Comparative studies of organic matter petrography of the late palaeozoic black shales from Southwestern Poland

There are at least two sapropelic units associated with Late Palaeozoic black shales in Central Europe. The older unit, of Late Carboniferous age, is the lower part of the Anthracosia Shales in the Intrasudetic Basin, and the younger one is the well-known Zechstein Kupferschiefer in both the Foresudetic Monocline and the Northsudetic Basin. The first unit is of lacustrine origin, while the second one represents deposition in a shallow marine depositional environment. Both units contain high amounts of organic matter, thus being typical black shales.The organic matter dispersed in these shales was studied petrographically. In general, the vitrinite reflectance of the shales studied indicates variable, but moderate organic matter maturity (0.68–1.25%), equivalent to the oil window. Detailed microscopic studies of the organic material dispersed in the lower unit of the Anthracosia Shales showed that liptinite, especially alginite is the most abundant component. Secondary altered organic matter, i.e. solid hydrocarbons, rarely occurs. Organic components together with mineral matter constitute a lacustrine sapropelic association, a humic (terrestrial) association and an intermediary association. The character and predominance of alginite and lacustrine sapropelic association are indicative of an open-lacustrine depositional environment. In general, this organic composition is typical of type I kerogen.Microscopic analysis of the Kupferschiefer revealed a mixture of liptinite, vitrinite and inertinite macerals, and other organic components such as amorphous sapropelic mass (ASM) and solid bitumens. The most common organic components are liptinite macerals. Bituminite and alginite predominate, and are diagnostic macerals of this unit. The amount of bituminite locally exceeds 85 vol.%. Other liptinite macerals such as sporinite and liptodetrinite, are present in significantly lower amounts, one exception being ASM, which may be present in higher amounts. Humic constituents (vitrinite and inertinite) are rare, present in small amounts in the Kupferschiefer beds. The organic matter composition points to type II kerogen for this unit.     

藏北高原海陆相油页岩生物标志化合物对比研究

重点报道了藏北高原双湖地区早侏罗世海相油页岩和可可西里地区中新世陆相油页岩生物标志化合物组合差异.在两套油页岩中均检出丰富的正构烷烃、类异戊二烯烷烃、萜类化合物及甾类化合物,但二者生物标志化合物组合明显不同.这种不同是在有机质演化程度差异的基础上,主要由原始生物输入和沉积环境差异造成的.海相油页岩正构烷烃具有低碳数优势, nC15、nC16或 nC17为主峰碳,无明显的奇偶碳数分布, Pr/Ph比值显示,多数海相油页岩具有姥鲛烷优势,缺乏β-胡萝卜烷,伽马蜡烷含量较低,海相油页岩原始有机母质构成中,既有丰富的菌藻类等低等水生生物,还有一定比例的陆生高等植物混合输入的特点,属贫氧-缺氧、弱氧化-弱还原沉积环境,进一步证明了早托尔期这种富碳缺氧黑色油页岩是一次全球性海平面上升事件的产物.陆相油页岩正构烷烃具有高碳数优势,主峰碳数为 nC23或 nC29,奇碳数优势突出, Pr/Ph比值显示,陆相油页岩具有强烈植烷优势,β-胡萝卜烷含量相对较高,伽马蜡烷 /αβ C30霍烷比值为 0.31～ 0.60,陆相油页岩原始有机母质构成中,既有高含量的高等陆生植物,还有一定数量低等水生生物混合输入,且在剖面序列中有由早期 C3型陆生高等植物向晚期 C4型转变,特别是剖面顶部油页岩中具有丛粒藻 Botryococus输入的特点,从而导致罕见的重δ13C异常,属缺氧、强还原湖泊沉积环境,反映了晚中新世湖泊演化历史中生态系统的转型和更新这一重要事件.古湖泊演化早期具有水体盐度分层,以出现高含量的β-胡萝卜烷和伽马蜡烷为标志,为咸水湖,晚期湖平面上升,湖泊水体盐度逐渐降低.     

Atmospheric weathering of Scandinavian alum shales and the fractionation of C,N and S isotopes

Subaerial exposure and oxidation of organic carbon (C_org)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial C_org oxidation are expected to shift new biomass δ¹³C_org composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ¹³C_org at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, C_org-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, C_org-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of C_org without producing a δ¹³C shift between acid rock drainage precipitates and shale. Moreover, ¹³C enrichment in inorganic carbon of precipitates does not support microbial C_org oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ³⁴S = δ³⁴S_shale − δ³⁴S_precipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ¹⁵N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of C_org, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.     

