Marine and Petroleum Geology 80 (2017) 358e368

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Marine and Petroleum Geology

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Research paper

Geochemical evolution of OligoceneeMiddle Miocene sediments in

the deep-water area of the Pearl River Mouth Basin, northern South
China Sea
Licheng Cao a, *, Lei Shao a, Peijun Qiao a, **, Shuhui Chen a, b, Mengshuang Wu b
a
State Key Laboratory of Marine Geology, Tongji University, Shanghai 200092, China
b
Shenzhen Branch of China National Offshore Oil Corporation, Guangzhou 510240, China

a r t i c l e i n f o a b s t r a c t

Article history: The deep-water area of the Pearl River Mouth Basin in the South China Sea has received much scientific
Received 9 June 2015 attention since the Ocean Drilling Program (ODP) Leg 184 in 1999 due to its potential economic prospects
Received in revised form and distinct tectono-sedimentary evolutionary processes. In this study, we present the composition of
16 May 2016
major and trace elements from two newly sampled deep-water boreholes (BY6 and LW3) in the Baiyun
Accepted 12 December 2016
Available online 14 December 2016
Sag of the southern Pearl River Mouth Basin. The geochemical evolution in the OligoceneeMiddle
Miocene, as well as potential controlling factors, are investigated based on a comparative study with
previous data from ODP site 1148 and borehole PY33. The Chemical Index of Alteration (CIA) and AeCN
Keywords:
South China sea
eK plot reveal that the observed weathering trends are not compatible for the four discussed boreholes.
Pearl River Mouth Basin Sedimentary sorting is primarily observed in borehole PY33, where data trend away from the A apex to
Deep-water the feldspar join in the AeCNeK plot and show a spread of Al2O3/SiO2 and Nb/Zr ratios. Compared to
Geochemistry chemical weathering and hydrodynamic sorting, provenance has a greater impact on sediment
composition of the deep-water area. From the north, the Pearl River was the primary sediment supply.
However, a positive Eu anomaly and the provenance discrimination diagrams (i.e., La/Th versus Th/Yb
and Zr/Co versus Th/Co) reveal the mafic nature of borehole BY6 sediments in the ZhuhaieLower Zhu-
jiang (32.0e18.5 Ma) and Upper Hanjiang (13.8e10.5 Ma) formations. These compositions are unusual
and differ from the well-defined felsic sources in the majority of the Baiyun Sag; these discrepancies are
likely related to multistage magmatism. The sediments at site 1148 are characterized by slightly enriched
heavy rare earth elements and relatively high Zr/Co ratios, which could possibly be caused by zircon
enrichment from local sources.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction crustal evolution (McLennan et al., 1993; Nesbitt et al., 1996;

Following the golden period of mineralogical analysis in the
mid-20th century, major advancements have been made in the use
of bulk elemental analysis to provide quantitative insights into
siliciclastic sediments and sedimentary rocks. Extensive
geochemical studies have greatly widened the knowledge of sedi-
mentary provenance, tectonic setting, and weathering, as well as
* Corresponding author. State Key Laboratory of Marine Geology, Tongji
University, 1239 Siping Road, Shanghai 200092, China.
** Corresponding author. State Key Laboratory of Marine Geology, Tongji
University, 1239 Siping Road, Shanghai 200092, China.
E-mail addresses: licheng.cao@gmail.com (L. Cao), qiaopeijun@tongji.edu.cn
(P. Qiao).
McLennan, 2001). Although detrital single-grain analysis is gain-
ing popularity, whole-rock geochemistry is still worthwhile
because of its wide applicability and holistic viewpoint. At the same
time, the ever-increasing compositional databases and numer-
icalestatistical analyses steadily facilitate the revision and inven-
tion of various geochemical diagrams and proxies (e.g., Sohn, 2013;
Verma and Armstrong-Altrin, 2013).
Our understanding regarding the geological evolution of the
South China Sea has benefited greatly from previous studies on the
Ocean Drilling Program (ODP) Leg 184 in FebeApril 1999. The
oldest sedimentary record of the Early Oligocene age, recovered
from site 1148 (Fig. 1), provides excellent material for exploring the
Asian Monsoon (Shipboard Scientific Party, 2000; Clift et al., 2014).
Early geochemical studies on this site have revealed several

http://dx.doi.org/10.1016/j.marpetgeo.2016.12.010
0264-8172/© 2016 Elsevier Ltd. All rights reserved.
 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
Fig. 1. Bathymetric map of the study area in the northern South China Sea showing the location of two sampled boreholes (BY6 and LW3; stars) and simplified geological map of the
Pearl River drainage basin. Topography data are from Ryan et al. (2009). The tectonic units of the Pearl River Mouth Basin are shown: BYS, Baiyun Sag; CSD, Chaoshan Depression;
DSU, Dongsha Uplift; LWS, Liwan Sag; NU, Northern Uplift; PYLU, Panyu Low-uplift; SHU, Shenhu Uplift; Z1D, Zhu-1 Depression; Z2D, Zhu-2 Depression; Z3D, Zhu-3 Depression.
Previous borehole PY33 and ODP site 1148 are also displayed with circles.
occurrences of compositional variations in the Oligocene strata (Li
et al., 2003; Shao et al., 2004), but the interpretation of their syn-
rift sedimentary provenance remains controversial. For example,
Li et al. (2003) and Wei et al. (2012) propose a southern provenance
from either Northwest Borneo or North Palawan, whereas com-
bined evidence from clay mineralogy, Nd isotopes, and palynology
(e.g., Clift et al., 2002; Wu et al., 2003; Shao et al., 2008) suggests a
northern source from South China. Notwithstanding the uncer-
tainty of sedimentary source, elemental concentrations and ratios
of the Miocene transgressive deposits remain largely constant
across studies. Although most researchers interpret this as a rela-
tively stable provenance from the Pearl River (Li et al., 2003; Wei
et al., 2012), another plausible explanation could be that site 1148
is far away from the main sedimentary body, rendering its
composition relatively insensitive to provenance and eustatic sea
level change (Pang et al., 2006a). The modern Pearl River is the
largest river at the northern margin of the South China Sea (Fig. 1),
with a drainage area of 490,000 km2 and a discharge of 260 km3/a
(Milliman and Farnsworth, 2011). Lithology within the Pearl River
drainage basin is complicated, but largely consists of carbonate and
sedimentary rocks in the upstream region and acidic igneous rocks
in the coastal area of South China (Fig. 1). Sediment composition
derived from the Pearl River seems to have changed since the
Oligocene, possibly due to the stepwise westward expansion of the
Pearl River drainage basin in the Miocene (Shao et al., 2013b) as
well as the anthropogenic activities in the Holocene (Hu et al.,
2013).
Before the mid-1990s, a lack of knowledge regarding regional
geology resulted in multiple failures of deep-water exploration
efforts in the Pearl River Mouth Basin (Pang et al., 2007). Although
it was once believed that the deep-water area lacked economic
prospects, sandy sources from the large-scale Pearl River delta
system could be abundant. Following the discovery of natural gas
reservoirs (e.g., borehole PY33; Fig. 1) on the northern side of
continental slope (Pang et al., 2006b), the geological evolution of
the deep-water area has received widespread attention. Extensive
seismic surveys reveal that the deep-water depressions actually
359
experienced more complex tectono-sedimentary evolution than
revealed during early studies of site 1148. This includes anomalous
post-rift subsidence (Xie et al., 2006, 2014), unidirectional migra-
tion of submarine canyons (Zhu et al., 2010; Ding et al., 2013; Gong
et al., 2013), and episodic intrusions of magma and fluid (Sun et al.,
2012, 2014a). However, geochemical analysis in this area is still
scarce. In this study, we discuss the composition of major and trace
elements in OligoceneeMiddle Miocene sediments from two deep-
water boreholes (BY6 and LW3). Previous data from ODP site 1148
(Li et al., 2003) and commercial borehole PY33 (Shao et al., 2005,
2008) are compared with new data to fully evaluate the regional-
scale implications for chemical weathering, hydrodynamic sort-
ing, sedimentary provenance, and tectonics.
