deep sea carbonates reading the carbon isotope signal the carbon isotope signal in deep sea sediments reflects a mix of 1 global changes in the rates of exchange of the ocean s carbon reservoir with biosphere soil and sediments 2 global and regional changes in surface water productivity 3 internal shifts in water mass structure and circulation basin basin fractionation oxygen minimum development and 4 organism specific fractionation effects due to changes in micro habitat and or ontogenic fractionation vital effects additional complications arise from differential preservation it is impossible to entirely isolate these various factors as a rule of thumb long period signals that are parallel for planktonic and benthic data reflect external global fractionation patterns whilst short period signals are more likely tied to internal patterns water mass fractionation the various approaches to interpretation are illustrated with three case studies the glacial holocene transition the messinian carbon shift and the miocene monterey excursion

kinematics of cenozoic extension on the south china sea continental margin and its implications for the tectonic evolution of the region abstract in the northern south china sea several large sedimentary basins developed during the cenozoic characterized by episodic rifting clockwise rotation of the rifts an eastward aging breakup unconformity and intensifying crustal extension to the east these features may be summarized by a scissors model the maximum rifting occurred north of the maximum thermal subsidence which was in turn north of the seafloor opening in contrast the nansha microcontinent south of the south china sea basin was dominated by compressional deformation during the cenozoic extension was of subordinate significance and manifested mainly by block faulting and tilting in the late early oligocene maximum tilting occurred in the southern part of the nansha microcontinent at distance from the deep sea basin of the south china sea the asymmetric development of extensional structures around the south china sea basin may be explained by the simple shear model proposed by wernicke 1981 the tectonic development of the south china sea was the consequence of various interactions of three major plates and may be summarized into three stages with dominating influences of respectively the retreat of the west pacific subduction zone in the late cretaceous the hard collision and impinging of india to tibet since the late eocene and the fast northward subduction of the indian ocean australian plate since the late early miocene

origin and distribution of terrestrial organic matter in the nw mediterranean gulf of lions exploring the newly developed bit index the branched and isoprenoid tetraether bit index is based on the relative abundance of nonisoprenoidal glycerol dialkyl glycerol tetraethers gdgts derived from organisms living in terrestrial environments versus a structurally related isoprenoid gdgt crenarchaeol produced by marine crenarchaeota the bit index varies between 0 and 1 representing marine and terrestrial organic matter om end members respectively hopmans et al earth planet sci lett 224 107 116 2004 in this study the applicability of the bit index to trace terrestrial om is tested in combination with other organic parameters toc c n ratio 13corg total lipid and n alkane in the gulf of lions a river dominated continental margin of the western mediterranean we analyzed a variety of soils and riverbed sediments from the continent as well as surface sediments from the shelf and canyons the bit index in soils and riverbed sediments shows high values 0 9 while it varies between 0 02 and 0 83 in marine sediments decreasing seaward from the inner shelf to the slope for marine surface sediments high bit values are associated with lower 13corg values as well as higher toc contents and higher n alkane concentrations our results confirm that the bit index can be applied in coastal marine environments in order to characterize terrestrial om as proposed by hopmans et al 2004 therefore the bit index is a useful addition to the proxies presently available for studying the origin and distribution of om in continental margins and especially valuable in multiproxy studies

cenozoic denudation history of southern hainan island south china sea constraints from low temperature thermochronology abstract as a large block of continental crust hainan island located in the western south china sea forms a rift shoulder to the adjacent offshore yinggehai and qiongdongnan basins and lies in the footwall of their main boundary faults we present 11 apatite fission track aft data and 16 u th sm he ages to elucidate the island s cenozoic morphotectonic evolution our data indicate that much of southern hainan island experienced a well defined cooling episode commencing in late eocene oligocene time during this time most samples cooled from 110 c to 55 15 c at a rate of 4 0 c ma following which the cooling rate decreased to 2 5 c ma assuming a constant paleogeothermal gradient of 23 c km similar to that of the present day since oligocene time when most samples cooled into the base of the aft partial annealing zone the total eroded section is estimated at a minimum of 3 5 km about two thirds of which was removed during the oligocene rapid cooling phase this implies that elevation of southern hainan island has decreased since the oligocene and this is supported by independent paleobotanical evidence although a further cooling episode since 5 ma is also suggested by aft thermal history models cooling occurred from relatively low temperatures 45 50 c where annealing kinetics are not well understood so this cannot be rigorously assessed despite evidence for increased sedimentation in offshore basins at this time our data suggest that the no 1 fault of the adjacent offshore yinggehai basin to the west which is thought to be an offshore extension of the red river fault zone was mainly active from late eocene through much of the oligocene but declined rapidly after 22 ma the marked reduction of potential sediment supply rate from hainan island into neighboring basins after that time suggests that miocene to recent sedimentation in the yinggehai basin was mainly supplied by the red river

