Ye Yu·Changmin Zhang·Shaohua Li· Rui Zhu·Jiangyan Liu·Chenggang Qin· Zhongtao Zhang
Influences of Tibetan Plateau uplift on provenance evolution of the paleo-Pearl River
Ye Yu·Changmin Zhang·Shaohua Li· Rui Zhu·Jiangyan Liu·Chenggang Qin· Zhongtao Zhang
A comparative analysis of the geochemical characteristics of sediments from the Oligocene Zhuhai Formation(32—23.8 Ma),the Miocene Zhujiang Formation(23.8—16.5 Ma),andtheHanjiangFormation (16.5—10.5 Ma)and a comprehensive analysis of the geochemical characteristics of rocks surrounding the paleo-Pearl River drainage contribute to understanding the influences of the Tibetan Plateau uplift on provenance evolution of the paleo-Pearl River.The results show that the geochemical characteristics of sediments from the Oligocene Zhuhai Formation are very different from the geochemical characteristics of sediments from the Miocene Zhujiang and Hanjiang Formations.The∑rare earth elements(REE)of mudstone is relatively high in the Zhuhai Formation,204.07—293.88 ppm(average 240.46 ppm),and low in the Zhujiang and Hanjiang Formations,181.32—236.73 ppm(average 203.83 ppm)and 166.84—236.65 ppm (average 199.04 ppm),respectively.The chemical index of alteration(CIA)for these samples has a similar trend to the∑REE:the CIA of the Zhuhai Formation is relatively high and the CIA of the Zhujiang and Hanjiang Formations is relatively low.The uplift of the Tibetan Plateau is crucial to the westward expansion of the paleo-Pearl River drainage.
Tibetan Plateau uplift·Pearl River Mouth Basin·Paleo-Pearl River·Provenance evolution· Geochemical characteristics
Recently,as a very complicated hotspot,the formation and uplift of the Tibetan Plateau have been of interest to many geologists all over the world(Song et al.2001;Kent-Corson et al.2009;Qu et al.2009;Zhang et al.2009;Liu et al.2010;Shen et al.2010;Miao et al.2011;Wang et al. 2012a,b).The formation of the Tibetan Plateau is the combined result of crustal incrassation and uplift,which are caused by the collision of the Indian and Eurasian blocks;ground denudation and equilibrium;and thermal processes(England and Houseman 1988;Ruddiman et al. 1989;Liu et al.2001).At present,there is consensus that the uplift of the Tibetan Plateau is multistage and heterogeneous,that the speed of uplift was initially slow and increased gradually,and that since the Pleistocene the plateau has been in a sudden to accelerated uplift period. Four intensive uplift periods—45—38,25—17,13—8,and 3 Ma to present—have been established by synthetic analysis of low-temperature thermo-chronology data,sedimentarydepositrecords,andstructuraldeformation records of different areas(Zhong and Ding 1996;Wang and Ding 1998;Pan 1999;Wang et al.2009,2011).The continental collision between India and Eurasia not only formed the Tibetan Plateau,but also drove the uplift of the surrounding area to varying degrees(Burbank 1992;Kazuo and Asaniko 1992;Wang et al.1999).The history and paceof tectonic subsidence was very similar in the Yinggehai Basin and interior basins of the western Yunnan Plateau(Wang et al.2000,2004).The uplift history of the western Yunnan Plateau was divided into four stages,including initial uplift(23—19 Ma),rapid uplift(16.2—11 Ma),sudden uplift(5.3—1.6 Ma),and accelerated uplift(1.6—0 Ma)(Wang et al.2000).
Y.Yu(?)
