Zhuo Wang1,2, Pingchang Sun1,2, Jiangfeng Du3, Yuanji Li1,2, Junxian Wang1,2, Liyun Hou1,2, Yinbo Xu4, Yueyue Bai5. 1. College of Earth Sciences, Jilin University, Changchun, Jilin 130061, China. 2. Key-Lab for Oil Shale and Paragenetic Minerals of Jilin Province, Changchun, Jilin 130061, China. 3. CNOOC Research Institute Co., Ltd., Beijing 100028, China. 4. Oil and Gas Survey, China Geological Survey, Beijing 100083, China. 5. Sino Probe Center, Chinese Academy of Geological Sciences, Beijing 100037, China.
Abstract
Paleocene-Eocene hyperthermal events are a current research focus in the fields of sedimentology and paleoclimatology. The Fushun Basin in northeast China contains continuous continental Eocene fine-grained rocks, and a series of Eocene hyperthermal events in the Fushun Basin have been identified. Because of the high cost of high-precision isotope data testing, it is necessary to find new and alternative paleoclimate parameters. In this study, Eocene coal and oil shale-bearing layers in the Fushun Basin are used as research objects. The high-precision data of magnetic susceptibility, color reflectance, rock composition, and cluster analyses are used to conduct a vertical comparison in the same category and compare that analysis with the identified Eocene hyperthermal events in the Fushun Basin. The preliminary results show that high-frequency-dependent susceptibility, high color reflectance a* (redness)/L* (lightness) values, and high kaolinite content in the study area have good correspondence with global hyperthermal events and can be used as effective parameters for the identification of continental basin hyperthermal events. The detailed magnetic susceptibility and color reflectance data also reveal that the Eocene strata in the Fushun Basin recorded the Late Lutetian Thermal Maximum (LLTM) and 13 short-term hyperthermal events during the Early Eocene Climatic Optimum (EECO). These results indicate that the parameters of rock physical properties can be used to study the evolution of the paleoclimate in geological history, and it has universal practicability in continental and marine fine-grained sedimentary rocks.
Paleocene-Eocene hyperthermal events are a current research focus in the fields of sedimentology and paleoclimatology. The Fushun Basin in northeast China contains continuous continental Eocene fine-grained rocks, and a series of Eocene hyperthermal events in the Fushun Basin have been identified. Because of the high cost of high-precision isotope data testing, it is necessary to find new and alternative paleoclimate parameters. In this study, Eocene coal and oil shale-bearing layers in the Fushun Basin are used as research objects. The high-precision data of magnetic susceptibility, color reflectance, rock composition, and cluster analyses are used to conduct a vertical comparison in the same category and compare that analysis with the identified Eocene hyperthermal events in the Fushun Basin. The preliminary results show that high-frequency-dependent susceptibility, high color reflectance a* (redness)/L* (lightness) values, and high kaolinite content in the study area have good correspondence with global hyperthermal events and can be used as effective parameters for the identification of continental basin hyperthermal events. The detailed magnetic susceptibility and color reflectance data also reveal that the Eocene strata in the Fushun Basin recorded the Late Lutetian Thermal Maximum (LLTM) and 13 short-term hyperthermal events during the Early Eocene Climatic Optimum (EECO). These results indicate that the parameters of rock physical properties can be used to study the evolution of the paleoclimate in geological history, and it has universal practicability in continental and marine fine-grained sedimentary rocks.
Paleogene global paleoclimate change has always been a research
focus in geological circles, among which the study of hyperthermal
events is the most representative. During the late Paleocene and early
Eocene, a series of transient global warming events occurred against
the background of global warming.[1−4] These global warming events are called hyperthermal
events. The most famous is the Paleocene–Eocene thermal maximum
(PETM). In marine strata, the amount of research on Paleogene hyperthermal
events is relatively high, and carbon isotope excursions (CIEs) in
marine sediments can adequately indicate hyperthermal events. Frequent
hyperthermal events during the Eocene (55–47 Ma) have been
identified in marine records worldwide. Specifically, the absolute
ages of approximately 28 short-term hyperthermal events recognized
in the Eocene are based on δ13C data from marine
sediments collected in the Integrated Ocean Drilling Program (IODP).[4−9] In recent years, many hyperthermal events similar to the PETM in
nature have been found, such as the Eogene Thermal Maximum (ETM),
J, L, M, N, O, P, Q, R, S, T, U, V, and W.[8−12] According to previous studies, the Cenozoic climate
can be divided into four states: hothouse, warmhouse, coolhouse, and