a novel proxy for terrestrial organic matter in sediments based on branched and isoprenoid tetraether lipids we propose a novel tracer for terrestrial organic carbon in sediments based on the analysis of tetraether lipids using high performance liquid chromatography mass spectrometry hplc ms analysis of terrestrial soil and peats shows that branched tetraether lipids are predominant in terrestrial environments in contrast to crenarchaeol the characteristic membrane lipid of non thermophilic crenarchaeota which is especially abundant in the marine and lacustrine environment based on these findings an index was developed the so called branched and isoprenoid tetraether bit index based on the relative abundance of terrestrially derived tetraether lipids versus crenarchaeol this bit index was applied to surface sediments from the angola basin where it was shown to trace the outflow of the congo river furthermore analyses of particulate organic matter from the north sea showed relatively higher bit indices in water column particulate organic matter near large river inputs a survey of globally distributed marine and lacustrine surface sediments shows that the bit index in these environments correlates with the relative fluvial input of terrestrial organic material making this index generally applicable the new proxy allows the rapid assessment of the fluvial input of terrestrial organic material in immature sediments up to 100 ma old

cool wet conditions late in the younger dryas in semi arid new mexico abstract a thick alluvial sequence in central new mexico contains the scholle wet meadow deposit that traces upstream to a paleospring the wet meadow sediments contain an abundant fauna of twenty one species of freshwater and terrestrial mollusks and ten species of ostracodes the mollusks and ostracodes are indicative of a local high alluvial water table with spring supported perennial flow but without standing water pollen analysis documents shrub grassland vegetation with sedges willow and alder in a riparian community stable carbon isotopes from the wet meadow sediments have 13c values ranging from 22 8 to 23 3 indicating that 80 of the organic carbon in the sediment is derived from c3 species the wet meadow deposit is ams dated 10 400 to 9700 14c yr bp corresponding to 12 300 to 11 100 cal yr bp and overlapping in time with the younger dryas event yd the wet meadow became active about 500 yr after the beginning of the yd and persisted 400 yr after the yd ended the scholle wet meadow is the only record of perennial flow and high water table conditions in the abo arroyo drainage basin during the past 13 ka

control of sulfate pore water profiles by sedimentary events and the significance of anaerobic oxidation of methane for the burial of sulfur in marine sediments abstract gravity driven mass flow deposits proven by sedimentary and digital echosounder data are indicative for prevailing dynamic sedimentary conditions along the continental margin of the western argentine basin in this study we present geochemical data from a total of 23 gravity cores pore water so 4 is generally depleted within a few meters below the sediment surface by anaerobic oxidation of methane aom the different shapes of so 4 profiles concave kink and s type can be consistently explained by sedimentary slides possibly in combination with changes in the ch 4 flux from below thus mostly representing transient pore water conditions since slides may keep their original sedimentary signature a combined analysis and numerical modeling of geochemical physical properties and hydro acoustic data could be applied in order to reconstruct the sedimentary history we present first order estimates of the dating of sedimentary events for an area where conventional stratigraphic methods failed to this day the results of the investigated sites suggest that present day conditions are the result of events that occurred decades to thousands of years ago and promote a persisting mass transport from the shelf into the deep sea depositing high amounts of reactive compounds the high abundance of reactive iron phases in this region maintains low hydrogen sulfide levels in the sediments by a nearly quantitative precipitation of all reduced sulfate by aom for the total region we estimate a so 4 or ch 4 flux of 6 6 10 10 moles per year into the zone of aom projected to the global continental slope and rise area this may sum up to about 2 6 10 12 moles per year provided that the sulfur is completely fixed in the sediments it is about twice the global value of the recent global sulfur burial in marine sediments of 1 2 10 12 moles per year as previously estimated thus aom obviously contributes very significantly to the regulation of global sulfur reservoirs which is hitherto not sufficiently recognized this finding may have implications for global geochemical models as sulfur burial is an important control factor in the development of atmospheric oxygen levels over time