茂名油页岩沉积有机质特征及古气候意义

基于海洋沉积确定的始新世晚期至渐新世早期(约33.5 Ma)的气候过渡期是新生代全球性气候事件,但长期以来相关的陆相沉积记录研究则比较缺乏。本文对形成于始新世晚期至渐新世早期的茂名油柑窝组油页岩样品进行了有机质丰度、烃类组成、单体烃碳同位素组成等分析,以期研究低纬度陆相沉积有机质对古近纪始新世-渐新世气候过渡期(EOT)的响应。研究结果显示,埋藏较浅的上部层位样品正构烷烃碳同位素组成显著正偏,为-19.1‰~-25.9‰,平均值为-22.2‰;而下部层位样品正构烷烃碳同位素组成在-23.7‰~-30.2‰,平均值为-26.3‰。两个样品正构烷烃碳同位素组成之差在1.5‰~8.1‰,平均值之差为4.6‰。正构烷烃碳同位素组成的显著差异指示了EOT低纬度陆相古气候变化引起的陆相有机质响应,而这种响应与当时大气CO2浓度和海洋温度降低导致的气候和植物群落变化密切相关,即可能存在着C3植物向C4植物的转化、C4植物的迅速增加并最终导致沉积有机质碳同位素组成的变化;也可能是由于大气CO2浓度降低导致的大气CO2碳同位素组成整体正偏的结果。很显然,进一步详细的连续剖面分析将对研究古近纪EOT低纬度陆相古气候变化提供重要科学依据。     

库车坳陷中生代海侵事件对有机质的影响

对库车河剖面三叠侏罗系重要生烃组段进行了有机质生物标志化合物及单体烃同位素研究,研究结果表明,海侵层位与非海侵层位在生物组成和生标特征等方面明显不同,海侵带来了不同的生物体,使有机质类型发生了改变。在生物标志化合物参数方面表现为Ｐｒ／Ｐｈ小于１,甾烷含量丰富,甾烷中Ｃ_２７化合物丰度与Ｃ_２９相当,三环萜烷有Ｃ_２１＜Ｃ_２３＞Ｃ_２４的分布特点,单体烃同位素表现出富集轻碳同位素的特点。中生代海侵事件对塔北隆起区及库车拗陷油气资源具有重要的意义。     

不同土壤有机质组分对憎水有机物的吸附机理研究

采用完全混合一步平衡反应实验方法，选择菲、萘、三氯苯和二甲苯作为憎水有机物(HOCs)的探针，研究了它们在土壤及其中的胡敏酸、胡敏素等有机质组分中的等温平衡吸附行为，探讨了非线性吸附的机制。结果表明，HOCs在水与土壤体系中表现为非线性吸附，其非线性的吸附行为主要受到土壤有机质(SOMs)的控制。SOMs具有高度不均匀的性质，HOCs表现出非线性吸附行为是其在不同的SOMs相扩散转移以及在相对聚结的胡敏素和“黑炭”的表面吸附的结果。     

羌塘盆地中生界海相黑色泥页岩特征及页岩气远景区预测

青藏高原羌塘盆地中生界发育上三叠统肖茶卡组（T3x）、中侏罗统布曲组（J2b）和上侏罗统索瓦组（J3s）3套海相黑色泥页岩,形成于有机质比较丰富且易于保存的营养型还原性沉积环境,以台地相为主,其次为盆地相和三角洲相;厚度在41～474 m范围内,有机碳（TOC）含量平均值为0.25%～8.34%,有机质类型主要为Ⅱ型干酪根,镜质体反射率（Ro）平均值为1.21%～3.0%,处于高-过成熟生气阶段,脆性矿物以石英、长石为主,含量为65%～70%,页岩孔隙度约2%。与美国主要盆地产气页岩各项指标相比较,羌塘盆地中生界海相黑色泥页岩具有厚度大、有机质丰度低、热演化熟度高、脆性矿物种类多、石英含量较低、长石和粘土矿物含量较高及孔隙度低的特征,具备了形成页岩气基本地质条件,是我国海相页岩气勘探的沉积盆地之一,综合评价预测的页岩气远景区以上三叠统肖茶卡组（T3x）分布范围大,其次是布曲组（J2b）和索瓦组（J3s）。     

