海拉尔盆地乌尔逊凹陷片钠铝石的碳氧同位素组成及流体来源探讨

作为胶结物或交代自生矿物,片钠铝石(分子式为NaAlCO_3(OH)_2)大量发育于海拉尔盆地乌尔逊凹陷下白垩统南屯组、大磨拐河组砂岩中。根据片钠铝石稳定同位素组成,探讨了片钠铝石中碳的来源。片钠铝石的δ~(13)C分布连续,其范围为-5.253‰～-1.210‰(PDB),δ~(18)O分布范围为-24.896‰～-20.960‰(PDB),考虑到海拉尔盆地探井中未钻遇碳酸盐地层,片钠铝石属岩浆成因碳酸盐范畴。结合与片钠铝石平衡的CO_2的δ~(13)C值,含片钠铝石井和幔源CO_2气井分布相吻合且位于燕山期花岗岩或附近的深大断裂带上,认为海拉尔盆地乌尔逊凹陷岩浆活动-砂岩成岩(片钠铝石形成)-幔源CO_2气成藏不论在物质成分上还是在时空上均具备较好的耦合关系,形成片钠铝石所需的CO_2气为与燕山期岩浆作用有关的幔源CO_2气,深大断裂是深部CO_2气向上运移到浅部砂岩的主要通道,片钠铝石形成时因油气充注而介入少量生物成因碳。     

海拉尔盆地乌尔逊凹陷无机CO2气储层的岩石学与碳氧同位素特征

海拉尔盆地乌尔逊凹陷无机 CO_2气储集砂岩中含有大量片钠铝石,是查明无机 CO_2气注入对砂岩的改造和形成的自生矿物组合的理想砂岩。通过偏光显微镜、扫描电镜、X-射线衍射分析和 MAT253稳定同位素质谱仪等,确定了含片钠铝石砂岩中的胶结物与自生矿物类型、成岩共生序列和引起片钠铝石形成的 CO_2的成因。CO_2气注入前形成的自生矿物组合主要为方解石、次生加大石英和高岭石,在次生加大石英形成过程中发生了第一期油气注入。CO_2气注入晚于第一期油气注入,CO_2气注入后形成的自生矿物组合主要为片钠铝石和铁白云石。第二期油气注入发生在 CO_2气注入后。片钠铝石的δ~(13)C 为-5.3～-1.5‰PDB,与片钠铝石平衡的δ~(13)C_(CO2),为-10.7～-7.0‰PDB,与海拉尔盆地 CO_2气的δ~(13)C_(CO2)值(-11.36～-8.02‰PDB)一致,表明形成片钠铝石的 CO_2和气藏中的 CO_2均来源于无机 CO_2与有机 CO_2混合背景,总体上以无机 CO_2为主。结合含片钠铝石砂岩与 CO_2气的分布都受控于深大断裂和γ5花岗岩的特点,CO_2气和形成片钠铝石的 CO_2绝大部分属于幔源-岩浆型。含片钠铝石砂岩中保存了 CO_2驱油的迹象。     

海拉尔盆地与澳大利亚Bowen-Gunnedah-Sydney盆地系片钠铝石碳来源的比较研究

作为胶结物、交代物或孔洞充填物,片钠铝石[NaAlCO(3OH)2]大量发育于海拉尔盆地和澳大利亚BGS盆地系。根据片钠铝石稳定同位素组成,对比分析片钠铝石的碳来源。BGS盆地系片钠铝石的1δ3C分布连续,分布区间为-4.0×10-3～4.1×10-3,计算出的与片钠铝石平衡的CO2气的1δ3CO2值分布区间为-11.3×10-3～-4.6×10-3,结合片钠铝石的分布和区域地质背景,认为片钠铝石中的碳来源于岩浆活动而带来的无机CO2气;海拉尔盆地片钠铝石1δ3C值分布连续,为-4.64×10-3～2.12×10-3,计算出的与片钠铝石平衡的CO2气的1δ3CO2值分布区间为-11.82×10-3～-5.11×10-3,结合海拉尔盆地探井中未钻遇碳酸盐地层、含片钠铝石井和幔源CO2气井分布相吻合且位于燕山期花岗岩区或其附近的深大断裂带上,认为形成片钠铝石所需的CO2气为与燕山期岩浆作用有关的幔源CO2气,片钠铝石形成时因油气充注而介入少量生物成因碳。     