thermogenic hydrocarbons from the offshore calypso hydrothermal field bay of plenty new zealand hydrothermal gases from shallow seafloor vents in the bay of plenty new zealand contain co2 ch4 and the higher gaseous hydrocarbons up to i n c4h10 the gases are similar to those discharged at fumaroles on the nearby white island carbon isotope compositions for co2 fall between 3 4 and 5 5 pdb and reflect a shallow magmatic carbon source the 13c values of ch4 range from 24 6 to 28 9 pdb and the d values vary between 122 and 135 smow the ch4 isotope values and the presence of the higher hydrocarbon compounds such as c2h6 and c3h8 with 13c values near 20 pdb suggest hydrocarbon production by high temperature maturation of sedimentary organic matter and mixing 1 1 of the thermogenic ch4 with abiogenic ch4 long chained hydrocarbons occur in dredged samples close to the active vents their n alkane distribution has a high to moderate odd even predominance and an extensive hopane series indicative of higher land plant waxes and prokaryotic membranes in the source substantial amounts of unsubstituted polynuclear aromatic hydrocarbons pah mark the transition from aliphatic to aromatic dominated bitumens consistent with extensive source maturation resulting from thermal stress the bitumens are interpreted as pyrolysates derived from buried near coastal vegetation and terrestrial detritus under various thermal regimes mixed with immature seafloor organic matter

geochemical responses and implications for gas hydrate accumulation case study from site shc in shenhu area within northern south china sea abstract a knowledge of gas hydrates is critical for understanding complex geological geophysical and biogeochemical processes and for explaining the proposed link between gas hydrate destabilization and global sea level changes with the aim of discussing the geochemical characteristics and implications for gas hydrate accumulation this study assesses the changes in a series of organic and inorganic geochemical gas hydrate bearing sediments within a core section obtained at site shc in the shenhu area of the northern south china sea that range from the late miocene to the present high s c ratios 0 53 5 6 and low toc contents

precise dating of low temperature deformation strain fringe analysis by 40ar 39ar laser microprobe pyritized graptolites from the welsh basin united kingdom slate belt acted as rigid bodies during cleavage formation and epizonal white micas formed within the resulting strain shadows orthogonal to the principal stress orientation although the quantities of mica are small they are a pure synkinematic mineral and have been dated by ar 40 ar 39 infrared laser microprobe as a means to dating cleavage four samples of strain fringe mica from different hand samples yielded ages ranging from 394 4 3 1 to 397 8 1 8 ma 2sigma with a mean age of 396 1 1 4 ma 2sigma by focusing on minerals that are unequivocally synkinematic this technique provides a novel solution to the problems of isotopically dating slaty cleavage previous studies have predominantly relied on dating whole rock slate samples or separated illite grains by ar 40 ar 39 techniques problems encountered included 1 separating the effects of isotopic contamination by detrital phases 2 ar 39 loss during the irradiation of illite mineral separates and 3 thermally induced ar 40 loss in nature from fine grained minerals by circumventing these problems this new method provides the first unequivocal and high precision age data for acadian deformation in the well characterized welsh basin slate belt with such precision the method may afford geologists the opportunity to track tectonic fronts across orogens and assess the rates of accretion processes in areas that are peripheral to sites of continent continent collision

