Gas chromatographic determination of lignin in sediment

After the oxidation of river and marine sediments with CuO under alkaline conditions, the phenolic compounds in the oxidation products are determined gas chromatographically and compared to that of lignin oxidation products. The method of CuO oxidation is compared to that of nitrobenzen. The quantitative determination of produced phenolic compounds by capillary gas chromatography is examined and the blank and repetibility of the method are tested.     

The fate of terrestrial organic matter in two Scottish sea lochs

Sea lochs are zones of rapid organic matter (OM) turnover. Most of this OM is of allochthonous origin, being introduced into the lochs via freshwater input. In this study the behaviour of terrestrially derived OM was elucidated using a combination of parameters which indicate OM diagenesis in the near surface sediments from two Scottish sea lochs, Loch Creran and Loch Etive. Alkaline CuO oxidation was used to determine lignin phenols which serve as biomarkers for terrestrial OM in sediments. Stable carbon isotope, total carbon and nitrogen and total OM (including the labile and refractory fractions) compositions were also determined.     

Dissolved Vanillin as Tracer for Estuarine Lignin Conversion

Lignin is produced only by vascular plants and therefore can be used as a tracer for terrestrial organic carbon input to the estuarine and marine environments. Lignin measurements have been done by analyses of the oxidation products such as vanillin or 4-hydroxybenzaldehyde.In the Elbe Estuary, free dissolved vanillin was analysed in order to test whether such measurements yield information on terrestrial carbon inputs into the Estuary and on the vanillin derived from lignin oxidation. In the period 1990–1992, concentrations of dissolved vanillin in the Elbe ranged from 0 to 60 μg l⁻¹(mean: 8 μg l⁻¹). Higher values were found in areas of increased microbial activity such as the turbidity zone and the river mouth where the water chemistry is influenced by large tidal flats. No correlation was found between dissolved vanillin and suspended matter concentrations, although lignin is normally associated with suspended particulate matter, nor was a covariance seen between dissolved vanillin and the terrestrial carbon inputs into the Estuary. Apparently, biological conversion of lignin was faster than the transport processes, and local sources were more dominant for the vanillin concentration than riverine sources. The dissolved vanillin turnover was fast and, consequently, a significant amount of lignin may be converted within an estuary. In sediments from the Estuary, the concentrations of dissolved vanillin were similar to those found in the water phase and showed no clear vertical profile. The sediment is unlikely to be the source for vanillin.     

Sources,transport, and partitioning of organic matter at a highly dynamic continental margin

Continental shelves play a major role as transition zone during transport of multiply-sourced organic matter into the deep sea. In order to obtain a comprehensive understanding of the origin and fractionation processes of organic matter at the NW Iberian margin, 40 surface sediment samples were analyzed for a structurally diverse range of lipid biomarkers, lignin phenols, grain size distribution, organic carbon content (TOC), its stable carbon isotopic composition (δ¹³CTOC), and the organic carbon to nitrogen ratio (TOC/TN). The biomarker inventory reflected a heterogeneous mixture of organic matter from various marine and terrestrial sources. Soil- and vascular plant-derived continental organic matter, indicated by lignin phenols and plant-derived triterpenoids, was primarily associated with the silt fraction and transported by river run-off. The spatial distribution patterns of higher plant-derived waxes, long-chain n-alkanes, n-alcohols, and n-fatty acids suggested distinct different transport mechanisms and/or sources. The branched tetraether index, a molecular proxy expressing the relative abundance of branched dialkyl tetraethers vs. crenarchaeol and considered to signal soil-derived organic matter, was not as sensitive as the other molecular indicators in detecting continental organic matter. Hydrodynamic sorting processes on the shelf resulted in a separation of different types of terrestrial organic matter; grass and leaf fragments and soil organic matter were preferentially transported offshore and deposited in areas of lower hydrodynamic energy. Algal lipid biomarker distributions indicated a complex community of marine plankton contributing to organic matter. Spatial and seasonal patterns of phytoplankton growth primarily controlled the distribution of algal organic matter components. The interplay of all of these processes controls production, distribution, and deposition of organic matter and results in three distinct provinces at the Galicia–Minho shelf: (I) fresh marine organic matter dominated the inner shelf region; (II) high inputs of terrestrial organic matter and high TOC content characterized the mid-shelf deposited mudbelt; (III) lower concentrations of relatively degraded organic matter with increased proportions of refractory terrestrial components dominated the outer shelf and continental slope.     