长岭断陷火山岩储层内碳酸盐矿物碳氧同位素组成及其成因

碳酸盐矿物是火山岩储层内重要的矿物成分,长岭断陷火山岩储层内的自生碳酸盐矿物主要是方解石.本文通过对营城组储层内方解石矿物的碳氧同位素特征分析,探讨储层内碳酸盐矿物成因.研究表明,长岭断陷火山岩储层内方解石δ13 CV-PDB值范围为-12.7‰～0.4‰,δ18OV-SMOw值范围为3.8‰～12‰,具有高δ18O值.与方解石平衡的CO2碳同位素计算值范围较宽,为-16.0‰～2.2‰,表明其形成物质的多源性.在δ18 O-δ13C图解中显示,形成碳酸盐矿物的CO2来源于幔源-岩浆无机成因的CO2和有机质演化过程中产生的CO2,以无机成因CO2源为主.这些无机成因CO2、有机成因CO2和沉积有机质热演化产生的有机酸溶于流体,形成酸性流体.火山岩储层中碳酸盐矿物的形成实质就是这种酸性流体与储层围岩反应的结果.     

白云鄂博富稀土元素碳酸岩墙的 碳和氧同位素特征

重点解剖了一条距白云鄂博超大型REE-Nb-Fe矿床东矿北东方向2 k m、切割白云鄂 博群H1及H3岩性段的细粒方解石碳酸岩岩墙的碳和氧同位素地球化学特征。结果表明,碳酸 岩的碳同位素组成变化范围较小(δ13C值为－6.6‰ ～ －4.6‰),与正常地幔碳δ 13C值－5±2‰一致;而氧同位素组成变化范围较大(δ18O值为11.9‰～17.7‰ ),显著高于地幔的δ18O值5.7±1.0‰,表明碳酸岩浆在结晶过程中或之后曾与 低 温热液流体发生了同位素交换。碳酸岩墙中白云石与方解石之间的碳和氧同位素分馏均小于 0‰,处于不平衡状态,说明该碳酸岩墙中的白云石与方解石并非同成因矿物,白云石可能 为次生成因的。     

蒙古国塔木察格盆地塔南凹陷铜钵庙组火山碎屑岩中片钠铝石胶结物的成因

塔木察格盆地塔南凹陷铜钵庙组火山碎屑岩中发育大量的片钠铝石自生矿物。通过偏光显微镜、扫描电镜及X射线衍射分析等,查明了火山碎屑岩中的胶结物与自生矿物类型和成岩共生序列。含片钠铝石火山碎屑岩的成岩共生序列为粘土包壳-方解石-一期微晶石英-一期高岭石-二期微晶石英、二期高岭石、片钠铝石-铁白云石;通过MAT253稳定同位素质谱仪确定了片钠铝石和铁白云石的稳定同位素组成为片钠铝石的δ¹³C_PDB为-8.15‰~-2.81‰,与片钠铝石平衡的CO₂的δ¹³C_CO2为-12.91‰~-7.55‰,通过与海拉尔盆地及BGS盆地系碳氧同位素数据的类比,表明片钠铝石中的碳主要为幔源岩浆来源,形成片钠铝石的钠和铝主要来源于安山岩岩屑、长石晶屑碎屑、玻屑和火山灰等;铁白云石的δ¹³C_PDB为-6.76‰~-2.65‰,与片钠铝石的碳氧同位素数据相似,结合相关地质实例及地球化学模拟实验,可以推断铁白云石中的碳也是幔源岩浆来源,铁白云石中的铁离子主要来源于安山岩岩屑、玻屑、火山灰和蒙脱石等矿物。     

