Deposition of sapropel S1 sediments in oxic pelagic and anoxic brine environments in the eastern Mediterranean: differences in diagenesis and preservation

Sediments from a boxcore in the previously anoxic brine-filled Poseidon Basin, eastern Mediterranean, have been studied and compared to sediments deposited in a `normal' eastern Mediterranean environment. The boxcore can be divided into three main sedimentary intervals based on AMS-radiocarbon ages, foraminiferal and geochemical zonations. From the base of the core upwards these are: (1) 12.3–31.2 cm, organic-rich sediments redeposited from within the brine; (2) 6.6–12.3 cm, sediment containing a `cold' foraminifera fauna redeposited from above the brine into the basin while the brine was still present; (3) 0–6.6 cm, oxic pelagic sediment accumulated since the reoxygenation of Poseidon Basin which occurred ∼1800 yrs BP. Near the base of the latter unit, a Mn-oxide peak has formed and it marks the present boundary between oxic and suboxic environments. A progressive downward oxidation front, which is usually found in `normal' sapropel S1 sediments, has never formed in Poseidon Basin sediments. This has resulted in the preservation of the relationship between organic carbon and organic-related trace elements, e.g. Se, in the organic-rich sediments of Poseidon Basin, whereas such a relationship has been obliterated in `normal' sapropel S1 sediments. On the basis of the carbonate content as well as the Sr/Ca ratio, preservation of carbonates appears to be better in the brine sapropel sediments of BC15 than it is in `normal' sapropel S1 sediments. The high opal content of BC15 shows that biogenic opal is also much better preserved. The overall lower C<sub>org</sub>/Ba ratio in BC15 suggests a better preservation of barite relative to that of organic carbon in shallow brine sediments, but is as yet inconclusive for the organic carbon preservation potential of brine relative to `normal' unoxidised sediments.     

Modes of sapropel formation in the eastern Mediterranean: some constraints based on pyrite properties

Pyrite formation within and directly below sapropels in the eastern Mediterranean was governed by the relative rates of sulphide production and Fe liberation and supply to the organic-rich layers. At times of relatively high SO²⁻₄ reduction, sulphide could diffuse downward from the sapropel and formed pyrite in underlying sediments. The sources of Fe for pyrite formation comprised detrital Fe and diagenetically liberated Fe(II) from sapropel-underlying sediments. In organic-rich sapropels, input of Fe from the water column via Fe sulphide formation in the water may have been important as well. Rapid pyrite formation at high saturation levels resulted in the formation of framboidal pyrite within the sapropels, whereas below the sapropels slow euhedral pyrite formation at low saturation levels occurred. δ³⁴S values of pyrite are −33‰ to −50‰. Below the sapropels δ³⁴S is lower than within the sapropels, as a result of increased sulphide re-oxidation at times of relatively high sulphide production and concentration when sulphide could escape from the sediment. The percentage of initially formed sulphide that was re-oxidized was estimated from organic carbon fluxes and burial efficiencies in the sediment. It ranges from 34% to 80%, varying significantly between sapropels. Increased palaeoproductivity as well as enhanced preservation contributed to magnified accumulation of organic matter in sapropels.     

Eastern Mediterranean sapropel S1 interruption: an expression of the onset of climatic deterioration around 7 ka BP

We discuss the palaeoclimatic interpretation of unprecedented high-resolution micropalaeontological studies of short-term (2 to 4 centuries) interruptions within early Holocene organic-rich layer (sapropel) S1 from the eastern Mediterranean. Results for cores from the Adriatic and Aegean seas that contain `double' S1 sapropels indicate that these interruptions, which are centred roughly around 7000 years <sup>14</sup>C<sub>nc</sub> BP, are genuine and related to climatic deterioration. This interpretation is endorsed by a coeval dry event recorded in terrestrial records and indications of climatic deterioration affecting human migration patterns and early societies in Egypt. The presence of sapropel interruptions in the two major source areas of deep water for the entire eastern Mediterranean likely implies that similar intervals may be found throughout the basin, provided that sedimentation rates and sampling resolutions allow the detection of events with a duration of only several centuries. Moreover, our results show that the `sapropel mode' of circulation comprises a delicate balance between reduced ventilation and enhanced productivity, which is easily disturbed through surface water cooling triggering a short time of improved deep water ventilation.     

