Thermal alteration experiments on organic matter in recent marine sediment—II. Isoprenoids

Several isoprenoid compounds were isolated from a heat-treated marine sediment in the southern California continental shelf (from Tanner Basin) which were not present in the original sediment. Among the compounds identified were: phytol, dihydrophytol, C₁₈-isoprenoid ketone, phytanic and pristanic acids, C₁₉- and C₂₀-monoolefins, and the alkanes 2,6,10-trimethylpentadecane, pristane and phytane. The significance and possible routes leading to these compounds is discussed.     

Thermal alteration experiments on organic matter in recent marine sediment—I. Pigments

Sediment from Tanner Basin, located at the outer continental shelf off southern California, was analyzed for photosynthetic pigments and their derivatives, namely carotenes and chlorins. Samples of the sediment were also exposed to raised temperatures (65°, 100°, 150°C) for various periods of time (1 week, 1 month, 2 months). Analysis of the heat-treated sediment revealed the presence of α-ionene and 2,6-dimethylnaphthalene, thermal-degradation products of β-carotene. Chlorins were converted to nickel porphyrins of both DPEP and etio series. Possible mechanisms and geochemical significance of these transformations are presented.     

Thermal alteration experiments on organic matter in recent marine sediment—III. Aliphatic and steroidal alcohols

Recent sediments from Tanner Basin (off southern California) and Bandaras Bay (in Gulf of California) have been analyzed for normal, isoprenoid and steroidal alcohols using chromatographic (column, GLC, TLC), and spectroscopic (u.v., i.r., MS) methods, prior to and after heat-treatment (from 65 to 150°C). Normal saturated alcohols (C₁₄-C₂₄) and monounsaturated alcohols (C₂₂-C₂₄) were identified, as well as the isoprenoid alcohols, phytol and dihydrophytol.Two series of sterols (Δ⁵ and Δ⁷) were found in Tanner Basin, and Δ⁵-sterols and triterpenes, in Bandaras Bay sediment. Sterols from both sediments contained the corresponding stanols.     

Bacterial reworking of terrigenous and marine organic matter in estuarine water columns and sediments

Amino acids and the bacterial biomarkers muramic acid and d-amino acids were quantified in the ultrafiltered dissolved, particulate and sedimentary organic matter (UDOM, POM and SOM) of the St. Lawrence system (Canada). The main objectives were to better describe the fate of terrigenous and marine organic matter (OM) in coastal zones and to quantify the bacterial contributions to OM composition and diagenesis. Regardless of their origin, the carbon (C) content of the particles substantially decreased with depth, especially near the water-sediment interface. Major diagenetic transformations of organic nitrogen (N) were revealed and important differences were observed between terrigenous and marine OM. Amino acid contents of particles decreased by 66-93% with depth and accounted for 12-30% of the particulate C losses in marine locations. These percentages were respectively 18-56% and 7-11% in the Saguenay Fjord where terrigenous input is important. A preferential removal of particulate N and amino acids with depth or during transport was measured, but only in marine locations and for N-rich particles. This leads to very low amino acid yields in deep marine POM. However, these yields then increased to a level up to three times higher after deposition on sediments, where SOM showed lower C:N ratios than deep POM. The associated increase of bacterial biomarker yields suggests an active in situ resynthesis of amino acids by benthic bacteria. The N content of the substrate most likely determines whether a preferential degradation or an enrichment of N and amino acid are observed. For N-poor OM, such as terrigenous or deep marine POM, the incorporation of exogenous N by attached bacteria can be measured, while the organic N is preferentially used or degraded in N-rich OM. Compared to the POM from the same water samples, the extracted UDOM was poor in N and amino acids and appeared to be mostly made of altered plant and bacterial fragments. Signs of in situ marine production of UDOM were observed in the most marine location. The POM entering the St. Lawrence Upper Estuary and the Saguenay Fjord appeared made of relatively fresh vascular plant OM mixed with highly altered bacterial debris from soils. In contrast, the POM samples from the more marine sites appeared mostly made of fresh planktonic and bacterial OM, although they were rapidly degraded during sinking. Based on biomarker yields, bacterial OM represented on average ∼20% of bulk C and approximately 40-70% of bulk N in POM and SOM, with the exception of deep marine POM exhibiting approximately two times lower bacterial contributions.     