松南油伴生CO2气的成因及其对油气藏的影响

以松辽盆地南部长岭断陷油伴生气和含片钠铝石砂岩为对象,研究松南伴生CO2气的成因,并在此基础上,讨论幔源-岩浆CO2混入对油气动态成藏的影响。通过对伴生气组分,碳、氧及氦同位素数据的分析,发现松南油伴生CO2气的体积分数为1.57%～75.25%,主体在20%以上,δ13 CCO2值为-9.90‰～-4.00‰,R/Ra为0.95～4.46,说明松南油伴生气中CO2的体积分数很高,伴生CO2气主体为幔源-岩浆成因。如果幔源-岩浆CO2气大量混入油藏,将发生CO2驱油,形成次生油气藏。由松南油气藏的典型剖面特征及片钠铝石中原生烃类包裹体的发现,证实松南存在幔源-岩浆CO2驱油的事实。在幔源-岩浆CO2与油气混合成藏地区,寻找幔源-岩浆CO2充注驱油成因的次生油气藏已成为新的勘探思路。     

乌尔逊凹陷含片钠铝石砂岩分布

海拉尔盆地乌尔逊凹陷发现含片钠铝石砂岩，片钠铝石为一种成岩自生矿物。将含片钠铝石砂岩和CO2气的井位综合对比，结合该区构造断裂带分布与γ5花岗岩分布特征以及含片钠铝石砂岩与CO2气纵深分布数据的研究，确定含片钠铝石砂岩的分布与断裂带以及γ5花岗岩的分布具有耦合关系，同时含片钠铝石砂岩与CO2气的分布也具有区域相关性。从而可以确定片钠铝石可以作为CO2气的示踪矿物。     

海拉尔盆地乌尔逊凹陷含片钠铝石砂岩捕获CO_2总量的估算

为揭示CO2地质埋存过程中砂岩对于CO2以矿物形式的捕获能力,以海拉尔盆地乌尔逊凹陷下白垩统铜钵庙—南屯组含片钠铝石砂岩为研究对象,基于含片钠铝石砂岩的时空分布,结合片钠铝石的含量和分子式开展了砂岩以片钠铝石形式固存CO2总量的研究。研究表明,海拉尔盆地乌尔逊凹陷下白垩统铜钵庙—南屯组中片钠铝石资源总量约为81.9亿t,含片钠铝石砂岩捕获的CO2总量约为25.0亿t。     

塔里木盆地西南依格孜牙组与卡拉塔尔组灰岩碳、氧同位素特征

对塔里木盆地西南依格孜牙组和卡拉塔尔组灰岩碳、氧同位素特征研究结果表明,上白垩统依格孜牙组δ13C(PDB标准)平均值为3.79‰,δ18O(PDB标准)平均值为-3.49‰;古近系卡拉塔尔组灰岩δ13C(PDB标准)平均值为2.09‰,δ18O(PDB标准)平均值为-4.54‰.与前人和世界其他剖面数据对比认为,碳同位素比较稳定,能够反映其沉积时的特征,而氧同位素变化较大,可能受沉积后作用的影响.依格孜牙组与卡拉塔尔组灰岩碳同位素具较大差异,主要受陆源环境(？)物质的注入,海水盐度、生物作用和古大气CO2含量等因素的影响.     