Hunan Provincial Key Laboratory of Shale Gas Resource
Utilization,Hunan University of Science and Technology,
Xiangtan 411201,China
e-mail:yuye1983@163.com
C.Zhang(?)·S.Li·R.Zhu·J.Liu
MOE Key Laboratory of Exploration Technologies for Oil and Gas Resource,Yangtze University,Wuhan 430100,China
e-mail:zcm@yangtzeu.edu.cn
C.Qin·Z.Zhang
Shenzhen Branch of China National Offshore Oil Corporation,Guangzhou 510240,China
Sediment composition changed during the Late Oligocene(23.8 Ma)in the Baiyun Sag in the northern South China Sea,from sandy deposits into argillaceous sediments(Clift et al.2002;Li et al.2003,2007a,b,2011;Pang et al. 2005,2007;Shao et al.2008).At the same time,the continental-shelf slope break migrated from the southern Baiyun SagtothenorthernBaiyunSag,whereithasremained(Peng et al.2005;Shao et al.2007;Qin et al.2011;Liu et al.2011;Zhang et al.2011).These sedimentary geological phenomenacoincidedwithaseriesofgeologicaleventsincludingthe rapid uplift of the Tibetan Plateau 25—17 Ma and the initial uplift of the western Yunnan Plateau 23—19 Ma,both of which are on the western side of the Pearl River drainage.In order to understand whether these events are related,a comparative analysis was conducted of the geochemical characteristics of sediments from the Oligocene Zhuhai Formation(32—23.8 Ma),the Miocene Zhujiang Formation(23.8—16.5 Ma),andtheHanjiangFormation (16.5—10.5 Ma)and comprehensive analyses of the geochemical characteristics of rocks surrounding the paleo-Pearl River drainage were conducted to reveal the influences of the Tibetan Plateau uplift on provenance evolution of paleo-Pearl River.
The Pearl River Mouth Basin(PRMB)is one of the four majorCenozoicbasinsinthenorthernSouthChinaSea(Hao etal.1995,2000;ZhouandYao2009).ThePRMBislocated tothesouthmarginoftheSouthChinacontinentandbetween HainanIslandandTaiwanIsland,coveringabout 17.5×104km2(Wang et al.2012a,b;Fig.1).It can be divided into five large-scale,first-order,northeast-trending tectonic units(Chen and Pei 1993),namely,the northern fault terrace belt and northern depression belt(including the Zhu I and Zhu III depressions);the central uplift belt(includingthe Shenhu,Panyu low,and Dongsha uplifts);the southern depression belt(including the Baiyun Sag and the Chaoshan depression);and the southern uplift belt(Fig.1). Eight seismic sequences developed longitudinally in the PRMB:the Wenchang,Enping(39—32 Ma),Zhuhai(32—23.8 Ma),Zhujiang(23.8—16.5 Ma),Hanjiang(16.5—10.5 Ma),Yuehai,and Wanshan Formations and the Quaternary System(Chen et al.2003;Zhu et al.2008).The Wenchang and Enping Formations are mainly continental deposits in the vicinity of the sampling well;the Zhuhai,Zhujiang,and Hanjiang Formations are mainly large-scale neritic shelf deposits,shelf-margin,and slope deposits,respectively,while the Yuehai Formation and later deposits are mainly slope deepwater deposits(Wang et al.2012a,b).
The Pearl River Basin contains the west,north,and east Rivers and various water systems of the Pearl River delta. Among these,the west River is the main river(Wang et al. 2006;Liu et al.2007).The Pearl River drainage is located on the south of the Nanling Range,north of the South China Sea and east of the Tibetan Plateau.In its central region,hills alternate with basins.Toward the mouth of the river,there is an alluvial plain which decreases in elevation from west to east(Fig.1).The Pearl River flows through Yunan,Guizhou,Guangxi,Guangdong,Hunan and Jiangxi provinces,covering about 45.4×104km2(Dai et al.2007).
3.1Sampling position
The sampling well is located in the northern Baiyun Sag of the PRMB(Fig.1).Based on the core description,lithologic identification,and sedimentary facies analysis,we determined the following.The Enping Formation,which is 898.32 m thick,is mainly braided river deposits characterized by thick-bedded feldspathic lithic glutenite,having coarser grain size,poorer sorting and roundness,and a logging curve that shows a tooth box.The Zhuhai Formation has a sedimentary thickness of 687.68 m.The lower part of the Zhuhai Formation(mainly lithic quartz sandstone,with lower compositional and textural maturity)is primarily delta plain facies impressed by a mediumbedded distributary channel and flooding plain;the upper part of the Zhuhai Formation is mainly delta front facies including subaqueous distributary channel,distributary mouth bar,and subaqueous distributary interchannel;and a funnel-shaped logging curve.The sedimentary thickness of the Zhujiang Formation is 895.5 m;the lower part of the Zhujiang Formation(mainly quartz sandstone and lithic quartz sandstone,with higher compositional and textural maturity)includes subaqueous distributary channel and distributary mouth bar deposition,while the upper part consists of shelf mud deposition and shelf sand ridges marked by siltstone.The Hanjiang Formation has a sedimentary thickness of 1,153.51 m;the lower part of the Hanjiang Formation is an offshore shelf deposit while the upper part consists of delta front facies formed with the fall of sea level and including mouth and distal bars.The Hanjiang Formation contains mainly quartz sandstone with a finer grain size,higher compositional and textural maturity,and better sorting and roundness.Representativesamples were obtained from the drill core and cuttings in the sampling well.Twenty samples of mudstone,which are used to define provenance,were taken from the Zhuhai Formation(six samples),the Zhujiang Formation(seven samples),and the Hanjiang Formation(seven samples). Mudstone is more suitable for provenance analysis owing to its relative geochemical homogeneity(Cullers 1995). Twenty-nine samples of clastic rock,used to determine the extending range of the paleo-Pearl River drainage,were taken from the Enping Formation(five samples),the Zhuhai Formation(six samples),the Zhujiang Formation(ten samples),and the Hanjiang Formation(eight samples).