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.     

Nature and reactions of dissolved organic matter in the interstitial waters of marine sediments

Two organic rich sediments, an oxic muddy sand and a silty mud containing sulphate reducing and methane producing metabolic zones, were sampled from Loch Duich, a fjord type estuary in the N.W. coast of Scotland. Dissolved organic carbon (DOC), as measured by dry combustion and UV absorption, remained constant (8.3–15.8 mg C/l) with depth in the oxic pore waters at a concentration at least twice that of the overlying seawater. DOC in the anoxic pore waters increased linearly with depth from 13.6 at the surface to 55.9–70.5 mg C/l at 80cm. Most of the DOC was present in the high molecular weight (HMW) fraction as separated by ultrafiltration; the low molecular weight (LMW) fraction remained constant (10.0 mg C/l) in both oxic and anoxic pore waters. Spectroscopic data showed the ‘humic’ fraction of the HMW dissolved organic matter was mainly fulvic acid, a small proportion (approx 1%) of humic acid, and a third fraction, possibly melanoidins, which increased relative to fulvic acid with depth. These data confirm the pathway of humification (NissenBaum et al, 1971; nissenbaum and Kaplan, 1972) where HMW organic matter accumulates in pore waters as condensation products of LMW organic substances.     

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.     

Selective preservation of soil organic matter in oxidized marine sediments (Madeira Abyssal Plain)

In ocean margin sediments both marine and terrestrial organic matter (OM) are buried but the factors governing their relative preservation and degradation are not well understood. In this study, we analysed the degree of preservation of marine isoprenoidal and soil-derived branched glycerol dialkyl glycerol tetraethers (GDGTs) upon long-term oxygen exposure in OM-rich turbidites from the Madeira Abyssal Plain by analyzing GDGT concentrations across oxidation fronts. Relative to the anoxic part of the turbidites ca. 7-20% of the soil-derived branched GDGTs were preserved in the oxidized part while only 0.2-3% of the marine isoprenoid GDGT crenarchaeol was preserved. Due to these different preservation factors the Branched Isoprenoid Tetraether (BIT) index, a ratio between crenarchaeol and the major branched GDGTs that is used as a tracer for soil-derived organic matter, substantially increases from 0.02 to 0.4. Split Flow Thin Cell (SPLITT) separation of turbidite sediments showed that the enhanced preservation of soil-derived carbon was a general phenomenon across the fine particle size ranges (<38 μm). Calculations reveal that, despite their relatively similar chemical structures, degradation rates of crenarchaeol are 2-fold higher than those of soil-derived branched GDGTs, suggesting preferential soil OM preservation possibly due to matrix protection.     

Land-derived organic matter in surface sediments from the Gulf of Mexico

Lignin oxidation products and ¹³C/¹²C ratios were compared as indicators of land-derived organic matter in surface sediments from the western Gulf of Mexico. Whole sediments were reacted with cupric oxide to yield phenolic oxidation products that indicated the types and relative amounts of the lignins that were present.Measurements of lignin concentration and carbon isotope abundances both indicated a sharp offshore decrease of land-derived organic matter in most areas of the western Gulf. This decrease results primarily from mixing of terrestrial and marine organic matter. The terrestrially derived material in these sediments has a lignin content similar to that of grasses and tree leaves. Flowering plants contribute most of the sedimented lignin compounds. These lignins apparently occur in the form of well-mixed plant fragments that are transported to sea by rivers and deposited primarily on the inner continental shelf.     

