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1.
Immature samples of the Permian Kupferschiefer from the Lower Rhine Basin in N.W. Germany were analysed for tetrapyrrole pigment type and abundance. The sediment, thought to have been deposited in a marine regime with enhanced salinity, was found to contain high concentrations of metalloporphyrins. The porphyrins are complexed to nickel (Ni) and oxovanadium (V=0), but high abundances of iron (Fe) porphyrins were also detected using UV/visible spectroscopy and mass spectrometry. The presence in the latter of series of aetioporphyrins, cycloalkanoporphyrins, di-cycloalkanoporphyrins and benz-cycloalkanoporphyrins was confirmed by accurate mass measurements; HPLC co-injection of deoxophylloerythroetioporphyrin (C32 DPEP) with the demetallated iron porphyrins indicated its presence in the sediment as an iron complex. The study provides the first evidence for the occurrence of Fe porphyrins in geological samples other than coals and lignites, and reports the highest concentrations in sedimentary organic matter to date. 相似文献
2.
黔北下寒武统黑色岩系的沉积环境与地球化学响应 总被引：2，自引：0，他引：2
下寒武统黑色岩系在我国华北、华南及塔里木盆地等广泛发育,但富有机质泥页岩的分布特征及其控制因素未有定论。本文对黔北地区下寒武统牛蹄塘组(及同时期地层)不同沉积相带典型剖面中的富有机质泥页岩及其上下层位进行了地球化学分析,识别出寒武纪早期不同沉积相带氧化还原环境的明显差异。台内凹陷相主要岩性为黑色页岩,底部为不等厚的薄层磷块岩和硅质岩或硅磷质结核,沉积的黑色页岩厚度大,有机质丰度高,V、Ni、Mo、U等微量元素显著富集,反映了贫氧-缺氧环境,以及短暂动态的硫化环境,Mo/TOC反映了其为局限盆地特征;上斜坡相为贫氧到氧化的沉积环境,但更多地是表现为氧化的沉积环境,其中牛蹄塘期存在局部的硫化环境,沉积的黑色页岩厚度小,但有机质丰度最高,V、Ni、Mo、U等微量元素的富集程度较低;盆地相为黑色硅质岩与富有机质的黑色硅质页岩间互沉积,同期沉积厚度较小,有机质丰度相对较低,V和U的富集程度大于台内凹陷相,而Ni和Mo的富集程度则低于台内凹陷相,指示了缺氧环境,期间伴随有贫氧和短暂的氧化环境存在,且可能存在局部的硫化环境,Mo/TOC反映了中等的局限程度。总的来说,黔北下寒武统黑色岩系的有机质丰度、厚度以及微量元素富集程度等特征主要受控于不同的氧化还原环境。 相似文献
3.
Metalloporphyrins have been found in black trona water, a solution of sodium salts of organic acids occurring naturally in the Green River Formation of Wyoming. The porphyrins consist largely of nickel deoxophylloerythrin, a C-33 acid, and two lower methylene homologues, C-32 and C-31 acids, and possibly structural isomers of these. The C-32 acid is noticeably more abundant than either the C-33 or C-31 acids. Minor amounts of nickel etioporphyrins also are present. These porphyrins are believed to have been derived from the chlorophyll α synthesized by algae that inhabited Eocene Lake Gosiute. The transformations to porphyrins occurred under the influence of high pH, a reducing environment, and geological time. 相似文献
4.
R. Bonnett 《International Journal of Coal Geology》1996,32(1-4)
The background to recent developments in investigations on coal porphyrins is reviewed. Essentially all the work of the past ten years has been with lignites and coals of the humic series. The concentrations of porphyrins and metalloporphyrins are low (0-ca. 10 μg g−1), which makes for difficulties in isolation and analysis.The preferred methods of isolation and analysis are summarised. The coal porphyrins differ from the porphyrins from crude oil, oil shale and related deposits in a variety of ways which are discussed. The major differences are the predominance of the etio series over the cycloetio series (DPEP series), the presence of Fe and Ga porphyrins (rather than Ni and VO porphyrins), and the presence of mesoporphyrin IX in lignite.Recent results tend to support Treibs' original idea (1935) that, for the coal porphyrins, both chlorophyll and iron porphyrin (haem) sources are important. The application of a weighted mean molecular mass of the porphyrins present as a biological marker in determining coal rank (Porphyrin Index of Coalification) is illustrated. Current activity is directed to the isolation and identification of individual iron complexes, and here a combination of thin layer chromatography and paramagnetically shifted 1H-NMR spectroscopy (of dicyanoferrihaems), together with direct comparison with authentic haems especially synthesised for the purpose, has been rewarding. 相似文献
5.