icehouse. The hothouse state lasted from 56 Ma to 47 Ma, and the temperature
was 10 °C higher than that at present. The warmhouse states were
from 66 Ma to 56 Ma and from 47 Ma to 34 Ma.[13]Few studies have focused on Paleogene hyperthermal events
in continental
sedimentation. The identification of hyperthermal events has been
carried out only in some areas on land.[14,15] In the Fushun
Basin, northeastern China, according to the δ13C
total organic carbon (TOC) values, the ages of CIEs and a comparison
with the IODP sites, three Eocene continental hyperthermal events
were recognized: ETM2, ETM3, and the long-term Early Eocene Climatic
Optimum (EECO).[15] In southern China, the
magnitude of the CIEs and the changes in temperature and precipitation
during the PETM have been revealed by using carbonate-associated sulfate
sulfur and oxygen isotopes and reconstructing the carbon isotopes
(Δ) of C3 plants.[16,17] On the basis
of lacustrine sediments from deep drill core SKD1 and mineralogical
and geochemical evidence, a high-resolution record of the PETM event
in the Jianghan Basin is proposed for the first time. The palynological
record from the black shale of the lowermost Yangxi Formation exposed
in the western Jianghan Basin has revealed the impact of the hyperthermal
event on terrestrial ecosystems.[18] In Tibet,
China, the study of shallow marine carbonates in the Tethys Himalaya
of southern Tibet reveals the biotic response to sea level change
in shallow marine environments during the PETM and the carbon isotope
expression of the PETM in a shallow-water–carbonate platform.[19] The stratigraphic record of the Paleocene–Eocene
Thermal Maximum in the Xigaze forearc basin (southern Tibet) and in
NW Himalaya (India) represents one of the few records of the PETM
in active continental margins worldwide.[20,21]The Fushun Basin in northeast China contains complete continental
Eocene strata that are mainly organic-rich, fine-grained rocks, which
are the best carriers for establishing paleoclimate evolution archives.
On the basis of previous studies on magnetic stratigraphy, biostratigraphy,
and isotopic stratigraphy, the chronostratigraphic framework of the
study layer is preliminarily constrained.[22,23] On the basis of the new Ar–Ar isotopic dating of the volcanic
tuff of the Lizigou Formation, the possible oldest age at the bottom
of the Guchengzi Formation coal seam is 55.07 ± 1.18 Ma.[14] Combined with the stable isotope analysis of
organic matter carbon in thick coal seams, it is found that the sedimentary
records include the Paleocene–Eocene thermal maximum (PETM),
ETM2/H1, H2, I1, and I2. However, the sedimentary records are limited
to a single coal seam, while the analysis of hyperthermal events has
not been carried out for other coal-bearing strata and oil shale strata.
In the study of Li et al. (2022),[15] based
on U–Pb isotope dating (54.72 ± 0.20 Ma) and astronomical
dating analysis, in the sedimentary periods of the Guchengzi Formation
and Jijuntun Formation (54.72–46.5 Ma) in the Fushun Basin,
the δ13CTOC and contemporaneous marine
strata δ13C values were compared to identify the
short-term hyperthermal events of ETM2 and ETM3, and the long-term
warming events (long-term hyperthermal events) of the EECO (∼53–46.5
Ma) and 22 short-term hyperthermal events were identified within EECO
events, namely, L, M, N, O, P, Q, R, S, T, U, V, W, C22nH3, C22nH4,
C22nH5, C21rH1, C21rH2, C21rH3, C21rH4, C21rH5, C21nH1, and C21nH2.According to the geological time scale (GTS2012),[24] the sedimentation of the upper Lizigou Formation to the
Guchengzi Formation and Jijuntun Formation in the study area occurred
from 54.72 to 47.8 Ma and from 47.8 to 41.2 Ma.[15] According to the global paleoclimate characteristics in
the same period, the Fushun Basin in the Paleocene in this stage was
in a warmhouse–hothouse background overall; however, high-precision
isotope analysis is particularly expensive. On the basis of the multistage
records of hyperthermal events in the Fushun Basin, this study uses
the Eocene Guchengzi Formation coal, mudstone, carbonaceous mudstone,
and Jijuntun Formation oil shale in the Fushun Basin as the research
object and carries out the identification of hyperthermal events and
the study of paleoclimate evolution based on systematic magnetic susceptibility,
color reflectance, and mineral composition data, which are helpful
to improve the Paleogene paleoclimate archives of northeast Asia and
provide alternative indicators for studying paleoclimate evolution,
such as hyperthermal events.
Geological Setting
The Fushun Basin, located in southern Fushun City, Liaoning Province,
China, is a famous coal-bearing and oil shale-bearing basin in China.
The Hun River is located in the northern part of the basin, and hills
are located in the south. The basin starts from the Guchengzi River
in the west and the Dongzhou River in the east. It is approximately
19 km long and 4 km wide, with a total area of approximately 76 km2 (Figure ).