Partitioning of organic matter in continental margin sediments among density fractions

Hydrodynamic processes sort and redistribute organic matter (OM) and minerals on continental margins. Density fractionations were conducted on sediments from diverse margins (Mexico margin, Gulf of Mexico, Mississippi River delta, Eel River margin) to investigate the nature, provenance and age of OM among density fractions. Mass, elemental (C and N), lignin, and surface area distributions, as well as stable carbon and radiocarbon isotopic compositions were measured. The lowest density fractions (< 1.6 g cm^− 3) contained the highest organic carbon (OC) (up to 45%) and lignin concentrations (up to 8 mg g^− 1) due to abundant woody debris, whereas high density fractions (> 2.5 g cm^− 3) were OC-poor (%OC < 0.5) mineral material. Most sediment mass was found in the mesodensity fractions (1.6 to 2.5 g cm^− 3) that contained the highest proportion of OC (up to ~ 75%) for each sediment. Stable carbon isotope compositions (δ¹³C − 25.5‰ to − 22.9‰) show terrigenous OC as a significant component of density isolates from the river-dominated sediments (Gulf of Mexico, Mississippi River, and Eel margin), whereas the Mexico margin, least influenced by riverine input, was dominated by autochthonous marine OC (δ¹³C ~ − 21.5‰). Radiocarbon compositions of density fractions indicate significant pre-aged OC (Δ¹⁴C as low as − 900‰) in river-influenced sediments but not on the Mexico margin (Δ¹⁴C > − 200‰). Ratios of vanillic acid to vanillin (Ad/Al)v among lignin oxidation products increase with increasing particle density suggesting variable lignin sources or selective degradation of lignin among the different density fractions.     

Chemical and GC-MS characterization of marine particulate lipids

The lipid fraction of particulate organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GS), and gas chromatography—mass spectrometry (GS—MS). Gravimetric concentrations in the Gulf of Mexico were in the range of 12–70 μg 1^?1 for near-surface samples and 9–52 μg 1^?1 for near-bottom samples. The lipids accounted for ～20% of the particulate organic carbon. Particulate lipids were found to be a much more complex mixture of organic compounds than the dissolved lipids and their composition was much more variable. The majority of the extracted weight was recovered in the polar liquid chromatography fraction (49–85%). The major components of the analyzable particulate lipids were similar to those of the dissolved lipids, namely, n-alkanes, pristane, phytane, and methyl, ethyl and propyl fatty acid esters. Often olefins, alkylated benzenes, quinones, and the unresolved GC area contribute a substantial part to the total particulate lipids. Minor components included ketones, phenols, indanes, acids, benzoates, aromatics and possibly derivatives of inositol, dioxane, and pyran. The low concentrations observed confirm that the area is relatively pristine though some evidence for chronic low-level oil pollution was present. Seasonal, diurnal, vertical and areal variations were observed in the particulate lipids. Lipid concentrations not only decreased with depth but they were also a decreased percentage of the organic carbon present. This may indicate the loss of labile carbon with depth due to reworking in the euphotic zone. Anoxic conditions appeared to promote the preservation of lipid materials in the particulate phase, n-Alkanes and fatty acid esters were common to both the particulate and dissolved phases and had similar distributions.     