Origin and transformation of organic matter in Pliocene–Pleistocene Mediterranean sapropels: organic geochemical evidence reviewed

Drilling of deep-water post-Messinian sedimentary sequences by ODP Legs 160 and 161 in the Mediterranean Sea has shown that occurrence of organic-carbon-rich sapropels and sapropel-like sediments extends from the Levantine Basin westward into the Alboran Basin. In the eastern Mediterranean, sapropel deposition started in the Early Pliocene, whereas in the Western Basin the onset of sapropel formation occurred later, in the Early Pleistocene. Precessional cycles are apparently the primary external forcing for sapropel formation. Nevertheless, the pattern of sapropel occurrence suggests that the precessional influence is modulated by the glaciation cycles. Large differences were observed in the organic carbon contents of sapropels recovered in the eastern and western Mediterranean. Correspondence between organic carbon contents, Rock-Eval hydrogen index values and elemental C/N ratios indicate that both variations in the production and preservation of marine organic matter have led to the accumulation of high amounts of organic matter in sapropels. Molecular organic geochemical compositions of sapropels from the eastern Mediterranean further confirm that the major fraction of organic matter in sapropels is derived from marine algal sources and has undergone variable oxidation. Enhanced marine productivity and improved preservation of organic matter is central to sapropel formation. Accumulation of increased amounts of land-derived material at times of sapropel formation is also evidenced, supporting the hypothesis of significant periodic freshwater discharges.     

Neogene sapropels in the Mediterranean: a review

For 50 years the existence of sapropels (organic-carbon-rich sediments) deposited within Plio–Pleistocene sediments of the Mediterranean Sea has been known. Initially, research concentrated on material recovered in relatively short gravity/piston cores taken from the eastern basins where sequences were found to be well developed/preserved and had extensive spatial coverage. In the main, previous studies concentrated upon establishing a workable stratigraphy, spatial correlation of individual layers and determining the probable depositional mechanisms. However, despite a plethora of research papers, some issues still remain unresolved. This is in part due to a lack of agreement between investigators; sampling and analytical short comings, restricted sample size and the fact that, in many instances, like was not being compared with like. Recently, the limit of sapropels in the western basin has been further extended. As a result, the palaeoceanographic/palaeoclimate models which had previously been developed for deposition of sapropels in the eastern basin have been modified. Most recently, strong links have been established between astronomical cyclicity and sapropel formation. This review paper provides a summary of sapropel research to date, and ongoing sapropel research in the Mediterranean, some of which appears in this thematic issue of Marine Geology. It is fitting that this thematic issue of Marine Geology be dedicated to the memory of Colette Vergnaud-Grazzini and Rob Kidd who in many ways helped to initiate the resurgence in sapropel studies in the 1970s in the Mediterranean —perhaps in 50 more years we will know all of the answers!     

Sedimentology and geochemistry of an exceptionally preserved last interglacial sapropel S5 in the Levantine Basin (Mediterranean Sea)

A combined study of lithological, geochemical and physical sediment properties is reported from a completely laminated S5 sapropel, recovered in three gravity cores (M40-4 SL67, M51-3 SL103, M51-3 SL104) from the Pliny Trench region of the eastern Mediterranean. The thickness of the studied sapropel S5 varies between 85 and 91 cm and tops most S5-sapropels in the Mediterranean. Based on optical features like color and thickness of laminae, the sapropels were subdivided into thirteen distinct lithostratigraphic zones. These zones, as well as the finer layering pattern within them, could be followed exactly among the three cores, indicating that the processes responsible for this variation acted at least on a regional scale. The sapropel sediment is characterized by exceptionally high porosity, which is strongly correlated with Si/Ca. This relationship implies that the sapropel is in essence an organic-matter rich diatomite and its exceptional thickness can be explained by preservation of diatoms forming a loosely packed sediment fabric. Compared to other S5 sapropels, the preservation of diatoms has apparently led to a twofold increase in the thickness of the sapropel layer. Relative abundances of 10 elements were determined at ultra-high resolution (0.2 mm) by XRF-scanner over the complete length of each sapropel including several cm of enclosing marl. An analysis of the chemical data indicates that the lowermost 13 cm of the sapropel is chemically more similar to the underlying marl and that the sediment chemistry shows different signals at different scales. The strongest pattern is the contrast between the sapropel and the surrounding marl, which is accentuated in elements indicative for redox conditions as well as terrigenous sediment input and productivity. Within the sapropel, a mm- to cm-scale layering is observed. The abundances of many elements are systematically linked to the pattern of these layers, indicating a common origin, related to productivity and/or terrigenous sediment and/or redox conditions. This pattern indicates a link to a regional climatic process, making the S5 sapropel horizon in M40-4 SL67, M51-3 SL103 and M51-3 SL104 a potential high-resolution archive of climatic variability during the last interglacial in the Mediterranean Sea and its adjacent landmasses.     