Figure 1
Regional
geological map of the Fushun Basin. (a) Fushun Basin global
location (50 Ma).[3,15] (b) Fushun Basin location map.[22,25] (c) Distribution of the Fushun Basin in the Dunhua–Mishan
fault zone.[22,25] (d) Stratigraphic column of the
Fushun Basin.[22,25] (e) Geological structural unit
of the Fushun Basin.[22]
Regional
geological map of the Fushun Basin. (a) Fushun Basin global
location (50 Ma).[3,15] (b) Fushun Basin location map.[22,25] (c) Distribution of the Fushun Basin in the Dunhua–Mishan
fault zone.[22,25] (d) Stratigraphic column of the
Fushun Basin.[22,25] (e) Geological structural unit
of the Fushun Basin.[22]The Fushun Basin is located on the western side of the Dunhua–Mishan
(“DunMi”) fault zone, which is the northern extension
of the Tanlu fault zone. It is a small continental strike-slip fault
basin formed on Proterozoic gneiss that formed during the Paleogene
rift cycle.[26] Its sedimentary fill comprises
the Paleocene Laohutai and Lizigou Formations and the Eocene Guchengzi,
Jijuntun, Xilutian, and Gengjiajie Formations. Oligocene strata are
absent.[22] This research focuses on the
Guchengzi Formation and Jijuntun Formation. The Guchengzi Formation
consists of a thick coal seam intercalated with carbonaceous shale,
and the thickness of the coal seam decreases from west to east and
from south to north. The Jijuntun Formation is composed of thick oil
shale and is stably distributed throughout the whole region.[27,28] The coal and carbonaceous mudstone of the Guchengzi Formation were
deposited in a swamp environment, and the oil shale of the Jijuntun
Formation was deposited in shallow and deep lake environments.[29]
Samples and Methods
Samples
The Guchengzi Formation (54.51–47.80
Ma) and Jijuntun Formation (47.8–41.2 Ma) in the Fushun Basin
are organic-rich, fine-grained sediments that were continuously deposited
in the Eocene,[15] and they are important
records for studying Eocene hyperthermal events. Therefore, in this
study, the coal and carbonaceous mudstone of the Guchengzi Formation
and the oil shale of the Jijuntun Formation in the Liaofudi 1 well
in the Fushun Basin were systematically sampled. The sampling interval
was approximately 0.5 m. Sixty-eight samples were collected from the
Guchengzi Formation, including 28 carbonaceous mudstones, 10 mudstones,
and 30 coals. A total of 157 samples were collected from the Jijuntun
Formation, including 2 mudstones and 155 oil shales. A total of 225
samples were collected, dried, and ground into powder (200-mesh).
The samples were tested for color reflectance and magnetic susceptibility,
and a core of the Jijuntun Formation was scanned by infrared spectroscopy.
All experiments were completed in the Key-Lab for Oil Shale and Paragenetic
Minerals of Jilin Province.
Principle and Experimental
Method of Magnetic
Susceptibility
In this paper, the magnetic susceptibility
of 225 samples obtained from the target layer was analyzed. During
the measurements, 5–6 g samples were placed in a nonmagnetic
2 cm × 2 cm × 2 cm polystyrene box for testing. The MS2B
susceptibility tester of the British Bartington Company was used to
carry out the magnetic susceptibility test and followed the standard
of GB/Z 26082-2010 nanomaterial DC magnetic susceptibility (magnetic
moment). The magnetic susceptibility test was repeated 10 times, and
the error between data points from the same sample was less than 0.02
× 10–8 m3/kg. The low-field frequency
was 0.47 kHz, and the high-field frequency was 4.7 kHz. Each sample
was tested with a range of 0.1 10 times, and the averages of the low-field
susceptibility (χlf), high-field susceptibility (χhf), and frequency-dependent susceptibility (χfd%) were obtained through Multisus software, where χfd% = (χlf – χhf)/χlf × 100%.
Principle and Experimental
Method of Color
Reflectance
The Commission International d’Eclairage
1976 L*a* and b* (CIELAB) color expression and measurement system specified by the
International Lighting Commission in 1976 is quoted,[30] in which the L* (lightness) value represents
brightness (L* = 0% represents black and L* = 100% represents white), a* (redness)
value represents redness (a positive value tends toward red, and a
negative value tends toward green), and b* (yellowness)
value represents yellowness (a positive value tends toward yellow,
and a negative value tends toward blue); these values indicate color
reflectance characteristics.A total of 225 samples were individually
placed on the white background reference color plate, compacted, and
flattened to ensure that the sample surfaces were uniform, smooth,
and flat. A WR-18 color difference instrument (the test parameters
were as follows: the light source was a CIED65 standard light source,
and the aperture was 4 mm) was used to measure the color reflectance.
Three positions were randomly selected on each sample for testing,
and then the average value was calculated to obtain the color reflectance
value of the sample. The color reflectance was followed by the SH/T
0168-92 petroleum product color reflectance determination standard,
the color reflectance test was repeated three times, and the error
between data points from the same sample was less than 0.05%.
Infrared Spectrum Scanning
This paper
used a Hylogger core hyperspectral scanner to scan only the Jijuntun
Formation core by infrared spectroscopy. On the basis of the reflection
spectrum analysis technology, the reflection spectrum of the core
in the wavelength range of 400–2500 nm was collected and measured
by spectrometry, and different minerals were calculated and identified
according to their spectral diagnostic characteristics to form mineralogical
information. Because of the limitation of sample integrity, a total
of 174 rock component data points were measured. The main minerals
that were analyzed were kaolinite, quartz, smectite, carbonate, feldspar,
and mica. It should be noted that due to the limited precision of
the testing instruments, only high-content minerals could be identified.