Sources, pathways and sinks of particulate organic matter in Hudson Bay: Evidence from lignin distributions

Hudson Bay is a large, estuarine, shelf-like sea at the southern margin of the Arctic, where changes in seasonal ice cover and river discharge appear already to be underway. Here we present lignin data for dated sediments from eleven box cores and evaluate sources of terrigenous carbon, transport pathways, and whether terrigenous organic matter has been influenced by recent environmental change. Lignin yields (0.04 to 1.46 mg/100 mg organic carbon) decreased from the margin to the interior and from south to north, broadly reflecting the distribution of river inputs. Lignin compositional patterns indicated distinct regional sources with boreal forest (woody gymnosperm) vegetation an important source in the south, vs. tundra (non-woody angiosperm) in the north. Lignin patterns suggest redistribution of a fine-grained, mineral-associated fraction of the southern-derived terrigenous carbon to the northeast part of the Bay and ultimately into west Hudson Strait with the Bay's cyclonic coastal circulation. A small component of the carbon makes it to the central basins of Hudson Bay but most of the terrigenous organic material in that area appears to derive from resuspension of older, isostatically-rebounding coastal and inner shelf deposits. Most modern plant debris appears to be retained near river mouths due to hydrodynamic sorting, with the exception of the southwest inner shelf, where these materials extend > 30 km from shore. Temporal changes in the composition of terrigenous organic carbon recorded in most of the southern Hudson Bay cores perhaps reflect increases in erosion and cross-shelf transport from coastal deposits, possibly mediated by change in ice climate. In contrast, temporal changes in the northwest may relate to changes in the supply of modern plant debris under recent warmer conditions. On the western shelf, changes may relate to ice climate and the distribution of northern coastal water and/or changes in the delivery of materials by the Churchill River due to water diversion. Although the cores show evidence of change related to the ice climate, there is little evidence that ice itself transports terrigenous organic carbon within the system.     

Oceanographic and climatologic controls on the compositions and fluxes of biogenic materials in the water column and sediments of the Cariaco Basin over the Late Holocene

Materials collected by sediment traps over a 3-y period and sedimentary horizons from a gravity core covering the last 6000 y were used to investigate the effects of climate-related processes such as wind-driven upwelling and regional rainfall on the production, export and burial of particulate organic matter in the Cariaco Basin. A variety of chemical analyses, including organic carbon and nitrogen, biogenic opal, calcite, lithogenic contents, stable carbon isotopic ratios of organic matter and the yields of CuO reaction products derived from distinct biochemicals such as amino acids, fatty acids and lignins, were carried out for this purpose. Principal component analyses were used to investigate the trends in this multivariate data set. These analyses reveal marked temporal differences in the composition of the materials sinking through the water column, which were related to distinct oceanographic and climatic forcings. For example, autochthonous fluxes, characterized by elevated contents of organic carbon and opal as well as high yields of amino acid and fatty acid reaction products, displayed peaks during periods of intense wind-driven upwelling. In contrast, allochthonous materials, characterized by elevated lithogenic contents and elevated yields of lignin-derived products, were more important during periods of high rainfall, low wind and enhanced stratification. In addition to the strong seasonal contrasts, there was significant temporal variability at both shorter (monthly) and longer (inter-annual) time scales. Hence, other factors, such as zooplankton grazing and El Niño effects on local climatology, may also be important. Examination of the gravity core record yielded several significant trends. For example, there was a marked increase in sediment accumulation rates from 5000 to ca. 700 y before present with concomitant increases in the concentrations of organic carbon, opal and most biomarkers. These results suggest that the Cariaco Basin experienced a marked increase in primary productivity and particle flux to the underlying sediments since the Holocene Thermal Maximum. Also within the sedimentary record, we observed distinct variations in the relative contributions of autochthonous and allochthonous organic matter. The frequency of these variations is roughly 1500 y and appears to match ice-rafted debris records from the North Atlantic. Such coincidence indicates cold periods within the Holocene, which are related to minima in insolation, may have led to the southern migration of the inter-tropical convergence zone and the enhancement of wind-driven upwelling, primary productivity and autochthonous organic matter flux to the seabed in the Cariaco Basin. Alternatively, during warm periods, the opposite climatic conditions would have increased both the thermal stratification of the water column and average rainfall in the Cariaco Basin, leading to elevated inputs of allochthonous materials.     

Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

The sources and distribution of organic matter (OM) in surface waters and sediments from Winyah Bay (South Carolina, USA) were investigated using a variety of analytical techniques, including elemental, stable isotope and organic biomarker analyses. Several locations along the estuary salinity gradient were sampled during four different periods of contrasting river discharge and tidal range. The dissolved organic carbon (DOC) concentrations of surface waters ranged from 7 mg l⁻¹ in the lower bay stations closest to the ocean to 20 mg l⁻¹ in the river and upper bay samples. There was a general linear relationship between DOC concentrations and salinity in three of the four sampling periods. In contrast, particulate organic carbon (POC) concentrations were significantly lower (0.1–3 mg l⁻¹) and showed no relationship with salinity. The high molecular weight dissolved OM (HMW DOM) isolated from selected water samples collected along the bay displayed atomic carbon:nitrogen ratios ([C/N]a) and stable carbon isotopic compositions of organic carbon (δ¹³C_OC) that ranged from 10 to 30 and from −28 to −25‰, respectively. Combined, such compositions indicate that in most HMW DOM samples, the majority of the OM originates from terrigenous sources, with smaller contributions from riverine and estuarine phytoplankton. In contrast, the [C/N]a ratios of particulate OM (POM) samples varied significantly among the collection periods, ranging from low values of 5 to high values of >20. Overall, the trends in [C/N]a ratios indicated that algal sources of POM were most important during the early and late summer, whereas terrigenous sources dominated in the winter and early spring.In Winyah Bay bottom sediments, the concentrations of the mineral-associated OM were positively correlated with sediment surface area. The [C/N]a ratios and δ¹³C_OC compositions of the bulk sedimentary OM ranged from 5 to 45 and from −28 to −23‰, respectively. These compositions were consistent with predominant contributions of terrigenous sources and lesser (but significant) inputs of freshwater, estuarine and marine phytoplankton. The highest terrigenous contents were found in sediments from the river and upper bay sites, with smaller contributions to the lower parts of the estuary. The yields of lignin-derived CuO oxidation products from Winyah Bay sediments indicated that the terrigenous OM in these samples was composed of variable mixtures of relatively fresh vascular plant detritus and moderately altered soil OM. Based on the lignin phenol compositions, most of this material appeared to be derived from angiosperm and gymnosperm vascular plant sources similar to those found in the upland coastal forests in this region. A few samples displayed lignin compositions that suggested a more significant contribution from marsh C₃ grasses. However, there was no evidence of inputs of Spartina alterniflora (a C₄ grass) remains from the salt marshes that surround the lower sections of Winyah Bay.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Comparison of the quantitative determination of soil organic carbon in coastal wetlands containing reduced forms of Fe and S

The performance of the Walkley–Black wet oxidation chemical method for soil organic carbon (SOC) determination in coastal wetland soils (mangroves, coastal lagoons, and hypersaline tidal flats) was evaluated in the state of Ceará along the semiarid coast of Brazil, assessing pyrite oxidation and its effects on soil C stock (SCS) quantification. SOC determined by the chemical oxidation method (C_WB) was compared to that assessed by means of a standard elemental analyzer (C_EA) for surficial samples (<30 cm depth) from the three wetland settings. The pyrite fraction was quantified in various steps of the chemical oxidation method, evaluating the effects of pyrite oxidation. Regardless of the method used, and consistent with site-specific physicochemical conditions, higher pyrite and SOC contents were recorded in the mangroves, whereas lower values were found in the other settings. C_WB values were higher than C_EA values. Significant differences in SCS calculations based on C_WB and C_EA were recorded for the coastal lagoons and hypersaline tidal flats. Nevertheless, the C_WB and C_EA values were strongly correlated, indicating that the wet oxidation chemical method can be used in such settings. In contrast, the absence of correlation for the mangroves provides evidence of the inadequacy of this method for these soils. Air drying and oxidation decrease the pyrite content, with larger effects rooted in oxidation. Thus, the wet oxidation chemical method is not recommended for mangrove soils, but seems appropriate for SOC/SCS quantification in hypersaline tidal flat and coastal lagoon soils characterized by lower pyrite contents.     

