Organic chemical characterization of sediment-trap particulates from San Nicolas,Santa Barbara,Santa Monica and San Pedro Basins,California

Particulate matter was collected during September–October, 1977, in particle traps suspended 30–60 m above the floor of San Nicolas, Santa Barbara, Santa Monica and San Pedro Basins, off the coast of southern California. The trap particulates were analyzed for C₁₅–C₃₅ hydrocarbons using gas chromatography (GC) and GC-mass spectrometry. Kerogens and humic acids were characterized by H/C, N/C, δ¹³C, δ¹⁵N and δ³⁴S ratios, and by electron-spin resonance. Hydrocarbons arising from fresh and weathered petroleum, marine autochthonous and terrestrial sources were identified. The rates of petroleum deposition during the collection period followed the order: San Nicolas Basin < Santa Barbara Basin ~ Santa Monica Basin < San Pedro Basin, with the largest amount of weathered petroleum being deposited in San Pedro Basin. The rates of petroleum deposition are correlated more strongly with human activities such as shipping, and the discharge of municipal and industrial wastes, than with natural submarine oil seepage. Analyses of kerogens and humic acids indicate that the majority of the organic matter in the trap particulates is of marine origin. The water column overlying Santa Barbara Basin appears to have the highest marine productivity of the four basins studied.     

Sources of organic carbon in the Portuguese continental shelf sediments during the Holocene period

Organic C (OC) and total N (TN) concentrations, and stable isotope ratios (δ¹³C) in muddy deposit sediments of the Northern and Southern Portuguese continental shelf were used to identify sources of fine-sized organic matter (<63 μm) during the Holocene period. Sedimentary columns off the Guadiana (core CRIDA 05), Tagus (core MD 992332) and Douro (core KSGX 57) estuaries are characterised by elemental and isotopic values that reflect distinct sources of organic matter (OC/TN and δ¹³C ranging, respectively, from 8.5 to 21 and from −22.4‰ to −27‰). Intense supplies to the Guadiana continental shelf of fine terrigenous particles during the Younger-Dryas Event are closely linked with higher OC/TN values and lower δ¹³C ratios. During the postglacial transgression phase, an increasing contribution of marine supplies (up to 80%) occurred. Higher δ¹³C (up to −22.4‰) values and low OC/TN ratios (down to 8.5) are found as the sea level approaches the current one. The Upper Holocene records emphasize the return to enhanced terrestrial supplies except for the Little Climatic Optimum between the 11th and 15th centuries AD. This climatic event is especially obvious in the three cores as a return to marine production and a decrease in terrestrial sediment supply to the continental shelf. The return to a cooling event, the Little Ice Age, between the 15th and 19th centuries AD, is mirrored by decreased terrigenous supplies in core KSGX 57. Gradually increasing sedimentation in estuaries, as well as formation of coastal dune fields, have been hypothesized on the basis of increasing δ¹³C and decreasing OC, TN and OC/TN values.     

Carbon isotope composition of graptolite periderm and whole-rock from the Aeronian (Silurian, Llandovery) in Wales and Scotland and its use in chemostratigraphy

Here we show the use of graptolite periderm for chemostratigraphic study. Using material from the Aeronian (Silurian) interval from Wales and Scotland as examples, we show that the carbon isotope composition of the periderm (δ¹³C_grap.) provides a signal that is locally different but not consistently so from surrounding whole-rock samples (δ¹³C_whole-rock). Graptolite periderm δ¹³C seems not influenced by astogenetic stage of development or gross rhabdosome type and differences between δ¹³C_grap. from different metamorphic grades are minimal. Taken as a whole, the Aeronian interval examined shows little overall change, but large variations are seen on the small scale, possibly reflecting very local carbon cycling. For carbon isotope stratigraphy in such rocks, therefore, large-scale bulk sampling will likely reduce inhomogeneities and give more reproducible results. Furthermore, in situations (for instance associated with sea level fluctuations) where terrestrial organic matter has been incorporated into the sediment, then graptolite carbon may more faithfully reflect bulk marine organic matter.     