Fig.1 Tectonic diagram of the Pearl River Mouth Basin and present Pearl River drainage(redrawn from Li et al.2013)
3.2Analytical methods and testing results
The major element oxides were analyzed using inductively coupled plasma atomic emission spectrometry(ICP-AES)at the State Key Laboratory of Marine Geology,Tongji University.The trace elements,including fifteen rare earth elements(REE),were determined using inductively coupled plasma mass spectrometry(ICP-MS)at the State Key Laboratory of Marine Geology,Tongji University.Sr and Nd isotopic compositions were measured with multicollector inductively coupled plasma mass spectrometry(MC-ICP-MS)at the State Key Laboratory of Isotope Geochemistry in Guangzhou Institute of Geochemistry,Chinese Academy of Sciences.The detailed geochemical method and analytical precision have been described in other papers(Li et al.2002;Vervoort et al.2004).The analytical results for major elements,trace elements,REE,and Sr and Nd isotopic compositions are listed in Tables 1,2,3,and 4.
4.1Major elements
Major element abundances for mudstones in the Pearl River Basin are listed in Table 1.It can be seen that the content of SiO2,Al2O3,and Fe2O3are relatively high. Compared with the post-Archean Australian shales(PAAS from Taylor and Mclennan 1985),the mudstones of the PRMB are richer in SiO2(67.40%on average),F(xiàn)e2O3(10.15%on average),CaO(3.59%on average),and Na2O(2.01%on average);while poorer in Al2O3(11.73%onaverage),K2O(2.58%on average),MgO(1.71%on average),and TiO2(0.62%on average).The SiO2content in the Zhuhai Formation is relatively high(average 71.41%)while that in the Zhujiang and Hanjiang Formations is relatively low(average 64.20%and 67.16%,respectively).CaO and Fe2O3are relatively low in the Zhuhai Formation(averaging 1.12%and 7.75%,respectively),and relatively high in the Zhujiang and Hanjiang Formations(CaO average 3.51%and 5.79%,respectively;Fe2O313.24%and 9.13%,respectively).SiO2exists principally in granite and acidic magmatic rock,Ca is generally related to carbonate rock,and Fe is hosted mainly in basic rock,suggesting that the provenance of the Zhuhai Formation is different from that of the Zhujiang and Hanjiang Formations.
Table 1 Analytic results of major element oxides in mudstones (in wt%,except for Al2O3/TiO2 and CIA)
Sediment is thought to be derived from mafic rocks if the Al2O3/TiO2value is less than 14,while it is more likely to be derived from the granodiorite and tonalite if the value of Al2O3/TiO2is in the range of 19—28(Girty et al.1996).The Al2O3/TiO2value of the mudstone in the Pearl River Basin is in the range of 16.68—27.98.The Al2O3/TiO2value of the Zhuhai Formation is relatively high(average value 20.82),while those of the Zhujiang and Hanjiang Formations are relatively low(average value 18.33 and 18.38,respectively). It can be inferred that the source rock of the Zhuhai Formation is predominantly derived from granodiorite and tonalite and the source rock of the Zhujiang and Hanjiang Formations may include mafic rocks.