2. Geological setting
In this paper, the “deep-water area” refers to the area of bathyal
water depths (>200 m) in the northern South China Sea. The
sampled boreholes (BY6 and LW3) are located at the middle part of
the deep-water Baiyun Sag, at water depths of 1020 m and 1480 m,
respectively (Fig. 1). The Baiyun Sag is one of the largest depressions
in the Pearl River Mouth Basin with an area of approximately
20,000 km2. The maximum thickness of its Cenozoic sedimentary
sequences reaches 11 km, which can be partitioned into the flu-
vialelacustrineeneritic shelf facies of the Paleogene syn-rift and
the deep-water slopeebathyal facies of the Neogene post-rift
(Fig. 2; Pang et al., 2008).
Since the Late Cretaceous, the pre-existing Andean-type volca-
nic arc has been replaced by the passive continental margin in the
South China Sea (Taylor and Hayes, 1983). The subsequent exten-
sional setting is explained by several driving mechanisms, such as
the Indochina extrusion, the proto-South China Sea subduction,
and the upwelling mantle plume (Leloup et al., 2001; Hall, 2002; Xu
et al., 2012). In the Early Oligocene (~33 Ma; Li et al., 2015), crustal
extension reached a point where seafloor spreading was initiated,
forming a widespread breakup unconformity in the South China
Sea (Taylor and Hayes, 1983). After a short period of uplift and
360 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
Fig. 2. Stratigraphic table of the study area (mainly modified from Pang et al., 2008) with subsidence rate (Xie et al., 2014), regional sea level curve (Pang et al., 2006a), and
sedimentation rate (Xie et al., 2013).
erosion (Barckhausen et al., 2014), the Upper Oligocene strata of the
Baiyun Sag developed during a transition of depositional environ-
ments, possibly due to the southward ridge jump at approximately
25 Ma and the spreading acceleration that followed (Barckhausen
and Roeser, 2004). A significant unconformity, spanning 2.5e3
Ma, marks the initiation of the post-rift stage after the Late Oligo-
cene (Shipboard Scientific Party, 2000). Radiometric dating of
newly sampled basement basalts from the International Ocean
Discovery Program (IODP) Leg 349 is still in progress, thus the time
that spreading stopped remains controversial (ranging from 21 to
16 Ma; Briais et al., 1993; Barckhausen et al., 2014).
During the Early Miocene, the fault activities in the Baiyun Sag
decreased compared to the rift stage (Shao et al., 2013a) but most of
the WNW-trending faults remained active (Sun et al., 2014b). Fast
subsidence began simultaneously (Fig. 2), possibly triggered by
episodic emplacement of igneous intrusions (Shi et al., 2005; Sun
et al., 2014a; Zhao et al., 2014) or divergent flow of ductile low-
eremiddle crust (Clift et al., 2015). This anomalous subsidence was
accompanied by relative sea level rise, in contrast to the global sea
level curve at that time (Fig. 2; Pang et al., 2006a). Carbonate
platform growth favored by the Early Miocene transgression soon
ceased due to partial drowning events (Sattler et al., 2009; Fyhn
et al., 2013). By the Middle Miocene, a typical bathyal environ-
ment had already formed in the Baiyun Sag where the continuously
increasing accumulation space trapped a large volume of sediments
(Fig. 2; Xie et al., 2013). Meanwhile, a series of downslope-
extending channel systems developed on the northern continen-
tal slope (Ding et al., 2013; Gong et al., 2013). Another unconformity
overlaying the Middle Miocene strata was likely caused by the
subductive compression from the Philippine Plate at approximately
10.5 Ma. This tectonic reactivation caused regional fault activities,
compressive uplift, and erosion in the northern South China Sea
(Sun et al., 2014b).
3. Borehole description and analytical methods
The commercial boreholes BY6 and LW3 are owned by China
National Offshore Oil Corporation (CNOOC) and are located at the
western and eastern sides of the Baiyun Sag, respectively (Fig. 1).
Both of them are drilled into the Oligocene strata, but the shallow
sequence of the PlioceneeQuaternary was not logged by CNOOC
during drilling operations. Thus, the cored strata from bottom to
top are Zhuhai Formation (Oligocene), Zhujiang Formation (Lower
Miocene), Hanjiang Formation (Middle Miocene), and incomplete
Yuehai Formation (Upper Miocene) (Fig. 3). The ages of sequence
boundaries (Fig. 2) were determined by a combination of unpub-
lished seismic and palaeontological data from CNOOC.
The oldest sediments (Zhuhai Formation) in borehole BY6, from
5192 to 4539 m measured depth (MD), mainly consist of reddish-
brown to gray mudstones with intercalated layers of extrusive
rocks at the top and fine sandstones at the bottom (Fig. 3). The
overlying Zhujiang Formation can be divided lithologically into two
parts: the composite of limestones, mudstones, and interbedded
marlstones in the lower 4539e4046 m MD, and the gray to greyish
green mudstones in the upper 4046e3237 m MD. The Zhujiang
Formation is overlain by gray to blue-green mudstones (Hanjiang
Formation), with a thickness of 1172 m, which is locally inter-
bedded with silty mudstones and fine sandstones. The youngest
cored succession is a thin layer of silty mudstones (2065e2000 m
MD) from the Yuehai Formation.
A 2043 m-thick sedimentary sequence was cored in borehole
LW3 (Fig. 3). The Zhuhai Formation sediments (3843e3128 m MD)
differ from those of borehole BY6 and are mainly composed of
interbedded gray mudstones and fine sandstones. The overlaying
 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
Fig. 3. Lithostratigraphic column drilled at boreholes BY6 and LW3 and sampling
depths (dots) for chemical analysis. Core depths of different sequence boundaries in
each borehole are marked with *.
mudstones of the Zhujiang Formation, from 3128 to 2745 m MD, are
poorly laminated and interbedded with thin layers of fine sand-
stones. The top sedimentary units of borehole LW3 belong to the
MiddleeUpper Miocene strata (2745e1800 m MD; Han-
jiangeYuehai Formation) and are largely composed of gray mud-
stones and silty mudstones.
