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.     

Early diagenesis of carbohydrates and lignin in mangrove sediments subject to variable redox conditions (French Guiana)

A comparative study of lignin and neutral carbohydrate compositions, combined with C, N and δ¹³C analyses, was carried out on sedimentary cores, and on various vascular plant species collected in mangrove swamps of French Guiana. The main purpose of this study was to assess the diagenesis of carbohydrates and lignin in brackish to hypersaline fine-grained mangrove sediments characterized by great changes in redox conditions. Distribution of carbohydrates in sediments reflects both the lability of these compounds and their efficient recycling. They are subject to selective degradation, cellulosic glucose and xylose appearing to be the two most labile neutral sugars. In contrast a relative increase in arabinose, rhamnose, fucose and hemicellulosic glucose between plants and sediments, suggests that they may be more refractory and/or that they also derive from microbial synthesis. The total carbon from lignin-derived phenols is higher in sediments than in mangrove plants as a consequence of their rather refractory character. Nevertheless, evidence of lignin decomposition was found to be independent of local environmental conditions. The various redox processes that occur in mangrove sediments depend on plant species, stages in forest development and season. Different redox conditions induce different mechanisms for the decomposition of lignin and thus induce changes in phenol distributions. At depth, in most mangroves, an increase in (Ad/Al)_v ratios and in deoxy sugars (fucose and rhamnose) content was significantly correlated with increased proportions of oxidized allochthonous organic debris deriving from the Amazonian detrital discharge, thus suggesting a specific source effect rather than a diagenesis induced change. Therefore, this study illustrates that both lignin and cellulose, derived from vascular plant debris, can be degraded in waterlogged mangrove sediments, and that their distribution depends on environmental conditions.     

Early diagenesis of organic matter in recent Black Sea sediments: characterization and source assessment

The organic matter in 9 recent (not more than 250 years old) and ‘organic-rich’ sediments from the southern Black Sea shelf and upper slope have been characterized semi-quantitatively by Pyrolysis/Gas Chromatography/Mass Spectrometry (PY/GC/MS) and¹³C Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CPMAS-NMR) spectrometry. The organic matter of 7 of the studied sediments was found to be ligno-carbohydrate with a proteinaceous component, one sediment appeared to contain oxidized coal dust and one contained thiophenes in association with pyrite. The ligno component is derived from grasses and soft wood lignin. Material entrapped in an anoxic environment contained the highest proportions of carbohydrate and protein. All the samples had suffered diagenesis as is generally shown by the attachment of carboxyl groups and the removal of methoxyl groups. The evidence suggests that diagenesis occurred whilst the particles traversed the oxic water column.     

Thallium diagenesis in lacustrine sediments

Dated sediment cores and porewaters from two Canadian Shield lakes, located 40 km from Québec City (L. Tantaré) and 25 km downwind from an important smelter in northwestern Québec (L. Vose), were analyzed for thallium and other geochemical variables. Atmospheric deposition is the only source of anthropogenic Tl to these lakes. The porewater Tl concentration profiles in L. Tantaré display a peak below the sediment-water interface that suggests post-depositional Tl remobilization and transport to the overlying water and deeper sediments; such a dissolved Tl peak occurs just above the sediment-water interface in L. Vose. Modeling the porewater Tl profiles with a diagenetic reaction-transport equation reveals a zone of dissolved Tl production lying above a zone of Tl consumption in L. Tantaré sediments. In contrast, in L. Vose, Tl diffuses across the sediment-water interface from the anoxic hypolimnion and is fixed to the surficial sediments. The localization of the consumption zones, the shape of the dissolved Tl, sulfide and iron profiles, as well as calculations of saturation states are all consistent with the removal of Tl from porewater by co-precipitation with and/or adsorption to Fe sulfides. The concentrations of Tl removed from or added to sediments after their deposition (i.e., diagenetic Tl) amount to up to 36% of measured sediment Tl concentrations. Comparison of the reconstructed historical Tl records with those of polycyclic aromatic hydrocarbons (PAHs) and of Pb originating from coal burning or from smelting activities indicate that coal combustion is the major source of atmospheric Tl to L. Tantaré and that an additional important Tl source to L. Vose is the nearby smelter.     

