云南白水台钙华景区的水化学和碳氧同位素特征及其在古环境重建研究中的意义

采用水化学仪器自动记录、现场滴定和样品碳氧稳定同位素测试相结合等方法,对云南中甸白水台钙华景区的水化学和碳氧稳定同位素特征进行了综合分析。主要结论是:形成白水台钙华的泉水具有很高的钙和重碳酸根离子浓度,相应地,泉水的CO₂分压显著高于土壤生物成因所能产生的CO₂分压。结合泉水出露的地质条件及其碳稳定同位素特征(^δ13C=-1.23‰)的分析,进一步发现,高CO₂分压主要与深部地热成因的CO₂有关,而非原来普遍认为的“是温暖湿润气候的产物”。可见,白水台钙华属于热成因类钙华。由此,根据白水台不同时代钙华氧稳定同位素组成的差异,对钙华形成时的水温进行了计算。结果发现自白水台钙华形成以来,水温变化高达11℃,即从最老(<35万年)钙华形成时的21℃降至现在的10℃。这可能与本地区强烈抬升导致的气温降低有关,也可能反映出地热对水温的影响在降低。此外,本文对用热成因类钙华进行古环境重建研究中值得注意的问题也做了讨论。这些问题包括放射性碳测年中“死碳”(来自深部碳酸盐碳和深部CO₂)的干扰及由深源CO₂和CO₂自水中逸出导致的钙华¹³C富集,后者在利用类似热成因碳酸盐沉积的^δ13C进行古植被重建时也是必须考虑的问题     

中国东部CO2气地球化学特征及其气藏分布

中国东部CO₂气田(藏)发育广泛,分布复杂。本文对中国东部松辽、渤海湾、苏北、三水、东海、珠江口、莺琼、北部湾等盆地和内蒙古商都地区以及部分现代构造岩浆活动区CO₂气田(藏)和气苗中CO₂的地球化学特征进行了分析和研究,探讨了中国东部CO₂气的成因、来源及分布。中国东部CO₂气的含量主要分布区间为0~10%,其次为90%~100%,呈现典型的U字型。δ¹³C_CO2值则呈现典型的单峰式分布,峰值区间为-6‰~-4‰。CO₂含量、δ¹³C_CO2值和R/Ra值综合表明,中国东部高含CO₂气以幔源无机成因为主,混有部分有机成因气和(或)壳源无机气。中国东部已发现的36个无机成因CO₂气田(藏)在空间分布上与新近纪及第四纪北西西向玄武岩活动带展布一致,深大断裂和岩浆活动是无机成因CO₂富集、运移和分布最重要、最直接的两大主控因素。     

岩浆去气作用碳硫同位素效应

 根据开放体系条件下的瑞利分馏原理,并考虑岩浆中可能溶解的合碳和含硫组分,从理论上定量模式了岩浆去气作用对火成岩碳、硫同位素组成的影响。结果表明,岩浆CO₂去气作用能够导致岩石中碳酸盐显着亏损¹³C,其δ¹³C值能够从原始-5‰变化到-20‰(PDB);岩浆CH₄去气作用则导致岩石中碳酸盐相对富集¹³C,其δ¹³C值能够从原始-5‰变化到+4‰。岩浆SO₂去气作用可以导致岩石中硫化物显着亏损³⁴S,其δ³⁴S值能够从0‰变化到-8‰(CDT);岩浆H₂S去气作用则导致岩石中的硫化物相对富集4S,其δ³⁴S值能够从0‰变化到+6‰。因此,除源岩原始同位素不均一性和地壳物质混染能引起火成岩的碳、硫同位素组成发生较大变化外,岩浆去气作用也是重要原因之一。     

