四极质谱流体包裹体气体成分测定技术

将四极质谱、分子泵和超高真空流体包裹体击碎装置联机,利用冷阱与外置液氮去除部分水蒸气和杂气,建立分阶段提取不同世代流体包裹体并测定其气体成分的实验平台。以锡田钨锡多金属矿床中石英脉型钨锡矿矿石为研究对象,分阶段提取不同世代流体包裹体并测定其气体成分,对比分析矿石中共生石英–黑钨矿矿物对不同阶段释气成分、气体百分含量特征。研究表明初始阶段和后期阶段提取的流体成分一致,以N_2、CO_2和CH_4为主,含少量^(40)Ar、C_2H_6和~4He;但初始阶段N_2、CO_2和^(40)Ar气体浓度高于后期阶段,而CH_4、C_2H_6和~4He气体浓度低于后期阶段,指示初始阶段和后期阶段提取出不同期次的流体包裹体,即初始阶段提取的主要是次生包裹体,后期阶段提取的主要是原生包裹体,而中间阶段是两者的混合,表明四极质谱和超高真空流体包裹体提取装置联用能够实现分阶段提取不同世代流体包裹体且测定其气体成分。其中,次生包裹体富N_2、CO_2和^(40)Ar,而原生包裹体富CH_4、C_2H_6和~4He。

Detrital K-feldspar^(40)Ar/^(39)Ar Ages:Source Constraints of the Lower Miocene Sandstones in the Pearl River Mouth Basin,South China Sea

The South China Sea began to outspread in the Oligocene. A great quantity of terraneous detritus was deposited in the northern continental shelf of the sea, mostly in Pearl River Mouth Basin, which constituted the main paleo-Pearl River Delta. The delta developed for a long geological time and formed a superimposed area. Almost all the oil and gas fields of detrital rock reservoir distribute in this delta. Thirty-three oil sandstone core samples in the Zhujiang Formation, lower Miocene （23-16 Ma）, were collected from nine wells. The illite samples with detrital K feldspar （Kfs） separated from these sandstone cores in four sub-structural belts were analysed by the high-precision 40Ar/39Ar laser stepwise heating technique. All 33 illite 40Ar/39Ar data consistently yielded gradually rising age spectra at the low-temperature steps until reaching age plateaus at mid-high temperature steps. The youngest ages corresponding to the beginning steps were interpreted as the hydrocarbon accumulation ages and the plateau ages in mid-high temperature steps as the contributions of the detrital feldspar representing the ages of the granitic parent rocks in the provenances. The ages of the detrital feldspar from the Zhujiang Formation in the four sub-structural belts were different： （1） the late Cretaceous ages in the Lufeng 13 fault structural belt; （2） the late Cretaceous and early Cretaceous-Jurassic ages in the Huizhou 21 buried hill-fault belt; （3） the Jurassic and Triassic ages in the Xijiang 24 buried hill-fault belt; and （4） the early Cretaceous - late Jurassic ages in the Panyu 4 oil area. These detrital feldspar 4~Ar/39Ar ages become younger and younger from west to east, corresponding to the age distribution of the granites in the adjacent Guangdong Province, Southern China.

流体包裹体^(40)Ar/^(39)Ar定年技术与应用

同位素地质年代学的各种定年方法都有其特定的测定对象(矿物或全岩)和适用范围,致使许多金属矿床难以进行年龄测定.为解决此难题,建立了流体包裹体^(40)Ar/^(39)Ar定年方法,经过30年的探索发展和不断改进完善,已广泛应用于热液矿床、变质岩和石英脉的形成年龄测定,甚至成功应用于松辽盆地深层天然气成藏年龄研究.在详细介绍流体包裹体提取技术和气体纯化技术的基础上,着重总结我们团队运用流体包裹体^(40)Ar/^(39)Ar定年技术在热液矿床和天然气藏形成年龄研究方面取得的重要成果,以及气体混合线的概念及其年龄意义.

Opening and evolution of the South China Sea constrained by studies on volcanic rocks:Preliminary results and a research design

The South China Sea (SCS) is characterized by abundant seamounts, which provide important information about the evolution of the SCS and related deep processes. Cenozoic volcanism in the SCS and its surroundings comprises three stages relative to the spreading of the SCS:prespreading (>32 Ma), syn-spreading (32-16 Ma), and post-spreading (<16 Ma). The pre-spreading magmatism predominantly occurs on the northern margin of the SCS and in South China coastal areas and shows a bi-modal affinity. The syn-spreading magmatic activity was very limited on the periphery of the SCS, but may be concentrated in the SCS. However, seafloor samples of this stage are not available yet because of overlying thick sedimentary deposits. Post-spreading magmatism is widespread in the central and southwest sub-basins of the SCS, Hainan Island, Leizhou Peninsula, Thailand, and Vietnam. These are mainly alkali basalts with subordinate tholeiites, and display OIB-type geochemical characteristics. The Dupal isotope anomaly and presence of high-magnesian olivine phenocrysts suggests their possible derivation from the Hainan mantle plume. The temporal and spatial distribution of Cenozoic volcanism in the SCS and its surroundings may be accounted for either by plate stress re-organization before and after SCS spreading, or by ridge suction of plume flow during opening of the SCS. If the latter is the case, the volcanic rocks within the SCS basin may not be typical mid-ocean ridge basalts (MORB). It remains puz-zling, however, that the transition between the South China continental margin and the SCS basin does not have features typical of a volcanic rifted margin. Clearly, the relationship between mantle plume and SCS opening needs further evaluation. A better un-derstanding of the link between deep processes and opening of the SCS not only requires enhanced studies on igneous petrogene-sis, but also is heavily dependent on systematic sampling of seafloor rocks.

