Evaluation of on-line pyrolysis two-dimensional gas chromatography time-of-flight mass spectrometry (Py-GC × GC-ToFMS) on whole sediments from a Mediterranean sapropel sequence

Analysis of the molecular composition of the organic matter (OM) from whole sediment samples can avoid analytical bias that might result from isolation of components from the sediment matrix, but has its own analytical challenges. We evaluated the use of GC × GC-ToFMS to analyze the pyrolysis products of six whole sediment samples obtained from above, within and below a 1 million year old OM-rich Mediterranean sapropel layer. We found differences in pyrolysis products <n-C₂₂ between the OM-rich sapropel samples and the OM-poor background marls. The presence of alkyl pyrroles, probably derived from chlorophyll, in pyrolysates of the sapropels but not in those of the marls suggests that higher marine productivity and greater OM preservation accompanied deposition of the sapropels. Detection of tetramethyl benzenes considered to be pyrolysis products of isorenieratene in the sapropel samples is evidence that nitrogen-fixing green sulfur bacteria contributed to the high productivity. Greater abundances of shorter chain aliphatic hydrocarbons, pyrroles, furans and alkyl aromatics in the pyrolysates of sapropel samples relative to the marls confirm better preservation of marine OM in the sapropels. In addition, the presence of greater amounts of thiophenes in the sapropels than in the marls is consistent with the existence of euxinic conditions during sapropel deposition. The combination of whole sediment pyrolysis and GC × GC-ToFMS is promising, but the procedure requires careful selection of its multiple analytical variables, particularly the pyrolysis temperature and the operational features of the GC columns.     

Benthonic and planktonic foraminifera in relation to the Early Holocene stagnation in the Ionian Basin, Central Mediterranean

The distribution patterns of benthonic and planktonic foraminifera in cores from the Ionian Basin, central Mediterranean, were investigated in relation to the deposition of sapropel S-1. The sapropel is a dark organic-rich sediment deposited under anoxic conditions during the last marine stagnation in the Early Holocene. The major divisions between both benthonic and planktonic faunas correspond to changes in the core lithology and coincide with the transitions between pre-sapropel, sapropel/'oxidized layer' and post-sapropel sediments. The faunal evidence shows that the oxidized layer belongs to the sapropel sequence. The planktonic faunas have the same species composition as in the sapropel sediment and the high density of planktonic species continues into the oxidized layer. The oxidized layer is devoid of a benthonic fauna or contains a 'sapropel-associated' fauna composed of infaunal species with an affinity to high supply of organic material material and low oxygen. High depletion in the heavy oxygen isotope in the oxidized layer substantiates the faunal evidence. A peak in abundance of the planktonic species Globorotalia inflata at the top of the oxidized layer marks the time when turnover of the water masses ended the stagnation phase and sapropel sedimentation in the Ionian Basin at about 6000 BP. The distribution of the benthonic and planktonic foraminifera shows that the sapropel in the central part of the Ionian Basin was originally almost twice as thick as it is today. When oxygen returned to the deep sediments the top of the sapropel was oxidized to 4–7 cm below its original surface. Only the lower part of the sapropel is preserved. The remainder is now a red laminated layer, the 'oxidized layer'.     

A quantitative reconstruction of organic matter and nutrient diagenesis in Mediterranean Sea sediments over the Holocene