新疆罗北洼地湖相沉积物有机碳同位素的变化序列及其古环境意义

测定了新疆罗布泊地区湖相沉积物CK-2钻孔样品的总有机碳含量（TOC）及其同位素组成、碳酸盐含量和C/N比值等环境代用指标,以及石膏矿物的质谱-铀系年龄。测试结果表明,20～9kaB.P.期间沉积物δ¹³C_org.在-23.4‰～-16.1‰之间波动且阶段性明显,与TOC呈现良好的相关关系,整体变化趋势同南极Dome C冰芯中记录的全球大气CO₂浓度一致;C/N比值表明有机碳来源主要是陆生高等植物。因此大气CO₂浓度变化是影响20～9kaB.P.期间罗布泊湖相沉积物δ¹³C_org.值变化的主导因素,周围山体上C₃/C₄植物相对生物量的变化则是另一重要因素。依据δ¹³C_org.的变化序列将此时间段湖区古环境的演化分成6个阶段:20.0～14.1kaB.P.期间受到末次盛冰期的影响,气温偏低,湖水丰沛;14.1～13.3kaB.P.是一个气候不稳定期,冷暖波动较频繁,但以暖为趋势;13.3～12.8kaB.P.期间经历了一段冷期,于12.8kaB.P.结束了末次冰期,随后气候开始转暖至11.8kaB.P.;其后气温再次变冷并维持到10kaB.P.;最后从10kaB.P.进入全新世暖期。δ¹³C_org.序列明显向偏负方向变化,表明该地区变暖的趋势相当明显。罗布泊地区日益干旱化是全球气候变化的结果,尤其是受到全球CO₂浓度的不断升高所制约。     

河流碳通量与陆地侵蚀研究

河流碳通量系陆地侵蚀产物,它构成全球碳循环的一个重要环节。河流碳通量在数量上远小于全球碳循环的其他环节,但由于与陆地生态系统联系密切,故对它的研究尤为重要。全球每年河流碳通量约为1GtC（10⁹t碳）,其中约60％为无机碳、40％为有机碳。溶解态有机碳和颗粒状有机碳主要来源于土壤侵蚀,另有一部分有机碳来源于河湖中的浮游植物;溶解态无机碳主要源于大气中CO₂和碳酸盐;颗粒无机碳主要指未溶解的碳酸盐。亚洲季风区河流对全球河流碳通量具有较大贡献,而对其研究程度较低。河流碳通量研究既可为流域治理提供基础资料,也是进一步了解人为CO₂“未知汇”的途径之一。     

中东亚干旱半干旱区C3植物δ13 C值的分布 及其对气候的响应*

植物化石和土壤中的有机质碳同位素指标常用来反映古气候的变化,然而碳同位素这个指标在特定地区反映气候的定量关系缺乏检验。研究剖面选择自中国的秦岭(34°14'24″N,106°55'30″E)到蒙古人民共和国北部,接近贝加尔湖地区(51°35'08″N, 100°45'49″E)的研究剖面线,选择了3种C₃植物(Artemisia scoparia, Ajania achilleides 和 Artemisia frigida),在剖面线上沿南北方向上每隔4'到5'采取一个样点,共选取161个C₃植物茎叶样品进行了δ¹³ C值测定。同时收集了剖面线附近气象站的降水、气温等资料,用插值方法得到每个采样点的气温、降水数据。分析表明:C₃植物的δ¹³ C值分布范围为-30 ‰ ~-22 ‰ ,其平均值为-26.81 ‰ ,该平均值较全球C₃植物δ¹³ C平均值偏正。通过对比C₃植物δ¹³ C与年均温、年均降水量、生长季节的干燥度等随纬度的变化规律,发现C₃植物δ¹³ C、年均降水量、生长季节的干燥度有非常一致的变化趋势,而C₃植物δ¹³ C和年均温不具有一致性。通过一元回归分析也同样发现C₃植物δ¹³ C与年均降水量呈线性负相关关系(y=-0.0077x-24.838,n=161,R²=0.4418,p=0.01),与生长季节的干燥度呈线性正相关关系(y=0.7328x-28.806,n=161,R²=0.3685,p=0.01),而与年均温度没有明显的相关关系(y=-0.0461x-26.756,n=161,R²=0.0232,p=0.01)。在本研究区C₃植物δ¹³ C对年均降水量和生长季节的干燥度响应十分显著,而对温度的响应不明显。研究区具有明显的降水和温度的梯度分布特征,是验证植物碳同位素与气候关系的理想场所,而土壤中的有机质碳同位素与其地面上的植物碳同位素息息相关。研究也说明,在本研究区或其他气候植物组合相似的地区可以利用古土壤中的有机质碳同位素来定量或半定量地反映古气候的变化。     