Climate-induced changes in sedimentary regimes for organic matter supply on the continental shelf off northern Norway

With this study, I suggest that changes in biogeochemical processes in northern Norwegian fjords during the last glacial/interglacial transition (14.3 to 6.3 ka B.P.) are predominantly climate induced. Variable strength in Atlantic water inflow, intrusion of Arctic waters and sea-ice coverage, various nutrient supply, as well as several re-advances of continental ice-sheets are recorded by both bulk organic and selected biomarkers in sediments of the Andfjord. Stable isotope (δ¹³C_org, δ¹⁵N) and Rock-Eval pyrolysis data indicate a strong supply of terrestrial organic matter during stadials (e.g., Younger Dryas, Older Dryas) whereas enhanced input of marine organic matter prevailed during the interstadials (Bølling/Allerød). Profiles of selected biomarkers of marine origin show a characteristic climate-induced variation during the whole time interval, where relatively low concentrations of dinosterols and C₃₇ alkenones may indicate—similar to today—a minor contribution of their respective plankton groups (coccolithophorids, dinoflagellates). The prevalence of Arctic waters and seasonal sea-ice coverage during the Younger Dryas is indicated by a single maximum of 24-methylenecholesterol probably indicating the dominance of sea-ice diatoms and/or the prevalence of diatoms of Thalassiosiraceae in surface waters. The sediments of the Allerød, in contrast, show a pronounced maximum in dinosterols, indicating a better adaptation of dinoflagellates to an oceanic regime that is characterized by incipient intrusion of Atlantic water, highly variable sea surface temperatures, and well stratified water masses. The concentration of higher-molecular-weight n-alkanes, however, follows the deglacial-early Holocene trend of climate amelioration from the last deglaciation to the middle Holocene, with maxima during ice advances (stadials) and minima during the middle Holocene warm period.These new results significantly improve the understanding of climate-induced response on organic matter supply in fjords and provide a better knowledge of past variations of biogeochemical processes in high-latitude coastal environments.     

Carbon,hydrogen and nitrogen isotopes in solvent-extractable organic matter from carbonaceous chondrites

Solvent extractions were done on the carbonaceous chondrites Murray, Murchison, Orgueil and Renazzo, using CCl₄ and CH₃OH. Between 2 and 10% of the total carbon in these meteorites is extractable by ordinary techniques, most of it in CH₃OH. After demineralization with HF, perhaps as much as 30% of the total carbon in Murray may be extractable with CH₃OH. The extracts from Renazzo have isotopic ratios which suggest that they are mainly terrestrial organic matter, with lesser contributions from indigenous organics. The CH₃OH-soluble organic matter from Murchison and both untreated and HF-treated Murray has δ¹³C values of about +5 to + 10%. and δ¹⁵N values of about +90 to +100%., both of which are significantly higher than the bulk meteorite values. The Orgueil CH₃OH-extract also has a δ¹⁵N value well above the value in residual organic matter. Values for δD of +300 to +500%. are found for the CH₃OH-soluble organic matter. The combined data for C, H and N isotopes makes it highly unlikely that the CH₃OH-soluble components are derivable from, or simply related to, the insoluble organic polymer found in the same meteorites. A relationship is suggested between the event that formed hydrous minerals in CI1 and CM2 meteorites and the introduction of water-soluble (methanol-soluble) organic compounds. Organic matter soluble in CCl₄ has essentially no nitrogen, and δ³C and δD values are lower than for CH₃OH-soluble phases. Either there are large isotopic fractionations for carbon and hydrogen between different soluble organic phases, or the less polar components are partially of terrestrial origin.     

The variations of stable carbon isotope ratio of land plant-derived n-alkanes in deep-sea sediments from the Bering Sea and the North Pacific Ocean during the last 250,000 years

Two piston cores, one located far from the continents (The North Pacific Ocean: ES core), and another located comparatively closer to the continents (The Bering Sea: BOW-8a core) were investigated to reconstruct environmental changes on source land areas. The results show significant contribution of terrestrial organic matter to sediments in both cores. The δ¹³C values of n-C₂₇, n-C₂₉, and n-C₃₁ alkanes in sediments from the North Pacific ES core show significant glacial to interglacial variation whereas those from the Bering Sea core do not. Variations of δ¹³C values of land plant n-alkanes are related to the environmental or vegetational changes in the source land areas. Environmental changes, especially, aridity, rainfall, and pCO₂ during glacial/interglacial transitional periods can affect vegetation, and therefore C₃ / C₄ plant ratios, resulting in δ¹³C changes in the preserved land plant biomarkers. Maximum values of δ¹³C as well as maximum average chain length values of long chain n-alkanes in the ES core occur mostly at the interglacial to glacial transition zones reflecting a time lag related to incorporation of living organic matter into soil and transportation into ocean basins via wind and/or ability of C₄ plants to adapt for a longer period before being replaced by C₃ plants when subjected to gradual climatic changes. Irregular variations with no clear glacial to interglacial trends in the BOW-8a core may result from complex mixture of aerosols from westerly winds and riverine organic matter from the Bering Sea catchments. In addition, terrestrial organic matter entering the Bering Sea could originate from multiple pathways including eolian, riverine, and ice rafted debris, and possibly be disturbed by turbidity and other local currents which can induce re-suspension and re-sedimentation causing an obliterated time relation in the Bering Sea biomarker records.     