A multicomponent diagenetic model was developed and applied to reconstruct the conditions under which the most recent sapropel, S1, was deposited in the eastern Mediterranean Sea. Simulations demonstrate that bottom waters must have been anoxic and sulphidic during the formation of S1 and that organic matter deposition was approximately three times higher than at present. Nevertheless, most present day sediment and pore water profiles — with the exception of pyrite, iron oxyhydroxides, iron-bound phosphorus and phosphate — can be reproduced under a wide range of redox conditions during formation of S1 by varying the depositional flux of organic carbon. As a result, paleoredox indicators (e.g., C_org:S ratio, C_org:P_org ratio, trace metals) are needed when assessing the contribution of oxygen-depletion and enhanced primary production to the formation of organic-rich layers in the geological record. Furthermore, simulations show that the organic carbon concentration in sediments is a direct proxy for export production under anoxic bottom waters.The model is also used to examine the post-depositional alteration of the organic-rich layer focussing on nitrogen, phosphorus, and organic carbon dynamics. After sapropel formation, remineralisation is dominated by aerobic respiration at a rate that is inversely proportional to the time since bottom waters became oxic once again. A sensitivity analysis was undertaken to identify the most pertinent parameters in regulating the oxidation of sapropels, demonstrating that variations in sedimentation rate, depositional flux of organic carbon during sapropel formation, bottom water oxygen concentration, and porosity have the largest impact. Simulations reveal that sedimentary nutrient cycling was markedly different during the formation of S1, as well as after reoxygenation of bottom waters. Accumulation of organic nitrogen in sediments doubled during sapropel deposition, representing a significant nitrogen sink. Following reventilation of deep waters, N₂ production by denitrification was almost 12 times greater than present day values. Phosphorus cycling also exhibits a strong redox sensitivity. The benthic efflux of phosphate was up to 3.5 times higher during the formation of S1 than at present due to elevated depositional fluxes of organic matter coupled with enhanced remineralisation of organic phosphorus. Reoxygenation of bottom waters leads to a large phosphate pulse to the water column that declines rapidly with time due to rapid oxidation of organic material. The oxidation of pyrite at the redox front forms iron oxyhydroxides that bind phosphorus and, thus, attenuate the benthic phosphate efflux. These results underscore the contrasting effects of oxygen-depletion on sedimentary nitrogen and phosphorus cycling. The simulations also confirm that the current conceptual paradigm of sapropel formation and oxidation is valid and quantitatively coherent.     

The geochemical behavior and isotopic composition of Hg in a mid-Pleistocene western Mediterranean sapropel

The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average δ²⁰²Hg value of −0.91‰ ± 0.15‰ (n = 5, 1 SD) and Δ¹⁹⁹Hg value of 0.11‰ ± 0.03‰ (n = 5, 1 SD). Background sediments have an average δ²⁰²Hg of −0.76‰ ± 0.16‰ (n = 5, 1 SD) and Δ¹⁹⁹Hg of 0.05‰ ± 0.01‰ (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.     

Manganese-rich brown layers in Arctic Ocean sediments: Composition, formation mechanisms, and diagenetic overprint

We present inorganic geochemical analyses of pore waters and sediments of two Late Quaternary sediment cores from the western Arctic Ocean (southern Mendeleev Ridge, RV Polarstern Expedition ARK-XXIII/3), focussing on the composition and origin of distinct, brown-colored, Mn-rich sediment layers. Carbonate enrichments occur in association with these layers as peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg, suggesting enhanced input of both ice-rafted and biogenic carbonate. For the first time, we show that the Mn-rich layers layers are also consistently enriched in the scavenged trace metals Co, Cu, Mo and Ni. Distinct bioturbation patterns, specifically well-defined brown burrows into the underlying sediments, suggest these metal enrichments formed close to the sediment-water interface. The geochemical signature of these metal- and carbonate-rich layers most probably documents formation under warmer climate conditions with an intensified continental hydrological cycle and only seasonal sea ice cover. Both rivers and sea ice delivered trace metals to the Arctic Ocean, while enhanced seasonal productivity exported reactive organic matter to the sea floor. The coeval deposition of organic matter, Mn (oxyhydr)oxides and trace metals triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, and the degradation of labile organic matter. With the onset of cooler conditions, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, resulting in deposition of grayish-yellowish, metal-poor sediments. Oxygen depletion of Arctic bottom waters under these cooler conditions is not supported by our data, and did not cause the sedimentary Mn distribution. While the original composition and texture of the brown layers resulted from specific climatic conditions and corresponding diagenetic processes, pore water data show that diagenetic Mn redistribution is still affecting the organic-poor deeper sediments. Given persistent steady state conditions, purely authigenic Mn-rich brown layers may form, while others may be partly or completely dissolved. The degree of diagenetic Mn redistribution largely depends on the depositional environment, the Mn and organic matter availability, and apparently affected the Co/Mo ratios of Mn-rich layers. Thus, brown Arctic layers are not necessarily synchronous features, and should not be correlated across the Arctic Ocean without additional age control.     

