Nitrogen and carbon isotopic composition of marine and terrestrial organic matter in Arctic Ocean sediments:: implications for nutrient utilization and organic matter composition

Relationships between organic carbon, total nitrogen and organic nitrogen concentrations and variations in δ¹³C_org and δ¹⁵N_org are examined in surface sediments from the eastern central Arctic Ocean and the Yermak Plateau. Removing the organic matter from samples with KOBr/KOH and determining residual as well as total N shows that there is a significant amount of bound inorganic N in the samples, which causes TOC/N_total ratios to be low (4–10 depending on the organic content). TOC/N_org ratios are significantly higher (8–16). This correction of organic TOC/N ratios for the presence of soil-derived bound ammonium is especially important in samples with high illite concentrations, the clay mineral mainly responsible for ammonium adsorption. The isotopic composition of the organic N fraction was estimated by determining the isotopic composition of the total and inorganic nitrogen fractions and assuming mass-balance. A strong correlation between δ¹⁵N_org values of the sediments and the nitrate concentration of surface waters indicates different relative nitrate utilization rates of the phytoplankton in various regions of the Arctic Ocean. On the Yermak Plateau, low δ¹⁵N_org values correspond to high nitrate concentrations, whereas in the central Arctic Ocean high δ¹⁵N_org values are found beneath low nitrate waters. Sediment δ¹³C_org values are close to −23.0‰ in the Yermak Plateau region and approximately −21.4‰ in the central Arctic Ocean. Particulate organic matter collected from meltwater ponds and ice-cores are relatively enriched in ¹³C (δ¹³C_org=−15.3 to −20.6‰) most likely due to low CO₂(aq) concentrations in these environments. A maximum terrestrial contribution of 30% of the organic matter to sediments in the central Arctic Ocean is derived, based on the carbon isotope data and various assumptions about the isotopic composition of the potential endmembers.     

Contents and stable isotopic compositions of organic carbon and total nitrogen in the surface sediment of two coastal bays in Korea

Surface sediment from the coastal bays of Gwangyang and Masan in South Korea were analyzed for their contents and isotopic values of organic carbon and total nitrogen. The sources and diagenetic alteration of organic matter were also assessed. Total organic carbon varied from 0.22% to 3.48% (average = 1.40%, n = 75), and C/N ratios varied from 2.4 to 15.2 (average = 8.79, n = 75). δ¹³C_org ranged from −19.92‰ to −25.86‰ (average = −21.21‰, n = 75), and δ¹⁵N_TN ranged from 8.57‰ to 3.93‰ (average = 6.49‰, n = 75). Total organic carbon in both areas was associated with grain-size, with higher contents in finer grained sediment. The high carbon content observed in Masan Bay sediment correlated with its higher C/N ratio. δ¹³C_org and δ¹⁵N_TN varied widely, attributable to various influences such as the input of terrestrial organic matter and diagenetic alteration. The depleted δ¹³C_org and higher δ¹⁵N_TN observed in the sediment of Gwangyang Bay reflected terrestrial supply, implying that biogeochemical processes, i.e. bacterial degradation, were more active in Masan Bay sediment, which showed less depleted δ¹³C_org and higher δ¹⁵N_TN than Gwangyang Bay sediment. δ¹⁵N_TN was the more useful indicator of biogeochemical processes in the highly anoxic sediment. These results indicate that the δ¹³C_org and δ¹⁵N_TN of sedimentary organic matter in coastal bays can indicate the source and degree of diagenetic alteration of sedimentary organic matter.     

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.     

Origin of sedimentary organic matter in the north-western Adriatic Sea

In order to evaluate the origin and the transformation of organic matter on the shallow shelf of the NW Adriatic Sea, organic carbon, total nitrogen and stable isotope ratios of organic carbon were analysed in riverine suspended matter and sediments as well as in marine suspended and sedimentary organic matter, in marine phytoplankton and zooplankton.The deposition of organic matter is influenced by fine sediment concentration. Surface sediments were characterised by highly variable biogeochemical conditions on the sea floor, whereas sub-surface sediments showed a more homogeneous hypoxic/anoxic environment.Low C_org/N ratio and high organic carbon and nitrogen concentrations in riverine suspended organic matter indicate an important contribution of freshwater phytoplankton within rivers, particularly during low flow regimes, which adds to the marine phyto- and zooplankton at shelf locations.In order to evaluate the importance of terrestrial, riverine and marine sources of OM in shelf sediments, a three end-member mixing model was applied to shelf surface sediments using ¹³C/¹²C values for organic matter and N/C ratios. The model showed an elevated contribution of terrestrial organic substances at intermediate depths (10–15 m), mostly corresponding to an area of coarser grain-size, whereas the riverine and marine organic fractions were mainly accumulating near the coast and offshore, respectively.     