Phosphorus features in FT-IR spectra of natural organic matter

Fourier-Transform Infrared （FT-IR） spectroscopy has been used extensively to characterize natural organic matter （NOM）. Absorption bands at 1100-1000 cm^-1 in the FT-IR spectra of NOM have been frequently assigned to alcoholic and polysaccharide C-O stretching or to vibrations of SiO2-related impurities. However, these interpretations do not consider that a strong band associated with P-O bonds of phosphate also appears in the same region. We evaluated the correlation between absorbance in this region and P content of 19 NOM samples from terrestrial, aquatic and plant shoot sources. In the spectra of 10 humic and fulvic acid samples, shoulder to minor bands appeared around 1050 cm^-1. Absorbance intensity at 1050 cm^-1 （Y） was linearly related to P content （X） by the following： Y=4.38X＋0.3 l, with R2=0.90. We did not observe such a close correlation between absorbance and P content in two aquatic NOM samples. Apparently, this is because the aquatic NOM samples were concentrated by reverse osmosis, which would have concentrated not only humic and fulvic acids but also other soluble organic solutes present in natural waters. In the FT-IR spectra of seven dissolved organic matter （DOM） samples obtained from dried plant shoots, broad and/or multiple bands around 1075 cm^-1 were observed with a shoulder at 977 cm^-1. These characteristics were more like those of organic phosphate compounds （such as inositol hexaphosphate）. However, solution 31P nuclear magnetic resonance spectroscopic analysis showed no significant amount of organic phosphate present in these samples.     

中国海相碳酸盐岩评价中有关有机质丰度下限的几点讨论

综述了中国海相碳酸盐岩有机质下限研究的若干进展,认为针对不同需求,应提出碳酸盐岩烃源岩最低下限、有效烃源岩下限、战略选区下限3个不同的下限标准.高成熟碳酸盐岩原始有机质丰度恢复一直存在争议,根据生烃动力学,结合热史,可实现原始有机质总量的恢复.碳酸盐岩中泥质与有机质丰度、排烃能力是否相关仍存在争论,认为碳酸盐岩中泥质的作用仍有待进一步研究.     

中国海相碳酸盐岩评价中有关有机质丰度下限的几点讨论

综述了中国海相碳酸盐岩有机质下限研究的若干进展,认为针对不同需求,应提出碳酸盐岩烃源岩最低下限、有效烃源岩下限、战略选区下限3个不同的下限标准。高成熟碳酸盐岩原始有机质丰度恢复一直存在争议,根据生烃动力学,结合热史,可实现原始有机质总量的恢复。碳酸盐岩中泥质与有机质丰度、排烃能力是否相关仍存在争论,认为碳酸盐岩中泥质的作用仍有待进一步研究。     

华北克拉通南缘中元古代早期杂色页岩的古环境指示意义

中元古代大气氧含量是否有变化以及何时、如何变化的,目前是尚不清楚、存有争议的热点问题。细碎屑岩常被认为可反映其沉积时的水体环境,是记录古海洋氧化还原信息的重要载体。华北克拉通自18亿年之后,处于多期裂解的陆内伸展环境,发育一系列泥页岩,其中华北克拉通南缘崔庄组（~1648Ma）泥页岩沉积于陆棚-浅海环境。本次研究选取该组杂色页岩作为研究对象,扫描电镜和粉晶衍射结果显示,绿色和紫红色页岩主要矿物包括伊利石、石英、长石,还包含了云母、绿泥石、赤铁矿。赤铁矿分布在云母内部和绿泥石边缘,指示其来自于矿物蚀变。两种页岩中的伊利石均以纤维状分布在长石、石英和云母碎屑粒间孔隙,且主要为1M型,指示其经历了浅成岩作用。紫红色页岩与绿色页岩相比,剖面上风化程度较高。主量元素显示,两种页岩的源岩都经历明显的钾化作用,经过钾校正之后,风化指数（CIA）约为80~85,说明物源区经历强烈的风化作用。同时,全铁含量与澳大利亚后太古代页岩和北美页岩相似,铁并无明显富集,指示铁可能是陆源输入。稀土元素与澳大利亚后太古代相比明显Eu异常,无明显Ce异常,而过渡金属元素（V、Cr、Co、Ni）无显著富集,其比值显示该套页岩沉积于氧化的水体中。结合该时期海洋分层模型,推测中元古代早期浅海陆棚海水已出现氧化。黏土质泥页岩在该时期广泛发育,均指示陆壳风化作用强烈,该过程可能影响和控制氧气含量的变化。

     

Stable carbon isotopic analysis of sedimentary organic matter by stepped combustion

A stepped combustion technique, incremental heating in oxygen, has been used to study the carbon isotopic composition of carbonaceous sediments. This technique can afford data on the organic matter of the sediment and can give information on the structure, namely the variations in the isotopic composition of different portions, of the kerogen. Green River shale has been used as a model material and results indicate that it contains two distinct carbonaceous components, a carbonate and kerogen. Isotopic compositions for the kerogen measured by stepped combustion closely match those obtained by normal methods following preconcentration of the kerogen by mineral removal and solvent extraction.The variation in isotopic composition with combustion temperature has been used to investigate relationships with maturity and to look at its use as a possible correlation tool.     

