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Key Laboratory of Marine Sedimentology and Environmental Geology, First Institute of Oceanography, State Oceanic Administration, Qingdao 266061, China
Qingdao National Laboratory for Marine Science and Technology, Function Laboratory for Marine Geology and Environment, Qingdao 266071, China
Institute of Applied Geosciences, National Taiwan Ocean University, Keelung 20224, Taiwan
d
State Key Laboratory of Marine Environmental Science, Xiamen University, Xiamen 361005, China
e
Alfred-Wegener-Institut Helmholtz-Zentrum fr Polar- und Meeresforschung, Am AltenHafen 26, 27568 Bremerhaven, Germany
b
c
a r t i c l e
i n f o
Article history:
Received 3 February 2015
Received in revised form 25 June 2015
Accepted 14 July 2015
Available online 17 July 2015
Keywords:
Rare earth elements
Terrigenous detritus
Sea ice
Deep water ventilation
Mongolia High
Glacialinterglacial
Okhotsk Sea
a b s t r a c t
Sediment core OS03-1 retrieved from the Akademia Nauk Rise in Southern Okhotsk Sea was analyzed for
the contents of rare earth elements (REEs) and combined with carbon isotope (d13C) time series of benthic
foraminifera to infer changes in terrigenous accumulation and bottom water ventilation on glacialinterglacial timescales in the study area. The age model of OS03-1 was constructed by a combination of foraminifer d18O stratigraphy and 14C AMS dating, revealing that the 380 cm long core provides a window on
climate change in the southern Okhotsk Sea since 180 ka. A grain size-controlled-REE content shows
strong glacialinterglacial changes. The Cerium and Europium anomalies vary from 0.89 to 1.32 and from
1.14 to 1.37, respectively. The (La/Yb)N values range between 0.55 to 0.92. Both results suggest a significant contribution of volcanic debris in the core sediments. In addition, the relationships between Sm vs.
Nd suggest main contribution origin from the Amur River and sea ice during warm intervals and from the
sea ice during cold intervals, indicating that the sea ice played an important role in transporting terrigenous materials to the study site in the southern Okhotsk Sea. During the last 180 ka, the mass accumuP
lation rates (MAR) of REEs are relatively higher during glacials and lower during interglacials with a
peak accumulation during the early deglacial period. We infer that an intensied Mongolia High is
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responsible for the rst-order accumulation pattern of REEs in the southern Okhotsk Sea by mediating
the dynamic changes in sea ice extent. Furthermore, six d13C minima are associated with intensied Asian
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monsoon (AM) precipitation and maximum MARs of REEs, indicating that the dominance of barrier
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layer effects by high fresh water input through sea ice melting. The maximum MAR of REEs during
the Marine Isotope Stage (MIS) 5c coincides with the minimum of benthic foraminiferal d13C, indicating
a major interruption of ventilation in the bottom water in the Okhotsk Sea. The major low ventilation
event in the deep water of the Okhotsk Sea appears to be dampened by a cooling condition and a major
blooming of surface productivity preceded the event.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Understanding the sources, transportation pathways, and uxes
of terrigenous detritus in marine sediments is crucial to quantitatively assessing and explaining the stratigraphy of sedimentary
records under changing climatic and oceanic conditions
(MARGINSOfce, 2003). While the transportation of terrigenous
Corresponding author at: Key Laboratory of Marine Sedimentology and
Environmental Geology, First Institute of Oceanography, State Oceanic Administration, Qingdao 266061, China.
E-mail address: zoujianjun@o.org.cn (J. Zou).
http://dx.doi.org/10.1016/j.jseaes.2015.07.020
1367-9120/ 2015 Elsevier Ltd. All rights reserved.
detritus from the land to the ocean in the mid and low latitudes
of the western Pacic marginal seas is carried out mainly by rivers
and eolian processes (Chavagnac et al., 2008; Milliman and Meade,
1983), sea ice plays a dominant role in the high latitudes (Asahara
et al., 2012; Nuernberg and Ralf, 2004; Polyak et al., 2009;
Spielhagen et al., 2004). Thus changes in the transportation of terrigenous detritus are sensitive to the glacialinterglacial climate
change on regional to global scales.
