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 <front>
  <journal-meta>
   <journal-id journal-id-type="publisher-id">Russian Journal of Earth Sciences</journal-id>
   <journal-title-group>
    <journal-title xml:lang="en">Russian Journal of Earth Sciences</journal-title>
    <trans-title-group xml:lang="ru">
     <trans-title>Russian Journal of Earth Sciences</trans-title>
    </trans-title-group>
   </journal-title-group>
   <issn publication-format="online">1681-1208</issn>
  </journal-meta>
  <article-meta>
   <article-id pub-id-type="publisher-id">49655</article-id>
   <article-id pub-id-type="doi">10.2205/2022ES000807</article-id>
   <article-categories>
    <subj-group subj-group-type="toc-heading" xml:lang="ru">
     <subject>ОРИГИНАЛЬНЫЕ СТАТЬИ</subject>
    </subj-group>
    <subj-group subj-group-type="toc-heading" xml:lang="en">
     <subject>ORIGINAL ARTICLES</subject>
    </subj-group>
    <subj-group>
     <subject>ОРИГИНАЛЬНЫЕ СТАТЬИ</subject>
    </subj-group>
   </article-categories>
   <title-group>
    <article-title xml:lang="en">Thermodynamic Model of Deep Oil Origin and its Phase “Freezing”</article-title>
    <trans-title-group xml:lang="ru">
     <trans-title>Термодинамическая модель глубинного происхождения нефти и ее фазового «замерзания»</trans-title>
    </trans-title-group>
   </title-group>
   <contrib-group content-type="authors">
    <contrib contrib-type="author">
     <contrib-id contrib-id-type="orcid">https://orcid.org/0000-0001-6078-4650</contrib-id>
     <name-alternatives>
      <name xml:lang="ru">
       <surname>Маракушев</surname>
       <given-names>Сергей Алексеевич</given-names>
      </name>
      <name xml:lang="en">
       <surname>Marakushev</surname>
       <given-names>Sergey Alekseevich</given-names>
      </name>
     </name-alternatives>
     <email>shukaram@yandex.ru</email>
     <bio xml:lang="ru">
      <p>доктор биологических наук;</p>
     </bio>
     <bio xml:lang="en">
      <p>doctor of sciences in biology;</p>
     </bio>
     <xref ref-type="aff" rid="aff-1"/>
    </contrib>
    <contrib contrib-type="author">
     <name-alternatives>
      <name xml:lang="ru">
       <surname>Белоногова</surname>
       <given-names>Ольга Васильевна</given-names>
      </name>
      <name xml:lang="en">
       <surname>Belonogova</surname>
       <given-names>Olga Vasilievna</given-names>
      </name>
     </name-alternatives>
     <xref ref-type="aff" rid="aff-2"/>
    </contrib>
   </contrib-group>
   <aff-alternatives id="aff-1">
    <aff>
     <institution xml:lang="ru">Федеральный исследовательский центр проблем химической физики и медицинской химии Российской Академии Наук</institution>
     <city>Черноголовка</city>
     <country>Россия</country>
    </aff>
    <aff>
     <institution xml:lang="en">Federal Research Center for Problems of Chemical Physics and Medical Chemistry, Russian Academy of Sciences</institution>
     <city>Chernogolovka</city>
     <country>Russian Federation</country>
    </aff>
   </aff-alternatives>
   <aff-alternatives id="aff-2">
    <aff>
     <institution xml:lang="ru">Федеральный исследовательский центр проблем химической физики и медицинской химии РАН</institution>
     <city>Черноголовка</city>
     <country>Россия</country>
    </aff>
    <aff>
     <institution xml:lang="en">Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences</institution>
     <city>Chernogolovka</city>
     <country>Russian Federation</country>
    </aff>
   </aff-alternatives>
   <pub-date publication-format="print" date-type="pub" iso-8601-date="2022-12-31T00:00:00+03:00">
    <day>31</day>
    <month>12</month>
    <year>2022</year>
   </pub-date>
   <pub-date publication-format="electronic" date-type="pub" iso-8601-date="2022-12-31T00:00:00+03:00">
    <day>31</day>
    <month>12</month>
    <year>2022</year>
   </pub-date>
   <volume>22</volume>
   <issue>6</issue>
   <fpage>1</fpage>