水体中溶解有机物的特性与测量

系统评述了水体中溶解有机物的特性及测量方法。介绍了水体中溶解有机物的研究概况,指出了开展水体中溶解有机物定量监测的必要性;详述了水体中溶解有机物的激光诱导荧光测量方法、对水体中有机物荧光光谱进行分析的特征光谱荧光标记技术和荧光强度归一化处理技术,以及利用激光诱导荧光方法测量水体中溶解有机物浓度的标定方法;综述了多种因素对利用激光诱导荧光方法测量的影响。     

Forms and bioavailability of phosphorus associated with natural organic matter

Natural organic matter （NOM） is an important ingredient in soil which can improve physical, chemical, and biological properties of soils and nutrient supplies. In this study, we investigated the spectral features and potential availability of phosphorus （P） in the IHSS Elliott Soil humic acid standard （EHa）, Elliott soil fulvic acid standard Ⅱ （EFa）, Waskish peat humic acid reference （WHa）, and Waskish peat fulvic acid reference （WFa） by fluorescence spectroscopy, FT-IR, solution 31P NMR, 3-phytase incubation and UV irradiation. We observed more similar spectral features between EHa and EFa as well as between WHa and WFa than between the two humic acids or two fulvic acids themselves. Phosphorus in WHa and WFa was mainly present in the orthophosphate form. However, only about 5% was water soluble. After treatment by both UV irradiation and enzymatic hydrolysis, soluble orthophosphate increased to 17% of WHa P, and 10%o of WFa P. Thus, it appears that a large portion of P in Waskish peat humic substances was not labile for plant uptake. On the other hand, both orthophosphate and organic phosphate were present in EHa and EFa. Treatment by both UV irradiation and enzymatic hydrolysis increased soluble orthophosphate to 67% of EHa P and 52% of EFa P, indicating that more P in Elliott soil humic substances was potentially bioavailable. Our results demonstrated that source （soil vs. peat） was a more important factor than organic matter fraction （humic acid vs. fulvic acid） with respect to the forms and lability of P in these humic substances.     

湘西北下古生界海相页岩储层特征与含气性分析

基于野外地质和钻井资料,结合相关实验测试结果,对湘西北地区下古生界海相页岩储层特征进行了深入研究,并探讨了页岩甲烷含气性及影响因素。结果表明：牛蹄塘组黑色页岩以深水陆棚斜坡相沉积为主,厚度范围为50~250 m;龙马溪组为闭塞海湾沉积,底部黑色页岩发育。两组页岩有机质类型均属于Ⅰ型,有机碳含量平均为3.57%和1.16%,热演化程度较高,平均达2.61%和2.08%。受沉积环境和成岩作用影响,两组页岩均具有高石英、低黏土、少量碳酸盐矿物的组成特征。页岩储集空间可划分为3大类：矿物基质孔、有机质孔、微裂缝。受有机质和黏土矿物等因素影响,页岩内部孔隙结构参数各不同,但主体上孔径小于50 nm的微孔和中孔提供了大部分比表面积和孔体积,为气体存储主要场所。牛蹄塘组页岩甲烷最大吸附量平均为1.98 cm3/g;龙马溪组页岩甲烷最大吸附量较低,为1.16 cm3/g。其中有机质与黏土矿物对页岩甲烷吸附量均有一定的贡献,而过高的成熟度和含水量可导致页岩吸附能力下降。     

Palaeogeography of radiolarite and organic-rich deposits in Mesozoic Tethys

Siliceous and marine organic-rich deposits are sometimes associated, sometimes separate in space and time; however, both are generally accepted to be the result of high planktonic productivity. Among the siliceous marine deposits, the phtanite family facies is distinguished from the radiolarite family facies by several characteristics: They contain organic material and as a result are blackish (vs red/green for radiolarite facies), their time of deposition corresponds with strong faunal modifications and they are deposited generally in shallower environments. A palaeogeographic analysis of locations of Tethyan biosiliceous and marine organic-rich rocks, both resulting from a high planktonic palaeoproductivity, for three Mesozoic high sea-level intervals, Toarcian, Kimmeridgian and Cenomanian, show: (a) during Jurassic times these Tethyan deposits were dissociated, the siliceous deposits being closer to open ocean waters than the organic-rich ones. This is a common disposition in modern upwelling systems and suggests a common process; (b) during Cretaceous times these Tethyan deposits were often associated, i.e. both occur at the same site, and are probably the result of a different process from that in the Jurassic.     