海拉尔盆地乌尔逊凹陷与松辽盆地孤店CO2气田含片钠铝石砂岩的岩石学特征

海拉尔盆地乌尔逊凹陷南屯组与松辽盆地孤店CO₂气田泉头组发育大量含片钠铝石砂岩。通过偏光显微镜、扫描电镜、茜素红-S染色、X射线衍射、电子探针与INCA能谱分析等,对含片钠铝石砂岩的骨架碎屑组分、胶结物与自生矿物、成岩共生序列等岩石学特征进行了系统研究。研究表明,含片钠铝石砂岩的岩石类型为长石砂岩和岩屑长石砂岩,粒度以细粒、细-中粒为主,分选差-中等。砂岩中胶结物主要为次生加大石英、自生石英、片钠铝石、铁白云石和粘土矿物。其中,片钠铝石最高可达砂岩总体积的22％在砂岩中或以放射状、束状、菊花状、杂乱毛发状、毛球状、板状等集合体充填孔隙,或呈束状和板状交代长石和岩屑。电子探针与INCA能谱综合分析表明,片钠铝石主要由Na、Al、O、C等组成。在含片钠铝石砂岩中,成岩共生序列依次为粘土矿物包壳-次生加大石英、自生石英、自生高岭石-油气充注-CO₂充注-片钠铝石-铁白云石。其中,CO₂注入前形成的自生矿物组合主要为次生加大石英、自生石英和自生高岭石,CO₂注入后形成的自生矿物组合主要为片钠铝石和铁白云石。     

Dawsonite formation in the Beier Sag,Hailar Basin,NE China tuff: A natural analog for mineral carbon storage

We determined the rock types, the authigenic minerals, the paragenetic sequence, and the origin of dawsonite in pyroclastic rocks from the Yimin Formation of Beier Sag in the Hailar Basin, China. Dawsonite, a diagenetic mineral, is thought to result from a large influx of CO₂ and, therefore, this system represents a natural analogue for in-situ mineral carbon storage. The studied host rocks are mainly tuffs/tuffaceous sandstones which now contain up to 70 vol% authigenic carbonates, including dawsonite, ankerite, and siderite. The initial alteration of the tuffs yielded minor siderite. Kaolinite, illite and mixed illite/smectite then formed as product phases. Dawsonite and quartz subsequently precipitated in response to CO₂ influx apparently coupled to feldspar and perhaps kaolinte dissolution. Dawsonite reaches a maximum 25 vol% of the bulk rock. Mass balance suggests that this CO₂ influx was coupled to the external import of sodium and export of SiO₂. Ankerite and additional siderite precipitated during the late-stage alkaline diagenesis. The carbon isotope values of the dawsonite are in the range −4.1‰ to −2.2‰, indicating the magmatic origin of the CO₂. Vitrinite reflectance and thermal gradient constraints suggest that the dawsonite at this location formed at a temperature of ∼75 °C.     

海拉尔盆地乌尔逊凹陷幔源CO2充注对下白垩统砂岩储层质量的影响

海拉尔盆地乌尔逊凹陷下白垩统含片钠铝石砂岩部分记录了幔源CO_2-砂岩相互作用历史.为揭示幔源CO_2充注对储层质量的影响,通过偏光显微镜、扫描电镜观察和孔隙度、渗透率数据研究了海拉尔盆地乌尔逊凹陷含片钠铝石砂岩的岩石学和储层特征.幔源CO_2的充注导致了长石的部分溶解和片钠铝石及铁白云石的沉淀.长石的溶解形成了次生孔隙.片钠铝石以针状晶形为特征,其集合体呈束状、簇状、扇状和玫瑰花状.部分片钠铝石呈板状.片钠铝石以充填孔隙为主,少量交代长石和其他骨架碎屑颗粒.片钠铝石局部被铁白云石交代,说明铁白云石的形成晚于片钠铝石.片钠铝石的含量为1%～20%.相同深度段的含片钠铝石砂岩(n=597,h=1309.15～2140.71m)与普通砂岩(n=1550,h=1323.72～2141.3m)的孔隙度、渗透率数据统计表明,含片钠铝石砂岩的物性整体上低于普通砂岩,说明CO_2的充注导致了储层质量的改变.片钠铝石含量-孔隙度和片钠铝石含量-渗透率之间的关系,揭示片钠铝石含量是引起储层质量改变的主要因素.片钠铝石含量10%似乎是储层质量发生变化的界限,当片钠铝石含量＞10%,随片钠铝石含量增加,砂岩的孔隙度和渗透率降低;当片钠铝石含量＜10%,随片钠铝石含量增加,部分砂岩的孔隙度和渗透率表现出增加趋势.作者认为,片钠铝石含量高的砂岩长期处于高CO_2分压成岩环境,而片钠铝石含量低的砂岩则处于高CO_2分压成岩环境的时间相对较短.     