   <lpage>26</lpage>
   <history>
    <date date-type="received" iso-8601-date="2022-04-04T00:00:00+03:00">
     <day>04</day>
     <month>04</month>
     <year>2022</year>
    </date>
    <date date-type="accepted" iso-8601-date="2022-08-04T00:00:00+03:00">
     <day>04</day>
     <month>08</month>
     <year>2022</year>
    </date>
   </history>
   <self-uri xlink:href="https://rjes.ru/en/nauka/article/49655/view">https://rjes.ru/en/nauka/article/49655/view</self-uri>
   <abstract xml:lang="ru">
    <p>В большинстве современных исследований петрогенных резервуаров углерода в земной коре принято, что нефть и природный газ являются продуктами теплового генерирования из останков биологического органического вещества, накопленного в осадочных породах в течение геологического времени и погруженного в область высокого давления и температуры. В этой осадочно-миграционной («биогенной») концепции происхождения нефти была определена направленность предполагаемого эволюционного процесса трансформации углерода – захороненный биологический материал → кероген → нефть → газ как проявление прогрессивного метаморфизма (увеличение давления и температуры). Однако обнаружение керогена в составе метеоритов не позволяет предположить биологический источник углерода для образования этого полимерного «органического» вещества, что подразумевает неорганические источники углерода керогена – «нефтяные» и «газовые» углеводороды (HCs), зародившиеся в недрах их материнских тел (планетезималей). Генетическая связь нефти, природного газа и углеродного вещества черносланцевых формаций (керогена) на Земле также не вызывает сомнений, но в настоящей работе эволюция петрогенных резервуаров, в том числе нефтяных сланцевых пород в литосфере, рассматривается на основе глубинной неорганической концепции, в которой направленность процесса трансформации углерода противоположна биогенной концепции и представляется как HCs → природный газ → нефть → кероген. Анализ фазовых диаграмм и экспериментальных данных позволил определить два тренда эволюции неметановых углеводородов в недрах Земли. В верхней мантии «метастабильность» тяжелых (с более низким отношением Н/С) HCs возрастает с глубиной. Однако при температурах и давлениях, соответствующих поверхностным мантийно-коровым гидротермальным условиям, «относительная метастабильность» тяжелых HCs возрастает с приближением к поверхности. При подъеме этих глубинных HCs флюидов к поверхности в результате падения фугитивности водорода формируются петрогенные резервуары нефти в процессе фазового перехода газовые углеводороды → жидкая нефть. В физико-химических условиях нефтяного резервуара устанавливаются метастабильные обратимые фазовые равновесия между жидкими нефтью и H2O, газовыми HCs и CO2 и твердыми (псевдокристаллическими) «зрелыми» и «незрелыми» керогенами «нефтематеринских» пород. Уменьшение давления водорода и температуры приводит к стехиометрическому фазовому переходу («замерзанию») жидкой нефти в твердые керогены. Это происходит в результате дегидрогенизации нефти в процессах высокотемпературной фиксации CO2 и низкотемпературной гидратации HCs, являющимися основными геохимическими путями ее трансформации в кероген. Таким образом, образование углеродного вещества петрогенных резервуаров является результатом регрессивного метаморфизма глубинных HCs флюидов, природного газа, жидкой нефти и последующих аккумуляций нафтидов.</p>
   </abstract>
   <trans-abstract xml:lang="en">