The diagenesis of carbohydrates by hydrogen sulfide

Carbohydrates react with hydrogen sulfide under low temperature (100° to 200°C) yielding a variety of organosulfur compounds including thiophenes, thiols, sulfides and sulfones. A polymer is also produced, whose elemental composition is within the range of natural coals. When reductive dehydration is carried out in the presence of hydrocarbon, organosulfur compounds are formed in the carbon number range of the hydrocarbon used. In these processes, an active hydrogen transfer catalyst is produced which facilitates the passage of hydrogen between normal paraffins and saccharide units, distributing sulfur between these two families primarily in the form of thiophene rings. The simplicity of these systems—H₂S, carbohydrates, H₂O, hydrocarbon—and the facility of the chemistry would suggest that the carbohydrates and hydrogen sulfide may be important agents in the diagenetic processes leading to petroleum and coal. Carbohydrate reduction by hydrogen sulfide may constitute an important route through which certain organosulfur compounds found in petroleum and coal entered these materials in early diagenesis.     

Interstitial solutions and diagenesis in deeply buried marine sediments: results from the Deep Sea Drilling Project

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments.Pelagic clays and slowly deposited (<1 cm/10³yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters.In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/10³ yr the changes chiefly involve gains of Ca²⁺ and Sr²⁺ and losses of Mg²⁺ which balance the Ca²⁺ enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr²⁺ may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg²⁺ for Ca²⁺ during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca²⁺ and Sr²⁺ enrichment is again characteristic, but Mg²⁺ losses exceed Ca²⁺ gains with the excess being balanced by SO₄^{post staggered2?} losses. The data indicate that the reactions are similar to those noted above, except that the Ca²⁺ released is not kept in solution but is precipitated by the HCO₃^{post staggered?} produced in SO₄^{post staggered2?} reduction. In both these types of pore waters Na⁺ is usually conservative, but K⁺ depletions are frequent.In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na⁺, Si and CO₂, and slight enhancement in Cl^?. The changes are attributed to exchange of Na⁺ for Ca²⁺ in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity.Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO₄^{post staggered2?}, strong HCO₃^{post staggered?} enrichment, formation of NH₄^{post staggered+}, and methane synthesis from H₂ and CO₂ once SO₄^{post staggered2?} is eliminated. K⁺ and often Na⁺ (slightly) are depleted in the interstitial waters. Ca²⁺ depletion may occur owing to precipitation of CaCO₃. In most cases interstitial Cl^? remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl^? are observed in some sediments adjacent to continents.     

Provenance and diagenesis of organic matter in Late Cretaceous and Tertiary sediments from the southern Black Sea margin

The organic matter in the Late Cretaceous and Tertiary sediments from the southern Black Sea margin is assigned to the terrestrial-marine/terrestrial range of organic facies. Within this range, the stratigraphic section yields different organic facies types in response to different accumulation and preservation controlling processes. During the Late Companian-Maastrichtian, organic material from the shelf and slope was re-deposited in the deeper oxic parts of the basin. Rapid transport and sedimentation resulted in a higher degree of preservation of lipid-rich, terrestrial components (sporinite, cutinite, resinite) in comparison to the autochthonous sediments. The increase in organic carbon with increasing silt/clay content together with low carbon concentrations in the allochthonous sediments suggest that the accumulation of organic matter in the source areas was controlled by terrigenous influx and that the accumulation conditions were not favorable.In the Eocene (fore-arc basin), the higher content of marine organic matter can be explained by progressive shallowing of the environment and by reduced oxygen content in the bottom waters (reduced bioturbation).In the Miocene and Pliocene (back-arc basin), the organic fraction of the sediments from the basin margin is purely terrestrial and consists mostly of inertinite and reworked terrigenous liptinite indicating oxidative conditions. The dominance of inertodetrinite in the Miocene and of semifusinite in the Pliocene point to a change in the source area or to a higher energy transport or deposition conditions for the Miocene marginal sediments. In the basin interior, the higher content of marine organic matter is due to an oxygen deficiency or anoxic conditions in the bottom waters. Mineral associations indicate complete sulfate reduction and consequent methanogenesis. This is also implied in the hydrocarbon distributions. Periodic oxic conditions lead to a decrease in the marine liptinitic component. In the basin interior, however, the terrigenous fraction is still dominant, implying a continuous influx from the basin margins.The Late Cretaceous to Pliocene sediments are thermally immature (Rm<0.5%, T_max<435 °C).