西秦岭新生代高钾质玄武岩流体组成及其地幔动力学意义

西秦岭新生代高钾质玄武岩是认识大陆碰撞俯冲体制下地幔流体组成及深部动力学的岩石探针。本文采用分步加热质谱法测定了西秦岭高钾质玄武岩中斑晶及基质的流体化学组成和碳同位素组成,结果表明流体组分在200~400℃、400~800℃和800~1200℃阶段性释出,以H₂O为主,其次为CO₂和SO₂,并含有相对较高的He含量。从橄榄石斑晶到斜长石斑晶和基质H₂O和CO₂逐步升高。橄榄石斑晶流体挥发份主要释气峰温度(900~1200℃)明显高于中国东部地幔捕虏体及其它地区超镁铁质岩体中的橄榄石,流体组份以SO₂和CO₂等氧化性组份为主,其CO₂的δ¹³C值(-26.21‰~-20.85‰,平均-23.32‰)和CH₄的δ¹³C值(-42.35‰~-38.17‰,平均-40.03‰)低于基质的δ¹³C_CO2值(-16.43‰~-11.67‰,平均-13.22‰)和δ¹³C_CH4值(-44.22‰~-34.03‰,平均-39.70‰)。基质中CO₂和CH₄碳同位素组成具有机质热裂解特征。原始岩浆的流体挥发份主要为SO₂、N₂和CO₂,可能起源于较深的混杂地幔源区、演化于高f_O2的环境。流体挥发份化学和同位素组成表明高钾质玄武岩浆挥发份中存在地幔和地壳来源组分,幔源岩浆上升演化过程中可能加入了大量的H₂O和CO₂等,可能存在碳酸岩岩浆的混合或岩浆穿透区域碳酸盐地层的混染;其中的再循环壳源组分可能为古特提斯洋闭合俯冲或其后华北克拉通与扬子克拉通碰撞相关的再循环壳源沉积物脱出的流体组分。     

末次冰期黄土中蜗牛壳体碳酸盐同位素组成与其环境指示意义

为了揭示蜗牛化石壳体碳酸盐（文石）稳定同位素组成的古气候和古生态环境指示意义,对采集于河南荥阳邙山末次冰期黄土剖面上部中的粉华蜗牛（Cathaica pulveratrix）化石壳体碳酸盐进行了碳、氧稳定同位素分析,同时还对全岩有机物质（SOM）碳同位素组成以及全岩磁化率和粒度等气候替代指标进行分析,结果显示：剖面中反映蜗牛食物碳同位素组成的壳体δ¹³C_SSA的变化,与反映古植被碳同位素组成的全岩有机物质碳同位素组成（δ¹³C_SOM）无显著的相关关系,但是壳体¹³C相对于SOM的富集程度（Δδ¹³C_SSA-SOM）的变化与石笋氧同位素记录的末次冰期东亚夏季风强度演化同步一致;   壳体δ¹⁸O_SSA的变化不但与黄土磁化率、粒度等气候替代指标变化具有显著相关性,同样也与末次冰期东亚夏季风强度演化同步一致。这些特征,一方面说明受季风环流控制的气候温湿程度变化左右蜗牛夏季活动的几率和食物的类型,干冷气候条件下,相对温湿夏季成为蜗牛活动主要时期,相对富集¹³C苔藓、菌类和植物可能是蜗牛的主要食物;   另一方面暗示蜗牛化石壳体碳酸盐稳定同位素组成能够指示气候温湿程度和生态环境的变化。     

稳定碳同位素在第四纪古环境研究中的应用

文章对陆相沉积物、湖沼相沉积物以及脊椎动物牙齿中的δ¹³C研究作了系统的综述,特别对存在的问题提出了一些看法,认为黄土-古土壤序列中有机质δ¹³C与碳酸盐δ¹³C变化趋势相反的原因是CO₂与碳酸盐交换平衡时的分馏系数在古土壤堆积时和黄土发育时不一致造成的;陆相沉积物的有机质δ¹³C较碳酸盐δ¹³C能更加直接地反映沉积时地表植被状况,陆相沉积物的碳酸盐δ¹³C在古生态中的应用还有待于对它的形成机制和形成过程进行进一步的研究;我国黄土高原末次冰期的气候不利于C4的生长.文章强调古环境、古生态研究应该从现代过程入手,了解现代植物δ13C与气候参数的关系以及现代C4植物的分布规律.同时还认为分子化石的稳定同位素研究这一新研究手段将会给第四纪研究带来更新的活力.     