Temporal variability in the composition and abundance of terrestrially-derived dissolved organic matter in the lower Mississippi and Pearl Rivers

Here we report on temporal changes in the concentration and composition of lignin phenols in high molecular weight (< 0.2 μm, > 1 kDa) dissolved organic matter (HMW DOM) collected from the lower Mississippi and Pearl Rivers (MR and PR) (USA). Monthly water samples were collected at a station in the lower reach in each river from August 2001 to August 2003. Significantly higher concentrations of lignin and Λ₈ values (mg lignin phenols in 100 mg organic carbon) in the Pearl River than in the Mississippi River, reflected sporadic inputs of terrestrial DOM during rainstorm events from wetlands and forest soils. Larger seasonal variations in lignin concentration and composition in the Pearl River, compared to the Mississippi River, were attributed to shifts in organic matter sources from topsoil inputs during rainstorm events to groundwater inputs and in situ production during base flow in this small river. Conversely, lower Λ₈ and vanillic acid to vanillin ratios [(Ad/Al)v] in the HMW DOM of the lower Mississippi River may be a result of a lower export rate of lignin from agricultural soils due to lower carbon storage in the expansive agricultural systems of the Mississippi River watershed, as well as dilution of phytoplankton DOM inputs. Large seasonal changes in lignin concentration and Λ₈ (linked at times with river discharge), and minimal variability in the composition of lignin phenols, likely represented an integrated signal of soil-derived vascular inputs from the upstream drainage basin. If we are to better understand the controls of organic matter delivery to the coastal zone from both small and large rivers, sampling strategies need to be adjusted to account for the different scales of hydrologic response time and in situ processing associated with different residence times.     

Effect on marine sediment nitrogen fluxes caused by organic matter enrichment with varying organic carbon structure and nitrogen content

Enrichments with five types of organic carbon, differing in nitrogen content and type of organic carbon, were made to a marine sediment in order to study effects on nitrogen fluxes. The enrichments used were Ulva lactuca, Ascophyllum nodosum, Zostera marina, Ceratium spp., lignin, and mixtures of U. lactuca and A. nodosum. Fluxes of ammonium, nitrate, and phosphate were measured in short-term (48 h) microcosm experiments, using a carbon enrichment loading similar to that at the sampling site. Changes in microbial community growth and structure due to three types enrichments were also detected using molecular methods in a microcosm experiment run for 4 days to allow for detection at DNA-level.Ammonium fluxes changed from an efflux in the control to an influx for all enrichments apart from U. lactuca. The change was significantly related to the added material's C:N ratio when Ceratium spp. was excluded. All enrichments induced an influx of nitrate suggesting the formation of anoxic micro zones, but there was no relationship with C:N ratio. Instead, the magnitude of the nitrate influx is suggested to be related to the structure of the organic carbon, where enrichments containing a large pool of cellulose and lignin (Z. marina and lignin) gave rise to a lower influx, compared to algal material with more easily degraded organic matter like lipids and starch, which induced the highest influx of nitrate (Ceratium spp., U. lactuca, and A. nodosum). The occurrence of an ammonium influx together with increased nitrate influx and a lower efflux of phosphate in the enrichments suggests a growth of heterotrophic bacteria. This was also confirmed using molecular methods (PCR-DGGE) where the relative abundance of bacterial species in the enrichments increased.The sum of ammonium and nitrate fluxes showed that total nitrogen removal was enhanced in all enrichments compared to the nonenriched control sediment, but in different ways. Ceratium spp. induced the highest removal followed by A. nodosum, U. lactuca, Z. marina, and lastly, by lignin. The same pattern was observed also in a second experiment. These results indicate that easily degradable organic carbon, together with a lower C:N ratio of the added material, will remove nitrogen from the water phase, making the recycling of nitrogen to the overlying water mass smaller.     

