Abstract The Rock-Eval® device has been widely used to identify the type and the thermal maturity of sedimentary organic matter, as well as for quantifying the total organic carbon content. Traditionally, it is a screening tool to estimate the petroleum generation potential of source rocks using standardized parameters. More recently, a new Rock-Eval® method (Shale Play™) was proposed for the investigation of the hydrocarbon content of liquid-rich tight rock samples. In this study, we describe a dual vacuum and on-line system that was developed to recover most compounds that are thermally released during a Rock-Eval® Shale Play™ analysis. Thermally vaporized products are divided so that half is analyzed by the Rock-Eval® flame ionization detector (FID) while the other portion is cryogenically trapped in the on-line recovery system. The trapped products can then be transferred via a vacuum line system into a sample vial for subsequent molecular and/or isotopic composition analyses. The recovery vacuum line volumes were calibrated using known quantities of gas (CH4 and CO2). Sample transfer without isotopic fractionation was demonstrated for CO2 evolved from Rock-Eval® preparation of pure carbonate standards (siderite, magnesite and azurite). Recovery efficiencies were first measured on C8-C16 n-alkane standards and then on produced oil samples. Results indicate a high quantitative recovery and an accurate mass balance of most compounds released during the Shale Play™ Sh0 thermovaporization step (100–200 °C). Thermally vaporized compounds released at higher temperatures Sh1 (200–350 °C) are recovered at lower efficiencies, but are still suitable for subsequent characterization. The coupled Rock-Eval® and recovery system could have applications beyond petroleum geochemistry.

中文翻译：

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与 Rock-Eval® 设备耦合的在线回收系统：表征液体和固体样品的分析方法

摘要 Rock-Eval® 装置已被广泛用于识别沉积有机质的类型和热成熟度，以及量化总有机碳含量。传统上，它是使用标准化参数估计烃源岩生油潜力的筛选工具。最近，提出了一种新的 Rock-Eval® 方法（Shale Play™）来研究富含液体的致密岩石样品的碳氢化合物含量。在本研究中，我们描述了一种双真空和在线系统，该系统旨在回收 Rock-Eval® Shale Play™ 分析过程中热释放的大多数化合物。热汽化产品被分开，其中一半由 Rock-Eval® 火焰离子化检测器 (FID) 分析，而另一部分则被低温捕获在在线回收系统中。然后可以通过真空管线系统将捕获的产物转移到样品瓶中，用于随后的分子和/或同位素组成分析。使用已知数量的气体（CH4 和 CO2）校准回收真空管线体积。对于从 Rock-Eval® 制备纯碳酸盐标准（菱铁矿、菱镁矿和蓝铜矿）中释放出的 CO2，证明了无需同位素分馏的样品转移。采收率首先在 C8-C16 正烷烃标准品上测量，然后在采出油样品上测量。结果表明，在 Shale Play™ Sh0 热蒸发步骤 (100–200 °C) 期间释放的大多数化合物具有高定量回收率和准确的质量平衡。在较高温度 Sh1 (200–350 °C) 下释放的热汽化化合物以较低的效率回收，但仍适合后续表征。耦合的 Rock-Eval® 和回收系统可以应用于石油地球化学以外的领域。