Transformation of suspended particulate matter into sediment in the Kara Sea in September of 2011

The biogeochemical processes participating in the transformation of the particulate matter into sediment along the Yenisei River-St. Anna Trough (Kara Sea) meridional profile were studied using hydrochemical, geochemical, microbiological, radioisotope, and isotope methods. The water-sediment contact zone consists of three subzones: the suprabottom water, the fluffy layer, and the surface sediment. The total number, biomass, and integral activity of the microorganisms (dark ¹⁴CO₂ assimilation) in the fluffy layer are usually higher than in the suprabottom water and sediment. The fluffy layer shows a decrease in the oxygen content and the growth of the dissolved biogenic elements. It was provided by the particulate organic matter supporting the vital activity of the heterotrophs from the overlying water column and by the flux of reduced compounds (NH₄, H₂S, CH₄, Fe²⁺, Mn²⁺, and others) from the underlying sediments. The C_org isotopic composition of the fluffy layer and the sediments is 2–4 ‰ heavier than that of the particulate matter and sediment due to the presence of the isotopically heavy biomass of microorganisms. A change in the isotopic composition of the C_org in the fluffy layer and surface sediment as compared to the C_org of the particulate matter is a widespread phenomenon in the Arctic shelf seas and proves the leading role of microorganisms in the transformation of the particulate matter into sediment.     

Middle Miocene (Langhian) sapropel formation in the easternmost Mediterranean deep-water basin: Evidence from northern Cyprus

Mid-Miocene (Langhian; ∼15.4 Ma) sapropels formed within the easternmost Mediterranean basin, now uplifted in northern Cyprus. These sapropels represent the oldest known sapropels in a predominantly marl succession. Six well-developed sapropels were studied. Strontium isotope dating of twelve samples gave a preferred age of ∼15.4 Ma (Langhian); i.e. during the final phases of the Middle Miocene Climatic Optimum (MCO). The age of the best-preserved nannofossil assemblage (Langhian) is close to the strontium ages. The Langhian strontium ages are preferred over an alternative early Serravallian age for less well-preserved nannofossil assemblages. Total organic carbon contents in the sapropels reach maximum values of 3.9 wt.%. Relative to the host marls, the sapropels show enrichments in terrigenous-derived minerals and related major and trace elements. Sedimentological evidence indicates that the terrigenous sediments were eroded from the northern borderlands of the deep-water basin under warm, humid conditions. High fresh-water run-off from surrounding landmasses is likely to have promoted a low-salinity lid to the eastern Mediterranean deep-water basin. This, in turn, would have restricted deep-water ventilation and promoted widespread anoxia. Exceptionally high concentrations of chalcophile elements (e.g. Cu, Ni and Zn) are consistent with anoxic conditions. Abundant nutrient-rich fresh-water input is also likely to have stimulated siliceous productivity (although any siliceous microfossils did not survive diagenesis). A significant role for diagenesis in sapropel formation is indicated by the mobilisation of Ba from sapropels to marl directly beneath. Orbitally induced dry–wet oscillation, the mechanism invoked to explain the Pliocene to Holocene sapropels, apparently was already in place during the latest stages of the MCO when the Langhian sapropels accumulated. These sapropels accumulated immediately after the Middle Miocene closure of the Southern Neotethys when the Eastern Mediterranean Sea apparently became more sensitive to orbital cyclicity. The development of a semi-enclosed deep-water basin was, therefore, a prerequisite for sapropel formation.     