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Zusammenfassung Die organische Substanz in den Sedimenten der Oberkreide und des Tertiärs der südlichen Schwarzmeerregion ist dem terrestrischen bis marin-terrestrischen Bereich organischer Fazies zuzuordnen. Innerhalb dieses Bereiches weisen die stratigraphischen Abschnitte unterschiedliche organische Faziestypen auf, die auf unterschiedliche, die Akkumulation und den Erhaltungsgrad der organischen Substanz kontrollierende Prozesse zurückzuführen sind.Während des Obercampan-Maastrichtiums und des Paläozäns (fore-arc Becken) wurde organisches Material des Schelf/-hanges in den tieferen oxischen Beckenbereichen resedimentiert. Die rasche Zufuhr und Ablagerung führte zu einem gegenüber den autochthonen Sedimenten höheren Erhaltungsgrad an lipidreichen, terrestrischen Komponenten (Sporinit, Cutinit, Resinit). Die Zunahme an organischem Kohlenstoff mit steigendem Silt-/Tonanteil bei insgesamt niedrigen Kohlenstoffkonzentrationen in den Resedimenten läßt vermuten, daß die Akkumulation organischer Substanz in den Liefergebieten durch terrigene Zufuhr bestimmt wurde und die Akkumulationsbedingungen ungünstig waren.Für das Eozän ist ein erhöhter Eintrag an marinem organischem Material zu verzeichnen, der mit der zunehmenden Verflachung des Ablagerungsraumes (fore-arc Becken) und einer Reduzierung im Sauerstoffgehalt des Bodenwassers (abnehmende Bioturbation) erklärt wird.Für das Miozän und Pliozän (back-arc Becken) ist die organische Fraktion der Ablagerungen des Beckenrandes rein terrestrisch und besteht zum größten Teil aus Inertinit und wieder aufgearbeitetem terrigenem Liptinit, die oxidative Verhältnisse anzeigen. Die Dominanz von Inertodetrinit im Miozän und Semifusinit im Pliozän indiziert eine Änderung im Liefergebiet oder ein höheres Energieniveau beim Transport bzw. im Ablagerungsraum der miozänen Randsedimente. Im Beckeninneren ist ein erhöhter Anteil an mariner organischer Substanz festzustellen, der auf Sauerstoffverarmung oder anoxische Verhältnisse im Bodenwasser zurückgeführt wird. Die Mineralassoziationen in den Sedimenten weisen auf vollständige Sulfatreduktion und nachfolgende Methanogenese hin, die sich auch mit den Kohlenwasserstoffverteilungen nachvollziehen läßt. Periodisch oxische Bedingungen führen zu einer Reduzierung der marin-liptinitischen Komponente. Im Beckeninneren dominiert jedoch auch die terrigene Fraktion (Huminit/Vitrinit, Inertinit), was auf kontinuierliche Zufuhr vom Beckenrand schließen läßt.Die Sedimente der Oberkreide bis Pliozän sind thermisch unreif (Rm<0.5%, T_max<435 °C).

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Résumé La matière organique contenue dans les sédiments du Crétacé supérieur et du Tertiaire de la partie sud de la Mer Noire est à rapporter au domaine de facies organique terrestre à marin-terrestre. La série stratigraphique présente, dans les limites de ce domaine, divers types de facies organiques qui traduisent les divers processus qui régissent l'accumulation et la préservation.Au cours du Campanian supérieur-Maastrichtien, des matériaux organiques provenant du shelf et du talus continental ont été redéposés dans les parties oxygénées plus profondes du bassin. La rapidité du transport et de la sédimentation a entraîné la préservation de composants terrestres riches en lipides (sporonite, cutinite, résinite), dans une mesure plus élevée que dans les sédiments autochtones. L'augmentation de la teneur en carbone organique corrélative à celle de la fraction fine (boue et silt), de même que la faible concentration en carbone des sédiments allochtones indique que, dans la région-source, l'accumulation de matières organiques était régie par un afflux terrigène et que les conditions d'accumulation n'étaient pas favorables.A l'Eocène (bassin d'avant-arc) le contenu en matière organique marine est plus élevé, ce qui s'explique par la diminution progressive de la profondeur et par la réduction de la teneur en oxygène des eaux du fond (bioturbation réduite).Au Miocène et au Pliocène (bassin d'arrière-arc), la fraction organique des sédiments de la bordure du bassin est purement terrestre et consiste principalement en inertinite et en liptinite terrigène remaniée, ce qui indique des conditions oxydantes. La prédominance d'inertodétrinite au Miocène et de semifusinite au Pliocène indique soit une source différente, soit un transport ou un dépôt dans les conditions de plus haute énergie des sédiments miocènes marginaux. Vers l'intérieur du bassin, le contenu plus élevé en matière organique marine est dû à une déficience en oxygène ou à des conditions anoxiques dans les eaux de fond. Les associations minérales indiquent une réduction complète des sulfates et en conséquence une méthanogenèse, ce qui ressort également de la distribution des hydrocarbures. Des conditions oxydantes périodiques provoquent une diminution du composant liptinitique marin. Dans l'intérieur du bassin, toutefois, la fraction terrigène reste dominante, ce qui implique un afflux continu depuis les marges du bassin.Les sédiments d'âge crétacé supérieur à pliocène sont thermiquement immatures (Rm<0,5%; Tmax<435 °C).