The Okhotsk Sea is one of the western Pacic marginal seas
adjacent to the Eurasian continent in the high-latitude Northern
Hemisphere. The Okhotsk Sea is covered by pronounced seasonal
sea ice (Harada et al., 2006; Nuernberg and Ralf, 2004), and it
542
2. Study area
The Okhotsk Sea is the second largest marginal sea in the
Northwestern Pacic with an area of 1.59 106 km2 (Wang,
1999); it is bounded by the Siberian mainland to the west, the
Pacic to the east, and the Kamchatka-Sakhalin Island Arc to the
north and south (Fig. 1). The connection between the Okhotsk
and Japan Seas is restricted to two narrow and shallow straits,
the Soya Strait and the Tartar Strait, with sill depths of 55 m and
15 m, respectively. Through the Bussol Strait (2300 m), the
Kruzenshterna Strait (1800 m), and other shallower straits located
near the Kuril Islands, the Okhotsk Sea is connected to the
Northwestern Pacic (Fig. 1). In the northwest, the Sea has broad
continental shelves, often wider than 400 km (Lapko and
Radchenko, 2000). The ocean circulation in the Okhotsk Sea is very
complex, characterized by a large cyclonic gyre consisting of the
northward West Kamchatka current and the southward East
Sakhalin current (Fig. 1). Moreover, the hydrological and sedimentary processes in the Sea are strongly inuenced by Amur River
runoffs along with the cold shelf water mass and Soya warm current, determining the transportation paths and patterns of terrigenous material. Off the eastern of the Sea, the Kuroshio transports
warm, saline waters to the subarctic Pacic after deects from
543
Fig. 1. Map showing the location of core OS03-1 ( ) and the modern surface current pattern in the study area. The symbol represents the locations of cores mentioned in
the text. The contour indicates the observational mean sea ice concentration averaged for December, January and February (DJF) for the period of 19792013 in the Okhotsk
Sea (Cavalieri et al., 1996).
Fig. 2. (a) Prole of benthic foraminiferal d18O in core OS03-1. The blue and gray solid lines indicate the observed and 3-point running average of benthic d18O, respectively.
The red star and crosses indicate the age controlling points. (b) Comparison of the age model of core OS03-1 with the d18O curves of SPECMAP (Martinson et al., 1987), as well
as sediment cores LV28-42-4 (Nuernberg and Ralf, 2004) and GGC-27 (Brunelle et al., 2010) (refer to Fig. 1 for the location of these sediment cores). (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of this article.)
14
C dates using the CALIB 6.1.1 program (Reimer et al., 2009) and
correcting for a reservoir 14C age of 1000 years (Gorbarenko
et al., 2002a). However, the dating results for 6870 cm and 246
248 cm depths show apparently older ages (>40,000 yrs) than our
d18O age model. Given that radiocarbon dating is limited to maximum age of 40,000 years and above the limit C-14 ages are not
544
reliable. Therefore these two AMS 14C dates have not been considered for our age model construction.
Eighty-nine samples from core OS03-1 were analyzed for major
elements, trace elements, and REEs at the Key Laboratory of Marine
Sedimentology and Environmental Geology, State Oceanic
Administration in Qingdao, China. Since the ice-rafted detritus that
is normally characterized by larger grain size is one of the sediment components in OS03-1, the single rock or mineral in ice
rafted detritus would signicantly dominate the concentrations
of REEs. In order to minimize this grain size effect, we attempted
to analyze the sediment components of <63 lm only, through a
wet sieving before the major, trace element, and REEs analyses.
All the samples were rst digested with HNO3-HF (1:1) in closed
Teon beakers, and analyzed with ICP-OES (ICAP6300) and
ICP-MS (Thermo Scientic X SERIES 2) for elemental (Al, Ba and
REEs) analysis. The entire experimental process was under quality
control by a blank experiment, GSD-9 standard material and replicate measurements. The relative standard deviations of the major,
trace element, and REEs analyses are all <5%.
P
maximum REEs MAR could be linked to regional to global climate processes deserves further attention and will be discussed
in the next section.
The REEs were normalized by Post-Archaean Australian Shale
(PAAS) (Taylor and McLennan, 1985). The ratio of La to Yb, i.e.