CO_2 gas emplacement age in the Songliao Basin: Insight from volcanic quartz ^(40)Ar-^(39)Ar stepwise crushing

Due to a lack of suitable minerals, the gas/oil emplacement ages have never been accurately obtained before. CH4-CO2-saline- bearing secondary inclusions are found in quartz from the volcanic rocks of the Yingcheng Formation, the container rocks of the deep CO2 gas reservoir in the Songliao Basin. The inclusion fluid was trapped into microcracks in quartz during the gas em- placement and accumulation, providing an optimal target for the 40Ar-39Ar stepwise crushing technique to determine the CO2 gas emplacement age. 40Ar-39Ar dating results of a quartz sample by stepwise crushing yield a highly linear-regression isochron with an age of 78.4±1.3 Ma, indicating that the accumulation of the deep CO2 gas reservoir in the Songliao Basin occurred in the late Cretaceous. This is the first time to report an exact isotopic age for a CO2 gas reservoir, which indicates that the 40Ar-39Ar dating can serve as a new technique to date the oil/gas emplacement ages.

^(40)Ar/^(39)Ar geochronology constraints on hydrocarbon accumulation and destruction periods in the Bankeng paleo-reservoir in the southern margin of the middle Yangtze block

The exact determination of isotopic ages of hydrocarbon accumulation,reconstruction and destruction periods using traditional isotopic dating methods is complex because of the small numbers of minerals that correlate with hydrocarbons.The quantitative and direct study of hydrocarbon geochronology is therefore an important scientific problem for isotope geochronology and petroleum geology.This study obtains two isotopic ages from a quartz vein sample associated with bitumen in a reverse fault located in the Bankeng paleo-reservoir on the southern margin of the middle Yangtze block (the northern margin of the JiangnanXuefeng uplift) by inclusion 40Ar/39Ar stepwise crushing in a vacuum.Two different and good linear inverse isochrons that correspond to two age plateaus were determined.The two ages correspond to primary inclusions of about 228 Ma and secondary inclusions of about 149 Ma.These inclusion groups represent two distinct kinds of fluids.Quartz veins associated with bitumen in faulted paleo-reservoirs,which have a strict response relationship with tectonization and hydrocarbon accumulation,are the unified products of tectonic processes,hydrocarbon accumulation and reconstruction.Therefore,they can be used to constrain the hydrocarbon accumulation,reconstruction and destruction periods that are controlled by multiphase and complicated tectonic actions.The evolutionary processes of hydrocarbon accumulation can be divided into two periods consisting of a primary oil and gas reservoir formation period in the late Indosinian epoch (about 228 Ma) and a period of oil and gas reservoir reconstruction in the early Yanshan epoch (about 149 Ma).This study quantitatively reconstructs the hydrocarbon accumulation and destruction chronological framework of a giant hydrocarbon accumulation belt along the southern margin of the middle Yangtze block (the northern margin of the Jiangnan-Xuefeng uplift) controlled by multiphase and complicated tectonism.The two ages associated with hydrocarbons here correspond to the special controlling actions of continental tectonics in the Jiangnan-Xuefeng uplift that affected the timeline of reconstruction and destruction in this giant marine hydrocarbon accumulation.This study shows the feasibility and usefulness of dating inclusions with the 40Ar/39Ar technique for hydrocarbon geochronology,especially in the marine hydrocarbon accumulation region of southern China within a geological setting of old strata,high thermal evolution hydrocarbons,and complex,multiphase and multicycle tectonization.

A novel purification technique for noble gas isotope analyses of authigenic minerals

Noble and active gases are released from geological samples during gas extraction for noble gas isotope analyses. The active gases should be removed before inletting to mass spectrometers for the analyses. The normal noble gas preparation systems can clean up most geological samples. However, authigenic minerals from sedimentary rocks in oil/gas fields contain organic matter, which cannot be cleaned up by the normal preparation systems and thus influence the noble gas analyses. We introduce a novel gas purification system （PRC patent No. ZL201320117751.2）, which includes several reversible purification pumps with different absorbing and degassing temperatures. It can well clean up water steam, carbon dioxide and organic gas- es. Mica minerals are often used for 40Ar/39Ar dating. A muscovite sample （2082MS） which could not be cleaned up by the normal preparation system with two SAES NP10 getters, becomes the test sample for a comparative experiment in this study. The experiment is assigned into 4 sections with the organic gas removal system （OGRS） ＂Closed/Opened＂ in turn. When the OGRS is closed only with two NP10 getters for purification, the 40At intensities increase in curves with inlet time because of impurities, the 40Ar/39Ar dating results yield age errors about ＋2%-±1% （20-）. When the OGRS is opened for purification, in contrast, the 40Ar intensities decrease linearly with inlet time. This indicates that the gases have been cleaned up effectively, and the 40Ar/39Ar results yield ages with errors in ±0.4%. The OGRS is very helpful to obtain high-quality analysis data.