Cluster Analysis and Wavelet Analysis
Because
of the large amount of data, many kinds of components, and
high-frequency fluctuations in values, it is difficult to interpret
the paleoclimate. To more intuitively reflect the paleoclimate change
and carry out research on the corresponding relationship with the
identified hyperthermal events, the mathematical statistical software
SPSS24 was used to cluster indexes, such as the low-field susceptibility
(χlf), high-field susceptibility (χhf), frequency-dependent susceptibility (χfd%), brightness
(L*), redness (a*), and yellowness
(b*) (Figure ). Cluster analysis was carried out by using the method of
intergroup connection in systematic clustering, and then the clustering
results were counted. The data classified into a class after cluster
analysis were averaged, and the average value was used to replace
all the data in this class. The change in the trend of the obtained
result chart is more obvious than that of the untreated result chart,
which is conducive to analysis and discussion. The frequency susceptibility
was determined by the low-frequency magnetic susceptibility, and high-frequency
susceptibility was obtained, which is more representative. Therefore,
in this study, the frequency susceptibility was analyzed by MATLAB
software (Figure ).
Figure 2
Cluster
analysis process.
Figure 3
Magnetic susceptibility
and color reflectance experimental results.
(Fine dating scale of the Eocene strata in the Fushun Basin are according
to Li et al. (2022);[15] paleotemperature
data are according to Westerhold et al.;[13] the global temperature comes from the records of deep-sea benthic
foraminifer oxygen isotopes. The record was first converted to a deep-sea
temperature and then projected to the surface air temperature change.)
Cluster
analysis process.Magnetic susceptibility
and color reflectance experimental results.
(Fine dating scale of the Eocene strata in the Fushun Basin are according
to Li et al. (2022);[15] paleotemperature
data are according to Westerhold et al.;[13] the global temperature comes from the records of deep-sea benthic
foraminifer oxygen isotopes. The record was first converted to a deep-sea
temperature and then projected to the surface air temperature change.)
Results
In the time
stratigraphic framework built by predecessors,[14,15,22,23] considering
that the Guchengzi Formation (52.2–47.8 Ma) is
mainly coal-bearing swamp deposits and the oil shale of the Jijuntun
Formation (47.8–41.2 Ma) is stable shallow lake and deep lake
deposits,[15] the Guchengzi Formation Jijuntun
Formation can be divided into two stages according to the results
of magnetic susceptibility and color reflectance: the early stage
(52.2–47.8 Ma) and the late stage (47.8–41.2 Ma).
Rock Composition
The Guchengzi Formation
is mainly composed of thick coal seams with mudstone and carbonaceous
mudstone. The Jijuntun Formation is mainly composed of thick oil shale
deposits. From 52 Ma to 47.8 Ma, which is the depositional stage of
the Guchengzi Formation, from bottom to top, the rock composition
gradually transforms from carbonaceous mudstone intercalated with
coal seams and mudstone to thicker coal seam deposits, in which a
small section of tuffaceous sandstone deposits are interspersed; from
47.8 Ma to 42.1 Ma, which is the depositional stage of the Jijuntun
Formation, all thick oil shale deposition occurred, with alternating
dark gray oil shale, gray black oil shale, and black oil shale.Among these deposits, the measured rock component data show that
the minimum kaolinite content is 15.9%, and the maximum content is
84.2%. From 47.8 Ma to 42.1 Ma, the kaolinite content declined, except
at 47.5 Ma and 41.3 Ma, and the values fluctuated twice, with peaks
of 70.5% and 61.4%, respectively. Then, the kaolinite content continued
to decline until 41.2 Ma. The change in the trend of the mica content
is generally opposite that of the kaolinite content; quartz, smectite,
carbonate, feldspar, and other minerals appear intermittently, so
their trends are not analyzed (Figure ).
Figure 6
Relationship between whole-rock analysis
and paleoclimate (paleotemperature
data are according to Westerhold et al., 2020[13]).