The effect of organic matter and oxygen on the degradation of bacterial membrane lipids in marine sediments

The biodegradation of purified radiolabelled membrane lipids from a methanogenic bacterium and a pseudomonad were investigated in mangrove, beach and high marsh marine sediments under aerobic and anaerobic conditions. The effect of organic matter on the amount and rate of degradation was also examined by supplementing beach sediments with humic acids. In aerobic sediments, CO₂ was the major product of lipid degradation while under anaerobic conditions both CO₂ and CH₄ were major end products and the overall rates were reduced (up to 40%) relative to aerobic conditions. Total bacterial numbers increased during all incubations with the largest increases occurring in anaerobic sediments supplemented with humic acids. No lipid degradation occurred in aerobic or anaerobic sediments treated with formaldehyde or autoclaving. In low organic beach sediments, the ester-linked phospholipid of the pseudomonad was degraded much more rapidly than the diphytanyl glycerol diether of the methanogen with 69% of the phospholipid degraded in 96 hours versus only 4% of the methanogen lipid. Lipid degradation in both aerobic and anaerobic sediments was highly correlated to organic matter content with increasing amounts of organic matter inhibiting degradation. Long incubations (75 days) of the diphytanyl glycerol ether resulted in 51% degraded to CO₂ in low (0.5%) organic mangrove sediments while only 9% was mineralized in high (10.8%) organic marsh sediments. Physicochemical sorption of membrane lipids to the organic matrix is proposed as a mechanism which protects membrane lipids from microbial attack and degradation.     

Dissolved organic matter in pore water of carbonate sediments from Bermuda

Pore water samples from seven nearshore areas in Bermuda were obtained under in situ conditions and analyzed for dissolved organic carbon, dissolved carbohydrates, dissolved free amino acids and dissolved humic substances. The concentration of dissolved organic carbon is higher than in the overlying nearshore waters indicating significant diagenetic remobilization of carbon in these recently deposited carbonate sediments. Dissolved carbohydrates decrease with depth due to microbial utilization.     

Dissolved aluminium in interstitial waters of recent marine sediments

Measurements of the concentration and vertical distribution of dissolved aluminium and silica, and of pH. in interstitial waters of recent marine sediments from the North Sea and the Mediterranean Sea were performed to evaluate the behaviour of aluminium during early diagenesis. The results suggest that thermodynamic equilibria alone do not control the concentrations of dissolved species in the system Al-Si-O₂-H₂O during early diagenesis. Rather, these concentrations are governed by dynamic factors involving mineral dissolution-precipitation reactions and diffusion.     

Hydrothermal petroleum from lacustrine sedimentary organic matter in the East African Rift.

Cape Kalamba oil seeps occur at the south end of the Ubwari Peninsula, at the intersection of faults controlling the morphology of the northern basin of the Tanganyika Rift, East Africa. Oil samples collected at the surface of the lake 3-4 km offshore from Cape Kalamba have been studied. The aliphatic hydrocarbon and biomarker compositions, with the absence of the typical suite of polynuclear aromatic hydrocarbons, indicate an origin from hydrothermal alteration of immature microbial biomass in the sediments. These data show a similarity between a tar sample from the beach and the petroleum from the oil seeps, and confirm that the source of these oils is from organic matter consisting mainly of bacterial and degraded algal biomass, altered by hydrothermal activity. The compositions also demonstrate a < 200 degrees C temperature for formation/generation of this hydrothermal petroleum, similar to the fluid temperature identified for the Pemba hydrothermal site located 150 km north of Cape Kalamba. The 14C age of 25.6 ka B.P. obtained for the tar ball suggests that Pleistocene lake sediments could be the source rock. Hydrothermal generation may have occurred slightly before 25 ka B.P., during a dry climatic environment, when the lake level was lower than today. These results also suggest that the Cape Kalamba hydrothermal activity did not occur in connection with an increased flux of meteoric water, higher water tables and lake levels as demonstrated in the Kenya Rift and for the Pemba site. Hydrothermal petroleum formation is a facile process also in continental rift systems and should be considered in exploration for energy resources in such locales.     