秦岭大巴山地区紫阳毒重石矿床成因: 矿石组构、氧化还原敏感元素和碳-氧同位素证据

秦岭大巴山地区钡矿资源极为丰富,以蕴含世界罕见的层状毒重石矿床为特色。本研究在紫阳毒重石矿床中发现了玫花瓣状结构,经显微镜观察和电子探针分析表明,玫花瓣体由板柱状重晶石呈放射状排列而成,与前人报道的矿物组成明显不同。紫阳灰黑色毒重石矿石有较高的V、Ni、Cr、U、Mo含量,较低的Th/U比值(<0.04),较高的V/(V+Cr)比值(>0.8)和V/(V+Ni)比值(>0.9),指示寒武纪紫阳毒重石矿床的沉积环境为较还原的环境。紫阳毒重石矿石的C同位素分布在-10.9‰~-16.0‰, O同位素分布在18.1‰~22.3‰之间,表明毒重石中CO₃^2-是有机质通过氧化作用或脱羧基(生物有机质降解)作用提供的低¹³C的碳与同期海水提供的高¹³C的水溶性HCO₃^-或CO₃^2-的混合来源。综合研究表明,该区毒重石矿床的形成可能与寒武纪早期的海底热液成矿作用有关。     

δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

A reconnaissance study of stable isotope ratios in archaean rocks from the yilgarn block,Western Australia

Isotopic compositions of sulphur, carbon, and oxygen have been determined for constituents from a total of 103 samples of sedimentary rocks, mafic and ultramafic igneous rocks, nickel ores, and gold ores from the Archaean Yilgarn Block.

Sulphides in the bulk of the sedimentary rocks have δ³⁴S values close to 0‰ and appear to have precipitated from solutions which incorporated magmatic sulphur (either juvenile or derived from older rocks). There is no evidence for widespread sulphate reduction.

δ³⁴S values of sulphides in the nickel deposits and associated mafic/ultramafic igneous rocks are within the magmatic range. The small, high‐grade deposits of the Kambalda‐Nepean‐Scotia type have small positive δ³⁴S values, and the large, low‐to‐medium grade dunite‐associated deposits of the Mount Keith‐Perseverance type have small negative δ³⁴S values.

Sulphides in the Kalgoorlie gold ores are enriched in ³²S relative to those in their host dolerite, supporting an epigenetic origin for the gold, under moderately high fO₂ conditions.

The δ¹³C values do not provide unequivocal evidence for the source(s) of the reduced carbon (kerogen) in the sedimentary rocks. Whilst they are compatible with biogenic derivation, it is not possible to rule out contributions from pre‐biotic organic ‘soup’ or from hydrothermal solutions of deep‐seated origin.

Carbonate in the sedimentary rocks are predominantly in epigenetic, sulphide‐bearing veinlets. In many cases, their δ¹³C values suggest precipitation from hydro‐thermal solutions containing magmatically derived CO₂. In only two samples are the petrographic features and δ¹³C values compatible with marine carbonates. Talc‐carbonate altered ultramafic igneous rocks have δ¹³C values consistent with their incorporation of magmatically derived CO₂.

The ?δ¹³C (carbonate‐kerogen) values for most of the sedimentary rock studied fall in a narrow range around +10‰, suggesting isotopic exchange between oxidized and reduced carbon species at moderately high temperatures (>250°C).

δ¹⁸O values of carbonate from both sedimentary rocks and igneous rocks are mainly within the range +7.2‰ to +18.0‰. If the values are primary they are consistent with the formation of carbonate from hydrothermal solutions of magmatic and/or metamorphic origin. However, it is also possible the δ¹⁸O values are the result of post‐depositional equilibration with meteoric waters.     

Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic sparites are most depleted in 13C. Carbonates in oxide-rich iron-formations are more depleted in 13C than those in siderite-rich iron-formation whereas the kerogens in oxide banded iron-formations (BIF) are more enriched. This implies that the siderite-rich iron-formations were not derived from oxide-rich iron-formation through reduction of ferric iron by organic matter. Organic matter oxidation by ferric iron did, however, decrease the abundance of kerogen in oxide-rich iron-formation and led to the formation of isotopically very light sparry carbonates. Siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13C composition, with the siderites depleted in 13C by 4.6 per mil on average relative to calcmicrosparite. This means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13C by about 9 per mil relative to that from which the limestones precipitated. This implies an ocean system stratified with regard to total carbonate, with the deeper water, from which siderite-rich iron-formation formed, depleted in 13C. Iron-formations were deposited in areas of very low organic matter supply. Depletion of 13C may, therefore, derive not from degradation of organic matter but from hydrothermal activity, a conclusion which is supported by 18O composition of the carbonate minerals and trace element and rare earth element (REE) compositions of the iron-formations.     

海相碳酸盐岩中矿物结合有机质的组成及成烃演化

对高成熟程度的碳酸盐岩有机质进行了地球化学研究,发现在可溶有机质与干酪根之间存在着成熟度上的差异,这种差异是矿物对沥青组份的保护作用所致.矿物结合有机质无论在组成还是在分布上都与游离态有机质有较大不同,随着成熟度的增加,由于结合态有机质的释放,这种不同逐渐消失,研究表明,矿物结合有机质的释放约在过成熟阶段早期,其量可达几百个ppm.因而在碳酸盐岩地层中,除了干酷根成油气外,在高成熟区亦可能存在着由矿物结合有机质形成的“高温”石油.     

A Novel Type of Oil—generating Organic Matter —Crystal—enclosed Organic Matter

The comparative study of organic matter in carbonate rocks and argillaceous rocks from the same horizon indicates that the organic thermal maturities of carbonate rocks are much lower than those of argillaceous rocks .Ana extensive analysis of extracted and inclused organic matter from the same sample shows that inclused organic matter is different from extracted organic matter,and the thermal maturity of the former is usually lower than that of the latter in terms of biomarker structural parameters.It seems that carbonate mineras could preserve organic matter and retard organic maturation.The inclused organic matter,abundant in most carbonate rocks,will be released from minerals and transformed into oil and gas during the high-thermal maturity stage.     

Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., ²H/¹H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., OH, COOH, NH₂). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ∼2.5 to ∼3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong δ¹³C_kerogen vs. δ¹⁵N_kerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate δ¹³C_VPDB and δ¹⁸O_VSMOW values are consistent with thermal generation of ¹³C-depleted and ¹⁸O-enriched CO₂ from decarboxylation and pyrolysis of organic matter. Lower background concentrations of ¹³C-enriched carbonate in thermally unaffected coal may be linked to ¹³C-enrichment in residual CO₂ in the process of CO₂ reduction via microbial methanogenesis.Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic δD values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) δ¹³C and δ¹⁵N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen.     

高温高压条件下铁岭灰岩晶包有机质的饱和烃演化特征

对铁岭灰岩抽提除去沥青“Ａ”后的残渣进行高温高压模拟实验,模拟实验研究表明,晶包有机质的释放与温度与温度和压力有关,高压有利于晶包有机质释放。晶包有机质和干酪根主要释放出低碳数烷烃,Ｐｒ／ｎＣ１７、Ｐｈ－ｎＣ１８在热演化过程中变化不大,Ｐｒ／Ｐｈ则波动较大。     

Changes in the composition of bitumen extracts and chemical structure of kerogen during hydrous pyrolysis

The paper presents data on the composition of biomarkers from bitumen extracts and the chemical structure of kerogen from C_org-rich sedimentary rocks before and after hydrothermal treatment in an autoclave at 300°C. Samples selected for this study are kukersite and Ordovician Dictyonema shale from the Baltics, Domanik oil shale from the Ukhta region, Upper Permian brown coal from the Pre-Ural foredeep, carbonaceous shale from the Oxfordian horizon of the Russian plate, and Upper Jurassic oil shales from the Sysola oil shale bearing region. The rocks contain type I, II, III, and II-S kerogens. The highest yield of extractable bitumen is achieved for Type II-S kerogen, whereas Type III kerogen produces the lowest amount of bitumen. The stages of organic matter thermal maturation achieved during the experiments correspond to a transition from PC_2–3 to MC_1–2. The ¹³C NMR data on kerogen indicate that the aromatic structures of geopolymers underwent significant changes.     