Magnetic susceptibility
Overall,
the trends of χlf and χhf are basically
the same. In the early stage (I, 52.2–47.8 Ma), from bottom
to top, χlf and χhf show a downward
trend overall, but at the end of this stage, the two parameters suddenly
and rapidly increase, up to 32.1 × 10–8 m3/kg and 28.6 × 10–8 m3/kg
(approximately 47.8 Ma), during which four high-value fluctuations
occur, namely, 21.9 × 10–8 m3/kg,
19.3 × 10–8 m3/kg, 27.1 × 10–8 m3/kg, and 21.9 × 10–8 m3/kg for χlf and 18.8 × 10–8 m3/kg, 10.7 × 10–8 m3/kg, 26.8 × 10–8 m3/kg, and 19.6 × 10–8 m3/kg for
χhf; χfd values show an increasing
trend, but the overall range is 0.4–54%; the values reach the
maximum value of 77.78% at approximately 48.4 Ma and then rapidly
reduc to 8%.Late stage (II, 47.8–41.2 Ma), χlf and χhf generally show a slight downward
trend, with a small amplitude and low value fluctuations at approximately
45.0 Ma and 43.0 Ma, and the χlf minimum value is
3 × 10–8 m3/kg, 1.7 × 10–8 m3/kg, The lowest value of χhf can reach 1.4 × 10–8 m3/kg and 1.3 × 10–8 m3/kg; χfd has been kept low, ranging from 3.47–17.24%, and
the highest value of 53.3% at this stage appears at approximately
45.0 Ma.
Color Reflectance
On the whole, the
color reflectance L* value first increases and then
decreases, and the a* value and b* value generally show an upward trend. In the early stage (I, 52.2–47.8
Ma), from bottom to top, L* increased from 44.44%
to a stable high value, ranging from 54.66–68.68%, decreased
to 40.54% after approximately 49.2 Ma, and rapidly increased to 55.85%
at 47.8 Ma; a* and b* showed an
upward trend, but b* fluctuated more violently. a* gradually increased from 3.36% to 7.66% and then decreased
to 4.08% after approximately 49.2 Ma There was a small amplitude low
value fluctuation at 48.8 Ma, with a minimum of 3.31%. The b* value slowly increased from the initial 4.15% to a stable
high value, ranging from 10.05–13.44%. There was a small amplitude
low value fluctuation at 49.4 Ma, with a minimum of 1.21%, which rapidly
decreased to 2.50% at 47.8 Ma.In the late stage (II, 47.8–41.2
Ma), the change in the trend of the overall color reflectance value
was weak. From 47.8 Ma to 44.6 Ma, L* was relatively
stable, showing a slight downward trend, with small fluctuations in
the middle, and showing an upward trend at the end of this stage.
The overall trends of the a* value and b* value were approximately the same. At this stage, the values showed
a slight upward trend. After approximately 47.0 Ma, the values fluctuated
stably, ranging from 3.92–5.65% and 3.22–10.81%, respectively.
Discussion
Detailed Analysis of the
Paleoclimate
Magnetic Susceptibility,
Color Reflectance,
and Paleoclimate
Environmental magnetism has been successfully
applied to reconstruct the climate and environmental evolution of
marine and continental sediments.[31] The
magnetic susceptibility is a measure of the difficulty of magnetizing
a substance. It is mainly determined by the composition, content,
and particle size of magnetic minerals.[32−34] Previous studies have
shown that the magnetic minerals in the mineral composition of coal
and oil shale in the Fushun Basin are mainly pyrite and siderite.[35] In other words, it is related to the depositional
environment[36] and the sediment source.[37] The source rocks in the Eocene Fushun Basin
are mainly of mixed felsic and mafic affinity[28] and remain unchanged for a long time. At the same time, there were
only two sedimentary environments. The Guchengzi Formation formed
in a swamp environment. The Jijuntun Formation formed in shallow and
deep lake environments,[15] and we analyzed
the magnetic susceptibility and chromaticity in these two units. Therefore,
this analysis can reliably indicate the environmental change and climate
change in one sedimentary environment. The magnetic minerals mainly
come from the weathering process; when the climate is warm and humid,
the increase in weathering intensity leads to more ultrafine magnetic
particles in the source area, which may increase the frequency-dependent
susceptibility (χfd%). Therefore, in a high-temperature
and humid environment, the low-field susceptibility (χlf) is low, and χfd% is relatively high, while in
dry and cold environments, χlf is relatively high,
and χfd% is low.The color reflectance mainly
depends on the mineral composition (mainly carbonate) and organic
matter content of sediments. It is the most intuitive feature of sediments,
and the strata in this study are organic-rich fine granular rock deposits.
The color reflectance can be used to understand climate change,[38,39] and it can indicate climate change and the redox degree under different
climates. Previous studies have shown that in modern soils[36] and loess paleosols,[40] the changes in the a* values are very sensitive
to warm and humid climates. The redness (a*) of fine-grained
sediments is closely related to the temperature and precipitation
conditions affecting sediment oxidation during weathering.[41] The L* value reflects the change
in the carbonate content in sediments from arid to semiarid areas.[36] Under a dry and cold climate, the carbonate
content is high, the temperature is low, the precipitation is low,
the L* value of the sediment is high, and the a* value is low. In contrast, under humid and hot climate
conditions, the carbonate content is low, the temperature and precipitation
are high, the sediment L* value is low, and the a* value is high. Therefore, a higher a*/L* value indicates that the climate is relatively
humid and warm; in contrast, lower a*/L* values indicate relatively dry and cold climatic conditions.[42,43] The correlation between the b* value, which represents
yellowness (a positive value tends toward yellow, and a negative value
tends toward blue), and the a* value is obvious.