Christian B. Eckardt Lynne Dyas Peter W. Yendle Geoffrey Eglinton 《Organic Geochemistry》1988,13(4-6)
A novel method for handling and presenting multimolecular abundance data, derived from gas chromatographic-mass spectrometric analyses (GC-MS), is introduced. The method facilitates carbon number labeling of compounds, specifically in the case of porphyrins, by means of a porphyrin-index, which is part of a novel identification code for porphyrins. Identification code, relative abundance and structure information of each compound recognised are stored in a database, which affords a variety of characteristic displays and tables upon manipulation. The combined facilities allow the direct comparison of samples of different origin, maturity and/or palaeoenvironment. Correlation studies, such as oil/oil or oil/source rock, are also facilitated by comparison of characteristic “fingerprint” histogram patterns. The ability of the method is exemplified through analysis of the porphyrin distributions of Boscan oil, La Luna shale, Gilsonite bitumen and Serpiano shale. 相似文献
6.
江汉盐湖盆地原油中微量金属元素的分布及应用 总被引：2，自引：0，他引：2
利用发射光谱粉末法,定量测定江汉盐湖盆地72个原油样中的钴、锗、锆、钼、铬等13个微量金属元素后查明,这些元素在地层剖面上的分布有明显规律。除镁及铅以外,11种金属元素的含量随地层变老和原油成熟度增加而减少。如潜一段重质原油中钼、钴的含量比下伏地层高出15倍左右,锗只在潜一段原油中存在。11种元素的含量还随原油的比重、粘度、合硫量、沥青质、胶质及卟啉化合物的增加而增加。利用这些分布特点可区别不同油层的原油,也可推测油气运移的方向。 相似文献
7.
湘西北下寒武统黑色岩系是中国南方下寒武统黑色岩系的重要组成部分,富含钒镍钼等多金属元素。文中对湘西北下寒武统黑色岩系钒镍钼矿进行了微量元素研究,研究区内Ni、Cd、Mo、Sb、V、Zn、W、Ba等元素特别富集,高含量的Sb和Ba表明其为热水沉积;Mo含量极高说明其为缺氧的还原环境;高的V/（V+Ni）、V/Cr、Ni/Co以及δU值表明其沉积环境为缺氧环境;高的 U/Th表明本区有热水沉积作用;稀土元素配分模式、Ce和Eu异常及La/Yb Ce/La和La/Yb ΣREE图解投点表明其沉积环境为还原环境,并有热水沉积作用。可见黑色岩系形成于缺氧环境,热液活动为其提供了丰富的热液来源。 相似文献
8.
Martin P. Cooke Bart E. van Dongen Helen M. Talbot Igor Semiletov Natalia Shakhova Laodong Guo
rjan Gustafsson 《Organic Geochemistry》2009,40(11):1151-1159
Bacteriohopanepolyols (BHPs) are a diverse group of membrane lipids produced by a wide variety of bacteria and can be used as molecular biomarkers for bacterial processes and populations in both modern and ancient environments. A group of BHPs, including adenosylhopane and structurally related compounds, have been identified as being specific to soils, enabling the transport of terrestrial organic matter (terrOM) to the marine realm to be monitored. Estuary surface sediment samples were obtained from the five Great Russian Arctic Rivers (GRARs; Ob, Yenisey, Lena, Indigirka and Kolyma) and river sediments were obtained from two North American Rivers (Yukon and Mackenzie). Analysis of the BHP signatures, using high performance liquid chromatography–tandem mass spectrometry (HPLC–MSn), indicated the presence of 15 different BHPs originating from a variety of different bacteria, as well as a significant presence of terrestrially derived OM. Total BHP abundance and the contribution of the “soil-marker” BHPs to the total BHP pool increased eastwards among the GRAR sediments. This suggests increasing terrestrial OM or increased preservation of OM as a result of shorter periods of permafrost thawing. The North American rivers showed greatly differing BHP levels between the Yukon and Mackenzie rivers, with a greater BHP input and thus a relatively higher soil OM contribution from the Yukon. The Indigirka River basin in the eastern Siberian Arctic appeared to be the epicentre in the pan-Arctic BHP distribution trend, with the highest “soil-marker” BHPs but the lowest tetrafunctionalised BHPs. Aminobacteriohopanepentol, an indicator of aerobic methane oxidation, was observed in all the sediments, with the source being either the marine environment or methane producing terrestrial environments. 相似文献
9.