Origin and fate of particulate organic matter in the southern Beaufort Sea – Amundsen Gulf region,Canadian Arctic

To establish the relative importance of terrigenous and marine organic matter in the southern Beaufort Sea, we measured the concentrations and the stable isotopic compositions of organic carbon and total nitrogen in sediments and in settling particles intercepted by sediment traps. The organic carbon content of surface sediment in the Chukchi and southern Beaufort Seas ranged from 0.6 to 1.6% dry wt., without a clear geographical pattern. The C_ORG:N_TOT ratio ranged from 7.0 to 10.4 and did not vary significantly downcore at any one station. Values of δ¹³C_ORG and δ¹⁵N_TOT in the sediment samples were strongly correlated, with the highest values, indicative of a more marine contribution, in the Amundsen Gulf. In contrast, the organic matter content, elemental (C_ORG:N_TOT ratio) and isotopic (δ¹³C_ORG and δ¹⁵N_TOT) composition of the settling particles was different from and much more variable than in the bottom sediments. The isotopic signature of organic matter in the Beaufort Sea is well constrained by three distinct end-members: a labile marine component produced in situ by planktonic organisms, a refractory marine component, the end product of respiration and diagenesis, and a refractory terrigenous component. A three-component mixing model explains the scatter observed in the stable isotope signatures of the sediment trap samples and accommodates an apparent two-component mixing model of the organic matter in sediments. The suspended matter in the water column contains organic matter varying from essentially labile and marine to mostly refractory and terrigenous. As it settles through the water column, the labile marine organic matter is degraded, and its original stable isotope signature changes towards the signature of the marine refractory component. This process continues in the bottom sediment with the result that the sedimentary organic matter becomes dominated by the refractory terrigenous and marine components.     

Stable isotopes of carbon and nitrogen in suspended matter and sediments from the Godavari estuary

Spatial distribution of the carbon and nitrogen content and their isotopic enrichment in suspended matter and sediments were measured in the Godavari estuary to identify the sources and transformation mechanism of organic matter. Significant variability in isotopic distribution was found over the entire length of the Godavari estuary, suggesting multiple sources of organic matter. The mean isotopic ratios (δ¹³C_sed −25.1 ± 0.9, δ¹³C_sus −24.9 ± 1, δ¹⁵N_sed 8.0 ± 2 and δ¹⁵N_sus 6.5 ± 0.9‰) and elemental concentrations (C_sed 0.45 ± 0.2%, C_sus 0.9 ± 0.7%, N_sed 0.07 ± 0.05% and N_sus 0.16 ± 0.1%) support a predominantly terrigenous source. Significant enrichment in the isotopic ratios of δ¹³C from the upper to lower estuary in both suspended (−27.5 and −24.3‰, respectively) and sedimentary (−26.2 and −24.9‰, respectively) phases indicates a decrease in the influence of terrigeneous material toward the mouth of the estuary. A significant positive relationship exists between the δ¹³C of suspended and sediment, which indicates that these two organic carbon pools are likely coupled in the form of a significant exchange between the two phases. A positive relationship exists between chlorophyll a and suspended organic matter, which may mean that a significant source of organic carbon is the in situ produced phytoplankton. But, applying a simple mixing model to our isotopes, data yielded about 46% as the contribution of the terrestrial source to suspended matter, which may support the excessive heterotrophic activity in the Godavari estuary reported earlier.     

The reflection of the present distribution of the primary production in the bottom sediments of the Sea of Okhotsk

Using the authors’ data obtained during expeditions to the Sea of Okhotsk during the last decade, the primary phytoplankton production and the distribution of organic carbon and chlorophyll a degradation products (chlorin) in the bottom sediments were studied. Using the authors’ and published data, the spatial distribution of the production and paleoproduction indicators was plotted. The ratios of the chlorin and C_org content in the sediments was considered, and the correlation between these parameters was revealed. It was shown that the average annual primary production of phytoplankton and the paleoproduction indices were maximum in the coastal and upwelling zones and decreased towards the sea’s center. A quantitative correlation was found between the distribution of the present primary production in the photic layer and that of the rates of the accumulation of organic matter buried within the surface sediments. As a result, it was shown that the content of chlorin and C_org in the marine bottom sediments may be used to reconstruct the paleoproduction variability of the past.     