(La/Yb)N ranged from 0.55 to 0.92 with an average value of 0.74,
and the variations in the ratio of (La/Yb)N is approximately in parallel with the REEs contents (Fig. 3e). We also measured the
anomalies of Cerium (dCe) and Europium (dEu), two important
parameters reecting the sedimentary environments at this site.
The dCe and dEu were calculated by comparing the measured concentrations of Ce and Eu with their neighboring elements:
dEu = EuN/(SmN GdN)1/2; dCe = CeN/(LaN PrN)1/2, where N represents the normalization of PAAS. The PAAS-normalized results
exhibit a signicant positive Eu anomaly ranged from 1.1 to 1.4,
with an average of 1.2 (Fig. 3f), and the remarkable positive Ce
anomaly varied from 0.89 to 1.3 with an average of 1.0 (Fig. 3g).
5. Discussion
4. Results
P
REEs concentration and its parameters in core OS03-1. Horizontal gray bars indicate the volcanic ash layers. The dashed line indicates a dCe value of
545
Fig. 5. Scatter plots of (Sm)N versus (Nd)N and dCe versus dEu in core OS03-1.
further indicating that sea ice is the major transporting agent for
terrigenous detritus from coast to our core site.
5.2. Positive Cerium anomaly
We found a signicant positive Ce anomaly in those sediments
accumulated since 19 ka (Fig. 5b). However, the Ce anomaly was
not commonly observed in the sediments mainly composed of silicate (Zhu et al., 2012; Zou et al., 2010). The presence of a Ce anomaly in marine sediments could be attributed to several factors,
including the depositional environment, diagenetic conditions,
and the oxygen content of bottom water (Pattan et al., 2005).
Studies on REE concentrations in terrigenous, siliceous, calcareous,
and red clay from the central Indian Ocean have indicated that the
at shale-normalized REE patterns are associated with terrigenous
sediments, and positive Ce anomalies with siliceous sediments,
negative Ce and positive Eu anomalies with calcareous sediments,
and LREE-depleted patterns with pelagic red clays (Nath et al.,
1992). The typical features of abundances of REEs in different types
of Pacic pelagic sediments were demonstrated especially by various Ce anomalies in the shale-normalized REE patterns (Toyoda
et al., 1990). The Ce anomalies in the sediments of the Okhotsk
Sea and Bering Sea are mainly positive and are associated with
FeMn oxide mineral phases (Toyoda and Masuda, 1991). In contrast, negative Ce anomalies are mainly observed from calcareous
ooze or with phosphorus-enriched sediments. Based on all these
previous observations, we infer that the signicant positive Ce
anomalies in our OS03-1 core sediments can be attributed to the
formation of FeMn mineral oxides.
5.3. Accumulations of terrigenous detritus
Our analysis indicates that the MARs of REEs in core OS03-1
have changed greatly over the last 180 ka. The changes maybe
546
tightly linked to the regional and global climate, sediment provenance, and/or sea ice extent changes in the Okhotsk Sea. In order
to understand what mechanisms are responsible for the glacialinterglacial terrigenous detritus accumulations in the Okhotsk Sea,
P
we compared the MAR of
REEs in our core OS03-1 (Fig. 6) to
the record of the intensity of the Mongolian High (MH) (Li and
Liu, 2012), the sea surface temperature (SST) of MD012412 from
the southwestern Okhotsk Sea (Harada et al., 2006), June insolation
at 60N (Berger and Loutre, 1991), and stalagmite-based estimates
for summer Asian Monsoon (AM) precipitations in eastern China
(Wang et al., 2001, 2008; Yuan et al., 2004).
P
The low MARs of REEs in core OS03-1 during MIS 5e and MIS
1 are in accordance with a weaker MH (Li and Liu, 2012), higher
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Fig. 6. Comparison of the mass accumulation rate of REEs in core OS03-1 with the records of excess barium (Baexcess), benthic foraminiferal d13C (Wu et al., 2014), the
Mongolia High (Li and Liu, 2012), MD01-2412SST (Harada et al., 2006), June insolation at 60N (Berger and Loutre, 1991), and East China Caves d18O (Wang et al., 2001, 2008;
Yuan et al., 2004). Vertical gray bars indicate the intervals of six minimum events of benthic foraminiferal d13C.
