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<div class="articledetails article-header clearfix">
<p class="art-type">Research Article</p>
<p class="art-title">Paragenesis mechanism of anthraxolite and
vanadium: A case study of the Tanjianshan Group
in the Northern Margin of the Qaidam Basin</p>
<p class="art-author"><?php $authors="Chenglin Liu<sup>1,2*</sup>, Chao Dun<sup>1,2</sup>, Yuanyuan Yang<sup>3</sup>, Xiaohu Wang<sup>3</sup>, Chao Tong<sup>1,2</sup>, Zhihui Zhang<sup>1,2</sup>, Mengxue Chenand
Yu Li<sup>1,2</sup>"; echo (stristr($authors,$coauthor))?str_replace($coauthor,"<a href='".$extpath."authors/".$courl."' target='_blank'>".$coauthor."</a>",$authors):$authors; ?></p>
<p class="art-affl">
<sup>1</sup>College of Geoscience, China University of Petroleum, Beijing, 102249, China<br>
<sup>2</sup>State Key Laboratory of Petroleum Resource and Prospecting, China University of Petroleum, Beijing, 102249, China<br>
<sup>3</sup>Institute of Geomechanics, Chinese Academy of Geological Sciences, Beijing, 100081, China<br>
</p>
<p class="art-aff"><b>*Corresponding author: <?php $corresponding_author="Chenglin Liu"; echo ($coauthor!="" && $coauthor==$corresponding_author)?"<a href='".$extpath."authors/".$courl."' target='_blank'>".$coauthor."</a>":$corresponding_author;?></b>, College of Geoscience, China University of Petroleum, Beijing, 102249, China, E-mail: <a href="mailto:liucl@cup.edu.cn">liucl@cup.edu.cn</a>
</p>
<p class="art-aff"><b>Received:</b> March 15, 2017
<b>Accepted:</b> April 13, 2017
<b>Published:</b> April 18, 2017</p>
<p class="art-aff"><b>Citation: </b> Liu C, Dun C, Yang Y, et al. Paragenesis mechanism of anthraxolite and
vanadium: A case study of the Tanjianshan
Group in the Northern Margin of the Qaidam
Basin. <i>Int J Petrochem Res.</i> 2017; 1(1): 46-49. doi: <a href="https://doi.org/10.18689/ijpr-1000109">10.18689/ijpr-1000109</a></p>
<p class="art-aff"><b>Copyright:</b> &copy; 2017 The Author(s). This
work is licensed under a Creative Commons
Attribution 4.0 International License, which
permits unrestricted use, distribution, and
reproduction in any medium, provided the
original work is properly cited.</p>
<p><a href="<?php echo $extpath;?><?php echo $jres['journal_link'];?>/ijpr-1000109.pdf" class="btn btn-danger pull-right" target="_blank">Download PDF</a></p>
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<div class="articlecontent">
<p class="art-subhead">Abstract</p>
<p class="art-para">The enrichment of metallic elements in organic matter or oil and gas is a common
phenomenon, but how vanadium is concentrated in anthraxolite and the interaction
mechanism between organic matter and vanadium are not clear. The anthraxolite in the
Tanjianshan Group in the Northern Margin of the Qaidam Basin generally contains a
relatively high amount of vanadium. In order to discuss the origin of the anthraxolite
and why the anthraxolite is rich in vanadium, we conducted research on organic
geochemical analysis and petrochemistry. The results show that the extent of anthraxolite
evolution is extremely high, and the organic matter originated from plankton and was
formed in oxygen-poor and salt water. The relative contents and correlation ratios of
major and trace elements in sediments indicate that the enrichment of vanadium
minerals is almost irrelevant to marine hot water deposition. It is inferred that the initial
deposition of vanadium may be mainly associated with biological and biochemical
processes, then the element migration and accumulation with hydrocarbon formation
and evolution, finally precipitation in anthraxolite.<br>
<br>
<b>Keywords:</b> Anthraxolite; vanadium; organic matter; biogeochemical mineralization
process; Tanjianshan group; the Northern Margin of Qaidam basin</p>
<p class="art-subhead">Introduction</p>
<p class="art-para">Researchers have been discovering the origin relationship between organic matter
and metal elements for a long time <a href="#1">[1]</a> <a href="#2">[2]</a> <a href="#3">[3]</a> <a href="#4">[4]</a> <a href="#5">[5]</a> <a href="#6">[6]</a> <a href="#7">[7]</a> <a href="#8">[8]</a> <a href="#9">[9]</a>. During our geological
survey in the Northern Margin of the Qaidam Basin, we have found that the anthraxolite
in the Upper Ordovician Tanjianshan Group contains more vanadium than that in the
crust, making us think it over: what role does vanadium play and how does it enrich in
the process of petroleum generation from hydrocarbon source rocks, and the evolution
of light oil to heavy oil, asphalt, and anthraxolite, a highly thermal evolution product of
organic matter.<br>
<br>
Geologists have a deep understanding of the phenomenon of metal enrichment in
butimen, heavy oil and oil sands <a href="#10">[10]</a> <a href="#11">[11]</a> <a href="#12">[12]</a>. The relevant deposits in the black rocks
such as vanadium, nickel and molybdenum occurrences are also getting valued by
researchers <a href="#13">[13]</a> <a href="#14">[14]</a> <a href="#15">[15]</a>. So, the studies of the relationship between organic matter and
metal minerals have become particularly important. At present, although it has been recognized that metal ions and their oxides may have
important effects in the hydrocarbon generation process, and
it has been put forward that clay minerals, transition metal