Geochemical analyses were performed on clastic sediments of
the ZhuhaieHanjiang Formation. Because core samples are not
easily available from commercial boreholes, cuttings were also
sampled to supplement data from the core samples. To cover all
sediment lithologies and stratigraphic positions, a total of 158 and
253 samples were selected from boreholes BY6 and LW3, respec-
tively (Fig. 3). All sample preparation and chemical analyses were
carried out at the State Key Laboratory of Marine Geology, Tongji
University, China. Bulk sediments were first washed with deionized
distilled water. To prevent external contamination of these small-
size samples, they were dried at 50
C for 48 h and then hand-
crushed in an agate mortar. Approximately 3 g of dry samples
were heated to 600
C for 2 h to remove organic matter and
interlayer water. Next, the samples were dissolved in a HF-HNO3
mixture, and major and trace elements were measured using ICP-
AES (Thermo ICP-IRIS Intrepid II) and ICP-MS (Thermo X-Series),
361
respectively. Three certified materials (i.e., GSR-5, GSR-6, and GSD-
9; provided by the Institute of Geophysical and Geochemical
Exploration, China) were repeatedly analyzed as unknown samples
to assess the precision and accuracy of the measurements. The
external precision (1s) was usually better than 5% and concentra-
tions obtained were in agreement with the recommended data of
these reference materials (Supplemental Data Table S1). Seven
sediment samples from this study were measured in duplicate, and
the relative differences in concentrations between duplicates were
usually lower than 5% (Supplemental Data Table S2). Detailed
analytical procedures are described by Li et al. (2003) and Wei et al.
(2006).
4. Results
Major and trace element concentrations of the Oligoce-
neeMiddle Miocene sediments from boreholes BY6 and LW3 are
presented in Supplementary Data Table S3. The variations in
abundance of representative elements (Fig. 4) reveal compositional
differences between the two boreholes. The elemental concentra-
tions of the Oligocene strata in borehole BY6 generally fluctuate at a
high frequency, whereas those of the coeval sediments in borehole
LW3 are relatively constant, except for the top of the Zhuhai For-
mation. It is noteworthy that the secular variation is not in accor-
dance with the formation subdivisions. Sediment compositions do
not seem to be maintained throughout each stage, which is espe-
cially evident in the Lower Miocene strata (Zhujiang Formation). In
borehole BY6, the Lower Zhujiang Formation shows a strong Ca
enrichment (33.1e49.0 wt%) and low contents of elements like Al,
Ti, rare earth element (REE), and Th. In contrast, the CaO content
becomes relatively low (3.5e19.3 wt%) in the Upper Zhujiang For-
mation and elemental abundance variations are not very signifi-
cant. This trend largely continues to the Lower Hanjiang Formation.
The contents of Al, REE, and Th in the Upper Hanjiang Formation are
slightly lower than those in the Lower Hanjiang Formation. Within
the Lower Zhujiang Formation of borehole LW3, elemental abun-
dances exhibit a gradual increase of Ca and a decrease of Al, Ti, REE,
and Th. Further upwards, three samples (analytical depths of 2398,
2408, and 2548 m MD) feature a remarkable Ca enrichment
(40.4e45.6 wt%) and depletion of other elements. These data are
abnormal with respect to the minimal change in elemental abun-
dances throughout the entire Upper ZhujiangeHanjiang Formation
and were not considered in further analysis. The large difference of
compositional signals within a single sedimentary succession has
been observed in previous provenance studies by Wang et al. (2015)
and Zimmermann et al. (2015). To facilitate later data presentation
and discussion, the sedimentary units were tentatively grouped
into five intervals (i.e., Zhuhai Formation, Lower Zhujiang Forma-
tion, Upper Zhujiang Formation, Lower Hanjiang Formation, and
Upper Hanjiang Formation) that largely match the trends in vari-
ation (Fig. 4).
4.1. Major elements
Fig. 5 shows the ternary diagram of the relative proportions of
Ca, Al, and Si. The majority of discussed data plot near the Si apex,
showing the dominance of detrital silicates in these sediments. The
LW3 data of the ZhuhaieUpper Hanjiang Formation mostly cluster
together, with average Si and Al concentrations of 60.4 and 15.9 wt
%, respectively. In contrast, some of the BY6 samples, especially
those from the Lower Zhujiang Formation, are clearly separate from
this cluster due to Ca dilution (Fig. 4), which can be correlated with
limy components in sedimentary sequences (Fig. 3). Ca enrichment
is observed in both boreholes from the plot of Upper Continental
Crust (UCC; Rudnick and Gao, 2003) normalized elemental
362 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
Fig. 4. Comparative variations of selected elemental abundances and ratios in Oligo-
ceneeMiddle Miocene sediments from boreholes BY6 and LW3.
distribution (Fig. 6). Aside from the Ca enrichment and Na deple-
tion, the UCC normalized values of the other major elements in LW3
Fig. 5. Ternary diagram showing the relative concentrations of Ca, Al, and Si of Oli-
goceneeMiddle Miocene sediments from boreholes BY6 and LW3. The sum of three
components (wt%) has been normalized to 100.
are close to 1. In borehole BY6, most of the major elements (except
Ca) of the Lower Zhujiang Formation generally display a slight
depletion, whereas Fe2O3 of the Upper Hanjiang Formation and
MgO and MnO of the Zhuhai Formation are enriched.
4.2. Trace elements
The selected trace elements from each stratum in LW3 show a
similar distribution pattern in the UCC normalized plot, with
moderate enrichment of Rb, Cs, and Th (Fig. 6). Most of the LW3
samples do not show much variation in the REE concentrations
P
(average REE ¼ 186.0 ppm; Fig. 4), as revealed in the plot of
Chondrite (Sun and McDonough, 1989) normalized distribution
(Fig. 7). This plot shows a light REE enrichment (average (La/
Lu)N ¼ 11.1) with a negative Eu anomaly (average Eu/Eu* ¼ 0.8;
Fig. 4). The trace element distributions of the Upper Zhu-
jiangeLower Hanjiang Formation from BY6 largely resemble those
in LW3. However, significant deviations can be observed for the
other strata in BY6, which have a slight to moderate depletion of
trace elements (Fig. 6). The markedly low content of REE is seen in
the Lower Zhujiang Formation due to the Ca dilution effect (Figs. 4
and 7). Meanwhile, the Eu anomalies in these sediments are highly
positive, with the average Eu/Eu* values ranging from 1.4 (Upper
Hanjiang Formation) to 9.4 (Lower Zhujiang Formation) (Fig. 4).
5. Discussion
5.1. Controls on geochemical composition
Borehole PY33 was cored at a water depth of 186.5 m, which
largely corresponds to the location between the northern conti-
nental slope and shelf (Fig. 1). Site 1148 of ODP Leg 184 is positioned
in an ultra-deep-water area, at a water depth of 3294 m. The
comparison of geochemical compositions from these two boreholes
 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368 363

Fig. 6. Upper Continental Crust (UCC; Rudnick and Gao, 2003) normalized major and trace elements of OligoceneeMiddle Miocene sediments from boreholes BY6 and LW3. The
standard deviation of elemental concentrations is given as upper error bar.

Fig. 7. Chondrite (Sun and McDonough, 1989) normalized rare earth element (REE) concentrations of OligoceneeMiddle Miocene sediments from the northern South China Sea. The
standard deviation of REE contents is shown as upper error bar.

with our new BY6 and LW3 data contributes to our overall under-
standing of the geological history of the deep-water area in the
northern South China Sea. Chemical data from ODP Leg 184 site
1146 (water depth of 2092 m; Liu et al., 2013) were not taken into
account due to absence of the Oligocene sedimentary record. All
geochemical data of boreholes 1148 and PY33 are derived from the
previous studies of Li et al. (2003) and Shao et al. (2005, 2008). The
methods of chemical analysis for the four discussed boreholes are
largely similar (Li et al., 2003), and would not bias the comparison
between these studies. A series of diagrams and parameters were
employed to explore potential controls on geochemical composi-
tion. Because the age model of commercial boreholes (BY6, LW3,
and PY33) is not as precise as that of ODP site 1148, a detailed inter-
borehole comparison with respect to specific time periods could
not be achieved in this study. The geochemical data from boreholes
1148 and PY33 were similarly partitioned into five intervals from
the Zhuhai Formation to the Upper Hanjiang Formation.