Investigation of the ingrowth of radioactive daughters of in Mediterranean sapropels as a potential dating tool

Five different sapropels (S1, S3–S6) from two sites (2750 m and 3308 m water depth) in the eastern Mediterranean were analysed for C_org content and specific activities of , , and . Anoxia in the sapropel sediments during or shortly after deposition leads to U enrichment, and the observed excess of over activity is consistent with a seawater source for authigenic U. In certain cases, the U profile shape in and around the sappropels is interpreted to indicate that oxidation shortly after sapropel formation has caused a post-depositional downwards migration of both U isotopes. Systematic variability of the activity ratio across the sapropel units indicates that a different diagenetic process has also led to preferential relocation of produced in situ from the parent. The construction of quasi-isochrons in successively older sapropel units demonstrate that radioactive secular equilibrium is approached by a systematic ingrowth of over time from the marked initial disequilibrium between and the U isotopes. The effects of post-depositional diagenesis violate the isochron model boundary conditions, however, and lead to a deviation of the isochron ages from the expected stratigraphic ages. Following assessment of each data point, some improvements in the calculated ages were achieved in one case by exclusion from the calculations of those points most severely affected by open system behaviour.     

沉积物微量金属元素在重建水体环境变化中的意义

沉积物所记录的微量金属含量与形态的变化是指示人类活动影响下水体环境变化的有效指标,主要用于指示沉积物重金属污染、水体初级生产力变化和氧化还原条件等方面的水体环境状况。总体而言,沉积物中微量金属含量在近一个世纪以来显著上升,反映了采矿、冶金、污水排放、化肥使用、煤炭和石油燃烧等各种人类活动造成水体和沉积物重金属污染的记录作为浮游植物微量营养元素,Cu、Zn、Ni、Ba、Cd等在沉积物中的记录可以指示水体初级生产力水平。U、Mo、V、Cu、Cd、Mn等氧化还原敏感元素在沉积物中的富集或贫化,及其比值(如Re/Mo、Cd/U、Th/U和V/Sc)的变化,是指示水体和沉积物氧化还原环境的有效指标。但需要指出的是,在受人类活动影响的水体中,这些生产力和氧化还原指标很少能指示水体生产力或氧化还原状况,可能主要与人类活动同时造成这些金属元素大量污染输入而掩盖了其自生来源和内在变化的沉积记录有关。所以,对沉积物中微量金属元素来源的判别(陆源碎屑输入、人为输入和水体自生来源)是重建水体环境变化的重要前提。本文总结了多种化学和统计学方法(包括同位素示踪法、化学提取法、富集因子法和主成分分析法等)在沉积物金属来源判别中的应用另外,成岩作用等多种因素会干扰沉积物金属记录对环境变化的指示作用,所以构建多元素指标来综合判断沉积物记录所反映的环境信息是今后的研究所必须关注的     

Higher plant vegetation changes during Pliocene sapropel formation

The δ¹³C values of higher plant wax C_27–33 n-alkanes were determined in three, time-equivalent Pliocene (2.943 Ma) sapropels and homogeneous calcareous ooze from three different sites forming an east-west transect in the eastern Mediterranean Basin in order to study the composition of the vegetation on the continents surrounding the Mediterranean Sea. A two-end member mixing model transformed the measured δ¹³C values into the contribution of C₄ plants to the terrestrial vegetation. These calculations indicated a high C₄ plant contribution (i.e. 40–50%) in the periods just before and just after sapropel formation. During sapropel deposition the C₄ plant contribution increased by up to 20% at all sites. This is interpreted to record the increased overall plant coverage of the Mediterranean borderlands resulting from the change in formerly barren desert areas into C₄ grass-dominated savannahs as a response to the wetter climate during sapropel deposition. Enhanced accumulation rates (ARs) of long-chain n-alkanes (C_27–33) and n-alkan-1-ols (C_26–30) towards the middle of the sapropel in concert with a decrease in the Ti/Al ratio confirm an increased delivery of terrigenous organic matter at all sites. These biomarkers were probably predominantly fluvially transported to the Mediterranean Sea, not only by the Nile but by fossil wadi river systems on the northern African continent.     