Chemical weathering in the source area can modify the chemical composition of rocks.For example,the labile cations(e.g.,Na+,Ca2+,K+)are commonly removed during chemical weathering processes and the loss of stable cations(Al3+,Ti4+)can be retarded from the residua(Fedo et al.1995).The degree of chemical alteration lies heavily on the intensity of the weathering process,and the original parent rock types can be determined through tracing back the weathering process(Condie et al.1992). Nesbitt and Young(1982)suggested a chemical index of alteration(CIA)to estimate the intensity of weathering:
In the equation,the oxides are expressed as molar proportions and CaO*represents the Ca in silicate minerals only.The CIA of Zhuhai Formation is relatively high(64.68 on average),and the CIA of Zhujiang and Hanjiang Formations are relatively low(52.08 and 55.59 on average,respectively)(Table 1).This suggests that the intensity of chemical weathering is relatively strong in the Zhuhai Formation compared to the Zhujiang and Hanjiang Formations.A damp and warm paleoclimate is one of the reasons why the intensity of chemical weathering is relatively strong in the Zhuhai Formation in contrast to thecooler,dryer paleoclimate of the Zhujiang and Hanjiang Formations in which chemical weathering is relatively weak.
Table 2 Analytic results of trace elements in the mudstones (in ppm)
Samples from the Zhuhai Formation are located in the leading end of the weathering tendency(dotted line),suggesting an intense weathering history;and the samples from the Zhujiang and Hanjiang Formations fall in the middle-to-tail end of the weathering tendency,suggesting a moderate-weak weathering history(Fig.2).This result is consistent with the analytic results of CIA.In the opposite direction of weathering tendency,the extended solid line 1 trends toward the felsic rock area,indicating the samples from the Zhuhai Formation are derived from felsic source rocks;and the extended solid line 2 trends between mafic and felsic rocks,indicating the samples from the Zhujiang and Hanjiang Formations are derived from a more mafic source.
4.2Trace elements
The trace element abundances of mudstones in the Pearl River Basin appear in Table 2.There is an abundance of Ba(379.39 ppm on average),Sr(181.39 ppm on average),Cr(130.95 ppm on average),Rb(129.95 ppm on average),and Zr(106.39 ppm on average).Compared with the abundance of trace elements in the upper continental crust,the studied mudstones are rich in Rb,Cr,and Mo(average 22.68 ppm);while poor in Ba,Sr,and Zr.Compared with the abundance of trace elements in the lower continental crust,the studied mudstones are rich in Ba,Rb,Zr,Mo,and Cu(average 46.55 ppm);andpoorinSr,Cr,andCo(average16.92 ppm). The trace element abundance of mudstones in the Zhuhai,Zhujiang,and Hanjiang Formations have their own characteristics:the average values of Rb,Ba,Cs,Th,and U in the Zhuhai Formation(Rb,167.22 ppm;Ba,413.7 ppm;Cs,14.09 ppm;Th,21.74 ppm;U,3.92 ppm)arenotablyhigher than in the Zhujiang(Rb,119.96 ppm;Ba,343 ppm;Cs,7.64 ppm;Th,15.19 ppm;U,2.62 ppm)and Hanjiang(Rb,107.99 ppm; Ba,386.37 ppm;Cs,6.98 ppm;Th,13.73 ppm;U,2.44 ppm)Formations;the average values of Sr and Mo in the Zhuhai Formation(Sr,128.49 ppm;Mo,10.1 ppm)are lower than in the Zhujiang(Sr,193.65 ppm;Mo,30.6 ppm)and Hanjiang (Sr,214.49 ppm;Mo,25.53 ppm)Formations.
Generally,the more intensive the chemical weathering,the higher the ratio of Rb/Sr.There is an opposite trend in the ratio of Sr/Cu.Therefore,the ratios of Rb/Sr and Sr/Cu can be used to indicate the intensity of chemical weathering(Jin et al.2011;Xu et al.2012).From Table 2,it can be seen that the ratio of Rb/Sr in the Zhuhai Formation is relatively high(average 1.39),and those in the Zhujiang and Hanjiang Formations are relatively low,(average 0.64 and 0.53,respectively).The trend in Sr/Cu ratios mirrorsthat of the Rb/Sr ratios,with a lower Sr/Cu ratio(3.26 on average)in the Zhuhai Formation,an intermediate Sr/Cu ratio(5.2 on average)in the Zhujiang Formation,and a higher Sr/Cu ratio(6.31 on average)in the Hanjiang Formation.It can be inferred that the intensity of weathering gradually weakened from the Zhuhai Formation to the Hanjiang Formation and that the climate changed at the same time,concurrent with the uplift of the Tibetan Plateau,which led to a decrease in precipitation and cooling of the climate(Chen et al.1999).