Late Cretaceous (Late Turonian,Coniacian and Santonian) petroleum source rocks as part of an OAE,Tarfaya Basin,Morocco

Late Turonian, Coniacian and Santonian source rock samples from a recently drilled well (Tafaya Sondage No. 2; 2010) in the Tarfaya Basin were analyzed for quantity, quality, maturity and depositional environment of the organic matter (OM). To our knowledge such a thick sequence of organic matter-rich Turonian to Santonian source rocks was investigated in that great detail for the first time. Organic geochemical and organic petrological investigations were carried out on a large sample set from the 200 m thick sequence. In total 195 core samples were analyzed for total organic carbon (C_org), total inorganic carbon contents and total sulfur (TS) contents. Rock-Eval pyrolysis and vitrinite reflectance measurements were performed on 28 samples chosen on the basis of their C_org content. Non-aromatic hydrocarbons were analyzed on selected samples by way of gas chromatography–flame ionization detection (GC–FID) and GC–mass spectrometry (GC–MS). The organic matter-rich carbonates revealed a high source rock potential, representing type I kerogen and a good preservation of the organic matter, which is mainly of marine (phytoplankton) origin. HI values are high (400–900 mg/g C_org) and in a similar range as those described for more recent upwelling sediments along the continental slope of North Africa. TS/C_org ratios as well as pristane over phytane ratios indicate variable oxygen content during sediment deposition. All samples are clearly immature with respect to petroleum generation which is supported by maturity parameters such as vitrinite reflectance (0.3–0.4%), T_max values (401–423 °C), production indices (S₁/(S₁ + S₂) > 0.1) as well as maturity parameters based on ratios of specific steranes and hopanes.     

High organic carbon deposition in the northern margin of the Aleutian Basin (Bering Sea) before the last deglaciation

High-resolution geochemical, isotope and elemental data from core PC23A in the northern margin of the Aleutian Basin (Bering Sea) were used to reconstruct distinct paleoceanographic features of the last deglaciation (pre-Boreal[PB], Bølling-Allerød[BA], Younger Dryas[YD]). The PB and BA intervals are characterized by increased siliceous (diatom) and calcareous (coccolithophores and foraminifers) productivity represented by high biogenic opal and CaCO₃ contents, respectively. The enhanced productivity can plausibly be attributed to an elevated sea-surface nutrient supply from increased melt-water input and enhanced Alaskan Stream injection under warm, restricted sea-ice conditions. High C_org/N ratios and low δ¹³C values of sediment organic matter during the PB and BA intervals reflect the contribution of terrestrial organic matters. The PB and BA intervals were also identified by laminated sediment layers of core PC23A, characterized by high Mo/Al and Cd/Al ratios, indicating that the bottom water condition remained anoxic. High δ¹⁵N values during the same period were attributed mainly to the increased nutrient utilization and subsequent denitrification of seawater nitrate. Part of high δ¹⁵N values may also be due to incorporation of inorganic nitrogen in the clay minerals. It is worthy of note that high total organic carbon (TOC) deposition occurred approximately 3,000 years before onset of the last deglaciation. Simultaneous high C_org/N ratios and low δ¹³C values clearly suggest that the high TOC content should be related to terrestrial organic carbon input. Low δ¹⁵N values during the high TOC interval also confirm the contribution of terrigenous organic matter. Although abundant calcareous phytoplankton production under cold, nutrient-poor conditions represented by Baex data was reported for high TOC deposition preceding the last deglaciation in an earlier study of the Okhotsk Sea, the main reason for the enhanced TOC deposition in the Bering Sea is an increased terrigenous input from the submerged continental shelves (Beringia) with a sea-level rise; this is further supported by Al enrichment of bulk sediments during the high TOC deposition.     

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.     

全新世大暖气广西钦州湾红树林衰退的红树林源有机质贡献示踪及其对亚洲季风的响应

The response of mangrove ecosystems to the Asian monsoon in the future global warming can be understood by reconstructing the development of mangrove forests during the Holocene climatic optimum(HCO), using proxies preserved in coastal sediments. The total organic matter in sediments of a segmented core, with calibrated age ranges between 5.6 and 7.7 cal. ka BP and corresponding to the HCO, from the Qinzhou Bay in Guangxi, China, is quantitatively partitioned into three end-members according to their sources: mangrove-derived, terrigenous,and marine phytoplanktonic, using a three-end-member model depicted by organic carbon isotope(δ13Corg) and the molar ratio of total organic carbon to total nitrogen(C/N). The percentage of mangrove-derived organic matter(MOM) contribution is used as a proxy for mangrove development. Three visible drops in MOM contribution occurred at ca. 7.3, ca. 6.9, and ca. 6.2 cal. ka BP, respectively, are recognized against a relatively stable and higher MOM contribution level, indicating that three distinct mangrove forest degradations occurred in the Qinzhou Bay during the HCO. The three mangrove forest degradations approximately correspond to the time of the strengthened/weakened Asian winter/summer monsoon. This indicates that even during a period favorable for the mangrove development, such as the HCO, climatic extremes, such as cold and dry events driven by the strengthened/weakened Asian winter/summer monsoon, can trigger the degradation of mangrove forests.     

