Contents and isotopic speciation of sedimentary carbon and nitrogen in sediment core MD01-2404, the Okinawa Trough

Total organic carbon to total nitrogen ratio (C/N) and their isotopic composition (d13CTOC vs. d15NTN) are oft-applied proxies to discern terrigenous from marine sourced organics and to unravel the ancient environmental information. In high depositional Asian marginal seas, matrixes, including N-bearing minerals, dilution leads to illusive and even contradictive interpretations. We use KOH-KOBr to separate operationally defined total organic matter into oxidizable (labile) and residual fractions for content and isotope measurements. In a sediment core in the Okinawa Trough, significant amounts of carbon and nitrogen existed in the residual phase, in which the C/N ratio was ~9 resembling most documented sedimentary bulk C/N ratios in the China marginal seas. Such similarity creates a pseudo-C/N interrupting the application of bulk C/N. The residual carbon, though composition unknown, it displayed a d13C range (-22.7 to -18.9 per mil, mean -20.7 per mil) similar to black carbon (-24.0 to -22.8 per mil) in East China Sea surface sediments. After removing residual fraction, we found the temporal pattern of d13CLOC in labile fraction (LOC) was more variable but broadly agreed with the atmospheric pCO2-induced changes in marine endmember d13C. Thus, we suggested adding pCO2-induced endmember modulation into two-endmember mixing model for paleo-environment reconstruction. Meanwhile, the residual nitrogen revealed an intimate association with illite content suggesting its terrestrial origin. Additionally, d15N in residual fraction likely carried the climate imprint from land. Further studies are required to explore the controlling factors for carbon and nitrogen isotopic speciation and to retrieve the information locked in the residual fraction.

Sea surface temperature oscillations in southern Okinawa Trough during last 2700 years from ODP Hole 195-1202B

Most of the temperature reconstructions for the past two millennia are based on proxy data from various sites on land. Here we present a bidecadal resolution record of sea surface temperature (SST) in Southern Okinawa Trough for the past ca. 2700 years by analyzing tetraether lipids of planktonic archaea in the ODP Hole 1202B, a site under the strong influence of Kuroshio Current and East Asian monsoon. The reconstructed SST anomalies generally coincided with previously reported late Holocene climate events, including the Roman Warm Period, Sui-Tang dynasty Warm Period, Medieval Warm Period, Current Warm Period, Dark Age Cold Period and Little Ice Age. However, the Medieval Warm Period usually thought to be a historical analogue for the Current Warm Period has a mean SST of 0.6-0.8°C lower than that of the Roman Warm Period and Sui-Tang dynasty Warm Period. Despite an increase since 1850 AD, the mean SST in the 20th century is still within the range of natural variability during the past 2700 years. A close correlation of SST in Southern Okinawa Trough with air temperature in East China, intensity of East Asian monsoon and the El-Niño Southern Oscillation index has been attributed to the fluctuations in solar output and oceanic-atmospheric circulation.

(Table T1) Pore water chemistry of ODP Site 195-1202 sediments, southern Okinawa Trough

Pore water was collected from sediment cores from Holes 1202A and 1202D in the southern Okinawa Trough during Ocean Drilling Program (ODP) Leg 195. Because drilling at this site was completed only a few hours out of port during the end of the leg, whole rounds of sediment core 5 or 10 cm long were sealed and stored at ~3°C until pore water could be extracted from them during Leg 196, using a titanium squeezer designed by Manheim and Sayles (1974) and standard handling techniques (Shipboard Scientific Party, 2002, doi:10.2973/odp.proc.ir.195.103.2002).

Geochemical data and mineralogical properties of bulk sediment composition of ODP Hole 195-1202B

During Leg 195 of the Ocean Drilling Program, Site 1202 was drilled in the subtropical northwestern Pacific Ocean beneath the Kuroshio (Black Current) between northern Taiwan and the Ryukyu Island Arc on the northern flank of the I-Lan Ridge at 1274 m water depth. The upper 110 m of the Site 1202 section, composed of dark grey calcareous silty clay, provide an expanded record of environmental changes during the last 28 kyr. The sediments were deposited at high sedimentation rates between 3.0 and 5.0 m/kyr and peak values of 9.0 m/kyr between 15.1 and 11.2 ka BP. Variations in the modes and sources of detrital sediment input, as inferred from sediment granulometry, mineralogy, and elemental XRF-scanner data, reflect changes in environmental boundary conditions related to sea-level changes, Kuroshio variability, and the climate-driven modes of fluvial runoff. The provenance data point to increased sediment supply from northwestern Taiwan between 28 and 19.5 ka BP and from East China sources between 19.5 and 11.2 ka BP. The change in provenance at 19.5 ka BP reflects increased fluvial runoff from the Yangtze River and strong sediment reworking from the East China Sea shelf in the course of increased humidity and postglacial sea-level rise, particularly after 15.1 ka BP. The Holocene was dominated by sediments that originated from rivers in northeastern Taiwan. For the pre-Holocene period prior to 11.2 ka BP, low portions of sortable silt (63-10 ?m) show that the Kuroshio did not enter the Okinawa Trough, because of low sea-level. In turn, high proportions of sortable silt and sediment provenance from northeastern Taiwan point to strong ocean circulation under the direct and persistent influence of the Kuroshio during the Holocene. The reentrance of the Kuroshio to the Okinawa Trough was heralded by two pulses in relative current strengthening at 11.2 and 9.5 ka BP, as documented by stepwise increases in sortable silt in the lower Holocene section. From a global perspective, environmental changes in the southern Okinawa Trough show affinities to climate change in the western Pacific warm pool with little influence of climate teleconnections from the North Atlantic realm, otherwise seen in many other marine and terrestrial palaeoclimate records from southeastern Asia.

