Lower to Upper Cretaceous sediments. The samples exhibit total organic carbon (TOC) content of 1.06–2.17%; Rock-Eval S2 values of 0.08–2.27 mg HC/g; and petroleum source potential (SP), which is the sum of S1 and S2, of 0.10–2.61 mg HC/g, all indicating the presence of poor to fair hydrocarbon generative potential. Hydrogen index (HI) values vary from 7 to 128 mg HC/g organic carbon and oxygen index (OI) ranges from 37 to 195 mg CO₂/g organic carbon, indicating predominantly Type III kerogen with perhaps minor amounts of Type IV kerogen. The maturity of the samples, as indicated by T _max values of 428–446°C, ranges from immature to thermally mature with respect to oil generation. Measured vitrinite reflectance values (%Ro) of representative samples indicate that these samples vary from immature to mature, consistent with the thermal alteration index (TAI) (spore colour) and fluorescence data for these samples. Organic petrographic analysis also shows that amorphous organic matter is dominant in these samples. Framboidal pyrite is abundant and may be indicative of a marine influence during deposition. Although our Rock-Eval pyrolysis data indicate that gas-prone source rocks are prevalent in this part of the Orange Basin, the geochemical characteristics of samples from an Aptian unit at 3318 m in one of the wells suggest that better quality source rocks may exist deeper, in more distal depositional parts of the basin.     

碳酸盐岩有机质丰度测试新方法

常规有机碳测试中仅对残余固相进行测试而忽略了酸解液,而前人研究证实酸解液中含有一定量的有机质。为了准确定量碳酸盐岩样品的总有机碳(TOC),提出蒙脱石增稠元素分析的新方法。本次研究以配比标样(CaCO₃+SiO₂+有机质标样)作为研究对象,对配比标样进行传统有机碳测试以及酸解后利用蒙脱石增稠进行元素分析的新方法测试。结果显示加入有机质标样为小分子有机酸(盐)的配比标样的传统有机碳测试的相对误差为98.5%~99.6%,加入大分子有机质的配比标样传统有机碳测试的相对误差较小,为11.9%~48.1%。而酸解后蒙脱石增稠进行元素分析测试的方法中,总有机碳(TOC)的相对误差为0.76%~19.46%。不同有机碳浓度的配比标样的元素分析法测试结果的相对误差随着有机碳浓度的增大而减小。新有机碳测试方法中,由于除去无机碳后将残渣与酸解液混合均匀并增稠,避免了有机碳的流失,更能客观反映样品总有机碳(TOC)。     

Geochemistry and metal potential of triassic carbonaceous silicites in Sikhote Alin

In the Triassic siliceous formation of Sikhote Alin, carbonaceous silicites occur in the late Olenekian-middle Anisian member (4–20 m) of alternating cherts and clayey cherts (“phtanite member”) near the section base. The silicites are represented by radiolarian and spicule-radiolarian cherts alternating with clayey cherts. They contain up to 8.5% C_org. In the majority of sections, the rocks underwent structural and mineral transformation at the mesocatagenetic stage. The slightly oxidized organic (primarily, marine sapropelic) matter contains quinones, methyl, methylene, and ether groups. The content of neutral bitumens in rocks shows a wide variation range. The carbon isotopic composition in phtanites and clayey phtanites (δ¹³C from ?27.3 to ?30.2‰) is identical to that in many Paleozoic-Mesozoic bitumens and oils. As compared with other Mesozoic sedimentary rocks of Sikhote Alin, the carbonaceous silicites are enriched in V, B, Mo, Ni, Cu, and Ag. Anomalously high concentrations of Ba are recorded in phtanite rock sections at the Gornaya and Khor rivers and in the vicinity of Khabarovsk. Modal value of the Au content in phtanites and clayey phtanites is three or four times higher than the clarke value in carbonaceous silicites and reaches anomalous values in some sections (e.g., Ogorodnaya River section). Carbonaceous silicites of this section are also enriched in Pt. Positive Au-C_org correlation is recorded in clayey phtanites of the Ogorodnaya River section containing more than 0.5% C_org. In organic fractions, Au and Ag are concentrated in alcohol and alcohol-benzene bitumens, asphalt acids, and asphaltenes. Migration of bitumens from high-carbonaceous clayey phtanites to the pore-fissure space of cherts and phtanites also fostered the concentration of these metals in some low-carbonaceous layers of the member.     