5.1.1. Chemical weathering
Chemical weathering normally involves a conversion of volcanic
glass and unstable minerals, like feldspar and mica, to clay, and can
be evaluated by the characteristics of alkali and alkaline earth
elements. Although diagenesis may also participate in a similar
manner in mineralogical conversion, it tends to be difficult to
discriminate between these two processes geochemically
(McLennan et al., 1993). The Chemical Index of Alteration (CIA)
introduced by Nesbitt and Young (1982) is widely utilized to
quantitatively measure the removal of mobile cations (e.g., Ca2þ,
Naþ, and Kþ) relative to residual constituents, such as Al3þ, during
chemical weathering. The index is calculated by the equation:
CIA ¼ molar [Al2O3/(Al2O3 þ CaO* þ Na2O þ K2O)]  100, where
CaO* represents the CaO content of silicate minerals. In order to
avoid overcorrection of the measured CaO content (Garzanti and
Resentini, 2015), we adopt the method of McLennan (1993) and
use the minimum value of CaO and Na2O to represent CaO*. The CIA
value, along with other chemical and clay proxies from ODP 184
sites, reveal a gradual decline in chemical alteration since the Early
Miocene (Clift et al., 2014) likely resulting from the global cooling
effect. In this study, the CIA values of the Upper ZhujiangeHanjiang
Formation in BY6 show a steady decrease ranging from 83.2 to 69.1
(Fig. 4), which is largely compatible with the CIA results of site 1148
(73.5e78.3). As for the deeper sediments of borehole BY6, two
sharp drops in CIA within the ZhuhaieLower Zhujiang Formation
are followed by a maximum at approximately 18.5 Ma. In contrast,
364 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
the CIA values of each stratum within LW3 do not exhibit much
variation (average value ¼ 68.3; Fig. 4), indicating a relatively
moderate weathering intensity since the Oligocene.
In the Al2O3e(CaO*þNa2O)eK2O ternary diagram (i.e., AeCNeK
diagram; Fig. 8), the weathering trend of the Upper Zhu-
jiangeUpper Hanjiang Formation in BY6 largely parallels the AeCN
boundary, suggesting a dominance of chemical weathering on
plagioclase. Plagioclase is more susceptible to destruction than K-
feldspar, which leads to a preferential leaching of Ca2þ and Naþ
over Kþ (Nesbitt and Young, 1984, 1989). The data of the Zhu-
haieLower Zhujiang Formation deviate from this predicted
weathering trend by intersecting the AeCN boundary, indicating a
mixed control on alkali and alkaline earth elements. The LW3 data
generally overlap along the line of predicted weathering trend, but
the weathering intensity of each formation cannot be well distin-
guished. In comparison, data from boreholes PY33 and 1148 are
more irregularly distributed in the AeCNeK plot, and show clear
deviations from the weathering trend line. Based on both the CIA
values and AeCNeK plot, the weathering effect is not the sole or
primary factor modifying geochemical composition because the
observed weathering trends from the Oligocene to the Miocene are
not consistent among these four boreholes.
5.1.2. Sedimentary sorting
Sedimentary sorting usually results in a strong heterogeneity in
grain size, shape, and density of mineralogical composition and is
traditionally investigated at the macroscopic level. Although grain
size analysis was not conducted in this study, the effect of hydro-
dynamic sorting can still be geochemically monitored to a certain
degree. Recent studies on drainage basins have demonstrated
quantitatively that sorting processes lead to significant geochem-
ical and isotopic variability between different grain size fractions
(Garzanti et al., 2009; Garçon et al., 2014). Heavy minerals, such as
zircon, are often deposited in sandy sediments on the continental
margin because of high densities and resistance to chemical
weathering and diagenetic processes. Thus, Zr depletion indicated
by a high Nb/Zr ratio is a common feature of deep-water sediments
due to the “zircon effect” (Carpentier et al., 2009). Coarse-grained
sediments also tend to contain high contents of quartz and feld-
spar, and thus a low Al2O3/SiO2 ratio, while clay-sized minerals (i.e.,
high Al2O3/SiO2) are usually abundant in fine-grained components.
Fig. 8. Al2O3e(CaO*þNa2O)eK2O (AeCNeK) ternary diagram of OligoceneeMiddle Miocene sediments from the northern South China Sea. All components are calculated in molar
units. The compositions of Upper Continental Crust (UCC; Rudnick and Gao, 2003) and other minerals (Nesbitt and Young, 1984, 1989) are plotted for reference.
Al hosted mainly in slow-settling fine-grained and platy phyllosi-
licates, decreases with increasing grain size, whereas Na and Ca
hosted largely in faster-settling plagioclase increase, and K hosted
in both phyllosilicates and K-feldspar remains roughly constant
(Garzanti and Resentini, 2015). Consequently, the CIA value can
decrease markedly with grain size resulting in an apparent
decrease in chemical weathering intensity (Zhou et al., 2015).
However, CIA values of our samples were not seriously biased by
the grain size of bulk sediments. For example, the intercalated
layers of fine sandstones from the bottom of borehole BY6 (Zhuhai
Formation; Fig. 3) do not show distinctly lower CIA values
compared with those of the overlying mudstones from the Upper
ZhujiangeUpper Hanjiang Formation (Fig. 4).
During the Early Miocene marine transgression (Fig. 2), fine-
grained components with high Nb/Zr and Al2O3/SiO2 ratios were
presumed to dominate the sediments in the Baiyun Sag under the
gradually developed deep-water environment. However, the BY6
samples from the Upper ZhujiangeUpper Hanjiang Formation are
characterized by decreases in both Al2O3/SiO2 (0.10e0.38) and Nb/
Zr (0.08e0.26) ratios (Fig. 9), which likely indicates a gradually
coarsening trend with Zr enrichment. A similar decrease in Nb/Zr
(0.11e0.13) ratios is also found in the coeval sediments from site
1148 regardless of largely invariant Al2O3/SiO2 ratios (average
value ¼ 0.22). Thus, these geochemical variations are most likely
caused by sedimentary source rather than sorting effect. The BY6
data of the ZhuhaieLower Zhujiang Formation are rather scattered,
which may be due to lithological diversity (Fig. 3). The Miocene
data (Lower ZhujiangeUpper Hanjiang Formation) from LW3
generally cluster together, with average Al2O3/SiO2 and Nb/Zr ratios
of 0.29 and 0.15, respectively. However, the Oligocene data (Zhuhai
Formation) from this borehole deviate from this cluster with higher
Nb/Zr (0.13e0.23) ratios, possibly due to the relatively low Zr
concentration. The PY33 samples show a poorly defined tendency
of decreasing Nb/Zr ratios from the Zhuhai Formation to the Upper
Hanjiang Formation. The high enrichment of SiO2 (average
value ¼ 70.0 wt%) in PY33 leads to generally low ratios of Al2O3/
SiO2. At the same time, the fluctuation in grain size within each
formation in PY33, as indicated by the large range of Al2O3/SiO2
ratios (0.02e0.26), could be related to the relatively turbulent hy-
drodynamic environment on the continental shelf (Fig. 1). This
notion is supported by the AeCNeK plot (Fig. 8), where some PY33
 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
Fig. 9. Al2O3/SiO2 versus Nb/Zr plot showing possible variations of grain size and “zircon effect” (Carpentier et al., 2009). One anomalous value (0.10, 1.61) of the Lower Zhujiang
Formation in BY6 is not plotted.
samples (especially those from the ZhuhaieLower Zhujiang For-
mation) trend away from the A apex towards the feldspar join
(Nesbitt et al., 1996).