单体分子放射性碳同位素分析在海洋科学及环境科学研究中的应用

单体分子放射性碳同位素分析(CSRA)是近十几年来发展起来的一项新兴的分析手段,将所需的单体分子(生物标志物)从复杂的环境样品基质中分离并富集,再进行加速质谱仪(AMS)的放射性碳(14C)测定。这种分子水平的放射性碳同位素测定技术能够揭示出总有机质同位素组成的异质性,为解释有机碳的来源、迁移和转化等提供了新型的手段。在海洋科学研究中,单体分子放射性碳同位素分析已应用于计算碳在全球各储库的逗留时间并揭示和定量估算化石源有机碳的输入、指示沉积物的搬运过程、示踪微生物的代谢途径、改进沉积物年代学等;在环境科学研究中,单体分子放射性碳同位素分析可用于有毒物质(如多环芳烃)的源解析,示踪有机污染环境中微生物的代谢途径等。伴随着单体分子分离技术的改进及AMS灵敏度的提高,CSRA技术的应用会更加广泛。     

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

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

Burial and degradation of organic carbon in Louisiana shelf/slope sediments

The primary focus of this paper is to better understand carbon burial on the Louisiana continental margin using spatial scales that covered various shelf depositional areas far-field and near-field (sediment and organic carbon inputs relative to river mouth proximity) and covering a variety of sedimentation rates. Box-cores samples were collected in July 2003; cores were collected along two depositional transects extending westward and southward from the Southwest Pass (SW Pass). A key difference between the two transects sampled in this study was the greater occurrence of mobile muds derived from spillover from shallower regions along the westward 50 m isobaths. The dominant mechanism for mixing in the surface active zone (SAZ) on the inner Louisiana shelf was due to physical, not biological, forces. Burial efficiencies for organic carbon (57.2–91.5%) and total nitrogen (44.2–86.9%) ranged widely across all shelf stations. Lower burial efficiencies for bulk organic carbon, total nitrogen, and pigment biomarkers were associated with mobile muds west of Southwest Pass. Chlorophyll a concentrations were significantly higher than pheopigments at depth at the Mississippi River and Southwest Pass stations, making up 40.4 and 77.4% of total pigment concentrations in the (SAZ) and 46.2 and 63.2% in the accumulation zone (AZ), respectively. These results are in agreement with earlier plant pigment studies which showed that a large fraction of the phytodetritus delivered to the inner shelf was derived from coastal and river diatoms. The amount of lignin preserved with depth decreased with increasing residence time in the SAZ and diagenetic zone (DZ) along the canyon transect but not along the western transect. Trends for lignin concentration followed previously identified surface sediment trends indicating overall lower burial of refractory terrestrial material at depth with greater distance offshore.     

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.     

A comparison of lignin and stable carbon isotope compositions in quaternary marine sediments

Organic matter in four Quaternary sediment cores from the Gulf of Mexico and one core from the Washington State coast have been analyzed for lignin and stable carbon isotope compositions. Holocene sequences of all five cores contain organic matter with high relative abundances of ¹³C ($\text{δ}{}^{13}\text{C = ?19.0 to ?22.5\% versus PDB}$) and low lignin concentrations, both of which are consistent with a marine origin. Distinctly lower ¹³C concentrations ($\text{δ}{}^{13}\text{C = ?24.0 to ?25.5\%}$) occur in underlying glacial-age sequences from four of the five cores, including the core from the Washington coast where such trends are previously unreported. Although the carbon isotopic compositions of these Pleistocene sediments are typical of predominantly land-derived organic matter, they contain only about 5% of the lignin found in modern sediments of similar $\text{δ}{}^{13}\text{C}$ from adjacent continental shelves. The lignin-poor organic matter in the glacial-age deposits appears to be either marine-derived or terrigenous material that likely was depleted in vascular plant debris at the time of deposition.     