Diagenetic magnetic enhancement of sapropels from the eastern Mediterranean Sea

Diagenetic dissolution of magnetic minerals has been widely observed in organic-rich sediments from many environments. Organic-rich sediments from the eastern Mediterranean Sea (sapropels), recovered during Leg 160 of the Ocean Drilling Program, reveal a surprising catalogue of magnetic properties. Sapropels, from all sites studied across the eastern Mediterranean Sea, are strongly magnetic and the magnetization is directly proportional to the organic carbon content. The magnetization of the sapropels is dominated by a low-coercivity, probably single domain magnetic mineral (with an inverse magnetic fabric) that exhibits a clear decay in magnetic properties when exposed to air. During heating, the magnetic particles irreversibly break down between 360 and 400°C. The contrast between the magnetic properties of sapropels and surrounding sediments is marked, with remanence intensities of sapropels often being more than three orders of magnitude higher than those of underlying sediments. The contrast between the magnetic properties of sapropels and the surrounding sediments is apparently controlled by non-steady-state diagenesis: sulphate-reducing conditions dominated during sapropel deposition, while overlying sediments were deposited under oxic conditions. The mineral responsible for the magnetic properties of sapropels is most likely to have formed under sulphate-reducing conditions that existed during times of sapropel formation. Attempts to identify this mineral have been unsuccessful, but several lines of evidence point toward an unknown ferrimagnetic iron sulphide phase. The influence of diagenesis on the magnetic properties of cyclically-deposited eastern Mediterranean sedimentary sequences suggests that magnetic parameters may be a useful proxy for diagenesis in these sediments.     

Palynology and geochemistry of channel-margin sediments across the tidal–fluvial transition,lower Fraser River,Canada: Implications for the rock record

In the tidally influenced Fraser River, Canada, palynological and carbon isotope (δ¹³C_org) signatures of channel-margin sediments are compared to environmental parameters (e.g., grain size, water salinity) to establish how the signatures vary across the tidal–fluvial transition. Palynological assemblages in the Fraser River are dominated by tree pollen, which constitutes between 85% and 95% of all assemblages. Dinocyst abundances do not exceed 2% of the total palynological assemblage, and the number and diversity of dinocysts gradually decreases landward. The calculated landward limit for dinocysts is at approximately 83 river km, which is relatively close to the upstream limit of the tidal backwater (at ∼100 km). δ¹³C_org values show minimal variability across the tidal–fluvial transition, and the average value is approximately −26‰. The δ¹³C_org signature of river sediments indicates a dominance of terrestrially sourced organic matter regardless of brackish-water and tidal influence on sediment deposition.Six palynological and geochemical trends are identified as relevant to the rock record. 1) In deltaic environments, palynological and geochemical characteristics are less useful than sedimentological and ichnological characteristics for establishing depositional conditions. 2) In marginal-marine settings, low abundances and low species diversities of dinocysts, coupled with a “terrestrial” geochemical signature (δ¹³C_org < −25‰) do not necessarily indicate deposition in a terrestrial environment. 3) Dinocyst abundances above 1% of the total palynomorph population can indicate a significant marine influence on sediment deposition. 4) Mud beds, preferably bioturbated, should be preferentially sampled in order to maximize palynomorph recovery. 5) Marine palynomorphs can occur, albeit in very low concentrations, to the landward limit of the tidal–backwater zone. 6) Palynological and geochemical data should be compared across the paleo-depositional environment in order to establish general trends and remove local variations caused by biases such as grain size.     

Benthic foraminiferal successions across Late Quaternary Mediterranean sapropels

Benthic foraminiferal records across Late Quaternary Mediterranean sapropels S6, S5 and S1 are reviewed and re-considered in the light of recent advances in foraminiferal ecology. It is suggested that the main factor controlling the foraminiferal successions that occur immediately before and after sapropel deposition is the amount of time involved in the onset of anoxic conditions and in the re-oxygenation of the benthic environment. Faunas dominated by deep infaunal taxa such as Globobulimina and Chilostomella reflect a very gradual decrease or increase of bottom water oxygenation. Post-sapropel faunas dominated by small biconvex, trochospiral taxa, which are inferred to have a much more opportunistic life strategy, are typical of a very rapid re-oxygenation of the benthic environment after sapropel deposition. The time involved in re-oxygenation depends upon the mechanism causing sapropel formation. The faunal succession found above sapropel S5 suggests a basin with a strong density gradient in the upper part of the water column during sapropel deposition, followed by a rapid turnover of the following column and quick re-oxygenation of the benthic environment. In contrast, the faunal succession above sapropel S6 suggests a water column with a more gradual density gradient deeper in the basin, a progressive deepening of the halocline, and a very slow increase of bottom water oxygenation.     