Oxygen and Hydrogen Isotopes of Waters in the Ordos Basin,China: Implications for Recharge of Groundwater in the North of Cretaceous Groundwater Basin

Hundreds of precipitation samples collected from meteorological stations in the Ordos Basin from January 1988 to December 2005 were used to set up a local meteoric water line and to calculate weighted average isotopic compositions of modern precipitation. Oxygen and hydrogen isotopes, with averages of ?7.8‰ and ?53.0‰ for δ18O and δD, respectively, are depleted in winter and rich in spring, and gradually decrease in summer and fall, illustrating that the seasonal effect is considerable. They also show that the isotopic difference between south portion and north portion of the Ordos Basin are not obvious, and the isotope in the middle portion is normally depleted. The isotope compositions of 32 samples collected from shallow groundwater (less than a depth of 150 m) in desert plateau range from ?10.6‰ to ?6.0‰ with an average of ?8.4‰ for δ18O and from ?85‰ to ?46‰ with an average of ?63‰ for δD. Most of them are identical with modern precipitation. The isotope compositions of 22 middle and deep groundwaters (greater than a depth of 275 m) fall in ranges from ?11.6‰ to ?8.8‰ with an average of ?10.2‰ for δ18O and from ?89‰ to ?63‰ with an average of ?76‰ for δD. The average values are significantly less than those of modern precipitation, illustrating that the middle and deep groundwaters were recharged at comparatively lower air temperatures. Primary analysis of 14C shows that the recharge of the middle and deep groundwaters started at late Pleistocene. The isotopes of 13 lake water samples collected from eight lakes define a local evaporation trend, with a relatively flat slope of 3.77, and show that the lake waters were mainly fed by modern precipitation and shallow groundwater.     

Origin and depositional environments of source rocks and crude oils from Niger Delta Basin: Carbon isotopic evidence

Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC₁₂-nC₃₃) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ¹³C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin.     

海拉尔盆地贝尔凹陷含片钠铝石沉凝灰岩的成岩作用

以海拉尔盆地贝尔凹陷大磨拐河组-伊敏组的含片钠铝石火山碎屑岩为研究对象,采用偏光显微镜、扫描电镜及配套能谱、茜素红 S染色、阴极发光和X 射线衍射分析等技术手段,对研究样品的岩石类型、自生矿物种类及共生序列进行了详细研究。贝尔凹陷发育片钠铝石的宿主岩石类型为沉凝灰岩,自生矿物以发育片钠铝石、铁白云石和菱铁矿三种碳酸盐矿物为主,片钠铝石含量高达25%。成岩共生序列为菱铁矿Ⅰ→高岭石、石英次生加大→片钠铝石→微晶石英→方解石→铁白云石→菱铁矿Ⅱ→沥青。不同于国内外其它地区发现片钠铝石的主要产状为充填孔隙,本区内发育的片钠铝石以交代长石、石英、岩屑颗粒和高岭石基质为赋存特征,表明沉凝灰岩中的长石、岩屑、高岭石基质可以为其提供金属离子物质来源,并在CO2参与下,与成岩流体反应生成片钠铝石。大量碳酸盐矿物（15-44%）的发育证明了火山碎屑岩具有较高的CO2矿物捕获能力。     