Late-Quaternary supply of terrigenous organic matter to the Congo deep-sea fan (ODP site 1075): implications for equatorial African paleoclimate

Late-Quaternary sections (about 1 Ma) from the Congo deep-sea fan (ODP Leg 175, site 1075) were used to reconstruct the terrigenous organic matter supply to the easternmost equatorial Atlantic Ocean. Variations in quantity and quality of the riverine organic matter reflect the interaction between the paleoclimatic development within the continental catchment area and the paleoceanographic conditions in the Congo river plume. To characterize the delivery of organic matter from terrigenous and marine sources, we used elemental and bulk carbon isotopic analyses, Rock-Eval pyrolysis, lignin chemistry, and organic petrology. High-amplitude fluctuations occurring about every 15-25 ka reveal a mainly precessional control on organic sedimentation. Results from Rock-Eval pyrolysis indicate a mixed kerogen type III/II, as would be anticipated in front of a major river. Fluctuations in T_max from Rock-Eval pyrolysis demonstrate pronounced cyclic changes in the delivery of low- and high-mature organic matter. Contribution of the low-mature organic fraction was strongest during warm climates supporting enhanced marine production offshore of the Congo. Organic petrological observations confirm the existence of abundant terrigenous plant tissues, both non-oxidized (vitrinite) and oxidized (inertinite). Charcoal-like organic matter (fusinite) is attributed to periods of increased bush fires in the continental hinterland, and implies more arid climatic conditions. Results from ratios of specific phenolic lignin components suggest that terrigenous organic matter in Late-Quaternary sections of site 1075 mainly derives from non-woody angiosperm tissue, i.e., grasses and leaves. Correlation between the amount of specific lignin phenols and the bulk '¹³C_org signature fosters the conclusion that an appreciable amount of the terrigenous organic fraction derives from C4 plant matter. This may cause an underestimation of the terrigenous proportion of bulk organic matter when assessments are based on bulk carbon isotopic signatures alone.     

Chemical and GC-MS characterization of marine dissolved lipids

The chloroform-extractable ‘lipid’ fraction of dissolved organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GC), and gas chromatography—mass spectrometry (GC—MS). Gravimetric concentrations of dissolved lipids in the Gulf of Mexico were in the range of 60–160 μg 1^?1 in near-surface waters and 61–116 μg 1^?1 in near bottom waters and accounted for ～4% of the dissolved organic carbon. Over a 12-h sampling period and a 5-d sampling period extensive variability in dissolved lipid quantity and quality were observed. The major percentage of extractable weight was collected in the polar liquid chromatographic fraction (55–95%). Gas chromatographic concentrations of the aliphatic fractions were in the range of 0.014-0.187 μg 1^?1. Concentrations derived from gas chromatography were consistently lower than gravimetrically-derived concentrations. A number of compounds were tentatively identified by a combination of GC, GC—MS, and authentic standards. The major components of the analyzable dissolved lipids were n-alkanes (C₁₆C₃₂), pristane, phytane, methyl, ethyl and propyl esters of fatty acids. Minor components included olefins and cycloalkanes, aromatics, short-chained acids, and possibly a lactone and an alcohol. All concentrations and compounds were indicative of a fairly pristine environment. The n-alkane distribution appears to be the result of marine and terrestrial inputs superimposed on a chronic low-level background of oil pollution. It is suggested that the fatty acid esters and other fragment molecules are the résult of the degradation of humic substances. A number of potential indicators of source were isolated.