泥岩压实程度与热成熟度关系分析

大量实际资料证实了沉积岩压实程度与有机质热演化程度之间存在密切关系。本文分别从泥岩压实机理和控制热成熟度的时间、温度因素两个方面讨论了影响泥岩孔隙度和热成熟度指标的内在因素，从理论上确定了两者的相关性：泥岩孔隙度和热成熟度都是埋深和经历地质时间的函数。由于干酪根类型的不同，会造成泥岩孔隙度与热成熟度之间的关系存在明显差别。在成岩过程中，泥岩超压段内欠压实泥岩的孔隙度与热演化程度同样具备相关性。压实     

Comparison of natural gases accumulated in Oligocene strata with hydrous pyrolysis gases from Menilite Shales of the Polish Outer Carpathians

This study examined the molecular and isotopic compositions of gases generated from different kerogen types (i.e., Types I/II, II, IIS and III) in Menilite Shales by sequential hydrous pyrolysis experiments. The experiments were designed to simulate gas generation from source rocks at pre-oil-cracking thermal maturities. Initially, rock samples were heated in the presence of liquid water at 330 °C for 72 h to simulate early gas generation dominated by the overall reaction of kerogen decomposition to bitumen. Generated gas and oil were quantitatively collected at the completion of the experiments and the reactor with its rock and water was resealed and heated at 355 °C for 72 h. This condition simulates late petroleum generation in which the dominant overall reaction is bitumen decomposition to oil. This final heating equates to a cumulative thermal maturity of 1.6% R_r, which represents pre-oil-cracking conditions. In addition to the generated gases from these two experiments being characterized individually, they are also summed to characterize a cumulative gas product. These results are compared with natural gases produced from sandstone reservoirs within or directly overlying the Menilite Shales. The experimentally generated gases show no molecular compositions that are distinct for the different kerogen types, but on a total organic carbon (TOC) basis, oil prone kerogens (i.e., Types I/II, II and IIS) generate more hydrocarbon gas than gas prone Type III kerogen. Although the proportionality of methane to ethane in the experimental gases is lower than that observed in the natural gases, the proportionality of ethane to propane and i-butane to n-butane are similar to those observed for the natural gases. δ¹³C values of the experimentally generated methane, ethane and propane show distinctions among the kerogen types. This distinction is related to the δ¹³C of the original kerogen, with ¹³C enriched kerogen generating more ¹³C enriched hydrocarbon gases than kerogen less enriched in ¹³C. The typically assumed linear trend for δ¹³C of methane, ethane and propane versus their reciprocal carbon number for a single sourced natural gas is not observed in the experimental gases. Instead, the so-called “dogleg” trend, exemplified by relatively ¹³C depleted methane and enriched propane as compared to ethane, is observed for all the kerogen types and at both experimental conditions. Three of the natural gases from the same thrust unit had similar “dogleg” trends indicative of Menilite source rocks with Type III kerogen. These natural gases also contained varying amounts of a microbial gas component that was approximated using the Δδ¹³C for methane and propane determined from the experiments. These approximations gave microbial methane components that ranged from 13–84%. The high input of microbial gas was reflected in the higher gas:oil ratios for Outer Carpathian production (115–1568 Nm³/t) compared with those determined from the experiments (65–302 Nm³/t). Two natural gas samples in the far western part of the study area had more linear trends that suggest a different organic facies of the Menilite Shales or a completely different source. This situation emphasizes the importance of conducting hydrous pyrolysis on samples representing the complete stratigraphic and lateral extent of potential source rocks in determining specific genetic gas correlations.