IODP 311航次底栖有孔虫碳稳定同位素对天然气水合物地质系统的指示

为了探索海洋天然气水合物背景下有孔虫特征的响应,对综合大洋钻探计划(IODP) 311航次岩芯沉积物中底栖有孔虫Uvigerina peregrina和Bulimina mexicana进行了初步研究。通过对冷泉站位U1328和毗邻的非冷泉站位U1327沉积物中底栖有孔虫Uvigerina peregrina和Bulimina mexicana的显微形貌特征和碳、氧稳定同位素测试等,证实有孔虫壳体未受到后期成岩作用的改造和自生碳酸盐岩的交代影响,有孔虫壳体的碳稳定同位素呈现明显的负偏。其中U1327站位中U.peregrina δ¹³C为-0.67‰～-2.75‰（PDB）,B.mexicana δ¹³C为-0.51‰～-1.52‰（PDB）;U1328站位中U.peregrina δ¹³C为 -0.72‰～-2.71‰（PDB）,B.mexicanaδ¹³C为 -0.58‰～-1.45‰（PDB）。底栖有孔虫壳体的碳稳定同位素负偏成因可能与水合物不稳定分解释放的甲烷厌氧氧化作用和食物源有关,因而可较好地指示海底天然气水合物系统地质背景。     

The nature and origin of sideritic ironstone bands in the Tertiary Lowmead and Duaringa Basins,Queensland

Sideritic ironstones in Tertiary lacustrine oil shale from the Lowmead and Duaringa Basins in Queensland, contain two distinctive types of siderite in the ironstone bands: sphaerosiderite in the mudstone and coal, and finely crystalline siderite in the lamosite. The petrological evidence indicates that the siderite in the ironstone bands formed eogenetically by growing displacively within the soft sediment. Chemically the siderite is very pure though the sphaerosiderite sometimes shows compositional zoning. Stable oxygen and carbon isotope analyses of the siderite show a wide range of values from ‐12.8‰ to ‐2.4 %₀ δ¹⁸O (PDB) and ‐5.5‰ to +12.9‰ δ¹³C (PDB) for the Lowmead Basin; and ‐9.6‰ to ‐1.2‰ δ¹⁸O (PDB) and ‐18.6‰ to +16.4‰ δ¹³C (PDB) for the Duaringa Basin. The oxygen isotope data indicate that the siderite formed in freshwater environments but not in isotopic equilibrium with the formation waters. Kinetic factors offer the most plausible explanation for the anomalously light δ¹⁸O values of many of the siderites. The carbon isotope data show that the carbonate for the formation of the siderite originated predominantly from methanogenic fermentation processes but there was also the varying influence of bacterial oxidation processes. The different petrological and isotopic characteristics of the ironstones broadly reflect variations in their depositional environments and the variable eogenetic conditions in which the siderite formed. There is no suitable single model to explain the genesis of all the different types of ironstones other than that a synsedimentary iron‐enrichment process is involved.     

Petrology and isotopic geochemistry of dawsonite-bearing sandstones in Hailaer basin, northeastern China

The CO₂ gas reservoir sandstones in the Hailaer Basin contain abundant dawsonite and provide an ideal laboratory to study whether any genetic relationship exists between dawsonite and the modern gas phase of CO₂. The origins of dawsonite and CO₂ in these sandstones were studied by petrographic and isotopic analysis. According to the paragenetic sequence of the sandstones, dawsonite grew later than CO₂ charging at 110–85 Ma. The dawsonite δ¹⁸O value is 7.4‰ (SMOW), and the calculated δ¹⁸O values of the water present during dawsonite growth are from −11.4‰ to −9.2‰ (SMOW). This, combined with the NaHCO₃-dominated water linked to dawsonite growth, suggests meteoric water being responsible for dawsonite growth. The δ¹³C values of gas phase CO₂ and the ratios of ³He/⁴He of the associated He suggest a mantle magmatic origin of CO₂-rich natural gas in Hailaer basin. Dawsonite δ¹³C values are −5.3‰ to −1.5‰ (average −3.4‰), and the calculated δ¹³C values of CO₂ gas in isotopic equilibrium with dawsonite are −11.4‰ to −7.3‰. These C isotopic values are ambiguous for the dawsonite C source. From the geological context, the timing of events, together with formation water conditions for dawsonite growth, dawsonite possibly grew in meteoric-derived water, atmospherically-derived CO₂ maybe, or at least the dominant, C source for dawsonite. It seems that there are few relationships between dawsonite and the modern gas phase of CO₂ in the Hailaer basin.