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, , - . , , . - , . , ( , , ), . , , . , (force-arc Basin) ( ). (back-arc Basin) , . , , . , , . , . . ( , ), . : (Rm<0,5 %; T_max<435° ).

     

Iodine diagenesis in non-pelagic deep-sea sediments

Measurements of sediment geochemistry and porewater speciation have been made using eight cores containing turbidite sections from the Madeira and Nares Abyssal Plains. The results have been used to evaluate how the diagenetic chemistry of iodine in these sediments compares with that in sediments undergoing steady-state diagenesis. The behaviour of iodine is related to the development of a redox front within the turbidite, between the organic-rich anoxic sediment and its oxic cap, and the downward migration of the front through the turbidite with time. In contrast to the steady-state case, sediment I contents and I/ C ratios increase downwards through the oxidised section reaching a maximum at the redox front (up to ~ 100 μ/g I; molar I/C~ 20 × 10⁻⁴) below which values drop dramatically (I/C ~ 5 × 10⁻⁴). A strong iodate enrichment (up to ~3 μmol kg⁻¹) is observed in the oxidised section of the sediment. At the front interconversion of I⁻ and IO⁻₃ species occur and below the front porewater IO⁻₃ is absent and I~ concentrations increase with depth (as in other cases of anoxic diagenesis) up to ~ 10 μmol kg⁻. In the oxidised section of the sediment the I enrichment has been supplied by upward transport of iodide with the increasing I content, with depth being accounted for by progressive diagenetic enrichment with time.     

Cadmium diagenesis in Laurentian Trough sediments

The depth distributions of Cd, Mn and Fe in pore water and sediment were determined on three replicate box cores collected at a 325 m deep station in the Laurentian Trough. The results reveal a surface layer in which the content of solid-phase Cd first decreases but then increases sharply with depth. In contrast, Mn decreases regularly over the same depth interval. In the oxygenated zone of this layer, Cd, probably associated with organic matter, is released to the pore water, resulting in concentrations that are more than an order of magnitude higher than in the overlying water column. Some of the dissolved Cd is returned to the water column and some migrates downward and is precipitated at depth. This part of the Cd cycle is virtually complete within the surface layer, the base of which corresponds to the base of the zone of Mn enrichment.In the subsurface layer, solid-phase Cd and Mn show little or no concentration change. However, dissolved Cd, which reaches often non-detectable concentrations (<0.05 nM) in this layer, increases once again deep within the anaerobic zone and attains concentrations even higher than in the surface layer. The presence of dissolved Cd complexes (revealed by 1.5 to 8 fold increases in electrochemically active Cd in pore water following UV-treatment) as well as inconsistent distributions of dissolved and solid-phase Cd, indicate complexities in diagenesis that merit further investigation.     