High values of b* and a* indicate
humid and hot climates, and low values indicate relatively dry and
cool climates. Compared with other methods, color reflectance is more
convenient and faster and has wide application prospects in climate
change research.[40]By comparing the
magnetic susceptibility data and color reflectance
data after clustering with the global average temperature given by
Westerhold et al. (2020),[13] a good corresponding
relationship with the paleotemperature can be obtained (Figure ). In the early stage (I, 52.2–47.8
Ma), the low-field susceptibility (χlf) at the beginning
first decreased, and a relatively obvious increase until 50.8 Ma occurred.
The a* values first increased, then fluctuated slightly
at approximately 5.7%, and then decreased. The change in the trend
of the b* value was basically the same as that of
the a* value, which generally increased first and
then decreased, indicating that the temperature increased first and
then decreased at approximately 52.2–50.5 Ma. During 49.8–48.0
Ma, the low-field susceptibility (χlf) maintained
a low value. The a*/L* values increased
gradually at this stage. The frequency-dependent susceptibility (χfd) at the end increased significantly, and the a* value, b* value, and a*/L* value decreased rapidly. These results show that at this
stage, the climate was generally warm and humid and finally became
hot and humid, while the hot and humid climate at the initial stage
was conducive to the formation of fine-grained ferromagnetic minerals;
thus, the frequency-dependent susceptibility (χfd) was initially high and was significantly reduced at the end, which
further indicates the transformation of the climate from hot and humid
to warm and humid; this transformation can also be used as a sign
of the transformation of the Fushun Basin paleoclimate from hothouse
to warmhouse conditions. The paleotemperature also showed a process
of first increasing, stabilizing, and finally decreasing from 52.2
to 47.8 Ma.
Figure 4
Relationship between magnetic susceptibility, color reflectance,
and paleoclimate (paleotemperature data are according to Westerhold
et al., 2020[13]).
Relationship between magnetic susceptibility, color reflectance,
and paleoclimate (paleotemperature data are according to Westerhold
et al., 2020[13]).In the late stage (II, 47.8–41.2 Ma), the low-field susceptibility
(χlf) fluctuated within a certain range and decreased
slightly overall. The a* and b*
values decreased rapidly at first and then changed little, basically
fluctuating at approximately 4.76% and 6.36%, respectively. Among
these values, the b* values fluctuated the most,
and the a*/L* values stabilized
and decreased slightly at the end of this stage, corresponding to
the decline in the paleotemperature. However, at 44.8 Ma and 43.1
Ma, the low-field susceptibility (χlf) appeared to
be low. After the frequency-dependent susceptibility (χfd) dropped to a low value, it remained stable, with occasional
high values, and a high value appeared at the corresponding position
where the low-field susceptibility (χlf) appeared,
which corresponds to the small warming process of paleotemperature
under the background of warmhouse conditions. The high values of the
frequency-dependent susceptibility (χfd), a* value, b* value, and a*/L* value at approximately 41.5 Ma can better correspond
to the Late Lutetian Thermal Maximum (LLTM).The comparative
analysis shows that although there are several
valley peak fluctuations in the middle of the magnetic susceptibility
curve, which does not correspond well to the paleotemperature curve,
the valley and peak values have good overall correspondence with the
peak and valley values in the temperature curve. Furthermore, combined
with the color reflectance curve and the paleotemperature curve, they
have a good correspondence. Therefore, the magnetic susceptibility
and color reflectance can be used to analyze the paleotemperature
trend.Generally, from 52.2 Ma to 41.2 Ma, the Fushun Basin
changed from
hot and humid to warm and humid. The sudden increase in the low-field
susceptibility (χlf) and the sudden decrease in the
infrequency-dependent susceptibility (χfd), as well
as the a* and b* values at the boundary
between the Guchengzi Formation and Jijuntun Formation (487 m (approximately
47.8 Ma)), can be used as a record of this transformation.
Identification of Hyperthermal Events
In conclusion,
both the frequency-dependent susceptibility (χfd)
and color reflectance can be used as paleoclimate indicators.
During hyperthermal events, the temperature rises, the climate is
hot and humid, and the color reflectance a*/L* values are high. In this climate, weathering is enhanced,
which leads to an increase in ultrafine magnetic particles and high-frequency-dependent
susceptibility (χfd). Therefore, when the paleoclimate
background is known, the use of magnetic susceptibility and color
reflectance can reveal hyperthermal events.In this paper, the
magnetic susceptibility and color reflectance indexes in the period
of 52.2 Ma to 47.0 Ma are selected and compared with δ13CTOC values in the same period.[3,17,44] The cluster analysis results of the two
representative indexes, χfd and a*/L*, are compared with the δ13CTOC values in the same period (as shown in Figure ). The δ13CTOC values revealed short-term extreme heat events L,
M, N, O, P, Q, R, S, T, U, V, W, C22nH3, C22nH4, C22nH5, C21rH1, C21rH2,
C21rH3, C21rH4, C21rH5, C21nH1, and C21nH2 during the EECO. The high
values of χfd and a*/L* have a good corresponding relationship, and the high values of
the two parameters correspond to the hot and humid climate. These
results show that the hyperthermal events can also be well recorded
by the frequency-dependent susceptibility and color reflectance index.