Mechanisms of land–sea interactions – the distribution of metals and sedimentary organic matter in sediments of a river-dominated Mediterranean karstic estuary

This paper examines disposal of metals and the origin, characteristics, and distribution of sedimentary organic matter (SOM) in a Mediterranean karstic estuary in the north-eastern Adriatic. This environment offers a real-time, small model system for studies of geochemical processes in microtidal Mediterranean estuaries that are infilling with sediments and classified as river-dominated disequilibrium estuaries. The results have shown that the longitudinal distribution of heavy metals in sediments follows the sedimentation dynamics and deposition pattern of river-borne, clay mineral particles. The highest concentration of metals was found in the restricted upper part of the estuary, characterized by rapid deposition of clay particles and terrestrial sedimentary organic matter, and decreases toward the open sea. The vertical distribution of metals in sediment cores depends on the prevailing pH and Eh conditions. Significant increases of the concentrations of metals in the uppermost strata are the result of recent anthropogenic inputs. The share of the terrestrial component in SOM, estimated by N/C_org atomic ratios and δ¹³C values, decreases with distance from the river mouth. The small vertical variation in δ¹³C values of SOM indicates that a fast sedimentation rate overrides the diagenetically determined decomposition. The results obtained indicate that river-borne inorganic particles, natural terrigenous organic material, and anthropogenic metal loads are trapped in sediments of the estuarine system. Under the prevailing conditions, there is negligible transport towards the open sea.     

Geochemistry of eastern Mediterranean sediments: Primary sediment composition and diagenetic alterations

Two cores recovered in the eastern Mediterranean were analysed for major, minor and trace elements. The primary chemical composition of the sediment is different at each location, probably because the lithological sources and the relative biogenic contributions differ.

Carbonates are important for the concentration of Ca, Mg and Sr, whereas aluminosilicates determine the concentration of Si, Al, K, Li, Y and Be, and to a lesser extent that of Fe, Cr, Ti, Mg, Zn and Zr. In sapropels, organic carbon and sulphur seem to be closely related. Bromine, Mo, P, Fe, V, Cu, Zn, Co, Ni and Cr are closely associated with organic and sulphidic compounds. The concentration versus depth profile for organic carbon in two sapropels points to a rapid establishment of conditions that gave rise to sapropel formation, followed by a gradual transition back to “normal” conditions.

The primary composition is overprinted by diagenetic processes. Sulphate-reducing conditions occurred during and just after sapropel deposition. A progressive oxidation front mechanism, which became active after sapropel deposition, is responsible for additional major geochemical changes. This diagenetic phenomenon has strong implications for the chemistry of Fe, Mn, Ni, Co, Zn, Cu, Cr, V, U, As and Sb.     

Carbon and nitrogen isotope excursions in mid-Pleistocene sapropels from the Tyrrhenian Basin: Evidence for climate-induced increases in microbial primary production

The modern Mediterranean Sea is oligotrophic, yet its sediment record contains layers of organic-carbon-rich sapropels at 21 ky (precessional) spacing that imply periods of elevated paleoproductivity that approached the high productivities of modern upwelling systems. Resolution to this paradox is provided by lines of evidence suggesting that the mode of primary productivity changed from one dominated by algae to one during times of sapropel deposition in which photosynthetic bacteria were important. We have made a high-resolution comparison of the organic carbon and nitrogen isotopic compositions of three sapropels and their background sediments in a 3-m sequence that corresponds to 1001 to 946 ka. Organic δ¹³C values systematically increase from − 26‰ to − 21‰ and δ¹⁵N values systematically decrease from 4‰ to < 0‰ as organic carbon mass accumulation rates increase in the sapropel layers. The increase in carbon isotope values mirrors the increases in primary productivity and associated organic matter export indicated by the increased mass accumulation rates. The decrease in nitrogen isotope values implies major contributions of nitrogen-fixing cyanobacteria to the total marine productivity. The precessional minima with which sapropels coincide were times of wetter climate that stratified the surface Mediterranean Sea, increased delivery of soil-derived phosphorus, and evidently amplified microbial primary production. Our high-resolution study reveals several relatively rapid excursions into and out of the high-productivity mode that suggest that sapropel deposition was a climate-sensitive surface-driven phenomenon that was not accompanied by basin-wide stagnation.     

