Last glacial emplacement of methane-derived authigenic carbonates in the Sea of Japan constrained by diatom assemblage,carbon-14, and carbonate content

We studied diatom assemblages and CaCO₃ contents of methane-derived authigenic carbonates from the eastern margin of the Sea of Japan and assessed the formation time of these samples. Radioactive ¹⁴C date was determined in selected samples to obtain the maximum age of the time. The results of our study suggest mass formation of carbonate nodules in a glacial period within ∼40 ky, consistent with a published U/Th dating result of carbonate nodules in the study area. Diatom assemblages and contents in the carbonate nodules (abundance of ∼10⁶/g, dominance of neritic-littoral species, warm/cold water species ratio lower than ∼25) differ from the near-seafloor sediments in the study area, which have characteristics of Holocene sediments in the Sea of Japan, and suggest cementation of glacial sediments. Laminated sediments in some nodule samples are glacial sediments because laminations are records of a low sea level period in the semi-enclosed ocean. Similarity of diatom assemblages and contents in all carbonate samples is another evidence of glacial sediments in nodules. Glacial sediments with oceanic cold water species as low as Holocene sediments restricts the sediment age to before 20 cal. ky BP. Carbonate contents higher than 78 wt% suggest the cementation of poorly compacted sediments near the seafloor, and the date of carbonate cementation is, therefore, close to that of the cemented sediments. Most carbonate nodule samples in this study were formed in a glacial period and detection of ¹⁴C restricts this period to within ∼40 ky.     

末次盛冰期以来冲绳海槽中部沉积物有机碳和磷的地球化学研究

利用元素及同位素地球化学方法研究了冲绳海槽中部沉积物岩芯中有机碳及磷的地球化学特征及影响因素。结果表明,冲绳海槽沉积速率（16.5~32.5 cm/ka）变化小,不是沉积物中有机碳埋藏的重要影响因素。相对于全新世氧化性底水环境,末次盛冰期/冰消期冲绳海槽缺氧底水环境提高了沉积物对有机碳的埋藏效率。冲绳海槽沉积物中各形态磷的相对含量与其他边缘海沉积物中的相似。交换态磷（Ex-P）含量低、变化小。末次盛冰期/冰消期缺氧底水环境下铁氧化物的还原溶解导致铁结合磷（Fe-P）释放以及自生磷矿物（Au-P）的形成。全新世氧化性底水条件有利于铁氧化物的有效再生及对磷的再吸附,但不利于Au-P的保存。总有机碳（TOC）和有机磷（Org-P）之间良好的相关性表明TOC埋藏对Org-P含量的重要控制作用。冲绳海槽沉积物中碎屑磷（De-P）含量低于长江口及东海陆架沉积物中的含量,这与陆源碎屑向外海传输减弱有关。在约9.3 ka BP（岩芯200 cm深度）,TOC、Fe-P、Org-P、De-P以及Fe_HR均出现的极小值可能由物质坡移造成。     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

酸化过程对不同碳酸钙含量的海洋沉积物中总氮及其同位素分析的影响

为节约成本和样品,一些学者同时分析海洋沉积物中的碳、氮及其同位素（TOC、TN、δ¹³C和δ¹⁵N）。分析沉积物中的δ¹³C,需要对样品进行酸化去除无机碳,但是这一酸化过程会使TN和δ¹⁵N的分析结果产生偏差,且偏差范围与沉积物中无机碳含量（CaCO₃）有关。本研究选取了低CaCO₃含量（1-16%）和高CaCO₃含量（20-40%）的海洋沉积物样品,比较了酸化过程对TN和δ¹⁵N的影响。研究结果表明,酸化过程对海洋沉积物中TN和δ¹⁵N的分析结果产生了显著影响。对于低CaCO₃含量的样品,酸化导致样品中TN流失了约0-40%,δ¹⁵N偏移了约0-2‰;而对于高CaCO₃含量的样品,酸化导致样品中TN流失了约10-60%,δ¹⁵N偏移了约1-14‰。表明酸化对TN和δ¹⁵N的影响已经超过了仪器的误差范围0.002%（TN）和0.08‰（δ¹⁵N）,将影响TN和δ¹⁵N的环境指示意义。因此,即使海洋沉积物样品中CaCO₃含量很低,也必须用原样分析TN和δ¹⁵N以避免酸化过程的影响。     