The isotopic composition of particulate organic carbon in mountain rivers of Taiwan

Small rivers draining mountain islands are important in the transfer of terrestrial particulate organic carbon (POC) to the oceans. This input has implications for the geochemical stratigraphic record. We have investigated the stable isotopic composition of POC (δ¹³C_org) in rivers draining the mountains of Taiwan. In 15 rivers, the suspended load has a mean δ¹³C_org that ranges from −28.1±0.8‰ to −22.0±0.2‰ (on average 37 samples per river) over the interval of our study. To investigate this variability we have supplemented suspended load data with measurements of POC in bedrock and river bed materials, and constraints on the composition of the terrestrial biomass. Fossil POC in bedrock has a range in δ¹³C_org from −25.4±1.5‰ to −19.7±2.3‰ between the major geological formations. Using coupled δ¹³C_org and N/C we have found evidence in the suspended load for mixing of fossil POC with non-fossil POC from the biosphere. In two rivers outside the Taiwan Central Range anthropogenic land use appears to influence δ¹³C_org, resulting in more variable and lower values than elsewhere. In all other catchments, we have found that 5‰ variability in δ¹³C_org is not controlled by the variable composition of the biomass, but instead by heterogeneous fossil POC.In order to quantify the fraction of suspended load POC derived from non-fossil sources (F_nf) as well as the isotopic composition of fossil POC (δ¹³C_fossil) carried by rivers, we adapt an end-member mixing model. River suspended sediments and bed sediments indicate that mixing of fossil POC results in a negative trend between N/C and δ¹³C_org that is distinct from the addition of non-fossil POC, collapsing multiple fossil POC end-members onto a single mixing trend. As an independent test of the model, F_nf reproduces the fraction modern (F_mod) in our samples, determined from ¹⁴C measurements, to within 0.09 at the 95% confidence level. Over the sampling period, the mean F_nf of suspended load POC was low (0.29 ± 0.02, n = 459), in agreement with observations from other mountain rivers where physical erosion rates are high and fossil POC enters river channels. The mean δ¹³C_fossil in suspended POC varied between −25.2±0.5‰ and −20.2±0.6‰ from catchment to catchment. This variability is primarily controlled by the distribution of the major geological formations. It also covers entirely the range of δ¹³C_org found in marine sediments which is commonly thought to derive from mixing between marine and terrigenous POC. If land-sourced POC is preserved in marine sediments, then changes in the bulk δ¹³C_org observed offshore Taiwan could instead be explained by changes in the onshore provenance of sediment. The range in δ¹³C_org of fossil organic matter in sedimentary rocks exposed at the surface is large and given the importance of these rocks as a source of clastic sediment to the oceans, care should be taken in accounting for fossil POC in marine deposits supplied by active mountain belts.     

Spatial and Temporal Variability of Sediment Organic Matter Recycling in Two Temperate Eutrophicated Estuaries

This paper deals with the spatial and seasonal recycling of organic matter in sediments of two temperate small estuaries (Elorn and Aulne, France). The spatio-temporal distribution of oxygen, nutrient and metal concentrations as well as the organic carbon and nitrogen contents in surficial sediments were determined and diffusive oxygen fluxes were calculated. In order to assess the source of organic carbon (OC) in the two estuaries, the isotopic composition of carbon (δ ¹³C) was also measured. The temporal variation of organic matter recycling was studied during four seasons in order to understand the driving forces of sediment mineralization and storage in these temperate estuaries. Low spatial variability of vertical profiles of oxygen, nutrient, and metal concentrations and diffusive oxygen fluxes were monitored at the station scale (within meters of the exact location) and cross-section scale. We observed diffusive oxygen fluxes around 15 mmol m^?2 day^?1 in the Elorn estuary and 10 mmol m^?2 day^?1 in the Aulne estuary. The outer (marine) stations of the two estuaries displayed similar diffusive O₂ fluxes. Suboxic and anoxic mineralization was large in the sediments from the two estuaries as shown by the rapid removal of very high bottom water concentrations of NO _x ^? (>200 μM) and the large NH₄ ⁺ increase at depth at all stations. OC contents and C/N ratios were high in upstream sediments (11–15 % d.w. and 4–6, respectively) and decreased downstream to values around 2 % d.w. and C/N ≤ 10. δ ¹³C values show that the organic matter has different origins in the two watersheds as exemplified by lower δ ¹³C values in the Aulne watershed. A high increase of δ ¹³C and C/N values was visible in the two estuaries from upstream to downstream indicating a progressive mixing of terrestrial with marine organic matter. The Elorn estuary is influenced by human activities in its watershed (urban area, animal farming) which suggest the input of labile organic matter, whereas the Aulne estuary displays larger river primary production which can be either mineralized in the water column or transferred to the lower estuary, thus leaving a lower mineralization in Aulne than Elorn estuary. This study highlights that (1) meter scale heterogeneity of benthic biogeochemical properties can be low in small and linear macrotidal estuaries, (2) two estuaries that are geographically close can show different pattern of organic matter origin and recycling related to human activities on watersheds, (3) small estuaries can have an important role in recycling and retention of organic matter.     