The supply and preservation of ancient and modern components of organic carbon in the Canadian Beaufort Shelf of the Arctic Ocean

The provenance of organic matter in sediments from the Mackenzie River and Beaufort Shelf was investigated using the stable carbon and radiocarbon isotopic compositions of bulk organic matter and the stable carbon isotopic compositions of individual organic compounds, including lignin-derived phenols and lipid-derived fatty acids. Most river suspended sediments and shelf surface sediments contained organic carbon characterized by highly depleted Δ¹⁴C values that were consistent with average radiocarbon ages exceeding 7000 years. The stable carbon isotopic signatures of lignin phenols were uniformly depleted (−25≥δ¹³C≥−32‰), indicating the predominant contributions of C₃ vascular plant sources. The isotopic compositions of C₁₄ and C₁₆ fatty acids exhibited important contrasts between the river (−36‰ to −40‰) and shelf (−25‰ to −29‰) sediments that were consistent with contributions from freshwater algae and/or vascular plants in the former and marine phytoplankton in the latter. Using ¹⁴C isotopic mass balance, the abundances of modern and ancient organic matter were quantitatively constrained. The fate of organic matter in the Beaufort Shelf was explored by normalizing these abundances to the specific surface area of sediments. Ancient organic carbon, which may include old pre-aged soil material as well as fossil bitumen or kerogen, accounted for the majority (∼70%) of the particulate organic matter exported by the Mackenzie River and deposited in surface sediments of the Beaufort Shelf. Modern organic carbon accounted for ∼30% in both river and shelf sediments, with significant contributions from vascular plant-derived materials in both river and shelf samples and from marine algae in the shelf sediments. Respiration (and/or leaching) of particle-bound marine organic matter dominates the carbon metabolism in the Mackenzie Delta/Beaufort Shelf region. However, land-derived pools, including modern carbon derived from vascular plants as well as ancient carbon also appeared to undergo a degree of post-depositional degradation prior to burial in the shelf. These novel source apportionments are reflected in an updated carbon budget for the study area.     

The nature,distribution and origin of a sapropelic layer in sediments of the Silicia Basin,northeastern Mediterranean

A sapropelic layer with organic carbon contents of 1.0–1.5%, in contrast to the usual 0.2–0.5% of adjacent normal basin sediments, is found to be widespread in sediment cores collected from the Cilicia Basin, northeastern Mediterranean. The horizon is thought to be equivalent to the S₁ sapropel of other workers. It is finely laminated with no evidence of bioturbation, has a very markedly low magnetic susceptibility, and contains a significantly higher content of pollen and plant debris than is found in the normal basin sediment. The stable oxygen and carbon isotope values suggest that the layer formed during post-glacial climatic warming when fresh nutrient-rich surface water flowed into the Cilicia Basin from the surrounding land to produce a stratified water mass which allowed the development of anoxic bottom waters. The distribution of the sapropelic layer indicates that anoxic conditions extended to within approximately 350 m of sea level during deposition, a depth shallower than previously recorded in the Eastern Mediterranean.     

Compositions and transport of lipid biomarkers through the water column and surficial sediments of the equatorial Pacific Ocean

A systematic investigation of fluxes and compositions of lipids through the water column and into sediments was conducted along the U.S. JGOFS EgPac transect from l2°N to l5°S at 140°W. Fluxes of lipids out of the euphotic zone varied spatially and temporally, ranging from ≈0.20 – 0.6 mmol lipid-C m⁻² day⁻¹. Lipid fluxes were greatly attenuated with increasing water column depth, dropping to 0.002-0.06 mmol lipid-C m⁻² day⁻¹ in deep-water sediment traps. Sediment accumulation rates for lipids were ≈ 0.0002 – 0.00003 mmol lipid-C m⁻² day⁻¹. Lipids comprised ≈ 11–23% of C_org in net-plankton, 10–30% in particles exiting the euphotic zone, 2–4% particles in the deep EgPac, and 0.1-1 % in sediments. Lipids were, in general, selectively lost due to their greater reactivity relative to bulk organic matter toward biogeochemical degradation in the water column and sediment. Qualitative changes in lipid compositions through the water column and into sediments are consistent with the reactive nature of lipids. Fatty acids were the most labile compounds, with polyunsaturated fatty acids (PUFAs) being quickly lost from particles. Branchedchain C₁₅ and C₁₇ fatty acids increased in relative abundance as particulate matter sank and was incorporated into the sediment, indicating inputs of organic matter from bacteria. Long-chain C₃₉ alkenones of marine origin and long-chain C₂₀-C₃₀ fatty acids, alcohols and hydrocarbons derived from land plants were selectively preserved in sediments. Compositional changes over time and space demonstrate the dynamic range of reactivities among individual biomarker compounds, and hence of organic matter as a whole. A thorough understanding of biogeochemical reprocessing of organic matter in the oceanic water column and sediments is, thus, essential for using the sediment record for reconstructing past oceanic environments.     