Iodine diagenesis in pelagic deep-sea sediments

Nineteen sediment cores from the Madeira, Seine, Tagus and Nares Abyssal Plains and the Alboran Sea have been used to evaluate the speciation, fluxes and diagenesis of iodine in the deep sea. The sediments have surficial molar I/C ratios of 10–30 × 10⁻⁴ in excess of previous reported values for planktonic material (~1 × 10⁻⁴). Solid phase I contents decrease exponentially with depth corresponding to decomposition rate constants of 5–260 × 10⁻⁶ yr⁻¹ which vary with the carbon accumulation rate.Iodine species in the pore waters follow a vertical sequence of four zones: 1. a zone of I⁻ production where total dissolved iodine (∑I) concentrations initially increase at the seawater-sediment interface; 2. a zone of I⁻ oxidation where interconversion of I⁻ to IO⁻₃ occurs; 3. a zone of IO⁻₃ reduction where interconversion of IO⁻₃ back to I⁻ occurs which corresponds to the suboxic part of the sediment column; and 4. a further zone of I⁻ production which is confined to the lower anoxic part of the sediment column. Benthic ∑I fluxes in the Madeira Abyssal Plain measured from shipboard incubation experiments and calculated from porewater gradients are similar, averaging 0.55 and 0.36 × 10⁻⁸ μmol cm⁻² sec⁻, respectively.In the surface sediment the observed I enrichment results from a quasi-closed cycle for iodine initially involving release of I⁻ from decomposing marine organic matter followed by rapid removal onto organic matter at the sediment-seawater interface where I/C regeneration ratios of up to 200 × 10⁻⁴ are found, lodate reduction occurs during suboxic diagenesis, after denitrification and before MnO₂ reduction, consistent with the sequence of reactions predicted from the free energy yields for organic matter oxidation. There is some further I⁻ production in the anoxic section of sediments but at much smaller rates than occur during the interfacial diagenetic cycling.     

Composition and origin of clay minerals in Holocene sediments from the south-eastern North Sea

The distribution of clay minerals varies systematically in sediments from Holocene core material taken along a profile from the East Frisian coast to the Doggerbank. The proportion of illite increases with distance from the coast at the expense of kaolinite, whereas slight variations are seen in smectite and chlorite abundances. The chemical composition changes, and the K/Rb ratio and K-Ar isotopic age of illite increase seawards. This trend results from progressive mixing processes of riverine detritus with Pleistocene fluvioglacial material reworked during the Holocene transgression. However, the clay fluvial flux only became dominant during the decreasing rate of sea-level rise in the Late Holocene, especially near the shore. For example, modern sediments in tidal flats contain 75% of river-borne Holocene-supplied clay detritus, whereas this amount is only 10% in modern marine sediments at the Doggerbank.     

Carbon and nitrogen diagenesis in deep sea sediments

The sections penetrated on Leg 58 of the Deep Sea Drilling Project represent periods of geologic time during which depositional conditions apparently remained quite constant, thus offering an unusual opportunity to study the effects of diagenesis on organic material.Organic carbon and nitrogen contents decrease monotonically with increasing depth of burial before levelling off at minimum values of about 0.05-0.10 and 0.01%, respectively. The depths at which minima are reached vary from site to site, but the ages of the sediments at the minima are all about 2–5 Myr.These data indicate that diagenetic transformations are responsible for the gradual depletion of organic carbon and nitrogen. If diagenesis is at least partly the result of microbial activity, then the role of bacterial ecosystems in deep water sediments is much greater than has previously been thought.     

Composition and genesis of the organic matter in the bottom sediments of the East Siberian Sea

The chemical composition of organic matter (C_org, N_org, δ¹³C, δ¹⁵N, and n-alkanes) was studied in the top layer of bottom sediments of the East Siberian Sea. Possible ways were proposed to estimate the amount of the terrigenous component in their organic matter (OM). The fraction of terrigenous OM estimated by the combined use of genetic indicators varied from 15% in the eastern part of the sea, near the Long Strait, to 95% in the estuaries of the Indigirka and Kolyma rivers, averaging 62% over the sea area.     

On the relationship between silica and carbonate diagenesis in deep-sea sediments

Silica diagenesis and carbonate diagenesis are interrelated. This is confirmed by observations of DSDP Sites 462, 463, 465, 466, and 577. Carbonate sediments containing chert (1) tend to be more indurated and display more advanced diagenetic alterations, regardless of sub-bottom depth; and (2) microfossil components are more strongly affected (overgrown and/or dissolved), while the amount of micritic particles and larger, euhedral calcite crystals is greater. In addition, mass physical properties, porosity in particular, vary more widely in sediment sections containing chert. Furthermore, in the studied similarly composed sediments recrystallization of biogenic opal is indicated by a significant reduction of the specific surface area, reaching a minimum value when quartz is formed.One possible mechanism involved is the production of «surplus« dissolved carbonate created by the replacement of carbonate material by silica during the process of chert formation and silicification. The «extra« carbonate is then available for precipitation as overgrowths and cement outside the chert nodules and silicified zones. Hence silica diagenesis, if it occurs early enough in the sediment, bears some influence on carbonate diagenesis. It is therefore suggested that silica diagenesis be added to the list of factors included in the «diagenetic potential« equation ofSchlanger &Douglas (1974).