Geochemistry of felsic rocks and minerals of ODP Hole 135-841B

A felsic volcanic series (605-825 mbsf) overlain by upper Eocene shallow-water sediments (500-605 mbsf) and basalticandesitic sills that intruded into sediments of Holocene to Miocene age (0-500 mbsf) was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The volcanic sequence at Site 841 includes altered and mineralized calc-alkaline rhyolites and dacites, dacitic tuffs, lapilli tuffs, flow breccias, and welded tuffs. These rocks formed subaerially or in a very shallow-water environment suffering a subsidence of >5000 m since Eocene times. Calculations of gains and losses of the major components during alteration show most pronounced changes in the uppermost 70 m of the volcanic sequence. Here, Al, Fe, Mg, and K are enriched, whereas Si and Na are strongly depleted. Illite, vermiculite, chlorite, and hematite predominate in this part of the hole. Throughout the section, quartz, plagioclase, kaolinite, and calcite are present. Sulfide mineralization (up to 10 vol%) consisting mainly of disseminated pyrite (with minor pyrrhotite inclusions) and marcasite together with minor amounts of chalcopyrite is pervasive throughout. Locally, a few sulfide-bearing quartz-carbonate veins as well as Ti-amphibole replacement by rutile and then by pyrite were observed. Strong variations in the As content of sulfides (from 0 to 0.69 wt%) from the same depth interval and local enrichments of Co, Ni, and Cu in pyrite are interpreted to result from fluctuations in fluid composition. Calculations of oxygen and sulfur fugacities indicate that fO2 and fS2 were high at the top and lower at the bottom of the sequence. Sulfur isotope determinations on separated pyrite grains from two samples give d34S values of +6.4ë and +8.4ë, which are close to those reported from Kuroko and Okinawa Trough massive sulfide deposits and calc-alkaline volcanic rocks of the Japanese Ryukyu Island Arc. Calculated chlorite formation temperatures of 265°-290°C at the top of the sequence are consistent with minimum formation temperatures of fluid inclusions in secondary quartz, revealing a narrow range of 270°-297°C. Chlorite formation temperatures are constant downhole and do not exceed 300°C. The presence of marcasite and 4C-type pyrrhotite indicates a formation temperature of <= 250°C. At a later stage, illite was formed at the top of the volcanic series at temperatures well below 200°C.

Mineral content, major oxides and trace elements concentrations in clay from different IODP Holes of 331-C0013, 331-C0017, East China sea shelf and different Taiwan rivers

The Okinawa Trough (OT) in the East Asian continental margin is characterized by thick terrigenous sediment and ubiquitous volcanic-hydrothermal activities. In this study, the clays collected during IODP Expedition 331 to the middle OT (Iheya North Knoll) were analyzed for mineralogical and geochemical compositions. By comparing with the clays from the East China Sea shelf and surrounding rivers, we examine different clay origins. The hydrothermal field in the mid-OT is dominated by Mg-rich chlorite, while the recharge zone has clay mineral assemblages similar to the shelf and rivers, showing high content of illite, subordinate chlorite and kaolinite and scarce smectite. Compared to the terrigenous clays, the hydrothermal clays in the OT have high concentrations of Mg, Mn and Zr but low Fe, Na, K, Ca, Ba, Sr, P, Sc and Ti, while the hydrothermal clays in the mid-ocean ridge are relatively enriched in Fe and V and depleted in Al, Mg, Zr, Sc and Ti. Different fractionation patterns of rare earth elements also register in the terrigenous and hydrothermal clays, diagnostic of variable clay origins. We infer that the OT hydrothermal clay was primarily formed by the chemical alteration of detrital sediments subject to the hydrothermal fluids. The remarkably different compositions of hydrothermal clays between the sediment-rich back arc basin like OT and the sediment-starved ocean ridge suggest different physical and chemical processes of hydrothermal fluids and fluid-rock/sediment reactions under various geologic settings.