Distribution and burial of organic carbon in sediments from the Indian Ocean upwelling region off Java and Sumatra,Indonesia

Sediments were sampled and oxygen profiles of the water column were determined in the Indian Ocean off west and south Indonesia in order to obtain information on the production, transformation, and accumulation of organic matter (OM). The stable carbon isotope composition (δ¹³C_org) in combination with C/N ratios depicts the almost exclusively marine origin of sedimentary organic matter in the entire study area. Maximum concentrations of organic carbon (C_org) and nitrogen (N) of 3.0% and 0.31%, respectively, were observed in the northern Mentawai Basin and in the Savu and Lombok basins. Minimum δ¹⁵N values of 3.7‰ were measured in the northern Mentawai Basin, whereas they varied around 5.4‰ at stations outside this region. Minimum bottom water oxygen concentrations of 1.1 mL L^?1, corresponding to an oxygen saturation of 16.1%, indicate reduced ventilation of bottom water in the northern Mentawai Basin. This low bottom water oxygen reduces organic matter decomposition, which is demonstrated by the almost unaltered isotopic composition of nitrogen during early diagenesis. Maximum C_org accumulation rates (CARs) were measured in the Lombok (10.4 g C m^?2 yr^?1) and northern Mentawai basins (5.2 g C m^?2 yr^?1). Upwelling-induced high productivity is responsible for the high CAR off East Java, Lombok, and Savu Basins, while a better OM preservation caused by reduced ventilation contributes to the high CAR observed in the northern Mentawai Basin. The interplay between primary production, remineralisation, and organic carbon burial determines the regional heterogeneity. CAR in the Indian Ocean upwelling region off Indonesia is lower than in the Peru and Chile upwellings, but in the same order of magnitude as in the Arabian Sea, the Benguela, and Gulf of California upwellings, and corresponds to 0.1–7.1% of the global ocean carbon burial. This demonstrates the relevance of the Indian Ocean margin off Indonesia for the global OM burial.     

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze River) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0–2 cm) were 5–10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C₂₆-C₃₃ long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC₁₅ to nC₂₂ compounds. Long-chain (>C₂₀) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (<C₂₀) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk δ ¹³C_TOCTOC. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.     

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.     

Sedimentary and residual gas geochemical characteristics of the Lower Cambrian organic-rich shales in Southeastern Chongqing,China

To study the sedimentary environment of the Lower Cambrian organic-rich shales and isotopic geochemical characteristics of the residual shale gas, 20 black shale samples from the Niutitang Formation were collected from the Youyang section, located in southeastern Chongqing, China. A combination of geochemical, mineralogical, and trace element studies has been performed on the shale samples from the Lower Cambrian Niutitang Formation, and the results were used to determine the paleoceanic sedimentary environment of this organic-rich shale. The relationships between total organic carbon (TOC) and total sulfur (TS) content, carbon isotope value (δ¹³C_org), trace element enrichment, and mineral composition suggest that the high-TOC Niutitang shale was deposited in an anoxic environment and that the organic matter was well preserved after burial. Stable carbon isotopes and biomarkers both indicate that the organic matter in the Niutitang black shales was mainly derived from both lower aquatic organisms and algaes and belong to type I kerogen. The oil-prone Niutitang black shales have limited residual hydrocarbons, with low values of S₂, I_H, and bitumen A. The carbon isotopic distribution of the residual gas indicate that the shale gas stored in the Niutitang black shale was mostly generated from the cracking of residual bitumen and wet gas during a stage of significantly high maturity. One of the more significant observations in this work involves the carbon isotope compositions of the residual gas (C₁, C₂, and C₃) released by rock crushing. A conventional δ¹³C₁–δ¹³C₂ trend was observed, and most δ¹³C₂ values of the residual gases are heavier than those of the organic matter (OM) in the corresponding samples, indicating the splitting of ethane bonds and the release of smaller molecules, leading to ¹³C enrichment in the residual ethane.     