    <p>In most modern studies of lithospheric (petrogenic) carbonreservoirs in the earth’s crust, it is assumed that crude oil and natural gas (petroleum) are thermal generation products from the relics of biological organic matter accumulated in sedimentary rocks during geological time and deeply buried in a region of high pressure and temperature. In this sedimentary-migration (“biogenic”) concept of the origin of oil, the direction of the proposed evolutionary process of carbon transformation was determined: buried biological material → kerogen → oil → gas as a manifestation of progressive metamorphism (pressure and temperature increase). However, the discovery of kerogen in the meteorite’s composition does not allow us to suggest a biological source of carbon for the formation of this polymeric “organic” substance, but in turn allows us to suggest inorganic sources of kerogen, namely “oil” and “gas&quot;non methane hydrocarbons (HCs), originated in the depths of their parent bodies (icy planetesimals). The genetic relationship of oil, natural gas and carbon matter of black shale formations (kerogen) on Earth is also beyond doubt, and therefore, in this paper, the evolution of petrogenic carbon reservoirs, including oil shale rocks in the lithosphere, is considered on the basis of a deep inorganic concept, in which the direction of the carbon transformation process is the opposite of the biogenic concept and is represented as HCs → gas → oil → kerogen. The analysis of phase diagrams and experimental data made it possible to determine two trends in the evolution of non-methane hydrocarbons in the Earth’s interior. In the upper mantle, the “metastability” of heavy (with a lower H/C ratio) HCs increases with depth. However, at temperatures and pressures corresponding to the surface mantle-crustal hydrothermal conditions, the “relative metastability” of heavy hydrocarbons increases with approach to the surface. When deep HCs fluids rise to the surface, petrogenic oil reservoirs are formed as a result of the decreases in hydrogen fugacity and a phase transition: gas HCs → liquid oil. At the physical and chemical conditions of an oil reservoir, metastable reversible phase equilibria are established between liquid oiland H2O, gas HCs and CO2, and solid (pseudocrystalline) “mature” and “immature” kerogens of “oil source” rocks. A decrease in hydrogen pressure and temperature leads to a stoichiometric phase transition (“freezing”) of liquid oil into solid kerogens. This occurs as a result of oil dehydrogenation in the processes of high-temperature CO2 fixation and low-temperature hydration of oil hydrocarbons, which are the main geochemical pathways for its transformation into kerogen. Thus, the formation of carbon matter in petrogenic reservoirs is the result of regressive (retrograde) metamorphism of deep hydrocarbon fluids, natural gas, liquid oil, and naphthide accumulations.</p>
   </trans-abstract>
   <kwd-group xml:lang="ru">
    <kwd>фазовые диаграммы</kwd>
    <kwd>химические потенциалы</kwd>
    <kwd>метастабильные равновесия</kwd>
    <kwd>углеводороды</kwd>
    <kwd>флюиды</kwd>
    <kwd>петрогенные резервуары</kwd>
    <kwd>нафтидогенез</kwd>
    <kwd>нефть</kwd>
    <kwd>кероген</kwd>
    <kwd>черные сланцы</kwd>
    <kwd>регрессивный метаморфизм</kwd>
    <kwd>фиксация CO2</kwd>
    <kwd>гидратация.</kwd>
   </kwd-group>
   <kwd-group xml:lang="en">
    <kwd>phase diagrams</kwd>
    <kwd>chemical potentials</kwd>
    <kwd>metastable equilibria</kwd>
    <kwd>hydrocarbons</kwd>
    <kwd>fluids</kwd>
    <kwd>petrogenic carbon reservoirs</kwd>
    <kwd>naphthide genesis</kwd>
    <kwd>oil</kwd>
    <kwd>kerogen</kwd>
    <kwd>black shales</kwd>
    <kwd>regressive metamorphism</kwd>
    <kwd>CO2 fixation</kwd>
    <kwd>hydration</kwd>
   </kwd-group>
   <funding-group>
    <funding-statement xml:lang="ru">Работа выполнена в рамках государственного задания Института проблем химической физики РАН, номер государственной регистрации AAAA-A19-119071190045-0.</funding-statement>
    <funding-statement xml:lang="en">The work was carried out within the framework of the state assignment of the Institute of Problems of Chemical Physics of the Russian Academy of Sciences, state registration number AAAA-A19-119071190045-0.</funding-statement>
   </funding-group>
  </article-meta>
 </front>
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