geological features controlling factors and potential prospects of the gas hydrate occurrence in the east part of the pearl river mouth basin south china sea abstract logging while drilling lwd and wireline log cwl data were acquired during china s second gas hydrate drilling expedition gmgs 2 in the east of pearl river mouth basin south china sea disseminated and massive gas hydrates deposits were found at different sites gas hydrate bearing lithologies identified from the sample coring included the fine grained sediments and coarse grained sediments lwd logs from site gmgs2 08 indicate significant gas hydrate in clay bearing sediments including two layers with massive gas hydrate with a bulk density near to 1 08 g cm3 high electrical resistivities with a range of 2 5 2000 0 m and high p wave velocities are simultaneously observed in the hydrate bearing sediments the average gas hydrate saturation estimated from the pore water freshing analysis ranges from 45 to 55 of the pore space buried carbonate layers above the massive gas hydrate deposit discovered at sites gmgs2 08 indicate that the formations are likely to have formed initially at the surface and then were buried significant high amplitude seismic anomalies discontinuous bottom simulating reflection bsr and blanking zone are detected in the drilling zone the hydrate bearing sediments predominantly consist of silty clay and limestone grains in which the gas hydrates are deposited primarily in the form of laminated massive veins or nodule the gas hydrates occurrences are subjected to the sediment lithology new tectonic activities migration of fluid and gas and also the factors such as heat flow salinity and time which affect the nucleation of gas hydrates its natural morphologies present massive laminated nodular nugget and disseminated of which the former four often formed in shallow fault inter layer s weak cementation zone and on the seabed the buried gas hydrates with high saturation are good zones for gas hydrate exploitation

miocene tubular concretions in east coast basin new zealand analogue for the subsurface plumbing of cold seeps the uplifted accretionary prism of east coast basin in hikurangi margin north island new zealand exposes late miocene slope mudrocks whangaehu mudstone 10 carbonate in coastal cliffs north of cape turnagain that contain conspicuous tubular carbonate concretions 50 85 carbonate supporting near central conduits pipe and bulbous morphologies dominate ranging in exposed length up to 5 m and up to 1 m in diameter the concretions were formed by the precipitation of micritic dolomite and calcite cement within the host mudstone at shallow burial depths 100 m 13c values of the cement range from 22 to 13 pdb and are interpreted to reflect carbonate precipitation from either the extensive anaerobic oxidation of methane aom and or mixing of microbial methane and methanogenic co2 aom is confirmed by lipid biomarker evidence indicating that methane oxidation occurred in the sediments at the time of carbonate precipitation the mixed dolomite calcite mineralogies and the trend of 13c in the tubular concretions from strongly negative to strongly positive values are interpreted to reflect methane oxidation from the onset of ascent through to the end of a migration event depleted and enriched 18o values suggest an evolved fluid source influenced by the dissociation of gas hydrates collectively our results indicate that the tubular concretions within the upper slope mudstones delineate parts of the subsurface plumbing network of a cold seep system on the late miocene paleo hikurangi margin in which the fluids were sourced from ascending methane the intermediate location of the whangaehu concretions between older early miocene seep carbonates to the west and modern ones offshore to the east indicates a progressive eastwards shift with time of a long lived if only periodically active seep system the concretionary plumbing features at whangaehu provide a conceptual model for subsurface fluid pathways and seep related processes beneath the modern hikurangi margin seabed and possibly also for other modern and ancient cold seep carbonate systems

late neogene benthic stable isotope record of ocean drilling program site 999 implications for caribbean paleoceanography organic carbon burial and the messinian salinity crisis we report on epibenthic foraminiferal 18o and 13c and percentage coarse fraction records from caribbean ocean drilling program odp site 999 12 44 n 78 44 w water depth 2828 m spanning the interval from 8 5 to 5 3 ma low epibenthic 13c values and low amounts of sand sized particles mostly foraminifer shells indicate a poorly ventilated deep caribbean throughout the late miocene at this time the deep caribbean was dominated by a nutrient rich and corrosive water mass a generally constant 13c gradient between the caribbean and deep atlantic records during the late miocene suggests that the fluctuations in 13c reflect global changes in 13c of the dissolved inorganic carbon due to varying erosion of organic carbon from terrigenous soils and shelf sediments the observed 100 kyr cyclicity of epibenthic 13c is in good accordance with the variability of terrigenous input to the equatorial atlantic as recorded by magnetic susceptibility records of the ceara rise however some short term gradient changes between 7 0 and 4 5 ma indicate a poorer ventilation of the deep atlantic related to a reduced production of deep water in the atlantic the messinian salinity crisis between 6 0 and 5 3 ma did not affect the intermediate to deep water gradient between the caribbean and the atlantic comparison to the bahama platform record of odp site 1006 however indicates a poorer ventilation of the shallower northern caribbean basins coincident with the isolation of the mediterranean sea