5.1.3. Detrital provenance
Conservative elements are normally concentrated in refractory
minerals or absorbed by clay-sized minerals during the sedimen-
tary processes (McLennan et al., 1993). Selected trace elements
(e.g., REE, Sc, and Th) have been effectively applied to the prove-
nance studies of the northern South China Sea, as evident by recent
work on the Neogene sediments of the Yinggehai and Qiongdon-
gnan basins (Shao et al., 2010; Zhao et al., 2015) and the surface
sediments of the continental shelf (Wang et al., 2014). Most of the
LW3 and PY33 samples have highly similar Chondrite normalized
REE distributions (Fig. 7). The common Eu depletion and light REE
enrichment are also found in the 1148 samples, despite relatively
flat normalized curves of heavy REE. Meanwhile, the Lower Zhu-
jiang Formation in PY33 and the Zhuhai Formation in 1148 are
characterized by relatively low REE abundances, with average
values of 73.9 and 53.8 ppm, respectively. Even more noteworthy is
the sharp change in Eu anomalies in BY6, suggesting a shift in po-
tential provenances. Normally, the positive Eu anomaly of clastic
sediments can be attributed to either a mafic source or local
abundance of framework mineral plagioclase by sorting processes
(Clift et al., 2008; Shao et al., 2010). However, the later explanation
is unlikely because these data clearly do not plot along the pro-
jected direction of the A apex towards the feldspar join in the
AeCNeK plot (Fig. 8). Moreover, the separation of feldspar from
fine-grained components does not necessarily lead to the Eu
enrichment, as is the case for the PY33 samples (Fig. 7).
To further discriminate the nature of potential source rocks, La/
Th versus Th/Yb and Zr/Co versus Th/Co diagrams (McLennan et al.,
1980, 1993) were plotted (Fig. 10). The samples of the Zhu-
haieLower Zhujiang Formation in BY6 are distinct from those of the
Upper ZhujiangeLower Hanjiang Formation in both diagrams,
largely showing compositional variations towards more mafic
characteristics. The data of the Upper Hanjiang Formation, which
maintain a felsic distribution in the La/TheTh/Yb plot, can still be
distinguished by slightly decreased Th/Co and Zr/Co values. This
rare mafic indication agrees with the relatively small average pos-
itive Eu anomalies (1.4; Fig. 7). All of the LW3 samples feature high
Th/Yb, Th/Co, and Zr/Co ratios and low La/Th ratios, with a small
increase in felsic nature from the Miocene to the Oligocene (Fig. 10).
This trend is not observed in the PY33 samples despite similar
distribution ranges in both provenance diagrams. In contrast, the
1148 samples are different, with lower average Th/Yb ratios (4.6)
and higher average Zr/Co ratios (18.2). Higher Zr concentrations
365
(average value ¼ 128.4 ppm) combined with the gentle enrichment
of heavy REE (Fig. 7) may represent the occurrence of a large per-
centage of fine-grained zircons at site 1148. This oceanward Zr
enrichment is contrary to the predicted “zircon effect” of Carpentier
et al. (2009), and may be attributed to sediment supply from local
provenances. Thus, further provenance analysis of site 1148 is
required to determine if its sediments were sourced from the Pearl
River as previously inferred.
5.2. Tectonic and magmatic implications
Provenance and weathering studies are very common for sedi-
mentary rocks and sediments, whereas some doubts exist
regarding the discrimination of tectonic setting by chemical means
of detrital components (e.g., Ryan and Williams, 2007; von
Eynatten and Dunkl, 2012). This partially results from the fact
that chemical composition is constantly modified by multiple fac-
tors and tectonic processes may not be discernible from discrimi-
nation diagrams. Despite this, major-element-based diagrams are
still extensively utilized to extract tectonic information of unknown
sedimentary basins. Amongst existing diagrams, the Roser and
Korsch (1986) diagram performs better than others (Verma and
Armstrong-Altrin, 2013) and was employed to aid tectonic
discrimination of the northern South China Sea sediments (Fig. 11).
However, it still should be noted that the predicted tectonic setting
in sedimentary basin may correspond to the parent rocks from
which the clastic sediments were derived, and not the present
framework (Verma and Armstrong-Altrin, 2013). This phenomenon
can be exemplified by a recent geochemical study on the Meihe
Basin sediments from Northeast China (Bai et al., 2015). In the
current study, a large amount of the BY6, LW3, and PY33 data plot
within the field of active continental margin in the SiO2 versus K2O/
Na2O diagram (Fig. 11). This differs from the actual extensional
setting of the OligoceneeMiddle Miocene South China Sea (Taylor
and Hayes, 1983). Despite this inaccuracy, the BY6 data of the
ZhuhaieLower Zhujiang Formation and Upper Hanjiang Formation
can still be distinguished from those of the Upper ZhujiangeLower
Hanjiang Formation based on the lower SiO2 content.
During the Oligocene (32.0e23.8 Ma), the sediments from the
four boreholes were generally deposited in an environment ranging
from shelf delta to continental slope (Shao et al., 2008). The shelf
break was largely situated at the southern boundary of the Baiyun
Sag (Pang et al., 2009). As revealed by a large set of southward
progradational reflections in early seismic studies, the majority of
the Baiyun Sag received an abundant supply of sandy clastic sedi-
ments from the Pearl River (Pang et al., 2007; Xie et al., 2013). Apart
from minor modifications due to weathering and sorting effects,
366 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
Fig. 10. La/Th versus Th/Yb and Zr/Co versus Th/Co plots for the source discrimination of felsic and mafic characters (McLennan et al., 1980, 1993).
the geochemical compositions of LW3 and PY33 are comparable as
shown by REE distribution patterns and provenance discrimination
diagrams (Figs. 7 and 10). Farther south, sediment composition at
site 1148 clearly differs from that in the Baiyun Sag, with lower REE
concentrations and Zr enrichment likely caused by local sources.
Most of the BY6 data of the Oligocene strata (Zhuhai Formation)
display positive Eu anomalies (Fig. 7) and compositional variations
towards unweathered mafic rocks (Figs. 8 and 10). Combined with
the occurrence of intercalations of extrusive rock (Fig. 3), these
features seem to be related to basaltic magmatism in the peripheral
region of the South China Sea during the seafloor spreading process
(Huang et al., 2012). However, this magmatism was most likely
distributed at a local scale, as there was no obvious influence on
sediments in other boreholes.
In the early Early Miocene (23.8e18.5 Ma), the mafic prove-
nance still dominated the sediment composition of the Lower
Zhujiang Formation in BY6 (Fig. 10). These sediments, however,
have a more significant Eu enrichment compared to the Oligocene
sediments (Fig. 7). This compositional change tends to represent
the provenance from igneous intrusions rather than basaltic ex-
trusions, based on the gradual attenuation of extension in the
northern South China Sea shortly following the southward jump of
spreading ridge (Barckhausen et al., 2014). Evidence from seismic
data recorded a number of discordant high-amplitude anomalies
and associated volcanic mounds, although they are generally
recognized in the Middle Miocene strata (Sun et al., 2014a; Zhao
et al., 2014). The emplacement of dense intrusive bodies in the
thick Neogene sediments could be linked to acceleration of post-rift
subsidence (Shi et al., 2005; Xie et al., 2006). Clift et al. (2015)
recently proposed that the climatically controlled sediment load
is the direct cause of this substantial subsidence. However, this
model is at least incompatible with the low sedimentation rate
during the Early Miocene (Fig. 2; Xie et al., 2013). Along with
anomalous subsidence, a rapid rise in regional sea level began at
that time, leading to an abrupt change in sedimentary
environments of the Baiyun Sag (Pang et al., 2008; Shao et al.,
2008).