During the deglaciations, especially MIS 6/5 and MIS 2/1, rapid
increases in the MARs of REEs coincide with strong MH (Li and Liu,
2012), abruptly increased summer insolation (Berger and Loutre,
1991), low SST (MIS2/1) (Harada et al., 2006), and intensied summer AM precipitations (Wang et al., 2001, 2008; Yuan et al., 2004).
The rising sea levels associated with the global melting of ice
sheets brought increased erosion near the northern coast of the
Okhotsk Sea, while intensied summer AM precipitations led to
increased Amur River runoff, all of which are supposed to deliver
more terrestrial detritus to the Okhotsk Sea. Though freshwater
does not appear to be important in determining the variability in
the sea ice extent in the Okhotsk Sea (Ogi and Tachibana, 2006),
the expansion of sea ice under strong MH and low SST could serve
as an efcient transportation mechanism for terrigenous material
from the northern coast and/or the Amur River to our study site.
In particular, the maximum MARs of REEs during MIS 5c in our
record corresponds to the strong MH and low SST (Fig. 6), attesting
a possible sea ice mechanism for the increased accumulation of
terrigenous detritus. In summary, the changes in the MARs of terrigenous detritus in core OS03-1 are closely related to the regional
and global climates. More importantly, the extent of sea ice, which
is one of the most sensitive components in the climate system, has
played an important role in transporting terrigenous detritus to the
southern Okhotsk Sea, the place is far from the surrounding continents and islands (Fig. 1).
5.4. Deep ventilation in the Okhotsk Sea
Deep ventilation in the Okhotsk Sea that acted as pacemaker for
NPIW changes has varied greatly since the last glacial period (Max
et al., 2014; Okazaki et al., 2012). Both d13C of benthic foraminifera
and D14C between planktonic and benthic foraminifera suggested
that ventilation of NPIW was rigorous during H1 and YD and it
was coupled to processes of improved OSIW formation (Max
et al., 2014). Our records in core OS03-1 (water depth, 960 m) show
six benthic foraminiferal d13C minima in the southern Okhotsk Sea
over the last 180 ka, indicating weakened ventilation of regional
deep water (Wu et al., 2014) (Fig. 6). The d13C minima, in principle,
could be driven by high surface productivity, weakened formation
of Okhotsk Sea Intermediate Water, and/or barrier layer effects
that prohibit surface mixing caused by a thicker fresh water lens
formed from more runoff from the Amur River and the seasonal
melting of peripheral sea ice reaching our site.
Clearly, all six d13C minima are associated with intensied AM
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precipitation and maximum MARs of
REEs (Fig. 6), indicating
that a dominance of barrier layer effects by more fresh water and
more sea ice melting is responsible for the events. Increased surface productivity does not seem to be important in interpreting
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the d13C minima. However, the maximum MAR of REEs coincides
13
with the minimum of benthic foraminiferal d C during MIS 5c,
indicating that a major ventilation interruption in the bottom
water could be caused by barrier layer effects, and also further
dampened by a cooling condition, and possibly a major blooming
of surface productivity indicated by the maximum Baexcess (Fig. 6)
preceded the ventilation interruption since MIS 6.
6. Conclusions
Analysis of REEs in core OS03-1 from the Akademia Nauk Rise,
southern Okhotsk Sea, has revealed that the sediments accumulated over the last 180 ka were mainly composed of terrigenous
detritus, although some volcanic detritus also contributed to the
sediment components. The OS03-1 sediment REEs pattern shows
a signicant positive Ce anomaly which is attributed to the formation of FeMn mineral oxides. The MARs of terrigenous detritus
547
Acknowledgements
Financial support was provided by the National Natural Science
Foundation of China (Grant Nos.: 41476056, 40906035,
40710069004), Basic Scientic Fund for National Public Research
Institutes of China (No. 2010G24), International Cooperation
Project of Global Change and OceanAtmosphere Interaction
(GASI-GEOGE-04), and the Taiwan Ministry of Science and
Technology (NSC 103-2923-M-019 -001-MY3).
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