Late Quaternary sapropel sediments in the eastern Mediterranean Sea: Faunal variations and chronology

Distinctive planktonic foraminiferal assemblages which characterize particular late Quaternary sapropel layers in deep basin sediments from the eastern Mediterranean Sea have been identified using cluster analysis. Three distinct clusters allow for identification and intercore correlation of the nine sapropels deposited during the last 250,000 yr. Cluster 1, representing sapropel layers S1 and S9, exhibits low abundances of Neogloboquadrina dutertrei and high abundances of Globigerinoides ruber; Cluster 2, which groups S3, S5, and S7, contains high abundances of G. ruber, N. dutertrei, and Globigerina bulloides, and Cluster 3, which includes samples from S4, S6, and S8, is marked by extremely abundant N. dutertrei and G. bulloides, and rare G. ruber. Analysis of sedimentation rates in 14 cores reveals the following approximate ages for the sapropel layers: S2 = 52,000 yr B.P.; S3 = 81,000–78,000 yr B.P.; S4 = 100,000–98,000 yr B.P.; and S5 = 125,000–116,000 yr B.P. As previously suggested, sedimentation rates on the Mediterranean Ridge were determined to be relatively constant during the last 127,000 yr. In contrast, basin sedimentation rates have fluctuated markedly from lower rates during interglacial stage 5 to higher rates during the last glacial episode. These glacial/interglacial differences are most pronounced in the northern Ionian Basin, because of increased terrigenous sediment deposition during glacial episodes. Unusually high biogenic sedimentation rates occurred in an arc south of Crete during the deposition of sapropel S5, probably due to higher productivity in this region.     

Fossil pigments as a guide to the paleolimnology of Browns Lake, Ohio

Some aspects of the paleolimnology of Browns Lake, Ohio, have been ascertained by a study of preserved sedimentary plant pigments and conductivity of interstitial water. Temporal changes in the sedimentary environment, especially redox conditions, along with changes in the flora of the lake and the development of peat in the basin have brought about differential sedimentation and preservation of pigments. Measurement of changes in total and relative concentration and diversity of chlorophyll derivatives and carotenoids has provided important clues to late-glacial and postglacial evolution of the lake. Laminated sediments, rich in fossil remains, near the base of the core indicate eutrophic conditions and meromixis for several thousand years beginning shortly after lake inception. As meromixis broke down, the lake evolved gradually to holomictic conditions when sapropel was deposited. An advancing complex of reed swamp and fen forest began during midpostglacial time, providing ever-increasing amounts of highly organic, peaty sediments and continues to the present. The pond is now dystrophic, and increasing deposition of inorganic sediment is apparent at the top of the core, concomitant with land clearance and agriculture. In the same interval, an increase of water conductivity reflects recent agricultural practices and industrialization in the region.     

Enhanced regeneration of phosphorus during formation of the most recent eastern Mediterranean sapropel (S1)

Phosphorus regeneration and burial fluxes during and after formation of the most recent sapropel S1 were determined for two deep-basin, low-sedimentation sites in the eastern Mediterranean Sea. Organic C/P ratios and burial fluxes indicate enhanced regeneration of P relative to C during deposition of sapropel S1. This is largely due to the enhanced release of P from organic matter during sulfate reduction. Release of P from Fe-bound P also increased, but this was only a relatively minor source of dissolved P. Pore-water HPO₄²⁻ concentrations remained too low for carbonate fluorapatite formation. An increased burial of biogenic Ca-P (i.e., fish debris) was observed for one site. Estimated benthic fluxes of P during sapropel formation were elevated relative to the present day (∼900 to 2800 vs. ∼70 to 120 μmol m⁻² yr⁻¹). The present-day sedimentary P cycle in the deep-basin sediments is characterized by two major zones of reaction: (1) the zone near the sediment-water interface where substantial release of HPO₄²⁻ from organic matter takes place, and (2) the oxidation front at the top of the S1 where upward-diffusing HPO₄²⁻ from below the sapropel is sorbed to Fe-oxides. The efficiency of aerobic organisms in retaining P is reflected in the low organic C/P ratios in the oxidized part of the sapropel. Burial efficiencies for reactive P were significantly lower during S1 times compared with the present day (∼7 to 15% vs. 64 to 77%). Budget calculations for the eastern Mediterranean Sea demonstrate that the weakening of the antiestuarine circulation and the enhanced regeneration of P both contributed to a significant increase in deep-water HPO₄²⁻ concentrations during sapropel S1 times. Provided that sufficient vertical mixing occurred, enhanced regeneration of P at the seafloor may have played a key role in maintaining increased productivity during sapropel S1 formation.     