Table 3 Analytic results of rare earth elements in mudstones (in ppm)
Fig.2 Ternary plot of molecular proportions Al2O3—(Na2-O+CaO*)—K2O for the mudstones(redrawn from Fedo et al.1995)
REE and other high field strength elements may be almost completely preserved in the sediment due to their transitory residence in water,so the sources of felsic and mafic material can be distinguished by the ratios of compatible to incompatible elements.According to the characteristics of the elements mentioned above,Allegre(1978)proposed a source rock discrimination diagram of La/Yb-∑REE.According to Fig.3a,the parent rocks of the study area are mainly a mixture of granite,paleo-sedimentary calcareous mudstone,and alkali basalt,but the parent rocks of the Zhuhai Formation are predominantly granite and those of the Zhujiang and Hanjiang Formations are mainly paleo-sedimentary calcareous mudstone and alkali basalt. Based on the enrichment of La and Th in felsic rocks and the enrichment of Co,Sc,and Cr in basic rocks,Gu et al.(2002)proposed a source rock discrimination diagram of Co/Th—La/Sc.According to Fig.3b,the samples of the study area principally plot nearest to felsic volcanic rock. In fact,the rocks in the provenance area are complex,and the source rock is mainly felsic(Gu et al.2002).
Fig.3 Source rock discrimination diagrams for the mudstones on a∑REE versus La/Yb(redrawn from Allegre 1978),and b La/Sc versus Co/ Th(redrawn from Gu et al.2002)
4.3Rare earth elements
According to Table 3,there is a big fluctuation in the concentration of∑REE of mudstones in the Pearl River Basin,ranging from 166.83 to 293.88 ppm(average 213.12 ppm). The∑ REE of the Zhuhai Formation(240.46 ppm on average)is the highest.The light REE to heavy REE ratio(LREE/HREE)ranges from 2.82 to 3.98(3.84 on average). The(La/Yb)Nis used to identify the differentiation between LREE and HREE.Based on the(La/Yb)N,there is a highdegree of differentiation in the Zhuhai Formation,with an averageof8.27;andthereisalowdegreeofdifferentiationin Zhujiang and Hanjiang Formations,with averages of 5.11 and 6.34 respectively.The(La/Sm)Nis used to identify the differentiation in LREE,while the(Gd/Yb)Nis used to identify the differentiation in HREE.The differentiation in HREEissimilartothatbetweenLREEandHREE:thereisa high degree of differentiation in the Zhuhai Formation,with an average of 1.71;and there is a low degree of differentiation in the Zhujiang and Hanjiang Formations,with averages of 1.03 and 1.29,respectively.In contrast,δEu in the Zhuhai Formation is significantly lower than that in the Zhujiang and Hanjiang Formations,with an average of 0.55 in the Zhuhai Formation,an average of 0.76 in the Zhujiang Formation,andanaverageof0.7intheHanjiangFormation.
After the REE is normalized based on the chondrite concentration(Sun and McDonough 1989),the REE distribution patterns are similar to that of the upper continental crust,with LREE enrichment,flat HREE,and significant negative Eu-anomalies(Fig.4).It can be inferred that the source rocks of the Pearl River Basin may be derived from the upper continental crust.In addition,the∑ REE of mudstone in the Zhuhai Formation is high relative to that in the Zhujiang and Hanjiang Formations,which may be related to the different source rocks of the Zhuhai Formation compared to the Zhujiang and Hanjiang Formations.
Fig.4 Chondrite-normalized REE plot for the mudstones(chondrite normalizing factors from Sun and McDonough 1989)
Table 4 The Sr and Nd isotopic data of the clastic rocks
4.4Sr and Nd isotopic compositions
The Sr and Nd isotopic compositions of samples from the Pearl River Basin are presented in Table 4.Ratios of143Nd/144Nd vary from 0.51197 to 0.51209(0.51203 on average)and87Sr/86Sr vary from 0.72254 to 0.74591(0.73001 on average).The εNd(0)values are all negative(-11.8552 on average).The Sr and Nd isotopic compositions vary greatly between the Oligocene and Miocene strata.The143Nd/144Nd are high in the Oligocene Enpingand Zhuhai Formations,while low in the Miocene Zhujiang and Hanjiang Formations.For example,the143Nd/144Nd in the Oligocene Enping and Zhuhai Formations average 0.51208 and 0.51207,respectively;the corresponding values in the Miocene Zhujiang and Hanjiang Formations both average 0.51200.The87Sr/86Sr and εNd(0)have a similar trend to143Nd/144Nd in that both of them are higher in the Oligocene Enping and Zhuhai Formations and lower in the Miocene Zhujiang and Hanjiang Formations.This shows that there is a remarkable migration of the provenance of the paleo-Pearl River in the late stage of Oligocene Zhuhai Formation(the early stage of the Miocene Zhujiang Formation),resulting in a change in the composition of the source rock.