Depositional environment in the southern Ulleung Basin, East Sea (Sea of Japan), during the last 48 000 years

The present study is based on the sedimentological data from a piston core KCES1 off the southern Ulleung Basin margin, the East Sea (Sea of Japan). The data include sediment color (L^*), X-ray radiographs, grain size distribution and AMS¹⁴C date. Four kinds of sediments (homogeneous, laminated, crudely laminated and hybrid sediments) are identified according to the characters of the sedimentary structures that were considered to reflect changes in bottom-water oxygenation. Alternations of dark laminated/crudely laminated sediments and light homogeneous sediments represent millennial-scale variations that are possibly associated with the high-resolution changes in the East Asian monsoon (EAM). The relative contributions of the East China Sea Coastal Water (ECSCW) and the Tsushima Warm Current (TWC) were likely the main reasons for the repetition of the anoxic and oxic depositional conditions in the East Sea since the last 48 ka BP. During the interstadial, the strengthen summer EAM was attributed to the expansion of the ECSCW because of more humid climate in central Asia, and then more strongly low-salinity, nutrient-enriched water was introduced into the East Sea. The ventilation of deep water was restricted and therefore the dark laminated layer deposited under the anoxic bottom water condition. During the lowest stand of sea level in the last glacial maximum (LGM), the isolated East Sea dominated by stratiˉed water masses and the euxinic depositional environment formed. The homogenous sediments have been predominating since 17.5 ka BP indicating that the TWC has intruded into the East Sea gradually with the stepwise rise of sea level and the bottom water oxygen level was high. During the late Younger Dryas (YD) period, the last dark laminated layer deposited because the ventilation of bottom water was restricted by stronger summer EAM. The TWC strengthened and the bottom water became oxic again from 10.5 ka BP.     

Iodine chemistry in deep anoxic basins and overlying waters of the Mediterranean Sea

Iodate (IO₃⁻) is the predominant dissolved species of iodine in the oxygenated waters of the Mediterranean Sea. Iodide (I⁻) is present in significant quantities (up to 65 nM) in oxygenated waters in the photic zone and near the interface above the anoxic and saline Bannock Basin. Lesser quantities of I⁻ (< 10 nM) are found throughout the rest of the oxic water column. An additional unidentified dissolved iodine species is present immediately above the anoxic interface.Total dissolved iodine (ΣI) increases dramatically across the seawater/brine interface. Part of this increase is undoubtedly the result of the dissolution of iodine-rich evaporites during formation of the brine bodies at the Tyro and Bannock Basins. The vertical distribution of ΣI and other dissolved chemical species (particularly PO₄³⁻) in the Bannock Basin brine, however, suggests an additional, present-day, diagenetic source of dissolved iodine to the brine. Based on the increase in the concentration of the most soluble major ions across the seawater/brine interface, 5–7 μM of the 11.5-μM increase in ΣI concentration must be attributed to diagenesis.     

南海东北部晚更新世以来沉积环境演变的矿物-地球化学记录

对南海东北部69柱(20°07.10'N,118°49.0'E)沉积物岩心进行碎屑矿物-地球化学特征研究,结果表明,以孔深165cm为界可划分出晚更新世末次冰期沉积和全新世冰后期沉积,这一地层划分结果与根据浮游有孔虫氧、碳同位素分析得出的结果是一致的.末次冰期时自生黄铁矿和硫元素高度富集,钠与铝、镁与铝和钠与钾的比值均较高,重矿物和SiO₂含量较高,CaCO₃含量较低,反映当时是一种相对闭塞的缺氧环境,气候干寒,化学风化作用较弱,以机械风化作用为主;研究区主要接受粒径较粗的硅质沉积;陆源物质的稀释作用可能是造成碳酸盐含量相对较低的主要原因.冰后期褐铁矿出现高含量,钠与铝、镁与铝和钠与钾的比值均降低,Al₂O₃和CaCO₃含量增高,反映沉积环境渐变为开放的氧化环境,气候转变为化学风化作用较强的湿热气候;研究区以接受较细粒的铝硅酸盐沉积为主,冰消期时还出现了碳酸盐保存高峰事件.     