Analysis of arsenic speciation in mine contaminated lacustrine sediment using selective sequential extraction,HR-ICPMS and TEM

In order to determine how As speciation in lacustrine sediment changes as a function of local conditions, sediment cores were taken from three lakes with differing hydrologic regimes and subjected to extensive chemical and TEM analysis. The lakes (Killarney, Thompson and Swan Lakes) are located within the Coeur d’ Alene River system (northern Idaho, USA), which has been contaminated with trace metals and As, from over 100 a of sulfide mining. Previous analyses of these lakebed sediments have shown an extensive amount of contaminant metals and As associated with sub-μm grains, making them extremely difficult to analyze using standard methods (scanning electron microscopy, X-ray diffraction). Transmission electron microscopy offers great advantages in spatial resolution and can be invaluable in determining As speciation when combined with other techniques. Data indicate that because of differences in local redox conditions, As speciation and stability is dramatically different in these lakes. Killarney and Thompson Lakes experience seasonal water-level fluctuations due to drawdown on a downstream dam, causing changes in O₂ content in sediment exposed during drawdown. Swan Lake has relatively constant water levels as its only inlet is dammed. Consequently, Killarney and Thompson Lakes show an increase in labile As-bearing phases with depth, while Swan Lake data indicate stable As hosts throughout the sediment profile. Based on these observations it can be stated that As in lakebed sediments is much less mobile, and therefore less bioavailable, when water is kept at a constant level.     

The influence of oxic degradation on the sedimentary biomarker record II. Evidence from Arabian Sea sediments

Biomarker accumulation rates in nine different time slices in three cores on and at the foot of a submarine high in the northern Arabian Sea (the Murray Ridge) were measured to investigate the influence of oxygen exposure time on the preservation of biomarker signals in the sedimentary record. All three sites experienced the same history of surface water productivity and sediment supply but had different bottom-water redox conditions due to their different positions (in, just below, well below) relative to the present location of the intense oxygen minimum zone (OMZ). Past variations in the intensity and position of the OMZ, known from a wide variety of proxies (TOC content, distribution and abundance of planktonic and benthic foraminifera and pteropods, trace metals, and δ¹⁵N), enabled specific biomarker (i.e., n-alkanes, steroids, alkenones, alkyldiols, C₂₆ fatty acid, loliolide, biphytane diols, and archaeal tetraether lipids) accumulation rates at contrasting oxygen exposure times to be compared. The results indicate that these accumulation rates can vary by more than an order of magnitude for marine biomarkers. In addition, there are significant differences in the degree of oxic degradation of different types of biomarkers: Terrestrial n-alkanes are much more resistant than alkenones and n-alkyl diols, which are more refractory than steroids and biphytane diols. These differences in degree of oxic degradation indicate that biomarker distributions will change on increasing exposure to oxygen. These findings have a significant impact on the application of biomarkers to sedimentary settings in which oxygen exposure time is likely to change significantly.     

Comparative high-resolution chemostratigraphy of the Bonarelli Level from the reference Bottaccione section (Umbria-Marche Apennines) and from an equivalent section in NW Sicily: Consistent and contrasting responses to the OAE2

The Bonarelli Level (BL) from the upper Cenomanian portion of the reference Bottaccione section (central Italy) is characterized by the presence of black shales containing high TOC concentrations (up to 17%) and amounts of CaCO₃ near to zero. In the absence of carbonate and, consequently, of relative carbon- and oxygen-isotopic data, the elemental geochemistry revealed to be a very useful tool to obtain information about the palaeoclimatic and palaeoceanographic evolution of the Tethys Ocean during the OAE2. Based on several geochemical proxies (Rb, V, Ni, Cr, Si, Ba), the BL is interpreted as a high-productivity event driven by increasingly warm and humid climatic conditions promoting an accelerated hydrological cycle. The enrichment factors of peculiar trace metals (Zn, Cd, Pb, Sb, Mo, U) provide further insight about the H₂S activity at the seafloor during the organic-rich sediment deposition and permitted us to evaluate the use of Ba as palaeoproductivity tracer in conditions of high rate of sulphate reduction.By comparing geochemical records from the reference Bottaccione section (central Italy) with those previously obtained for the coeval Calabianca section (northwestern Sicily), different degrees of oceanic anoxia were delineated and ascribed to different abundance and type (degradable or refractory) of organic matter, which are limiting factors in the bacterial sulphate reduction reactions and in subsequent euxinic conditions at seafloor in the Tethys realm. Based on a ciclostratigraphic approach, consistent fluctuations at 100 ky scale in the chemostratigraphic signals from the two sections are inferred to be expression of a strong orbital-climatic forcing driving changes in the oceanic environment during the BL deposition.     