the characteristics of gas hydrates recovered from shenhu area in the south china sea abstract for the first time gas hydrate samples were recovered in the south china sea during a drilling campaign implemented in shenhu area in june 2007 laboratory based studies for the characteristics of gas hydrate were carried out on two hydrate bearing sediment samples observations found that gas hydrates occurred in the pores of fine grained sediments the hydrates were structure i based on the raman spectroscopic results the guest gas molecules in hydrate cages were predominantly methane 99 3 and trace amount of ethane 0 4 and propane 0 04 as determined with the method of gas chromatography as estimated from the intensities of raman peaks the cage occupancy rates were more than 99 in large cage and 86 in small cage respectively corresponding to a hydration number of 5 9

3d analogue modeling of the south china sea a discussion on breakup pattern the opening of the south china sea is one of the most important cenozoic events in se asia in order to investigate its tectonic evolution three analogue modeling experiments were compared the modeling results suggest that rifting pattern and orientation change of the rift zone were related to initial theological stratification affected by the ductile flow of silicone lower crust and honey asthenosphere the faults became flattened especially close to the breakup area we conjecture that the slope area may bear relatively hotter and thinner lithosphere than the shelf area from the beginning of rifting due to stretching and mantle upwelling associated with this regional extension which in turn lead to the change in initial rheological stratification and therefore the rifting pattern from shelf to slope in the experiments breakup developed first at isolated points which grew and coalesced to become a single spreading area the conjugate boundaries were either all concave or all convex where a rigid massif was located at the divergent boundary stretching history was different in this case the northern and southern areas thinned rapidly and developed into two deep troughs which may finally evolve into spreading centers the shape of the massif controls the orientation and boundary shape of the spreading area it is interpreted that crustal breakup was more viscous in style and the nw sub sea basin developed along the northern trough of the zhongsha xisha massif macclesfield bank c 2008 elsevier ltd all rights reserved

impact of anaerobic oxidation of methane on the geochemical cycle of redox sensitive elements at cold seep sites of the northern south china sea abstract cold hydrocarbon seepage is a frequently observed phenomenon along continental margins worldwide however little is known about the impact of seeping fluids on the geochemical cycle of redox sensitive elements pore waters from four gravity cores d 8 d 5 d 7 and d f collected from cold seep sites of the northern south china sea were analyzed for so42 mg2 ca2 sr2 dissolved inorganic carbon dic 13cdic dissolved fe mn and trace elements e g mo u the sulfate concentration depth profiles 13cdic values and dic ca2 mg2 so42 ratios suggest that organoclastic sulfate reduction osr is the dominant process in d 8 core besides osr anaerobic oxidation of methane aom is partially responsible for depletion of sulfate at d 5 and d 7 cores the sulfate consumption at d f core is predominantly caused by aom the depth of sulfate methane interface smi and methane diffusive flux of d f core are calculated to be 7 m and 0 035 mol m 2 yr 1 respectively the relatively shallow smi and high methane flux at d f core suggest the activity of gas seepage in this region the concentrations of dissolved uranium u were inferred to decrease significantly within the iron reduction zone it seems that aom has limited influence on the u geochemical cycling in contrast a good correlation between the consumption of sulfate and the removal of molybdenum mo suggests that aom has a significantly influence on the geochemical cycle of mo at cold seeps accordingly cold seep environments may serve as an important potential sink in the marine geochemical cycle of mo