Assemblages of benthic foraminifers in the White Sea

Based upon the composition of the dominant species of benthic foraminifers in the bottom sediments sampled at 50 sampling stations in the White Sea, their six assemblages (communities) were defined and mapped. The ranges of these communities depend on the environmental factors determined by the bathymetric, latitudinal, and circum-continental sea zonalities, the sea currents, the bottom upwellings, the continental runoff, the productivity of the waters, and the CaCO₃ content in the near-bottom water layers and bottom sediments.     

Benthic foraminiferal assemblages as indicators of the paleoceanographic conditions in the eastern Equatorial Pacific

Five assemblages of benthic foraminifers reflecting the changes in the properties of the intermediate water masses and the biological productivity during different periods of the last glacial-interglacial cycle are defined based on the abundances and relative contents of indicative species in the upper 9 m of giant Core MD02-2529 from the Cocos Ridge. High bioproductivity and low oxygen content in the bottom water layer and sediments are established for the interstadial period based on the high abundance of the species Uvigerina peregrina, U. hispida, and C. pachyderma (Assemblage I) and especially for the Last Glacial Maximum (Assemblage II) with the dominant role of the same species and E. smithi. The transition from the glaciation to the current interglacial (Termination I, Assemblage III) is characterized by a high share of the epifaunal species C. wuellerstorfi and H. subhaidingeri, which indicates enhanced hydrodynamic activity and ventilation of the intermediate water washing the bottom. The end of Termination I was marked by strengthened selective dissolution of carbonate microfossils due to the increased influx of fresh organic matter to the bottom and/or advection of more aggressive intermediate waters. The diverse Early Holocene assemblage (Assemblage IV) points to variable ecological niches, while the abundance of the infaunal U. hispida in Assemblage V indicates low productivity of the surface waters and a low oxygen concentration in the bottom sediments of the Late Holocene.     

渤海南部海域柱状沉积物中氮的形态与有机碳的分解

海洋沉积物中氮形态的研究是研究其生物地球化学循环的重要前提,柱状沉积物中氮的形态分布在一定程度上反映了其早期成岩作用的进程及结果.利用分级浸取分离方法首次对渤海南部海域自然粒度下5个柱状沉积物样品进行了分析,依据是否可由试剂提取将其分为可转化态和非转化态,系统地研究了可转化态中各形态氮的分布特征及早期成岩作用.研究表明,渤海南部海域自然粒度下柱状沉积物中,OSF-N和IEF-N是可转化态氮的优势形态.各形态氮的含量随深度变化趋势不同,成岩作用亦不同.沉积物中有机氮的分解速率常数为15.51×10-3a,且对各生源要素的分解速率常数有N>P>C>Si;OC/TN比值远小于OC/ON,说明沉积物中保留了大量无机氮(IN)和非转化的有机氮,OC/ON值随深度增加而减小是由于沉积物中富集了ON;柱状沉积物中,表层比深层可转化态氮占其总量的比例高,在局部区域由于深层沉积物中氮的“再活化”导致二者几乎相同.     

Regional features of variations in paleoproductivity of the Sea of Okhotsk in the Late Pleistocene and Holocene

Variations in the content of chlorin (a derivate of chlorophyll a) in 11 cores of bottom sediments from different parts of the Sea of Okhotsk are studied. The data show variations in paleoproductivity of this sea for the past 160000 years from the end of marine isotope stage (MIS) 6 until recently. A common pattern of the variation in paleoproductivity is established for the entire Sea of Okhotsk. During the interglacials (MIS 5e and 1), productivity increased, and in glacial periods, it decreased, probably due to the longer lasting marine ice cover throughout the year. The features of variations in productivity through time are recorded in the eastern part of the sea, which is more prone to the influence of inflowing Pacific waters.     

Chemical and isotopic evidence for the nature of the fluid in CH4-containing sediments of the Håkon Mosby Mud Volcano

The pore waters of CH₄-containing sediments of the Håkon Mosby Mud Volcano were rich in NH⁺ ₄, Br^-, and I^-; exhibited a high total alkalinity; but were poor in Cl^-and SO^2- ₄. The geological evidence and our data suggest that organic matter decomposition in preglacial or early interglacial sediments took place during early diagenesis (bacterial processes) and during metamorphism (thermogenic processes under the 3100-m-thick layer of glacial sediments), accompanied by mud volcano fluid generation. It is argued that the CH₄of the mud volcano sediments has a mixed, biogenic and thermogenic, origin.     