卟啉的研究现状及其应用 总被引：2，自引：0，他引：2
在前人研究资料及作者近年来的研究成果的基础上，综述了卟啉化合物地球化学研究的现状，包括金属卟啉的类型，卟啉的化学结构系列，高度脱链基卟啉和高碳数咔琳等及其它们在沉积物(如油页岩、煤和现代沉积物)中的分布特征和成因机理。指出了今后需要加强研究的领域，如沉积物中新的金属卟啉类型探讨和卟啉化学结构的确定等。文章还综述了卟啉化合物地球化学指标在地质勘探中的应用，如:评价生油岩质量，油源对比，油气运移研究，古沉积环境研究和有机质热成熟度研究等。 相似文献
10.
华北地区镍矿床(点)主要分布在内蒙古、河北省及河南省等地,已发现镍矿床(点)19处,其中大型矿床1处,中型矿床3处,小型矿床8处,矿点7处。新元古代和晚古生代是华北地区镍矿床形成的2个高峰期。矿床类型以岩浆型为主,其次为风化壳型和沉积变质型。沉积变质型镍矿床主要产在华北陆块区内,形成环境与裂陷盆地有关;岩浆型和风化壳型镍矿床主要产在克拉通边缘或造山带,形成环境与大陆边缘裂解或后碰撞伸展环境有关。分析认为,华北陆块北缘出露的镁铁质超镁铁质岩、二连贺根山地区蛇绿混杂岩及内蒙古南端秦祁昆造山带寒武系黑色岩系地层,均具有较好的镍矿资源找矿潜力。 相似文献
11.
FANG Chaogang ZHANG Chengcheng MENG Guixi XU Jinlong XU Naicen LI Hualing LIU Mu LIU Bo 《《地质学报》英文版》2024,98(1):150-167
The Late Permian was marked by a series of important geological events and widespread organic-rich black shale depositions, acting as important unconventional hydrocarbon source rocks. However, the mechanism of organic matter (OM) enrichment throughout this period is still controversial. Based on geochemical data, the marine redox conditions, paleogeographic and hydrographic environment, primary productivity, volcanism, and terrigenous input during the Late Permian in the Lower Yangtze region have been studied from the Putaoling section, Chaohu, to provide new insights into OM accumulation. Five Phases are distinguished based on the TOC and environmental variations. In Phase I, anoxic conditions driven by water restriction enhanced OM preservation. In Phase II, euxinic and cycling hydrological environments were the two most substantial controlling factors for the massive OM deposition. During Phase III, intensified terrestrial input potentially diluted the OM in sediment and the presence of oxygen in bottom water weakened the preservation condition. Phase IV was characterized by a relatively higher abundance of mercury (Hg) and TOC (peak at 16.98 wt%), indicating that enhanced volcanism potentially stimulated higher productivity and a euxinic environment. In Phase V, extremely lean OM was preserved as a result of terrestrial dilutions and decreasing primary productivity. Phases I, II and IV are characterized as the most prominent OM-rich zones due to the effective interactions of the controlling factors, namely paleogeographic, hydrographic environment, volcanism, and redox conditions. 相似文献
12.
Krzysztof Birkenmajer Przemys&#x;aw Gedl Ryszard Myczy&#x;ski Jaros&#x;aw Tyszka 《Cretaceous Research》2008,29(3):535-549
This is a critical assessment of the paper by Oszczypko et al. (2004: Cretaceous Research 25, 89–113), in which they tried to prove a mid-Cretaceous age for the Szlachtowa (“black flysch”) and Opaleniec Formations, in the Pieniny Klippen Belt, West Carpathians, both of which had previously been shown to be of Jurassic age. We argue that the mid-Cretaceous age assignment is a misinterpretation, primarily resulting from their field samples having been collected from some Cretaceous lithostratigraphic units, tectonically associated with the Jurassic formations, and/or from tectonic contact-breccias involving Jurassic and Cretaceous strata. In addition, we suggest that they have overlooked a number of significant palaeontological papers, published since 1962, which record the presence of in situ ammonites, aptychi, belemnites, thin-shelled bivalves (Bositra), gryphaeids, foraminifera, and ostracod assemblages, all indicating a Jurassic (mainly Aalenian), and not a Cretaceous, age for the Szlachtowa Formation, and also the in situ Jurassic (Bajocian) ammonites and thin-shelled bivalves (Bositra), Bositra-microfacies, and age-diagnostic foraminiferal assemblages of the Opaleniec Formation.Our presentation here of recently published dinocyst data from well-preserved assemblages further supports the Jurassic ages for the Szlachtowa (“black flysch”) and Opaleniec Formations. 相似文献
13.