geochemistry grouping and origins of crude oils in the western pearl river mouth basin offshore south china sea abstract thirty seven crude oils and 20 source rocks were selected for detailed molecular geochemical and isotopic analyses in order to establish the genetic relationships between the discovered oils and various petroleum source facies in the western pearl river basin offshore south china sea four groups of oils were identified the group i oils distributed in the southwestern wc19 1 field of wenchang b sag are characterized by high abundance of 4 methyl steranes relative to regular steranes low abundance of bicadinanes and high 13 c values showing good correlation with the medium deep lacustrine source facies in the wenchang formation the group ii oils represent the majority of the discovered oil reserves in the study area including those from the qionghai uplift and the northeast block of the wc19 1 oil field these oils have moderate concentrations of c 30 4 methylsteranes abundant bicadinanes and low 13 c values and correlate well with the shallow lake source facies of the wenchang formation in the wenchang b and a sags the group iii oils found in the wenchang a sag and surrounding areas are devoid of c 30 4 methylsteranes with abundant bicadinanes and similar 13 c values to those of the group ii oils these characteristics show close affinity with the coal bearing sequence in the enping formation thus suggesting a coaly source for these oils the group iv oils found only in the wc8 3 field display intermediate chemical compositions between the group ii and group iii oils most likely from mixed sources in the wenchang a sag these oil source genetic relationships suggest dominantly short distance oil migration and thus strong source facies controls on the geographic distribution of oil and gas fields within the western pearl river mouth basin

disentangling marine soil and plant organic carbon contributions to continental margin sediments a multi proxy approach in a 20 000 year sediment record from the congo deep sea fan abstract a 20 kyr long sediment sequence from the congo deep sea fan core geob 6518 1 one of the world s largest deep sea river fans has been analysed for bulk and molecular proxies in order to reconstruct the marine soil and plant organic carbon oc contributions to these sediments since the last glacial maximum the bulk proxies applied c n ratio and 13 c org ranged from 10 to 12 5 and from 24 5 to 21 vpdb respectively as molecular proxies concentrations of marine derived alkenones and terrestrial derived odd numbered n alkanes were used which varied between 0 2 and 4 g g dry weight sediment in addition the branched vs isoprenoid tetraether bit index a proxy for soil organic matter input was used which varied from 0 3 to 0 5 in this core application of binary mixing models based on the different individual proxies showed estimates for terrestrial oc input varying by up to 50 due to the heterogeneous nature of the oc application of a three end member mixing model using the 13 c org content the c n ratio and the bit index enabled the distinction of soil and plant organic matter as separate contributors to the sedimentary oc pool the results show that marine oc accounts for 20 to 40 of the total oc present in the deep sea fan sediments over the last 20 kyr and that soil oc accounts for about half 45 on average of the oc present this suggests that soil oc represents the majority of the terrestrial oc delivered to the fan sediments accumulation rates of the plant and soil oc fractions over the last 20 kyr varied by a factor of up to 5 and are strongly related to sediment accumulation rates they showed an increase starting at ca 17 kyr bp a decline during the younger dryas peak values during the early holocene and lower values in the late holocene this pattern matches with reconstructions of past central african humidity and congo river discharge from the same core and revealed that central african precipitation patterns exert a dominant control on terrestrial oc deposition in the congo deep sea fan marine oc accumulation rates are only weakly related to sediment accumulation rates and vary only little over time compared to the terrigenous fractions these variations are likely a result of enhanced preservation during times of higher sedimentation rates and of relative small fluctuations in primary production due to wind driven upwelling

tracing the paleo sulfate methane transition zones and h2s seepage events in marine sediments an application of c s mo systematics 1 microbially mediated anaebic oxidation of methane aom coupled with sulfate consumption within the sulfate methane transition zone smtz in marine sediments is a widely recorded biogeochemical reaction and has profound influence on the atmospheric ch4budget marine carbon cycle and composition of sediment pore fluids recognizing the paleo smtzs in the marine sediments rock records can throw light on the variation of paleo methane fluxes and occurrences of cold seep h2s ch4 events through geologic time here we present results from carbonate carbon pyrite sulfur and molybdenum analyses for two sediment cores overlying the methane hydrate deposits in the bay of bengal the results show intimate association of isotopically depleted carbonate carbon and enriched pyrite sulfur constraining the paleo smtz within the sediment column in addition anomalous enrichments of mo concentrations indicate hydrogen sulfide seepage events here we propose a geochemical tool using c s mo sytematics to decipher the paleo smtzs in marine sediments and rocks