封闭体系有机质与有机碳氢氮恢复动力学研究

在封闭体系的条件下,对典型的Ⅰ、Ⅱ、Ⅲ型干酪根在热演化过程中的损失进行生烃动力学研究,获得了Ⅰ、Ⅱ、Ⅲ型干酪根的总量、有机碳、氢以及氮质量损失动力学参数。用Kinetics软件计算了封闭体系干酪根有机碳丰度、氢碳原子比和氮碳原子比的恢复系数。认为在对高成熟—过成熟干酪根进行生烃评价时,Ⅰ、Ⅲ型干酪根残余有机碳丰度需要进行恢复,而Ⅱ型干酪根残余有机碳丰度不需要恢复。三种类型干酪根的氢碳原子比均需要进行恢复。     

临兴地区海陆过渡相页岩及页岩气地球化学特征

为揭示鄂尔多斯盆地东缘上古生界海陆过渡相页岩及页岩气地球化学特征,选取临兴地区页岩样,开展薄片鉴定、全岩和黏土含量、扫描电镜、有机碳、岩石热解、干酪根显微组分和干酪根碳同位素测试,分析页岩解吸气的气体组分和碳同位素组成。结果表明:临兴地区过渡相页岩矿物组分主要是石英和黏土矿物,含少量方解石、斜长石、钾长石、白云石和黄铁矿等。受矿物成因、沉积环境等多方面的影响,不同矿物组分与有机质赋存方式各异。石英与有机质存在2种赋存方式,黏土矿物存在3种赋存方式,黄铁矿存在4种赋存方式。有机质类型为Ⅱ₂–Ⅲ型,有机碳含量平均值大于2.0%,干酪根碳同位素介于–24.5‰~–23.2‰。镜质体反射率介于0.92%~1.30%,t_max值介于427~494℃,有机质热演化达到成熟阶段。页岩气中烃类气以甲烷为主,含有少量乙烷、丙烷,总体属于干气。甲烷碳同位素均值为–40.0‰,介于海相页岩气和陆相页岩气甲烷碳同位素之间;乙烷碳同位素值介于–26.8‰~–22.56‰,均大于–29‰,整体呈现出δ13C₁＜δ13C₂＜δ13C₃正碳序列。研究认为,该区页岩具备大量生成页岩气的潜力,页岩气主要来源于上古生界偏腐殖型页岩,属于由干酪根裂解而生成的有机热成因煤成气。      

Prognostication of hydrocarbon generative potential in the onshore and offshore Niger Delta,Nigeria using TOC content and rock-eval pyrolysis techniques

This article prognosticates the hydrocarbon generation potential of core samples from fields A, B, C and D in Niger delta, Nigeria. The objectives of this study are to characterize the quality of these core samples by organic geochemical analyses. A total of ten core samples collected from fields A, B, C and D in Niger delta were analyzed using total organic carbon （TOC） content analysis, rock-eval pyrolysis technique. The analytical results of the stud- ied core samples reveal that they have generally high total organic carbon contents （TOC）, suggesting that conditions in the Niger delta favour organic matter production and preservation. There is a variation in the kerogen types and this may be attributed to the relative stratigraphic positions of the core samples within the Niger delta. The rock-eval results indicate that the samples from fields C and D contain predominantly Type II kerogen with a capacity to gen- erate oil and gas and hence have good generative potential. The samples from fields A and B contain mainly Type III kerogen and are gas-prone with moderate generative potential.     

Source potential and palynofacies of Late Jurassic “Lemeš facies”, Croatia

Laminated limestone and calcareous shale outcrop samples from the Late Jurassic “Leme?” facies (Croatia) were investigated to characterize their organic facies and palynofacies and their hydrocarbon generative potential. The results indicate that the organic rich sediments of “Leme?” facies were deposited within a relatively shallow marine environment at low redox potential, characterized as an oxygen depleted depositional setting with stratified bottom waters of the carbonate platform (Adriatic Carbonate Platform). The organic rich samples contain a high portion of lipid rich amorphous kerogen of algal/phytoplankton origin, enriched by bacterial biomass. Most of the analyzed samples have total organic carbon contents (TOC) greater than 3%, Rock-Eval S2 >20 mg HC/g rock, yielding Hydrogen Index (HI) values ranging from 509–602 mg HC/g TOC. According to these results, the analyzed samples have very good to excellent oil generative potential. Relatively high sulfur content suggests that the kerogen is best described as Type II-S. Biomarker maturity parameters, as well as the fluorescence of the isolated kerogen, show that the organic matter is at early to peak oil thermal maturity. The observed level of thermal maturity indicates that these samples were once buried to depths of ～5.5–5.8 km before being uplifted in the late Tertiary. The surface outcrops of the “Leme?” facies suggest that these strata have significant source potential and are the likely source of oil in the Croatian External Dinarides.     