Geochemical environment of Cenomanian - Turonian black shale deposition at Wunstorf (northern Germany)

Major- and minor- element determinations were carried out on a high-resolution sample set obtained from a sediment drill core at Wunstorf (N. Germany). This study interval includes the black shale-bearing Hesseltal Formation associated with the Oceanic Anoxic Event 2 (OAE 2), also referred to as Cenomanian-Turonian Boundary Event (CTBE). Seven black shale packages, each containing several black shale layers, were defined by elevated TOC values, with black shale packages 1-4 deposited during OAE 2. Packages 5-7 extend above the level of the positive carbon-isotope excursion defining OAE 2, indicating that conditions favouring organic carbon burial must have prevailed longer in the Wunstorf Basin than elsewhere. Geochemical analyses revealed no significant differences between black shale packages deposited during and after OAE 2. Enrichment patterns of sulphur, iron and redox-sensitive and sulphide-forming trace metals point to suboxic to anoxic conditions existing at the sediment-water interface during black shale deposition, whereas sulphidic conditions prevailed deeper in the sediment. Variations in element/Al ratios follow cyclic patterns which are interpreted to represent climatically-induced changes in sediment supply. Reduced vertical mixing led to water-column stratification and caused black shale deposition.     

Holocene and late glacial palaeoceanography and palaeolimnology of the Black Sea: Changing sediment provenance and basin hydrography over the past 20,000 years

The elemental geochemistry of Late Pleistocene and Holocene sediments of the Black Sea, recovered in box cores from the basin margins and a 5-m gravity core from the central abyssal region of the basin, identifies two terrigenous sediment sources over the last 20 kyrs. One source region includes Anatolia and the southern Caucasus; the second region is the area drained by rivers entering the Black Sea from Eastern Europe. Alkali metal:Al and heavy:light rare-earth element ratios reveal that the relative contribution of the two sources shifted abruptly every few thousand years during the late glacial and early Holocene lacustrine phase of the basin. The shifts in source were coeval with changes in the lake level as determined from the distribution of quartz and the heavy mineral-hosted trace elements Ti and Zr.The geochemistry of the abyssal sediments further recorded a sequence of changes to the geochemistry of the water column following the lacustrine phase, when high salinity Mediterranean water entered the basin beginning 9.3 kyrs BP. Bottom water that had been oxic throughout the lake phase became anoxic at approximately 8.4 kyrs BP, as recorded by the accumulation from the water column of several redox-sensitive trace metals (Mo, Re, U). The accumulation of organic carbon and several trace nutrients (Cd, Cu, Ni, Zn) increased sharply ca. 0.4 kyrs later, at 8.0 kyrs BP, reflecting an increase of primary productivity. Its increase was coeval with a shift in the dinoflagellate ecology from stenohaline to euryhaline assemblages. During this profound environmental change from the lacustrine to the marine phase, the accumulation rate of the lithogenous sediment fraction decreased as much as 10-fold in response to the rise of the water level in the basin from a low stand ca. 9.3 ka to its current level.     

The biogeochemical distribution of trace elements in the Indian Ocean

The present review deals with the distributions of dissolved trace metals in the Indian Ocean in relation with biological, chemical and hydrographic processes. The literature data-base is extremely limited and almost no information is available on particle processes and input and output processes of trace metals in the Indian Ocean basin and therefore much research is needed to expand our understanding of the marine chemistries of most trace metals. An area of special interest for future research is the Arabian Sea. The local conditions (upwelling induced productivity, restricted bottom water circulation and suboxic intermediate waters) create a natural laboratory for studying trace metal chemistry.     

Geochemical Record of the Cenomanian–Turonian Anoxic Event in Tunisia: Is it Correlative and Isochronous to the Biotic Signal?