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Zusammenfassung Die Diagenese von biogenem Silikat und Karbonat steht in engem Zusammenhang, wie Beobachtungen an Sedimenten der DSDP Sites 462, 463, 465, 466 und 577 zeigen. Karbonatische Sedimente, die biogenes SiO₂ enthalten, zeichnen sich aus durch (1) größere Verfestigung und stärkere diagenetische Veränderungen — unabhängig von der Tiefe im Sediment, (2) mehr Lösung und Überwuchs an Mikrofossil-Komponenten, (3) höheren Anteil mikritischer Partikel wie auch größerer idiomorpher Kalzitkristalle, (4) stärkere Variation der sedimentphysikalischen Eigenschaften, speziell der Porosität und damit zusammenhängender Parameter.Die Umkristallisation des biogenen SiO₂ führt in ähnlich Zusammengesetzen Sedimenten zu einer drastischen Abnahme der spezifischen Oberfläche. Minimalwerte werden erreicht, wenn sich Quarz bildet.Diagenetisch wichtig ist die Produktion von zusätzlichem Karbonat durch die Silizifizierung von Karbonatschalen. Dieses »Überschuß«-Karbonat wird dann als Überwuchs, Zement oder außen an den »Hornstein«-Aggregaten gefällt. Demzufolge beeinflußt die Diagenese von biogenem SiO₂ auch die Karbonatdiagenese. Daher ist es sinnvoll, die Diagenese von biogenem SiO₂ mit zu den Faktoren zu rechnen, die das »diagenetische Potential« — wie esSchlanger &Douglas (1974) definierten — ausmachen.

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Résumé L'étude de sédiments provenant des sites DSDP 462, 463, 465, 466 et 577 montre qu'il existe une relation entre la diagenèse de la silice et celle du carbonate biogéniques. Les sédiments carbonatés qui renferment de la silice biogémque présentent: 1) une induration plus marquée et des modifications diagénétiques plus poussées — et ce indépendamment de la profondeur sous la surface du fond; 2) une dissolution et/ou un accroissement plus développés des micro-fossiles; 3) une plus grande teneur en particules micritiques et une plus grande taille des calcites idiomorphes; 4) un éventail plus large de leurs propriétés physiques, particulièrement de la porosité et des paramètres qui en dépendent.La cristallisation de l'opale biogénique, dans des sédiments de compositions semblables, se traduit par une réduction drastique de la surface spécifique, qui atteint une valeur minimale lorsque du quartz est formé.Un rôle diagénétique important est joué par l'excès de carbonate dissous engendré par la silicification de coquilles carbonatées; cet excès de carbonate est dès lors disponible pour la précipitation des auréoles d'accroissement et du ciment hors des nodules de chert et des zones silicifiées. Il s'ensuit que la diagenèse du SiO₂ biogénique influence la diagenèse du carbonate. Il conviendrait dès lors d'ajouter la diagenèse de la silice à la liste des facteurs qui interviennent dans l'équation du «potentiel diagénétique» deSchlanger etDouglas (1974).

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462, 463, 465, 466 577, . , , : 1) , ; 2) ; 3) , 4) , . SiO₂ . . . »« , , « ». , .. «, 1974 Schlanger & Douglas.

     

Biological diagenesis: dicarboxylic acids in recent sediments

A series of even carbon numbered α, ω-dicarboxylic acids ranging from C₁₆ to C₂₄ has been identified in recent sediments from various environments and sampling localities. A lacustrine sediment did not show detectable quantities of diacids. Consideration of quantitative relationships involving the diacids leads us to propose a dual origin for these diacids: deposition by mangroves is their main source in mangal areas while in situ production by sedimentary organisms is the only important source of diacids in a non-mangal marine environment. A fresh water lagoon shows an intermediate situation between these extremes.     