库车坳陷北部山前带中生界烃源岩有机岩石学

应用全岩有机岩石学分析方法,对库车坳陷北部山前带中生界三叠系和侏罗系烃源岩的显微组分、主要富氢组分、有机质类型及热演化程度进行了研究。结果表明：库车坳陷北部山前带侏罗系克孜勒努尔组烃源岩显微组分总含量最高,恰克马克组烃源岩最低。中生界烃源岩显微组分组成具有镜质组含量高、壳质组和惰性组相对发育、腐泥组贫乏的特征。不同层位具有一定差异性,克孜勒努尔组和塔里奇克组中镜质组含量较高,恰克马克组壳质组相对发育。孢子体、壳屑体、角质体和藻类体是其主要的富氢组分,恰克马克组富氢组分相对含量最高。烃源岩有机质类型以Ⅲ型和Ⅱ2型为主,有利于生气,镜质组反射率Ro为056%~187%,热演化程度处于成熟-高成熟阶段。克拉苏—依奇克里克构造带冲断前缘烃源岩显微组分总含量与热演化程度均相对较高,为烃源岩的最大成熟生烃中心。烃源岩高生烃潜力与高的壳质组含量和低的陆源有机质含量有关。     

Biomarker geochemistry of marine organic matter in the Hushan and Chaohu areas,Lower Yangtze region

Marine strata are widely exposed in the Hushan and Chaohu areas, Lower Yangtze region. As biomarker geochemistry of the strata has not been well documented, this paper deals with the biomarker composition of representative samples collected from the Silurian, Carboniferous and Triassic systems and their geological implications, thus providing clues to marine organic matter. On the basis of experimental results, it is shown that abundant biomarkers (e.g. n-alkanes, isoprenoids, terpanes and steranes) were detected. As organic matter in the strata is highly to over mature in general based on petrologic microobservation, some biomarkers (mainly n-alkanes) except terpanes and steranes cannot reflect the source, depositional environment and maturity of organic matter. Thus, primarily based on analyses of the terpanes and steranes, it is suggested that organic matter in the Silurian and Carboniferous strata is derived mainly from lower organisms, while higher plants are predominant in the Triassic organic matter. This further indicates that the depositional environment may have transformed from the marine to continental facies in the Late Triassic. These results provide new evidence for the study of regional depositional evolution, and have enriched the study of biological composition of organic matter. In addition, the biomarker geochemistry of organic matter at high to over maturation stage is addressed.     

柴达木盆地北缘中段侏罗系页岩有机质孔隙演化特征

柴北缘侏罗系页岩的有机碳含量高、厚度大、分布广,但有机质成熟度总体处于未成熟—低成熟阶段,制约了研究区页岩气的表征与评价。通过开放体系下的加热实验,系统刻画了不同温度下的页岩有机质孔隙发育特征及演化过程。分析认为,热模拟温度200~400℃是有机质孔隙发育的优势温度区间,孔隙数量多,从微孔到宏孔都非常发育,孔隙间可形成网状连通。之后随着温度进一步升高,孔隙会出现"塌陷"现象,对页岩气的赋存起到抑制作用。与此同时,有机质的孔隙发育也具有不均一性,不同有机质显微组分孔隙发育能力存在差异,以镜质组、壳质组等为主的有机质显微组分孔隙发育较迟缓,有机质转化不彻底,而以沥青质体、藻类体、无定形体等为主的有机质显微组分孔隙发育时间早、强度大、孔隙之间的连通性好,是页岩气储集空间的主要贡献者。另外,结合能谱分析,认为元素的重量百分比及Ca、Mg等碱土元素的含量也是影响有机质孔隙发育的主要因素。     

Determination of Hg and MeHg complexation with dissolved organic matter by fluorescence quenching titration

In natural waters inorganic mercury （Hg） and methylmercury （MeHg） are complexed with a variety of inorganic and organic ligands, such as OH^-, Cl^-, sulfide, thiols, and dissolved organic matter （DOM）. The bioavailability and toxicity of Hg and MeHg are related to their speciation, instead of their total concentrations. Among these species, Hg-DOM and MeHg-DOM complexes are the least known, due to the complexity and site-specificity of DOM in natural waters. Here we report the complexation between DOM and Hg or MeHg using fluorescence spectroscopy. The Suwannee River fulvic acid, peat humic acid, amino acid typotophan, and natural organic matter from the Suwannee River, Nordic River, and Delta Marsh were studied at their respective excitation/emission maxima,