Therefore, the frequency-dependent susceptibility is applied, and
the χfd and a*/L* values reveal the hyperthermal events; 13 short-term hyperthermal
events are identified, including N, O, P, Q, T, U, V, C22nH3, C21rH1,
C21rH2, C21rH3, C21rH5, and C21nH1. However, L, M, R, S, W, C22nH4,
C22nH5, C21rH4, and C21nH2 are not recognized, which may be affected
by factors such as the insufficient accuracy of magnetic susceptibility
and color reflectance tests and poor sensitivity of the color reflectance
index to paleoclimate change.
Figure 5
Comprehensive analysis chart of hyperthermal
events (the GTS2012
is from Ogg, 2012;[24] δ13CTOC values are from Li et al., 2022;[15] Possagno is from Luciani et al., 2016;[45] site 1258 is from Turner et al., 2014;[3] hyperthermal events are from Westerhold et al., 2018[4] and Galeotti et al., 2019.[9] Among the hyperthermal events, the symbol before the letter
“H” represents magnetochrons, such as C23r. The letter
“H” and the number after it represent hyperthermal events,
which are identified by CIEs.)
Comprehensive analysis chart of hyperthermal
events (the GTS2012
is from Ogg, 2012;[24] δ13CTOC values are from Li et al., 2022;[15] Possagno is from Luciani et al., 2016;[45] site 1258 is from Turner et al., 2014;[3] hyperthermal events are from Westerhold et al., 2018[4] and Galeotti et al., 2019.[9] Among the hyperthermal events, the symbol before the letter
“H” represents magnetochrons, such as C23r. The letter
“H” and the number after it represent hyperthermal events,
which are identified by CIEs.)By comparing the frequency-dependent susceptibility (χfd) curve and spectrum after wavelet analysis with the identified
hyperthermal events in the Fushun Basin and the global hyperthermal
events (Figure ),
cycles 1, 2, 4, 5, 6, and 7 in the χfd curve and
the spectrum can well correspond to the fluctuation of the global
average temperature, which increases first and then decreases. The
Late Lutetian Thermal Maximum (LLTM)[13] in
cycle 1 and 41.2 Ma to 42 Ma are relatively consistent, which can
be used as the basis for LLTM identification. The identification of
multistage hyperthermal events further shows that the Guchengzi Formation
has a hothouse background. The identification also confirms that the
paleoclimate of the Fushun Basin changed from hot and humid to warm
and humid from 52.2 Ma to 41.2 Ma. The identification is also sufficient
to prove that hyperthermal events can be completely recorded in the
extremely stable terrestrial lake sediments of the Fushun Basin, and
the frequency-dependent susceptibility (χfd) and
color reflectance indicators also provide a good indication of the
change in the paleoclimate. This indicator can be used as an alternative
index for fine paleoclimate identification and climate event identification
when the overall climate background is known.In addition, there
are differences and similarities in the recognition
of hyperthermal events by color reflectance, magnetic susceptibility,
and carbon isotopes. The difference is the accuracy of identification.
For example, hyperthermal events can be directly identified by organic
carbon isotopes, and the CO2 concentration and paleotemperature
are also estimated quantitatively by bulk δ13CTOC. Magnetic susceptibility and color reflectance can indicate
only the climate trend. The identification of hyperthermal events
can be carried out only under a known climate background based on
these parameters. The common point is that, in the identification
markers, both negative carbon isotope excursions (CIEs) and positive
excursions of magnetic susceptibility and color reflectance indicate
that the climate became warm and humid.
Rock
Composition and Paleoclimate
Because of shallow burial, the
vitrinite reflectance (Ro) is less than
0.5%, weak diagenesis occurred in the
study area,[29] and the fine-grained sedimentary
rocks are basically primary clay minerals. The paleoclimate has an
impact on organic matter and rock mineral composition.[46−50] Kaolinite is the main product of chemical weathering,[51−53] and a warm and humid climate is conducive to the formation and deposition
of kaolinite.[54] The existence of smectites
indicates cold climate characteristics;[55] quartz has a strong anticorrosion ability, and feldspar is far easier
to weather than quartz. Under the background of a warm and humid paleoclimate,
feldspar is less abundant and is easily transformed into clay.During 47.8–45.8 Ma, the kaolinite content decreased (from
84.2% to 61.4%), and a loss occurred near 47.6 Ma (Figure ), indicating that the climate changed from hot and humid
to dry and cool, which corresponds to the overall decline in the global
average temperature. From 45.8 to 44.5 Ma, the kaolinite content was
generally low, approximately 60%, indicating that the climate was
relatively dry and cool. The kaolinite content first increased and
then decreased at approximately 45.4 Ma, which is reflected in the
short relative high-temperature and high-humidity period against the
background of relatively dry and cool conditions, which is similar
to the variation in the global paleotemperature in the same period.