Shahid Naseem Shamim Ahmed Sheikh M. Qadeeruddin Khaula Shirin 《Journal of Geochemical Exploration》2002,76(1)
A pilot scale geochemical survey of sediments from the Winder Stream (SW Pakistan) and its tributaries was carried out. The Winder Stream mainly receives sediment from the southern extensions of the Mor and Pab Ranges in the District of Lasbela (Balochistan). In these two mountain ranges, rocks from Jurassic to Cretaceous age are exposed. Rocks of the Ferozabad Group comprise of carbonates and siliciclastics of Lower–Middle Jurassic age and occupy the dominant part of the Mor Range. These strata host syngenetic and epigenetic Zn–Pb–Ba mineralizations of Stratiform Sediment-Hosted (SSH) and Mississippi Valley Type (MVT) deposits.Quantitative estimates of mobile and immobile elements were made from active stream sediments of the Winder stream and its tributaries. The samples were analyzed for Ag, Zn, Pb, Cu, Ni, Co, V, Mn, Fe and Ba using atomic absorption spectroscopy. The abundance of these elements is discussed in relation to local geological conditions such as bedrock, climate, weathering, mobility and pH of the dispersing waters. A number of Zn anomalies have been distinguished in the study area. Kharrari (Zn, 360 ppm), Sand (Zn, 340 ppm) and Draber (Zn, 210 ppm) are demarcated as new areas for Zn mineralization. The present study also indicates prospects of Ag, Cu and V in the rocks of the Mor Range.Relationships between various elements have been identified from scattergrams and reflect genetic associations. Whereby the positive correlation between Cu–Zn (0.55, n=18) and Cu–Pb (0.63) is related to possible sulphide mineralization. 相似文献
14.
To assess whether the biochemical characteristics of peat can provide clues for past ecosystem changes or not, a study was carried out combining elemental analysis, micro-morphological counts and neutral monosaccharide determination of peat organic matter (OM) and the dominant living plants from a formerly cut-over peat bog in the Jura Mountains. Peat profiles (up to 50 cm depth) from two distinctive zones (bare peat, FRA and a regenerating stage, FRC) were compared with the reference profile (FRD) taken from an unexploited area of the bog. The results show contrasting OM composition along the profiles. In the upper sections of the FRD and FRC profiles, high C/N ratios and sugar contents (in the same range as in the source plants) and the large predominance of well preserved plant tissues indicate good preservation of primary biological inputs. In contrast, in peat from the FRA profile and deeper levels of the FRC profile, lower C/N ratios, lower amounts of sugars and a predominance of amorphous OM and mucilage suggest more extensive OM degradation. These features delineate a clear threshold between an uppermost “new” regenerating peat section and an “old” catotelm peat below. Nevertheless, even in the latter, the sugar contents remain relatively high (>80 mg/g) compared with other organic and mineral soils. Analysis of typical peat-forming plants and of bulk peat and fine grained fractions allowed identification of the following source indicators: xylose and arabinose for Cyperaceae; rhamnose, galactose and mannose for mosses; and ribose (and to a lesser extent, hemicellulosic glucose) possibly for microbial synthesis. 相似文献
15.
Xuan Tang Jinchuan Zhang Yang Liu Chao Yang Qian Chen Wei Dang Panwang Zhao 《Chemie der Erde / Geochemistry》2018,78(1):140-151
Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale. 相似文献
16.
中国南方扬子地区下寒武统黑色页岩分布广泛,主要由黑色页岩、黑色白云质页岩,黑色粉砂质页岩和黑色硅质页岩等组成;并伴生有较厚的磷块岩矿床、钒矿床和镍、钼多元素硫化物矿床。对黑色页岩岩石学特征、元素地球化学特征进行系统研究,并详细分析微量元素的富集成因,结果表明：黑色页岩主要形成于静水还原的浅海-半深海缓坡环境,层状元素富集带为沉积成因,海底热流体提供了丰富物质来源。总体上,Co、Be、Mn、Ga等元素含量较低;Cu、V、Ni、Mo等元素的含量较高,多数超过北美页岩平均值;以Ni、Mo为主的多元素富集层通常位于磷块岩之上,以黑色页岩、黑色白云质页岩中的硫化物和硫酸盐矿物为主要载体,其中有机碳（TOC）含量可达12.2%以上,远高于其他元素富集层,随着页岩内硅质成分增加,Ni、Mo、Fe、Co等元素含量明显降低;以V为主的多元素主要赋存于黑色硅质页岩中的水云母,与页岩内硅质成分具有较好的正相关关系;黑色页岩中稀土元素含量为(76.22~290.67)×10-6,轻重稀土比值LREE/HREE介于1.21~4.22,说明轻稀土更为富集,Sr/Ba值为0.04~0.34,δEu正异常,且北美页岩标准化配分曲线呈现平缓左倾,为沉积过程中存在海底热水流体提供了进一步证据。 相似文献
17.