Issue of the genesis of recent sediments on the Barents Sea shelf

This paper is a reply to the comment on our two previous publications (Krapivner, 2009a, 2009b) devoted to the genesis of recent sediments on the Barents Sea shelf in (Epshtein et al., 2011a, 2011b). It is substantiated that the physical nature of the reflection of recent sediments in seismoacoustic records, a very important point for the lithofacies analysis, is incorrectly interpreted by the above opponents. The paper presents geochronological and paleomagnetic data confirming invalidity of the popular concepts about the link between the cover of poorly consolidated sediments and the epoch of the last deglaciation. We show incorrectness of the statement of the opponents about the redeposited character of Pliocene-Quaternary marine biota of diamictons and the glacial processing of coarse-clastic material therein. Diverse properties of recent sediments and their topography artificially united into a complex of indicators of the glacial paragenesis are either simply explained in terms of the natural (for the Barents Sea) icemarine sedimentation or attributed to postsedimentary processes during intense neotectonic activity of the Barents Sea shelf.     

Effect of organic matter on DOM sorption on lake sediments

The effect of organic matter on the sorption of dissolved organic matter (DOM) on lake sediments is critical to understanding the fate and transport of contaminants at the sediment–water interface in lake ecosystems. Results indicate that DOM sorption on sediment is largely due to ligand exchange between the DOM and hydroxyl groups, and the amount of DOC sorbed is a linear function of added DOC. With increasing organic matter content the sediment has lower binding strength, higher releasing ability for DOM, and the higher amount of DOM sorbed by sediment naturally. There was no clear difference before and after the sediment was treated with H₂O₂, but the constant b implied that after the sediments were treated DOC release was promoted. Organic matter in the sediment tends to impede the sorption of DOC and results in a remarkable decrease in DOC sorption rates.     

Occurrence of Highly Mature Organic Matter in Marine Black Shale Petroleum Source Rocks of Basal Cambrian from Northern Tarim Basin, China

More and more evidence indicates that organic matter (OM) in immature organicrich sediments and sedimentary rocks is chemically adsorbed onto the outer surfaces of minerals and into interlayer (inner) surfaces of smectitic clay minerals in the form of amorphous molecular-scale carbon. But there have been few reports about the occurrence of highly mature OM in marine black shales ( petroleum source rocks ). The occurrence of highly mature OM in the black shales of basal Cambrian from northern Tarim Basin is studied in this paper. Based on the comprehensive analyses of total organic carbon contents (TOC) , maximum thermolysis tempera tures ( Tmax ) of OM, mineral surface areas (MSA) ,and scanning electronic microscopic (SEM) and transmission electronic microscopic (TEM) observations of the black shales, it is concluded that the highly mature OM in the marine black shales of the basal Cambrian from northern Tarim Basin occurs in particulates ranging in size from 1 to 5 μm in diameter. Through the contrast of the occurrence of the highly mature OM in the black shales with that of the immature ones in modern marine continental margin sediments, some scientific problems are proposed, which are worth to study further in detail.     

Factors affecting dissolved organic matter dynamics in mixed-redox to anoxic coastal sediments

Mixed-redox (suboxic, or oscillating between oxidizing and reducing conditions) to anoxic marine sediments from the Raritan -New York Bay complex and the Inner New York Bight of the eastern U.S. were studied to investigate the factors controlling the accumulation of pore-water dissolved organic carbon (DOC). DOC increased with depth at each of four study sites, but accumulation was generally limited in the mixed-redox zone relative to the anoxic zone. Humic-like fluorescence intensity also differed between mixed-redox and anoxic zones of the sediment, such that anoxic pore waters were relatively enriched in fluorescent, humic-like compounds.A pore-water DOC model was tested for its capacity to explain these geochemical patterns. Model results for a heavily irrigated and a non-bioturbated site both suggest that, excluding the uppermost few cm of the sediment column, pore-water DOC is predominantly comprised of poorly-reactive material with estimated degradation rate constants on the order of 10⁻³ yr⁻¹. Model results are also consistent with the suggestion that DOC accumulation is suppressed in the mixed-redox compared to the anoxic zones of the sediment due to rapid oxidation of high-molecular-weight DOC, and limited production and enhanced oxidation of the less reactive polymeric low-molecular-weight component of the DOC pool. An assessment of sorptive behavior of DOC in the surface sediments of the study area suggests that sorption can influence pore-water DOC distributions under conditions of high sedimentation and low bioirrigation.     

近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.