In Tunisia, five Bahloul spaced sections, Bargou, Jerisa, Guern Halfaya, Kherij and Gafsa were analyzed for biostratigraphy (foraminifera and radiolarians) and major and trace elements. This high-resolution biostratigraphic and chemostratigraphic integrated analyses for the Late Cenomanian–Early Turonian Bahloul Formation provide new insight into the palaeoceanographic evolution of the southern Tethyan margin. Relative low abundance of related terrigenous Ti/Al and K/Al ratios and enrichment of some productivity proxies such as Ba, Cu, and Ni (organic matter related trace elements) suggests that the Bahloul, deposited during a relatively short period (0.5 Ma), was of relatively elevated primary productivity and minimal detrital input. While higher D* values concurrent with lower Ti/Al ratios are interpreted as caused by enhanced fluvial material contribution, due to more humid climate during the OAE-2. Enhanced humidity triggered probably fluvial influxes, resulted in a sluggish water circulation and consequent anoxic/euxinic conditions favoring the preservation of organic matter at the bottom. Enrichments in redox-sensitive trace metals U, V, and Mo in the Bahloul Formation deposits and redox indices, such as V/(V+Ni), U/Th, V/Cr, and Ni/Co, indicate that oxygen-restricted conditions prevailed during the Late Cenomanian to earliest Turonian times and correlate well with relative abundances of some foraminiferal and radiolarian paleo-environmental relevant indicators. High Baxs values and Uauth may indicate anoxic conditions at least at the water–sediment interface during the Bahloul Formation deposition and provide information about low to moderate sulfate-reduction reactions.     

Organic geochemistry and pore water chemistry of sediments from Mangrove Lake,Bermuda

Mangrove Lake, Bermuda, is a small coastal, brackish-water lake that has accumulated 14 m of banded, gelatinous, sapropelic sediments in less than 10⁴ yr. Stratigraphic evidence indicates that Mangrove Lake's sedimentary environment has undergone three major depositional changes (peat, freshwater gel, brackish-water gel) as a result of sea level changes. The deposits were examined geochemically in an effort to delineate sedimentological and diagenetic changes. Gas and pore water studies include measurements of sulfides, ammonia, methane, nitrogen gas, calcium, magnesium, chloride, alkalinity, and pH. Results indicate that sulfate reduction is complete, and some evidence is presented for bacterial denitrification and metal sulfide precipitation. The organic-rich sapropel is predominantly algal in origin, composed mostly of carbohydrates and insoluble macromolecular organic matter called humin with minor amounts of proteins, lipids, and humic acids. Carbohydrates and proteins undergo hydrolysis with depth in the marine sapropel but tend to be preserved in the freshwater sapropel. The humin, which has a predominantly aliphatic structure, increases linearly with depth and composes the greatest fraction of the organic matter. Humic acids are minor components and are more like polysaccharides than typical marine humic acids. Fatty acid distributions reveal that the lipids are of an algal and/or terrestrial plant source. Normal alkanes with a total concentration of 75 ppm exhibit two distribution maxima. One is centered about n-C₂₂ with no odd/even predominance, suggestive of a degraded algal source. The other is centered at n-C₃₁ with a distinct odd/even predominance indicative of a vascular plant origin. Stratigraphic changes in the sediment correlate to observed changes in the gas and pore water chemistry and the organic geochemistry.     

Marine records of Holocene climatic variations

Holocene millennial climate variability is smaller than that of the last glaciation, due to the disappearance of large unstable ice sheets. Marine records show that the sea-surface temperature (SST) exhibited small variations, mainly in the high and low latitudes. They may be interpreted as a linear response to the mean annual insolation. Major changes in the hydrological cycle have been evidenced in the Asian and African monsoon area, resulting in enhanced precipitation and large river outflow in the Bay of Bengal and the Gulf of Niger. Enhanced rainfall over the Mediterranean Basin resulted in a weak circulation and sapropel formation below 800-m water depth in the eastern Mediterranean Sea. Finally small changes in the thermohaline circulation and the warm North Atlantic Drift have been detected in the Nordic Seas. The Holocene climatic variability is therefore similar to that of the Quaternary, but with small amplitude, while continents experienced large rainfall variations. To cite this article: J.-C. Duplessy et al., C. R. Geoscience 337 (2005).