Controls on organic carbon distribution in sediments from the eastern Arabian Sea Margin

 Sediment cores from the upper continental slope of the eastern Arabian Sea have high organic carbon (OC), CaCO₃, and sand content at the top. The values decrease with increasing depth in the Holocene and Upper Pleistocene. Topographic highs show highest OC and lower CaCO₃ in the Holocene clayey sediments and vice versa in the Pleistocene sandy sediments. The OC is immature and marine or a mixture of both marine and terrestrial in the Holocene sediments and is mostly terrestrial and/or reworked marine in the Pleistocene sediments. Productivity is the main controlling factor for the organic carbon enrichment. Texture and reworking also influence the organic carbon variations. Received: 29 May 1996/Revision received: 10 January 1997     

Geochemical and textural properties of carbonate and terrigenous sediments along the Jordanian coast of the Gulf of Aqaba

The physicochemical properties of 21 marine sediment samples were investigated, collected from five different localities along the Jordanian coast of the Gulf of Aqaba. According to the chemical parameters, sediments were categorized into three groups: carbonate (80% CaCO₃), composed mainly of materials of calcareous skeletal structures; terrigenous (<10% CaCO₃) depositional areas for land-derived materials from surrounding rocks and alluviums; and a admixture of the first two (19–37% CaCO₃). High significant linear correlations were found between organic carbon (OC) and total nitrogen (TN), indicating the occurrence of these components in a common phase (organic matter). Despite the co-occurrence of TP in organic matter, these two elements were negatively correlated, indicating anthropogenic sources of pollution such as phosphate exportation (hotel areas and clinker port sites) and industrial activities (industrial complex site). The study found that variations in texture properties and mud contents were due to differences in sediment sources, topography and their response during currents and waves. The finer, well-sorted sediments contain lower elemental concentrations of OC, calcium carbonate and TN (excluding TP) than coarser, poorly-sorted sediments.     

48ka以来日本海Ulleung海盆南部的海洋沉积环境演化

晚第四纪以来伴随底层水含氧量的剧烈变化,浅色和深色沉积层的交替出现是日本海半远洋沉积物的主要特征。沉积特征分析表明,日本海Ulleung海盆南部KCES1孔的沉积物具有四种不同的沉积构造:均质、纹层、纹层状和混杂构造。深色沉积层一般具有纹层和纹层状构造,并且与我国内陆的千年尺度东亚夏季风强弱变化记录有很好的对应关系,表明纹层沉积物也具有千年尺度的变化规律,从而进一步说明了冰川性海平面变化和东亚夏季风波动应该是Ulleung海盆南部底层水溶解氧含量变化的主要原因。在暖期,在东亚夏季风降水相对增强的影响下,低温、低盐的东海沿岸水对日本海表层水体的贡献要大于对马暖流的贡献,日本海水体间的交换减弱,最终造成缺氧的海底沉积环境。在冷期,夏季风强度的减弱(冬季风增强)加快了日本海西北部深层水的生成,Ulleung海盆南部的底层水含氧量高,相应地沉积了具均质构造的浅色沉积物;在末次盛冰期最低海平面时,日本海成为一个封闭的海盆,降雨量高于蒸发量,水体出现分层,底层水处于停滞缺氧状态。自距今17.5 ka(日历年,下同)以来底层水含氧量较高,对马暖流逐渐成为影响日本海海洋沉积环境的主要因素。Ulleung海盆南部底层水的含氧量在YD期间有一定程度的降低,东海沿岸水的短暂强盛制约了深层水的流通。自距今10.5 ka以来对马暖流强盛,日本海海底处于富氧的沉积环境。     

Nitrogen forms and decomposition of organic carbon in the southern Bohai Sea core sediments

Study on form characteristics of nitrogen in marine sediments is the primary method to research its biogeochemical cycling and nitrogen form characteristics in core sediments can reflect the process and results of early diagenesis in a certain degree. In this paper, Sequential extraction process in natural grain size was used for studying the existent forms of nitrogen in five core sediments of the southern Bohai Sea for the first time. Nitrogen was divided into two parts -transferable and fixed based on whether it could be extracted by the reagent. Distributions and early diagenesis of transferable nitrogen forms in the southern Bohai Sea were researched integratedly. Results indicate that IEF - N and OSF-N are predominant forms in transferable part in the studied core sediments. Contents of different nitrogen forms vary differently with depth, and have different diagenesis process. Decomposition constant of organic nitrogen (ON) and OC are about 15.51 × 10~(-3)a~(-1)and 4.79× 10~(-3)a~(-1) respective     