Palynofacies, palaeoenvironment, and source rocks evaluation of Ratawi Formation, Southern Iraq

Palynological analysis were done on 12 rock samples for Ratawi Formation from Rumailah well 131 and eight samples for the same formation from Zubair well 47, South Iraq, to extract sedimentary organic matters. Microscopic examination led to diagnose large numbers of spores, pollen, dinoflagellates (proximat, cavate, and chorate), foraminifera, melanogen, hylogen, and amorphogen. Three palynological facies were determined on the bases of percentages of sedimentary organic matter and palynomorphs from two sections. Analysis of these palynofacies clarified Ratawi Formation as deposited from environments ranging from delta and lagoon (suboxic–dysoxic) to shelf facies (anoxic near the shore–suboxic) with the presence of some layers deposited from semideep open marine environment (bathyal). Organic geochemical analysis of total organic carbon and Rock Eval pyrolysis were done to determine quantity, quality, and degree of maturation of the kerogen. Poor to medium proportion of total organic carbon of kerogen types II and III within a catagenesis stage are recorded in these rocks, and hence, poor hydrocarbon generation could be suggested for these strata.     

The significance of cherts as markers of Ocean Plate Stratigraphy and paleoenvironmental conditions: New insights from the Neoproterozoic–Cambrian Blovice accretionary wedge,Bohemian Massif

The Ediacaran to early Cambrian Blovice accretionary complex, Bohemian Massif, hosts abundant chert bodies that formed on an oceanic plate and were involved in subduction beneath the northern margin of Gondwana. Field relationships of cherts to their host, their microstructure and elemental as well as isotopic compositions revealed diverse processes of chert petrogenesis reflecting depositional environment and position on the oceanic plate. The deep-water cherts formed through a hydrothermal precipitation of silica-rich gels on outer trench swell of the subducted slab with none or only minor addition of terrigenous material. On the contrary, the shallow-water cherts formed in lagoons on seamount slopes, and at least some of them represent a product of hydrothermal replacement of former carbonate and/or evaporite precursors. For both chert types, the hydrothermal fluids were of low temperature and continuous pervasive hydrothermal alteration of oceanic crust, together with an elevated Si content in Neoproterozoic seawater, served as the major source of silica. On the other hand, minor carbon enrichment in chert is mostly linked to variable incorporation of organic matter that was deposited on the seafloor. Rare earth element (REE) systematics of the cherts indicate predominantly oxygenated environment for the shallow-water cherts whereas the deep-water cherts were deposited in diverse redox conditions, depending on their distance from hydrothermal vent. Using these data, we demonstrate that the cherts once formed a part of Ocean Plate Stratigraphy (OPS) now dismembered and mixed with terrigenous siliciclastic material to form OPS mélanges. Combining our data with those from the existing literature, we show that cherts can serve as significant markers of OPS since the Archean, recording a complex interplay between seafloor-related volcanic (production of MORB- and OIB-like magmas) and sedimentary processes, hydrothermal activity at mid-ocean ridges and seamount chains as well as at outer slopes of subducting slabs. However, the cherts also exhibit a secular change in composition and petrogenesis most profoundly affected by an overturn in seawater silica cycle across the Precambrian–Phanerozoic boundary.     