By the late Early Miocene (18.5e16.5 Ma) the continental shelf
break had largely retreated to the northern boundary of the Baiyun
Sag (Pang et al., 2009). Eu anomalies and other provenance dia-
grams (Figs. 7 and 10) for the Upper Zhujiang Formation of borehole
BY6 show a disappearance of the mafic nature of sedimentary
provenance. The Baiyun Sag and southern deep-water area were
dominated by felsic provenances. By the Middle Miocene, the
seafloor spreading in the South China Sea had already ceased (Li
et al., 2015). However, the reactivation of igneous provenance can
still be observed at regional scales during 13.8e10.5 Ma. This is
exemplified by the slightly mafic character of sediment composi-
tion from borehole BY6 (Fig. 10).
6. Conclusions
A comparison of major and trace elements of OligoceneeMiddle
Miocene sediments from the deep-water area in the northern
South China Sea reveals potential controls on the geochemical
evolution. The AeCNeK plot clearly shows that the data from the
four boreholes do not plot regularly along the predicated weath-
ering trend and the inter-formation variations are not consistent
(Fig. 8), suggesting other compositional modifications in addition to
chemical weathering. One possible factor is the sorting effect,
which is evident in borehole PY33 where the data trend away from
the A apex to the feldspar join in the AeCNeK plot; these samples
also feature large ranges in Al2O3/SiO2 and Nb/Zr ratios (Fig. 9).
Another more important factor is the sedimentary source. The
majority of the Baiyun Sag was continuously dominated by felsic
provenances from the Pearl River. In contrast, the sediments at site
1148 are characterized by slightly enriched heavy REE, relatively
high Zr/Co ratios, and low La/Th ratios (Figs. 7 and 10), which may
indicate Zr enrichment from local source areas. Meanwhile, Eu
anomalies, as well as provenance discrimination diagrams, reveal
 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
Fig. 11. SiO2 versus K2O/Na2O diagram for tectonic setting discrimination (Roser and Korsch, 1986). The major oxides data plotted here have been recalculated to 100% volatile-free.
multistage magmatic activities at borehole BY6. Apart from the
spreading-related basaltic extrusions during the Oligocene, mafic
intrusions are expected to cause Eu enrichment in the Lower
Zhujiang Formation (23.8e18.5 Ma) and Upper Hanjiang Formation
(13.8e10.5 Ma). The Miocene magmatism in the northern South
China Sea may have contributed to accelerated post-rift subsidence,
as well as facilitated fluid migration and hydrocarbon
accumulation.
Acknowledgements
We are grateful of Shenzhen Branch of China National Offshore
Oil Corporation for providing borehole samples and geological data.
This work is supported by the National Natural Science Foundation
of China (Grant No. 41576059 and 91128207) and the National
Science and Technology Major Projects (Grant No. 2011ZX05025-
006-02). The manuscript greatly benefited from detailed and
constructive comments made by Damien Do Couto and an anony-
mous reviewer. Robert Ondrak is thanked for careful suggestions
and editorial handling.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.marpetgeo.2016.12.010.
References
Bai, Y., Liu, Z., Sun, P., Liu, R., Hu, X., Zhao, H., Xu, Y., 2015. Rare earth and major
element geochemistry of Eocene fine-grained sediments in oil shale- and coal-
bearing layers of the Meihe Basin, Northeast China. J. Asian Earth Sci. 97 (Part
A), 89e101.
Barckhausen, U., Engels, M., Franke, D., Ladage, S., Pubellier, M., 2014. Evolution of
the South China Sea: revised ages for breakup and seafloor spreading. Mar. Pet.
Geol. 58 (Part B), 599e611.
Barckhausen, U., Roeser, H.A., 2004. Seafloor spreading anomalies in the South
China Sea revisited. In: Clift, P., Kuhnt, W., Wang, P., Hayes, D. (Eds.), Continent-
ocean Interactions within East Asian Marginal Seas. American Geophysical
Union,, Washington, D. C., pp. 121e125
Briais, A., Patriat, P., Tapponnier, P., 1993. Updated interpretation of magnetic
anomalies and seafloor spreading stages in the south China Sea: implications
for the Tertiary tectonics of Southeast Asia. J. Geophys. Res. 98, 6299e6328.
Carpentier, M., Chauvel, C., Maury, R.C., Mattielli, N., 2009. The “zircon effect” as
recorded by the chemical and Hf isotopic compositions of Lesser Antilles forearc
sediments. Earth Planet. Sci. Lett. 287, 86e99.
Clift, P., Lee, J.I., Clark, M.K., Blusztajn, J., 2002. Erosional response of South China to
arc rifting and monsoonal strengthening; a record from the South China Sea.
Mar. Geol. 184, 207e226.
Clift, P.D., Brune, S., Quinteros, J., 2015. Climate changes control offshore crustal
structure at South China Sea continental margin. Earth Planet. Sci. Lett. 420,
66e72.
Clift, P.D., van Hoang, L., Hinton, R., Ellam, R.M., Hannigan, R., Tan, M.T., Blusztajn, J.,
Duc, N.A., 2008. Evolving east Asian river systems reconstructed by trace
element and Pb and Nd isotope variations in modern and ancient Red River-
367
Song Hong sediments. Geochem. Geophys. Geosyst. 9, Q04039.
Clift, P.D., Wan, S., Blusztajn, J., 2014. Reconstructing chemical weathering, physical
erosion and monsoon intensity since 25 Ma in the northern South China Sea: a
review of competing proxies. Earth-Sci. Rev. 130, 86e102.
Ding, W., Li, J., Li, J., Fang, Y., Tang, Y., 2013. Morphotectonics and evolutionary
controls on the Pearl River Canyon system, South China Sea. Mar. Geophys. Res.
34, 221e238.
Fyhn, M.B.W., Boldreel, L.O., Nielsen, L.H., Giang, T.C., Nga, L.H., Hong, N.T.M.,
Nguyen, N.D., Abatzis, I., 2013. Carbonate platform growth and demise offshore
Central Vietnam: effects of Early Miocene transgression and subsequent
onshore uplift. J. Asian Earth Sci. 76, 152e168.
Garçon, M., Chauvel, C., France-Lanord, C., Limonta, M., Garzanti, E., 2014. Which
minerals control the Nd-Hf-Sr-Pb isotopic compositions of river sediments?
Chem. Geol. 364, 42e55.
Garzanti, E., Ando
, S., Vezzoli, G., 2009. Grain-size dependence of sediment
composition and environmental bias in provenance studies. Earth Planet. Sci.
Lett. 277, 422e432.
Garzanti, E., Resentini, A., 2015. Provenance control on chemical indices of
weathering (Taiwan river sands). Sediment. Geol. 336, 81e95.
Gong, C., Wang, Y., Zhu, W., Li, W., Xu, Q., 2013. Upper Miocene to quaternary
unidirectionally migrating deep-water channels in the Pearl River Mouth Basin,
northern South China Sea. AAPG Bull. 97, 285e308.