Early diagenesis of cadmium and cobalt in sediments of the Laurentian Trough

The depth distributions of hydroxylamine/acetic acid-extractable Co and Cd were determined in box-cores from a series of stations along the 1200 Km length of the Laurentian Trough. These were compared with the concentrations of total Co and Cd and the distributions of extractable Mn and Fe in the cores, as well as with the total Cd concentrations in sedimenting particles collected with a sediment trap. The results indicate a strongly contrasting behaviour of the two elements during early diagenesis, consistent with their respective chemistries and particle-associations. Cobalt occurs mainly in a non-reactive form and is buried with the accumulating sediments. A mobile component of Co is associated with Mn- and Fehydroxides and, like these compounds, follows a redox-sensitive pattern of dissolution in the reducing zone of the sediment—vertical migration—enrichment by precipitation in the oxidized surface layer—and redistribution along the bottom in paniculate form. Paniculate Cd arrives at the sediment surface bound to biogenic material, is rapidly solubilized during aerobic degradation of the organic matter, and migrates vertically both into the reducing zone of the sediments where it precipitates, and back into the water column where it may be recycled through biological processes. In an estuary, Co will be concentrated in the oxidized layer of the sediments and tend to migrate landward, while Cd will be most abundant in sediments underlying regions where plankton production is high relative to dilution by terrigenous particles.     

Organic matter diagenesis in shallow water carbonate sediments

Muddy carbonate deposits near the Dry Tortugas, Florida, are characterized by high organic carbon remineralization rates. However, approximately half of the total sedimentary organic matter potentially supporting remineralization is occluded in CaCO₃ minerals (intracrystalline). While a portion of nonintracrystalline organic matter appears to cycle rapidly, intracrystalline organic matter has an approximately constant concentration with depth, suggesting that as long as its protective mineral matrix is intact, it is not readily remineralized. Organic matter in excess of intracrystalline organic matter that is preserved may have a variety of mineral associations (e.g., intercrystalline, adsorbed or detrital). In surface sediment, aspartic acid contributed ∼22 mole % and ∼50 mole % to nonintracrystalline and intracrystalline pools, respectively. In deeper sediment (1.6-1.7m), the composition of hydrolyzable amino acids in both pools was similar (aspartic acid ∼40 mole %). Like amino acids, intracrystalline and nonintracrystalline fatty acids have different compositions in surface sediments, but are indistinguishable at depth. These data suggest that preserved organic matter in the nonintracrystalline pool is stabilized by its interactions with CaCO₃. Neutral lipids are present in very low abundances in the intracrystalline pool and are extensively degraded in both the intracrystalline and nonintracrystalline pools, suggesting that mineral interactions do not protect these compounds from degradation. The presence of chlorophyll-a, but absence of phytol, in the intracrystalline lipid pool demonstrates that chloropigments are present only in the nonintracrystalline pool. Sedimentary chloropigments decrease with depth at similar rates in Dry Tortugas sediments as found in alumino-silicate sediments from the Long Island Sound, suggesting that chloropigment degradation is largely unaffected by mineral interactions. Overall, however, inclusion and protection of organic matter by biominerals is a major pathway for organic matter preservation in this low-organic carbon, biomineral-rich regime.     

Composition of interstitial waters and forms of sulfur compounds in bottom sediments in the northeastern Black Sea

Study of sediments and water column in the Black Sea has been carried out for a long time. However, issues of the formation of seawater and sediments in the geological (ancient) and Recent marine history remain debatable so far. Studies of the physical, biological, and biogeochemical settings in the northeastern part of the Black Sea carried out onboard the R/V Professor Shtokman in 2009 yielded new data on this region. The present paper reports the results of study of the chemical composition of bottom sediments and interstitial waters from the meridional profile extending from the Kerch Peninsula to the central part of the eastern deep-water depression.     

Remobilization of Iodine in Marine Sediments During Early Diagenesis

Based on the sedimentary geochemical studies of the Antarctic Ocean and the various geochemical parameters available,this paper deals with the process of emobilization of iodine in marine sediments during early diagenesis.The results showed that the process is not always controlled completely by organic matter as was expected previously.On average the adsorption and oxide phases of iodine account respectively for 23% and 32% of the total in continental-shelf and hemipelagic surficial sediments.Chemical analysis has revealed that the upward diffusion flux and redox conditions would play an important role in the concentration of iodine in the surface sediments.And the species of iodine in the surfial sediments characteristic of high I/Corg ratios would bepredominated by the oxide and adsorption phases.As experimentally evidenced,it is the early diagenetic remoibilization of iodine associated with the oxide and adsorption phases that led to the decrease of I/Corg with increasing depth.Calculations suggested that the diffusion flux of iodine from the deep parts of te sedimentary columum upwards is on the same order of magnitude as the deposition flux of it from sea water.This may be one of the important factors leading to the depletion of iodine in sedimentary rocks.On the basis of the above discussion and calculations the author has proposed a model for the remobilization of iodine in marine sediments during early diagenesis.