加水热模拟中深湖与煤系泥岩地化特征比较

通过深湖泥岩和煤系泥岩的加水热模拟研究认为,在热模拟实验过程中,深湖泥岩和煤系泥岩显示不同特征,并且其演化有差别。深湖泥岩利于液态原油的生成,并且转化率高于煤系泥岩。深湖泥岩残余可溶有机质饱和烃含量高于煤系泥岩,非烃含量则低于煤系泥岩。深湖泥岩胶质 /沥青质和饱芳比均随温度升高而降低,而煤系泥岩的胶质 /沥青质随温度升高有增加趋势,其饱芳比的变化则不大或有降低趋势。深湖泥岩的T_max难以指示演化阶段,其干酪根碳同位素值明显轻于煤系泥岩,它们的值均随温度的升高而变重。     

Carbon isotopes of organic matter from the upper Jurassic oil shales from the Volgian-Pechora shale province and its accumulation mechanisms

The isotopic composition of carbon from the organic matter of late Jurassic oil shales from the Volgian-Pechora shale province is studied. The existence of a dependence between C_org content in the rock and the isotopic composition of kerogen carbon is ascertained. The content of the heavy carbon isotope increases with increasing C_org. This dependence is accounted for by the progressive accumulation of isotopically heavy hydrocarbons of the initial organic matter due to sulfurization. The data on the isotopic composition of individual n-alkanes of bitumen in the rocks and the data on the absence of isotopic fractionation between thermobitumen and the residual kerogen from oil shales from the Volgian-Pechora shale province obtained by treating shale in an autoclave in the presence of water are presented first in this paper.     

Paleocene-Eocene potential source rocks in the Avengco Basin,Tibet: Organic geochemical characteristics and their implication for the paleoenvironment

The Avengco Basin is located in the western part of the Tibetan Plateau and is similar to the Nima Basin in the central part of the plateau and the Lunpola Basin in the eastern part in terms of sedimentary characteristics and tectonic settings, which are well known to provide a good source rock potential. However, the organic geochemical characteristics of the Paleocene-Eocene potential source rocks in the Avengco Basin have been under debate. Thirty-four marl and mudstone outcrop samples of the Niubao Formation in the Avengco Basin were collected and subjected to the following analyses: total organic carbon (TOC), Rock–Eval pyrolysis, stable carbon isotopes of kerogen, gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS). Here, we present the results indicating the organic matter of the upper Niubao Formation is mainly composed of Type II kerogen with a mixed source, which is dominated by algae. However, the lower Niubao Formation has the less oil-prone Type II–III kerogen, and the sources of the organic matter are mainly terrestrial plants with less plankton. In addition, the samples are thermally immature to marginally mature. The Niubao Formation was deposited in an anoxic–oxic environment which was brackish with an imperceptible stratified water column. The upper Niubao Formation has a medium to good hydrocarbon-generating potential. However, the lower Niubao Formation has a zero to poor hydrocarbon-generating potential.     

Pseudo-oolites in rocks of the Ulundi Formation, lower part of the Archaean Fig Tree Group (South Africa)

The Ulundi Formation of the lowermost Fig Tree Group in the type area in the Barberton Mountain Land consists of a sequence of quartz—sericite schists, banded cherts and tuffaceous rocks up to 40 m thick. It overlies talc—carbonate schists assigned to the upper part of the Onverwacht Group. In the cherts, which in parts represent the sulfide facies of a banded-iron formation, silicified spheroids have been observed which appear to be diagenetically altered, locally zeolitized accretionary lapilli. Portions of the cherts formed through silicification of fine-grained felsic tuffs and contain abundant stylolite seams along which 4% of the rock thickness has been removed by intrastratal solution during deformation.A supposedly organogenic spheroidal structure, Ramsaysphera, has been previously described from the upper part of the Ulundi Formation. The spheroids, with diameters of up to 8 mm, occur in a distinct bed of up to at least 1.6 m thickness and can be traced in outcrop over an area which originally covered 17 × 30 km. The bed was deposited in fairly still water of several 100 m depth. The spheroids accumulated with only little finer-grained detrital material, the interstices between them being filled by cherty silica and minor amounts of dolomite. Up to 65% of the spheroids consist of tectonically elongated, originally round fragments of a micro-felsitic groundmass with remnants of phenocrysts. The majority of the remaining spheroids consists of concentrically banded bodies of siliceous material with minor amounts of chlorite and sericite, as well as small dolomite crystals. These spheroids represent highly altered granules of volcanic glass deposited from volcanic ash clouds through a body of water. The prototype of Ramsay-sphera also belongs to this group of spheroids, and there is little microscopic or macroscopic evidence for its explanation as an organic structure.