Phosphorus regeneration and burial in near-shore marine sediments (the Gulf of Trieste, northern Adriatic Sea)

According to bioassay studies and high dissolved nutrient N/P ratios in the seawater column, phosphorus (P) is thought to control marine productivity in the northern Adriatic Sea. P in near-shore marine sediments of the Gulf of Trieste, the northernmost part of the Adriatic Sea, was investigated using pore water P distributions, and benthic P flux studies under oxic and anoxic conditions. The data show that P regeneration is up to three-fold more extensive in sediments overlain by oxygen-depleted waters and proceeds in parallel with Fe and Mn enhanced benthic fluxes. It appears from the incubation experiments that degradation of sedimentary organic matter is the main contribution to the flux of P at the sediment–water interface, while the release of phosphate adsorbed on the iron oxide surface is of minor importance.It appears that about 50% of P in the Gulf of Trieste is retained within in the sediments, probably bonded to clay minerals and carbonate grains or precipitated as fluoroapatite. In these sediments total P (P_tot) is preserved preferentially over organic C (C_org). P regenerated from surficial sediments contributes about 1/3 of the P that is assimilated by benthic microalgae. The phytoplankton P requirement should be entirely supplied from fresh-water sources. These results suggest that oxygen depletion in coastal areas caused by eutrophication enhances P regeneration from sediments, providing the additional P necessary for increased biological productivity. The development of anoxic bottom waters in coastal areas enhances the recycling of P, exacerbating the nutrient requirement in the area. A geochemical record of P burial in a longer sedimentary sequence revealed an increasing trend of P_tot and organic P (P_org) contents occurring approximately 50 years BP (after 1950), probably due to increasing use of inorganic fertilizers and detergents in the area.     

Characterizing lipid biomarkers in methanotrophic communities of gas hydrate-bearing sediments in the Sea of Okhotsk

We studied specific lipid biomarkers of archaea and bacteria, that are associated with the anaerobic oxidation of methane (AOM) in a cold seep environment as well as the origin of sedimentary organic matter on the continental slope off NE Sakhalin in the Sea of Okhotsk. The organic geochemical parameters demonstrated that most of the sedimentary organic matter containing hydrate layers could be derived from marine phytoplankton and bacteria, except for a station (LV39-29H) which was remarkably affected by terrestrial vascular plant. Specific methanotrophic archaea biomarkers was vertically detected in hydrate-bearing cores (LV39-40H), coinciding with the negative excursion of the δ¹³C_org at core depths of 90–100 cm below the seafloor. These results suggest that methane provided from gas hydrates are already available substrates for microbes thriving in this sediment depth. In addition, the stable isotope mass balance method revealed that approximately 2.77–3.41% of the total organic carbon (or 0.036–0.044% dry weight sediment) was generated by the activity of the AOM consortium in the corresponding depth of core LV39-40H. On the other hand, the heavier δ¹³C values of archaeol in the gas hydrate stability zone may allow ongoing methanogenesis in deeper sediment depth.     

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.     

Degradation and dissolution of zooplanktonic organic matter and lipids in early diagenesis

A degradation experiment with zooplankton was carried out to investigate the diagenesis of zooplanktonic organic matter, lipids, and lipid classes. In addition, reactivities and the quantitative relation between bulk organic carbon and waxes (which are the biomarkers of zooplankton) were compared during the experiment to evaluate the possibility of estimating the contributions of zooplanktonic organic matter in organic carbon pools, such as settling particles and surface sediments, from the wax concentration. Lipids were found to be more labile than the bulk organic carbon. Major parts of the organic carbon and lipids which remained on day 120 were found in the particulate fraction, and the accumulations of stable organic carbon and lipids in the dissolved fraction were limited. Although the lipids were more labile than the bulk organic carbon in the early phase of the experiment, the degradation rate of lipids obviously decreased in the subsequent degradation period, demonstrating the presence of stable lipids in zooplankton. Whereas triglycerides readily decreased, phospholipids persisted, making a major contribution to particulate lipids throughout the experiment. Waxes and other structural lipids such as glycolipids were also stably preserved in particulate lipids, suggesting that stable lipids in particulate matter are composed of structural lipids and waxes during early diagenesis. The degradation rate of waxes showed values comparable to that of bulk organic carbon after 11 days of degradation, resulting in constant ratios of waxes/bulk organic carbon (0.8 ± 0.2%, n = 7) during the later incubation period (after 11 days). This result suggests that the ratio could prove useful in evaluating the zooplanktonic organic carbon in organic carbon pools such as surface sediments and settling particulates.