Hall, R., 2002. Cenozoic geological and plate tectonic evolution of SE Asia and the
SW Pacific: computer-based reconstructions, model and animations.pdf.
J. Asian Earth Sci. 20, 353e431.
€ ning, P., Hannigan, R., Hillier, S., Blusztajn, J., Wan, S., Fuller, D.Q.,
Hu, D., Clift, P.D., Bo
2013. Holocene evolution in weathering and erosion patterns in the Pearl River
delta. Geochem. Geophys. Geosyst 14, 2349e2368.
Huang, X.-L., Niu, Y., Xu, Y.-G., Ma, J.-L., Qiu, H.-N., Zhong, J.-W., 2012. Geochro-
nology and geochemistry of Cenozoic basalts from eastern Guangdong, SE
China: constraints on the lithosphere evolution beneath the northern margin of
the South China Sea. Contrib. Mineral. Petrol. 165, 437e455.
Leloup, P.H., Arnaud, N., Lacassin, R., Kienast, J.R., Harrison, T.M., Trong, T.T.,
Replumaz, A., Tapponnier, P., 2001. New constraints on the structure, thermo-
chronology, and timing of the Ailao Shan-Red River shear zone, SE Asia.
J. Geophys. Res. Sol. Ea. 106, 6683e6732.
Li, C.F., Lin, J., Kulhanek, D.K., Williams, T., Bao, R., Briais, A., Brown, E.A., Chen, Y.,
Clift, P.D., Colwell, F.S., Dadd, K.A., Ding, W.W., Herna ndez-Almeida, I.,
Huang, X.L., Hyun, S., Jiang, T., Koppers, A.A.P., Li, Q., Liu, C., Liu, Q., Liu, Z.,
Nagai, R.H., Peleo-Alampay, A., Su, X., Sun, Z., Tejada, M.L.G., Trinh, H.S., Yeh, Y.C.,
Zhang, C., Zhang, F., Zhang, G.L., Zhao, X., the Expedition 349 Scientists, 2015.
Expedition 349 summary. In: Li, C.-F., Lin, J., Kulhanek, D.K. (Eds.), Proceedings
of the International Ocean Discovery Program, vol. 349. South China Sea Tec-
tonics, College Station, TX, pp. 1e43. International Ocean Discovery Program.
Li, X.-h., Wei, G., Shao, L., Liu, Y., Liang, X., Jian, Z., Sun, M., Wang, P., 2003.
Geochemical and Nd isotopic variations in sediments of the South China Sea: a
response to Cenozoic tectonism in SE Asia. Earth Planet. Sci. Lett. 211, 207e220.
Liu, B., Wang, Y., Su, X., Zheng, H., 2013. Elemental geochemistry of northern slope
sediments from the South China Sea: implications for provenance and source
area weathering since Early Miocene. Chem. Erde-Geochem 73, 61e74.
McLennan, S.M., 1993. Weathering and global denudation. J. Geol. 101, 295e303.
McLennan, S.M., 2001. Relationships between the trace element composition of
sedimentary rocks and upper continental crust. Geochem. Geophys. Geosyst 2,
1021e1024.
McLennan, S.M., Hemming, S., McDaniel, D.K., Hanson, G.N., 1993. Geochemical
approaches to sedimentation, provenance, and tectonics. In: Johnsson, M.J.,
Basu, A. (Eds.), Processes Controlling the Composition of Clastic Sediments.
Geological Society of America, Colorado, pp. 21e40.
McLennan, S.M., Nance, W.B., Taylor, S.R., 1980. Rare earth element-thorium cor-
relations in sedimentary rocks, and the composition of the continental crust.
Geochim. Cosmochim. Acta 44, 1833e1839.
Milliman, J.D., Farnsworth, K.L., 2011. River Discharge to the Coastal Ocean: a Global
Synthesis. Cambridge University Press, New York.
368 L. Cao et al. / Marine and Petroleum Geology 80 (2017) 358e368
Nesbitt, H.W., Young, G.M., 1982. Early Proterozoic climates and plate motions
inferred from major element chemistry of lutites. Nature 299, 715e717.
Nesbitt, H.W., Young, G.M., 1984. Prediction of some weathering trends of plutonic
and volcanic rocks based on thermodynamic and kinetic considerations. Geo-
chim. Cosmochim. Acta 48, 1523e1534.
Nesbitt, H.W., Young, G.M., 1989. Formation and diagenesis of weathering profiles.
J. Geol. 97, 129e147.
Nesbitt, H.W., Young, G.M., McLennan, S.M., Keays, R.R., 1996. Effects of chemical
weathering and sorting on the petrogenesis of siliciclastic sediments, with
implications for provenance studies. J. Geol. 104, 525e542.
Pang, X., Chen, C., Peng, D., Zhou, D., Shao, L., He, M., Liu, B., 2008. Basic geology of
Baiyun deep-water area in the northern South China Sea. China Offsh. Oil Gas.
20, 215e222 (in Chinese with English abstract).
Pang, X., Chen, C., Peng, D., Zhu, M., Shu, Y., He, M., Shen, J., Liu, B., 2007. Sequence
stratigraphy of deep-water fan system of Pearl River, South China Sea. Earth Sci.
Front. 14, 220e229.
Pang, X., Chen, C., Wu, M., He, M., Wu, X., 2006a. The Pearl River deep-water fan
systems and significant geological events. Adv. Earth Sci. 21, 793e799 (in Chi-
nese with English abstract).
Pang, X., Chen, C., Zhu, M., He, M., Shen, J., Lian, S., Wu, X., Shao, L., 2009. Baiyun
movement: a significant tectonic event on Oligocene/Miocene boundary in the
northern South China Sea and its regional implications. J. Earth Sci. 20, 49e56.
Pang, X., Chen, C., Zhu, M., He, M., Shen, J., Liu, B., 2006b. A discussion about hy-
drocarbon accumulation conditions in Baiyun Deep-water Area, the northern
continental slope, South China Sea. China Offsh. Oil Gas. 18, 145e149 (in Chinese
with English abstract).
Roser, B.P., Korsch, R.J., 1986. Determination of tectonic setting of sandstone-
mudstone suites using SiO2 content and K2O/Na2O ratio. J. Geol. 94, 635e650.
Rudnick, R.L., Gao, S., 2003. Composition of the continental crust. In: Rudnick, R.L.
(Ed.), Treatise in Geochemistry, vol. 3. The Crust. Elsevier, Oxford, pp. 1e64.
Ryan, K., Williams, D., 2007. Testing the reliability of discrimination diagrams for
determining the tectonic depositional environment of ancient sedimentary
basins. Chem. Geol. 242, 103e125.
Ryan, W.B., Carbotte, S.M., Coplan, J.O., O'Hara, S., Melkonian, A., Arko, R.,
Weissel, R.A., Ferrini, V., Goodwillie, A., Nitsche, F., 2009. Global multi-
resolution topography synthesis. Geochem. Geophys. Geosyst. 10, Q03014.
Sattler, U., Immenhauser, A., Schlager, W., Zampetti, V., 2009. Drowning history of a
Miocene carbonate platform (Zhujiang Formation, South China Sea). Sediment.
Geol. 219, 318e331.
Shao, L., Lei, Y., Pang, X., Shi, H., 2005. Tectonic evolution and its controlling for
sedimentary environment in Pearl River Mouth Basin. J. Tongji Univ. Nat. Sci. 33,
1177e1181 (in Chinese with English abstract).