北秦岭庙湾组黑色岩系稀土元素地球化学特征及成因意义 总被引：2，自引：0，他引：2
笔者采用等离子质谱仪(ICP-MS)方法对北秦岭大荆区奥陶纪—志留纪庙湾组黑色岩系岩石的稀土元素及V、Ni、Cr、U、Th等微量元素含量进行了测定。结果显示岩石轻稀土元素相对重稀土元素富集, Eu异常值δEu为0.63~10.61(绝多数大于1.54)多呈正异常, Ce异常值δCe为0.65~1.02(平均为0.893) 异常微弱且有正负差异; U/Th值为0.38~4.07, w (V)/w (V +Ni)值为0.38~0.93以及w (Ce)/w (La)值为1.27~2.17。将这些特征值与前人研究成果对比, 并利用La/Yb-Ce/La和La/Yb-REE判别图解判别后, 认为北秦岭区庙湾组黑色岩系形成于活动陆缘一种干燥缺氧较深浅海环境, 黑色岩系形成过程中有热液作用参与。 相似文献
18.
The metaturbidites of the Palaeoproterozoic Jormua–Outokumpu thrust belt in eastern Finland enclose m- to km-scale ultramafic massifs that are distributed over an area of more than 5000 km2. These bodies, which almost entirely consist of highly depleted mantle peridotites (now metaserpentinites and metaperidotites), are intimately associated with massive to semimassive, polymetallic Cu–Co–Zn–Ni–Ag–Au sulphide deposits that sustained mining in the region between 1913 and 1988. Currently, one deposit (Kylylahti) is proceeding into a definitive feasibility study emphasising the renewed economic interest for Outokumpu-type deposits.The origin of these Outokumpu-type Cu–Co–Zn–Ni–Ag–Au deposits is now re-interpreted to be polygenetic. First, their formation requires deposition of a Cu-rich proto-ore within peridotitic sea floor at 1950 Ma. Close modern analogues to the proto-ore setting include, for example, the Logatchev and Rainbow fields at the Mid-Atlantic Ridge, where venting of high-T–low-pH hydrothermal fluid resulted in accumulations of Cu–Zn–Co–Ag–Au sulphides on serpentinised ultramafic seafloor. Second, the Ni-rich composition of Outokumpu sulphide ores calls for a separate source for nickel: Some 40 Ma after the deposition of the Cu-rich proto-ore – concomitant with the obduction of the ultramafic massifs – disseminated Ni sulphides formed through chemical interaction between obducting peridotite massifs and adjacent black schists. This process was related to listwaenite–birbirite type carbonate–silica alteration at margins of the ultramafic massifs. Due to this alteration, silicate nickel was released from the primary Fe–Mg silicates and redeposited as Ni sulphides in the alteration fringes of the massifs.We propose that syntectonic mixing of these two “end-member” sulphides, i.e., the primary Cu-rich proto-ore and the secondary Ni-sulphide disseminations, resulted in the uncommon metal combination of the Outokumpu-type sulphides. Late tectonic solid-state re-mobilisation, related to the duplexing of the ore by isoclinal folding, upgraded the sulphides into economic deposits. 相似文献
19.
A Colorado lean oil shale was found to have red-colored material on the faces of bedding planes and fractures. This red material is almost entirely the nickel chelate of a single C-29 porphyrin of deoxophylloerythroetioporphyrin type. The molecular weight of the chelate is 490 or 492, depending on which of the two major isotopes of nickel is chelated. A small amount of a methylene homologue 14 mass units higher in molecular weight is also present. Porphyrins extracted from the powdered shale are an extended homologous series of deoxophylloerythroetioporphyrin-type and possibly etio-type nickel porphyrins, as determined by mass spectrometry. The origin of the red porphyrins coating the shale fractures and bedding planes therefore was exogenous to these particular shale samples. 相似文献