elements and their sulphides, uranium have positive catalytic
effects on oil and gas generation <a href="#16">[16]</a> <a href="#17">[17]</a>. Different metal
elements and organic matter at different evolution stages
always have different physical and chemical properties, and
there is little research on vanadium in anthraxolite currently. Furthermore, studies on fossil energy resources and metal
deposits are often carried out independently in sedimentary
basins, and the corresponding research methods are quite
different. Organic chemical methods are usually used to study
oil and gas resources, and the petrochemical methods are
generally applied to study metal deposits. In this paper, these
measures are combined to discuss the enrichment of
vanadium in the anthraxolite, which is rare in previous studies. In this project, the anthraxolite in the Upper Ordovician
Tanjianshan Group in the Northern Margin of the Qaidam
Basin is being taken as the analysis object. The aim is to
explore the origin of the anthraxolite and explain how
vanadium is concentrated in anthraxolite. The relevant
achievements will be meaningful not only to petroleum and
metal ore origin theory, but also to their exploration in the
Qaidam basin and others with similar geological background.</p>
<p class="art-subhead">Experiments</p>
<p class="art-para">To make sure the formation mechanism of anthraxolite
and establish the enrichment pattern of vanadium, this study
carried out organic geochemistry and petrochemistry tests on
the samples from the Tanjianshan Group. Specifically, these
tests include extraction of organic matter (EOM), gas
chromatography-mass spectrometry (GC-MS) analyses of the
saturate fractions, vitrinite reflectance of source rock (Ro), major and trace elements analysis.<br>
<br>
EOM was extracted using the Soxhlet extraction method. Rock samples were crushed into 100 mesh grain size and the
powdered samples were extracted with chloroform in a
Soxhlet extractor and kept in water bath (80 &#176;C) for 48 h. EOM
was then obtained after rotary evaporation.<br>
<br>
The gas chromatography-mass spectrometry (GC-MS) analyses of the saturate fractions were performed using a
Thermo-Finnigan Trace-DSQ instrument. The gas
chromatography (GC) oven temperature was initially held at
50&#176;C for 1 min, programmed to 120&#176;C at 20&#176;C/min and to
250&#176;C at 4&#176;C/min and to 310&#176;C at 3&#176;C/min and held at 310&#176;C
for 30 min. Helium was used as carrier gas.<br>
<br>
Ro was tested using the MPV-SP microphotometer. Shales
were made into optical slices. The objects for measurement
were required to be amorphous homogeneous and matrix
vitrinites in the slices. The minimum number of measurement
points was 30, and these points were evenly distributed in the
slices.<br>
<br>
The major and trace elements of the sedimentary rocks
were analyzed mainly using a plasma spectrometer. Except for
FeO, all other major and trace elements were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Hydrofluoric acid and sulfuric acid were used to decompose
the sample, then the content of FeO was calculated by the
dichromate method.</p>
<p class="art-subhead">Results and discussion</p>
<p class="art-para"><b>Geochemical characteristics of anthraxolite</b><br>
The anthraxolite in the Upper Ordovician Tanjianshan
Group has the following geochemical characteristics: (1) the
contents of soluble organic matter are low, and the nonhydrocarbon
and asphaltene are dominant in the group
components; (2) the equivalent vitrinite reflectance of 3.74%-
4.72%, indicating that it is at the stage of over-maturity; (3) Among the regular steranes, the content of C<sub>27</sub> is higher than
that of C<sub>28</sub>andC<sub>29</sub>; (4) The ratio of Pr/Ph in paraffins is between
0.5 and 0.8, displaying a significant phytane dominance; (5) The gammacerane index (G/C30H) of tricyclic terpanes is
generally between 0.18 and 0.27.These features reveal that
the organic matter originated from plankton and formed in
oxygen-poor and saline water. The contents and features of
hopanes, steranes, triarylstanes and tricyclic terpanes of
anthraxolite are similar to that of the mudstone from the
Tanjianshan Group, different from other source rocks in the
study area, manifesting that the anthraxolite sourced from the
mudstone from the Tanjianshan Group <a href="#18">[18]</a> <a href="#19">[19]</a>.</p>
<p class="art-para"><b>Major and trace elements</b><br>
The relative contents and correlation ratios of major and
trace elements can reveal the formation environment of
sedimentary rocks <a href="#20">[20]</a> <a href="#21">[21]</a>.The ratio of n(SiO2)/n(Al2O3) of the
mudstone and limestone rich in anthraxolite is 3.05 to 4.49
with an average value of 3.67; the ratio of n(Al)/n(Al+Fe+Mn) is 0.52to0.79 with an average value of 0.61.The results indicate
that the enrichment of vanadium minerals is almost irrelevant
to marine hot water deposition. The organic matter originated
from plankton, so it is inferred that the initial deposition of
vanadium was mainly associated with biological and
biochemical processes of the sedimentary environments, and
then the element migrated and accumulated with hydrocarbon
formation, finally precipitation in anthraxolite.<br>
<br>