A synthetic pollen record of the eastern Mediterranean sapropels of the last 1 Ma: implications for the time-scale and formation of sapropels

The Quaternary climate of southern Europe (south Italy and Greece) is investigated by pollen analysis of the sapropels which were deposited in the deep eastern Mediterranean Sea during the last 1 million year (Ma). The time-scale of core KC01b in the Ionian Sea has been established by tuning its oxygen isotopic record to the ice volume model of Imbrie and Imbrie (1980). For the last 250,000 year (250 ka), the previous pollen studies and astronomical tuning have been confirmed. Sapropels were deposited under a large range of Mediterranean climates: fully interglacial, fully glacial, and intermediary, as revealed mainly by the balance between the respective pollen abundances of oak (Quercus) and sage-brush (Artemisia). The high value of the oak reveals the warm and wet climate of an Interglacial, and the high value of the sage-brush, the dry and cold climate of a Glacial. Whereas the Mediterranean climate is directly related to the variation of the high-latitude ice sheets, the deposition of sapropels is not so. In contrast with the wide climatic range, sapropels were deposited only when summer insolation in the low latitudes reached its highest peaks. However, between 250 ka and 1 Ma, that stable pattern is not yet established. Only six sapropels are observed, many expected ones do not appear, even as ghosts signalled by peaks of barium abundance, that remain after the post-deposition oxidation of organic matter. The pattern of sapropel formation in stable and direct relationship to highest insolation does not seem to apply. For five of those sapropels, neither climate extremes are observed; they mainly formed during intermediary types of Mediterranean climate. In contrast, one sapropel (and one ghost) relates to a relatively low peak of insolation, and its climate is of a unique, composite type not seen later. This might suggest an unsuspected, more complex pattern linking the formation of Mediterranean sapropels to the astronomical configuration.     

Recent sedimentation and sedimentary budgets on the western Iberian shelf

Thus study is based on 31 box-core samples collected mainly from the mud-patches of the Galician and North-Portuguese shelf. Each of these cores, some decimetres in length, have been described, radiographied and sampled each centimetre for grain-size analysis and measurement of the particulate organic carbon (C_org) content. ²¹⁰Pb excess profiles have been measured using gamma spectrometry, which, combined with the analysis of the vertical variations of the sedimentary facies, have allowed estimates of sedimentation rates. These rates were found to vary between 0.05 and 0.40 cm yr⁻¹. Considering the latitudinal variation of sedimentation rates around the 100m contour, we note that the maximum rates occurred off the Douro estuary in the southern sector and also near the Galician rias to the north. The organic content (C_org) of sediments varied between 0.4 and 2%. Latitudinally C_org showed a decrease from the South to the North. These results coupled with the sedimentary map (see Dias, Gonzalez, Garcia & Diaz del Rio, 2001) have permitted us to establish the detrital mass budget and an inventory of C_org burial.     

Carbonate removal by acidification causes loss of nitrogenous compounds in continental margin sediments

This study reports on measurements of organic carbon (C_org) and total nitrogen (N_tot) in surface sediments originating from 6 transects along the northwest European continental margin. After elimination of carbonates by an acidification technique using sulphurous acid, both elements were analysed in the same sediment sample using an elemental analyser. C_org and N_tot in the sample were comparatively low, ranging between 1 and 10 mg C and 0.2 to 1 mg N g⁻¹ dry sediment. In a second analysis, the samples were analysed without acid addition, resulting in N_tot concentrations of 0–50% higher compared to their acidified counterparts. As a consequence, molar C/N ratios derived from the analysis of C_org and N_tot in the acidified sample ranged between 6 to 11, while the N_tot separate analysis reduced C/N ratios to 6 to 8. It is suggested that the addition of sulphurous acid to eliminate inorganic carbon volatilises nitrogenous organic matter.