During 44.5–43.3 Ma, the kaolinite content first decreased
and then increased, indicating that the paleoclimate was first dry
and cool, and then the temperature rose and initiated a humid and
hot climate; this pattern corresponds to the global average temperature
first decreasing and then increasing. In the period of 43.3–41.2
Ma, the kaolinite content showed a gentle “double peak”,
indicating that the climate had two alternating upward and downward
evolution processes; in addition, two high peaks correspond to the
global average temperature, of which the last kaolinite content peak
corresponds to the Late Lutetian Thermal Maximum. This stratum was
deposited at 41.5 Ma, which is basically consistent with the occurrence
time of the LLTM in marine strata, further confirming the response
of kaolinite to hyperthermal events.Relationship between whole-rock analysis
and paleoclimate (paleotemperature
data are according to Westerhold et al., 2020[13]).In addition, from 47.8 to 41.2
Ma, smectites appear only in the
upper part of the Jijuntun Formation, which also shows that in the
Jijuntun Formation, the climate changed from hothouse to warmhouse
conditions, which also corresponds to the overall downward trend of
the global average temperature. In general, the trend of the kaolinite
content corresponds well with the global paleotemperature curve, which
can be used as a parameter for fine-scale paleoclimate research.
Quantitative Characterization Parameters
Overall, the magnetic susceptibility has a baseline under warmhouse
and hothouse conditions. The baselines of low-field susceptibility
(χlf) are 13.6 × 10–8 m3/kg under warmhouse conditions and 2.69 × 10–8 m3/kg under hothouse conditions. The baselines of high-field
susceptibility (χhf) are 11.14 × 10–8 m3/kg under warmhouse conditions and 1.76 × 10–8 m3/kg under hothouse conditions. The baselines
of frequency-dependent susceptibility (χfd%) are
8.19% under warmhouse conditions and 26.81% under hothouse conditions.
However, the overall range of the color reflectance values is small,
so it is difficult to identify the baseline. These baselines may be
used as the assessment index of warmhouse and hothouse conditions.
The baselines of magnetic susceptibility and color reflectance vary
in different regions due to differences in the clastic input, provenance
type, etc. Moreover, only under the known general paleoclimate background
can these parameters be used for fine paleoclimate analysis.Because of the comparability of global hyperthermal events, this
study provides alternative indicators for the study of paleoclimate
evolution and has a certain guiding significance for understanding
the evolutionary pattern of the modern Earth climate and future environmental
predictions.
Conclusion
The Paleogene
Guchengzi Formation and Jijuntun Formation in the
Fushun Basin were deposited under warmhouse and hothouse conditions.
In this study, relying on the high-precision data of magnetic susceptibility,
color reflectance, and rock composition, the method of cluster analysis
was used to reveal the fluctuation characteristics of the paleoclimate
under the background of warmhouse–hothouse conditions.The high-precision
magnetic susceptibility
values, color reflectance values, and clay mineral contents in the
time period have a good corresponding relationship with the identified
Eocene hyperthermal events and global average temperature in the Fushun
Basin, which can be used as the basis for paleotemperature change
and an effective alternative parameter for paleoclimate research.During 42.0 Ma to 41.2
Ma, based on
all data and according to the comparative analysis of δ13CTOC, 13 short-term hyperthermal events, including
N, O, P, Q, T, U, V, C22nH3, C21rH1, C21rH2, C21rH3, C21rH5, and C21nH1,
can be identified in the EECO long-term events.From 52.2 Ma to 41.2 Ma, the paleoclimate
generally presented a hot and humid to warm and humid trend. During
the period of 50.0 Ma to 48.0 Ma, the paleotemperature still underwent
a small warming stage against a hothouse background. The paleoclimate
cooled rapidly at 47.8 Ma, the paleoclimate quickly changed from a
hothouse background to a warmhouse background, and a small warming
process occurred during the period of 42.0 Ma to 41.2 Ma.
Authors: James C Zachos; Ursula Röhl; Stephen A Schellenberg; Appy Sluijs; David A Hodell; Daniel C Kelly; Ellen Thomas; Micah Nicolo; Isabella Raffi; Lucas J Lourens; Heather McCarren; Dick Kroon Journal: Science Date: 2005-06-10 Impact factor: 47.728
Authors: R Thompson; J C Stober; G M Turner; F Oldfield; J Bloemendal; J A Dearing; T A Rummery Journal: Science Date: 1980-02-01 Impact factor: 47.728
Authors: Philip F Sexton; Richard D Norris; Paul A Wilson; Heiko Pälike; Thomas Westerhold; Ursula Röhl; Clara T Bolton; Samantha Gibbs Journal: Nature Date: 2011-03-17 Impact factor: 49.962