<b>Discussion about the enrichment mechanism of vanadium
The initial the enrichment of vanadium</b><br>
The analysis of the major and trace elements in rocks has
approved that the sedimentary rocks in Tanjianshan Group is
mainly from land, with little involvement of hot water
deposition, thus proved that the vanadium is not related to
hydrothermal sedimentation. Organic geochemical analysis
indicates that the anthraxolite from the Tanjianshan Group
originated from the marine algae plankton and was formed in
the brackish water environment. Some planktons, such as
tunicate, brown algae, have positive effects on the enrichment
of vanadium <a href="22">[22]</a>. Nitrogen, phosphorus and potassium and
metal elements such as vanadium, nickel were brought to the
surface water by rivers and rising ocean currents. Vanadium
might be captured along with nitrogen, phosphorus and potassium taken in into planktons' bodies as nutrition, then it
became vanadium porphyrin, which could be well preserved
in the suboxic environment after planktons' death. The clay
minerals in the seawater also adsorbed vanadium during the
deposition process and replace part of the Al3+ into the clay
mineral lattice alongside the transfer of the clay minerals'
structure in the diagenetic process <a href="#13">[13]</a> <a href="#23">[23]</a>. It is therefore
speculated that the initial enrichment of vanadium in the
mudstone of the Tanjianshan Group is mainly related to the
adsorption of organism and clay minerals.(fig1.a)<br>
<br>
<b>The effects of liquid products generated by organic matter</b><br>
The black mudstone from the Tanjianshan Group entered
into the oil generation window in the Middle Devonian-Late
Devonian <a href="#18">[18]</a> <a href="#19">[19]</a>. Meanwhile oil and gas migrated into the
overlying sandstone and limestone reservoirs. The organic
matter released a series of organic functional groups and
compounds in the process of decay and thermal degradation, and metal elements escaped from the kerogen as organic
complexes. In the process of hydrocarbon generation, organic
matter also released humic acid and organic acid. On one
hand, these liquid products got vanadium in clay minerals and
organic matter activated, dissolved and extracted by changing
the PH, solubility and solution polarity in pore water of the
source rock. On the other hand, they served as a material
transport carrier, vanadium in the form of metal complex
migrated along the gradient of the fluid potential from the
source rock layer to the reservoirs through open faults and
cracks.(fig1.b).<br>
<br>
<b>The effects of tectonic movements</b><br>
During the period of geological history, the Tanjianshan
Group was in the tectonic setting of an active continental
margin. After the deposition of the Tanjianshan group, the
Northern Margin of the Qaidam Basin had experienced several
tectonic movements <a href="#18">[18]</a> <a href="#19">[19]</a>. Complex tectonic stress field
allowed many faults, fractures formed in the terrane, and
hydrocarbon fluids were able to migrate and accumulate
along these channels. At the end of Late Devonian, after the
first large-scale migration of oil and gas generated by the
hydrocarbon source rocks in the Tanjianshan Group, there
had been several magmatic intrusion in this area. Hydrocarbon
fluid baked under the high temperature from the magma
cracked, deteriorated, and ultimately evolved intoanthraxolite. At the same time, the baking of high temperature magma
provided favorable conditions for the removal of vanadium
from hydrocarbon fluids. Generally, the organic matter will be
decomposed between 150&#176;C and 200&#176;C <a href="#24">[24]</a>. The high temperature caused by magma broke the complexing balance
between organic matter and metal elements, the minerals
transported by the organic matter were precipitated due to
the decomposition of organic ligands and the lack of inorganic
ligands. The destruction of the metal complex structure
resulted in the release of vanadium element, and eventually it
get enriched in the solid butimen. (fig1.c).</p>
<!-- Table -->
<div class="art-img">
<img src="<?php echo $imgpath;?>images/IJPR-2017-109-g001.gif" class="img-responsive center-block"/></div>
<p class="text-center"><b>Figure 1: </b> The enrichment pattern of vanadium in the anthraxolite from
Tanjianshan Group</p>
<!-- Table -->
<p class="art-subhead">Conclusion</p>
<p class="art-para">The anthraxolite in the Upper Ordovician Tanjianshan
Group was formed by the pyrolysis and metamorphism of the
hydrocarbons generated from the black mudstone of the
Tanjianshan Group in the Northern Margin of the Qaidam
Basin. The petrochemistry analysis shows that the sedimentary
rocks of Tanjianshan Group were mainly composed of
terrigenous detritus and were not affected by hydrothermal
activities. In combination with the organic matter source of
anthraxolite, the enrichment of vanadium was related to
biological and biochemical processes of the sedimentary
environments, and the element migration and accumulation
during the hydrocarbon formation and evolution.</p>
<p class="art-subhead">Acknowledgement</p>
<p class="art-para">This work was supported by the National Natural Science
Foundation of China (Grant No. 41572099) </p>
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