Shao, L., Li, A., Wu, G., Li, Q., Liu, C., Qiao, P., 2010. Evolution of sedimentary envi-
ronment and provenance in Qiongdongnan Basin in the northern South China
Sea. Acta Petrol. Sin. 31, 548e552 (in Chinese with English abstract).
Shao, L., Li, X., Wang, P., Jian, Z., Wei, G., Pang, X., Liu, Y., 2004. Sedimentary record of
the tectonic evolution of the South China Sea since the Oligocenedevidence
from deep sea sediments of ODP Site 1148. Adv. Earth Sci. 19, 539e544 (in
Chinese with English abstract).
Shao, L., Meng, X., Zhang, G., Liang, J., 2013a. Feature of faults system and its in-
fluence on tectonic and sedimentary history of Baiyun Sag. J. Tongji Univ. Nat.
Sci. 41, 1435e1441 (in Chinese with English abstract).
Shao, L., Pang, X., Chen, C., Shi, H., Li, Q., Qiao, P., 2008. Late Oligocene sedimentary
environments and provenance abrupt change event in the northern South
China Sea. Front. Earth Sci. China 2, 138e146.
Shao, L., Zhao, M., Qiao, P., Pang, X., Wu, M., 2013b. The characteristics of the
sediment in northern South China Sea and its response to the evolution of the
Pearl River. Quat. Sci. 33, 760e770 (in Chinese with English abstract).
Shi, X., Burov, E., Leroy, S., Qiu, X., Xia, B., 2005. Intrusion and its implication for
subsidence: a case from the Baiyun Sag, on the northern margin of the South
China Sea. Tectonophysics 407, 117e134.
Shipboard Scientific Party, 2000. Leg 184 summary: exploring the Asian monsoon
through drilling in the South China Sea. Initial Reports, College Station, TX. In:
Wang, P., Prell, W.L., Blum, P., et al. (Eds.), Proceedings of the Ocean Drilling
Program, pp. 1e97.
Sohn, R.A., 2013. A method for inverting ratioeratio data to estimate end-member
compositions in mixing problems. Chem. Geol. 352, 63e69.
Sun, Q., Wu, S., Cartwright, J., Dong, D., 2012. Shallow gas and focused fluid flow
systems in the Pearl River Mouth Basin, northern South China Sea. Mar. Geol.
315e318, 1e14.
Sun, Q., Wu, S., Cartwright, J., Wang, S., Lu, Y., Chen, D., Dong, D., 2014a. Neogene
igneous intrusions in the northern South China Sea: evidence from high-
resolution three dimensional seismic data. Mar. Pet. Geol. 54, 83e95.
Sun, S.-S., McDonough, W.F., 1989. Chemical and isotopic systematics of oceanic
basalts: implications for mantle composition and processes. Geol. Soc. Spec.
Publ. 42, 313e345.
Sun, Z., Xu, Z., Sun, L., Pang, X., Yan, C., Li, Y., Zhao, Z., Wang, Z., Zhang, C., 2014b. The
mechanism of post-rift fault activities in Baiyun sag, Pearl River Mouth basin.
J. Asian Earth Sci. 89, 76e87.
Taylor, B., Hayes, D.E., 1983. Origin and history of the South China Sea basin. Part 2.
In: Hayes, D.E. (Ed.), The Tectonic and Geologic Evolution of Southeast Asian
Seas and Islands. American Geophysical Union, Washington D.C., pp. 23e56
Verma, S.P., Armstrong-Altrin, J.S., 2013. New multi-dimensional diagrams for tec-
tonic discrimination of siliciclastic sediments and their application to Precam-
brian basins. Chem. Geol. 355, 117e133.
von Eynatten, H., Dunkl, I., 2012. Assessing the sediment factory: the role of single
grain analysis. Earth-Sci. Rev. 115, 97e120.
Wang, C., Liang, X., Xie, Y., Tong, C., Pei, J., Zhou, Y., Jiang, Y., Fu, J., Wen, S., 2015. Late
Miocene provenance change on the eastern margin of the Yinggehai-Song Hong
Basin, South China Sea: evidence from UePb dating and Hf isotope analyses of
detrital zircons. Mar. Pet. Geol. 61, 123e139.
Wang, S., Zhang, N., Chen, H., Li, L., Yan, W., 2014. The surface sediment types and
their rare earth element characteristics from the continental shelf of the
northern south China sea. Cont. Shelf Res. 88, 185e202.
Wei, G., Li, X.-H., Liu, Y., Shao, L., Liang, X., 2006. Geochemical record of chemical
weathering and monsoon climate change since the early Miocene in the South
China Sea. Paleoceanography 21, PA4214.
Wei, G., Liu, Y., Ma, J., Xie, L., Chen, J., Deng, W., Tang, S., 2012. Nd, Sr isotopes and
elemental geochemistry of surface sediments from the South China Sea: im-
plications for Provenance Tracing. Mar. Geol. 319e322, 21e34.
Wu, G., Jungan, Q., Mao, S., 2003. Deep-water Oligocene pollen record from South
China Sea. Chin. Sci. Bull. 48, 2511e2515.
Xie, H., Zhou, D., Li, Y., Pang, X., Li, P., Chen, G., Li, F., Cao, J., 2014. Cenozoic tectonic
subsidence in deepwater sags in the Pearl River Mouth Basin, northern South
China Sea. Tectonophysics 615e616, 182e198.
Xie, H., Zhou, D., Pang, X., Li, Y., Wu, X., Qiu, N., Li, P., Chen, G., 2013. Cenozoic
sedimentary evolution of deepwater sags in the Pearl River Mouth Basin,
northern South China Sea. Mar. Geophys. Res. 34, 159e173.
Xie, X., Muller, R., Li, S., Gong, Z., Steinberger, B., 2006. Origin of anomalous sub-
sidence along the Northern South China Sea margin and its relationship to
dynamic topography. Mar. Pet. Geol. 23, 745e765.
Xu, Y., Wei, J., Qiu, H., Zhang, H., Huang, X., 2012. Opening and evolution of the
South China Sea constrained by studies on volcanic rocks: preliminary results
and a research design. Chin. Sci. Bull. 57, 3150e3164.
Zhao, F., Wu, S., Sun, Q., Huuse, M., Li, W., Wang, Z., 2014. Submarine volcanic
mounds in the Pearl River Mouth Basin, northern South China Sea. Mar. Geol.
355, 162e172.
Zhao, M., Shao, L., Liang, J., Li, Q., 2015. No red river capture since the late Oligocene:
geochemical evidence from the northwestern South China Sea. Deep-Sea Res.
122 (Part II), 185e194.
Zhou, X., Li, A., Jiang, F., Lu, J., 2015. Effects of grain size distribution on mineral-
ogical and chemical compositions: a case study from size-fractional sediments
of the Huanghe (Yellow River) and Changjiang (Yangtze River). Geol. J. 50,
414e433.
Zhu, M., Graham, S., Pang, X., McHargue, T., 2010. Characteristics of migrating
submarine canyons from the middle Miocene to present: implications for
paleoceanographic circulation, northern South China Sea. Mar. Pet. Geol. 27,
307e319.
Zimmermann, U., Andersen, T., Madland, M.V., Larsen, I.S., 2015. The role of U-Pb
ages of detrital zircons in sedimentologydan alarming case study for the
impact of sampling for provenance interpretation. Sediment. Geol. 320, 38e50.