Fig.5 Comparison of εNd(0)(a)and87Sr/86Sr(b)between the sediments in the Pearl River Basin and any possible sources surrounding the Pearl River drainage
The εNd(0)and87Sr/86Sr values from the Pearl River Basin samples have been compared with the εNd(0)and87Sr/86Srvaluesfromthesurroundingareaofthepaleo-Pearl River drainage(Deniel et al.1987;Chen et al.2006;Darbyshire and Sewell 1997;Ge 2003;Shao et al.2008;Yang et al.2007;Zhu et al.2003;Zhang and Wang 2003).The sediments of the Oligocene Enping and Zhuhai Formations have the same εNd(0)value as the granite in the coast of South China including Hong Kong,Hainan Island,and the basement of the PRMB(Fig.5).The sediments of the Miocene Zhujiang and Hanjiang Formations have εNd(0)values in the same range as the granite in the western Yunnan Plateau and are close to the granite of Tibetan Plateau(Fig.5a). The87Sr/86Sr values of the Oligocene Enping and Zhuhai Formations are different from the87Sr/86Sr values of the Miocene Zhujiang and Hanjiang Formations;the Miocene samples have values closer to those of the Tibetan Plateau granitesandtheEmeishanbasalt(Fig.5b).Itcanbeinferred that the headwaters of the paleo-Pearl River migrated in the late Oligocene(23.8 Ma),possibly extending to the western YunnanPlateau,oreventheeasternTibetanPlateau.Inother words,the headwaters of the paleo-Pearl River moved to the present location around 23.8 Ma.The rapid uplift of the Tibetan Plateau between 25—17 Ma leads to the new paleogeographical framework in the southwest of China which is characterized by a higher elevation in the west and lower elevation in the east.The paleogeographical framework which is mentioned above benefits the northwestward migration of the headwaters of the paleo-Pearl River in the late Oligocene(23.8 Ma).Then,it suggests that the uplift of Tibetan Plateau is crucial to theprovenance migration of the paleo-Pearl River.
(1) The source rocks of the Zhuhai Formation are simple and mainly felsic granite,while those of the Zhujiang and Hanjiang Formations are complex and mainly alkali basalt.
(2) The warmer,wetter paleoclimate is one of the reasons why the intensity of chemical weathering in the Zhuhai Formation is relatively strong in contrast to the Zhujiang and Hanjiang Formations where a cooler,dryer paleoclimate led to a lower intensity of chemical weathering.
(3) The source rocks of the paleo-Pearl River are mainly derived from southern China near the South China Sea in the stage of the Oligocene Enping and Zhuhai Formations.Concurrently with the uplift of theTibetan Plateau and the western Yunnan Plateau,the paleo-Pearl River drainage expanded to western China.The principal source of the paleo-Pearl River in the Miocene Zhujiang and Hanjiang Formations may be derived from the eastern Tibetan Plateau.
(4) There is a good corresponding relationship between the demarcation which is between Oligocene and Miocene(23.8 Ma)and the rapid uplift of the Tibetan Plateau.The provenance evolution of the paleo-Pearl River is predominantly controlled by the uplift of the Tibetan Plateau.
AcknowledgmentsThis work was supported by the National Major Scientific and Technological Special Project during the Twelfth Fiveyear Plan Period(Grant No.2011ZX05023-002).The authors appreciate the help of Professor Shao Lei and State Key Laboratory of Marine Geology(Tongji University)with the geochemical analysis,and Du Jiayuan,Liu Daoli with project support.
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1 July 2014/Revised:1 August 2014/Accepted:13 August 2014/Published online:22 January 2015 ?Science Press,Institute of Geochemistry,CAS and Springer-Verlag Berlin Heidelberg 2015