Bottom foraminiferal assemblages in the Deryugin Basin (Sea of Okhotsk) during the past 26000 years

Benthic foraminifers from a core of bottom sediments obtained in the Deryugin Basin at a depth of 1750 m were examined. Three distinct benthic foraminiferal assemblages that replaced one another throughout the last 26000 years were recognized. The assemblage dominated by Alabaminella weddellensis, Uvigerina auberiana, and Cassidulina translucens dwelled here from 26 to 24 ky B.P. The sediments of the glacial period between 26 and 12.18 ky B.P. contain no benthic foraminifers. The composition of the sediments suggests the existence of active bottom vents of gas-bearing fluids during that time. The dominance of Brizalina spissa, Uvigerina peregrina, and Cassidulina laevigata is characteristic of the period from 12.18 to 7 ky B.P., when the productivity of the surface waters in the region was high, and warm, poorly oxygenated waters spread over the bottom of the basin. During the past 7 000 years, the bottom conditions in the sea were similar to the present-day conditions and an assemblage with the dominance of Gyroidina orbicularis, Uvigerina auberiana, and Cassidulina teretis developed in the region.     

台湾海峡西部沉积物中碳的来源及埋藏

根据2005年夏季航次观测的沉积物中总有机碳(TOC)、无机碳(CaCO3)、总氮(TN)、悬浮体颗粒有机碳(POC)、沉积物粒度数据得出,台湾海峡西部表层沉积物TOC质量分数的范围为0.01～1.79,平均值为0.37±0.24,略高于20多年前台湾海峡南部海区,而低于台湾海峡中、北部海区;TOC的质量分数湾内比湾外...     

Methane seepage in the Shenhu area of the northern South China Sea: constraints from carbonate chimneys

Two authigenic carbonate chimneys were recovered from the Shenhu area in the northern South China Sea at approximately 400 m water depth. The chimneys’ mineralogy, isotopic composition, and lipid biomarkers were studied to examine the biogeochemical process that induced the formation of the chimneys. The two chimneys are composed mostly of dolomite, whereas the internal conduits and semi-consolidated surrounding sediments are dominated by aragonite and calcite. The specific biomarker patterns (distribution of lipids and their depleted δ¹³C values) indicate the low occurrence of methanotrophic archaea ANME-1 responsible for the chimneys’ formation via anaerobic oxidation of methane. A significant input of bacteria/planktonic algae and cyanobacteria to the carbon pool during the precipitation of the carbonate chimneys is suggested by the high contributions of short-chain n-alkanes (69% of total hydrocarbons) and long-chain n-alcohols (on average 56% of total alcohols). The oxygen isotopic compositions of the carbonate mixtures vary from 3.1‰ to 4.4‰ in the dolomite-rich chimneys, and from 2.1‰ to 2.5‰ in the internal conduits, which indicates that they were precipitated from seawater-derived pore waters during a long period covering the last glacial and interglacial cycles. In addition, the mixture of methane and bottom seawater dissolved inorganic carbon could be the carbon sources of the carbonate chimneys.     

Enhanced preservation of organic matter in sediments deposited within the oxygen minimum zone in the northeastern Arabian Sea

The presence of a strongly developed oxygen minimum zone (OMZ; [O₂]<2 μM) in the northeastern Arabian Sea affords the opportunity to investigate whether oxygen deficiency in bottom waters enhances the preservation of organic matter in the underlying sediments. We explored if the observed patterns of organic matter accumulation could be explained by differences in productivity, sedimentation rate, water depth, and mineral texture. The differences in the burial rates of organic matter in sediments deposited within or below the OMZ could not be explained on the basis of these factors. All collected evidence points to a coupling of low oxygen concentrations and enhanced organic matter preservation. Under more oxygenated conditions bioturbation as well as the presence of labile manganese and iron oxides are probably important factors for a more efficient microbially mediated degradation of organic matter. Pore water profiles of dissolved Mn²⁺ and Fe²⁺ show that reduction of manganese and iron oxides plays a minor role in sediments lying within the OMZ and a larger role in sediments lying below the OMZ.