Carbon isotope composition of organic seston and sediments in a Georgia salt marsh estuary

The distribution of δ¹³C values for organic seston and sediment was determined in three sounds in the Spartina marsh estuaries along the Georgia coast, which had high, moderate, and low inputs of freshwater. Organic matter in all three sounds had similar carbon isotope compositions, for the most part within the range of marine values (δ¹³C of ?18%. to ?24%.). It appears that river flow does not introduce significant quantities of particulate C₃ plant material (δ¹³C of ?25%. to ?28%.) to Georgia estuaries. Evaluation of δ¹³C values of estuarine seston and three size fractions of sediment indicated that while Spartina carbon (δ¹³C of ?13%.) can be an important component of organic matter in intertidal sediments (mean δ¹³C of ?14.3%. to ?20.0%.), it is less so in subtidal sediments (mean δ¹³C of ?18.8%. to ?21.2%.), and it is hardly present at all in the seston (mean δ¹³C of ?24.5%.). δ¹³C values of dissolved inorganic carbon (DIC) in several water samples ranged between ?2.5%. and ?5.6%., suggesting that the isotope composition of estuarine DIC is influenced by respiratory CO₂ derived from metabolism of ¹³C-depleted plant carbon. Phytoplankton production utilizing this comparatively light DIC could be a source of relatively negative δ¹³C carbon in the estuary. Additional origins of estuarine organic matter greatly depleted in ¹³C compared to Spartina carbon remain to be identified.     

Fractionation of hydrogen,oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C₂₁–C₂₅ n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ¹⁸O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C₂₃ n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ¹³C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C₂₃ n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.     

Hydrogen and carbon isotopes of petroleum and related organic matter

$\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios were measured for 114 petroleum samples and for several samples of related organic matter. δD of crude oil ranges from ?85 to ?181‰, except for one distillate (?250‰) from the Kenai gas field; δ¹³C of crude oil ranges from ?23.3 to ?32.5‰, Variation in δD and δ¹³C values of compound-grouped fractions of a crude oil is small, 3 and 1.1%., respectively, and the difference in δD and δ¹³C between oil and coeval wax is slight. Gas fractions are 53–70 and 22.6–23.2‰ depleted in D and ¹³C, respectively, relative to the coexisting oil fractions.The δD and δ¹³C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant.     

Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.     

Patterns and implications of plant-soil δC and δN values in African savanna ecosystems

Southern African savannas are mixed plant communities where C₃ trees co-exist with C₄ grasses. Here foliar δ¹⁵N and δ¹³C were used as indicators of nitrogen uptake and of water use efficiency to investigate the effect of the rainfall regime on the use of nitrogen and water by herbaceous and woody plants in both dry and wet seasons. Foliar δ¹⁵N increased as aridity rose for both C₃ and C₄ plants for both seasons, although the magnitude of the increase was different for C₃ and C₄ plants and for two seasons. Soil δ¹⁵N also significantly increased with aridity. Foliar δ¹³C increased with aridity for C₃ plants in the wet season but not in the dry season, whereas in C₄ plants the relationship was more complex and non-linear. The consistently higher foliar δ¹⁵N for C₃ plants suggests that C₄ plants may be a superior competitor for nitrogen. The different foliar δ¹³C relationships with rainfall may indicate that the C₃ plants have an advantage when competing for water resources. The differences in water and nitrogen use likely collectively contribute to the tree-grass coexistence in savannas. Such differences facilitate interpretations of palaeo-vegetation composition variations and help predictions of vegetation composition changes under future climatic scenarios.     

Geochemical record of anthropogenic impacts on Lake Valencia,Venezuela

Bulk geochemical parameters and organic matter biomarkers in a short, high resolution gravity core (Lake Valencia, Venezuela) were examined to reconstruct anthropogenic impacts on the lake’s conditions. During the period of ca. 1840–1990, sedimentary organic matter was characterized by high contents of total organic C (TOC) and total N (TN), low TOC/TN values as well as relatively enriched δ¹³C and δ¹⁵N signals, suggesting a primary autochthonous (algae and macrophytes) organic matter origin. The occurrence of large amounts of C₂₃ and C₂₅ relative to C₂₉ and C₃₁n-alkanes indicated substantial inputs from submerged/floating macrophytes. The variations of C₃₂ 15-keto-ol, tetrahymanol, diploptene, C₃₂ bishomohopanol, 2-methylhopane, dinosterol and isoarborinol concentrations over the investigated period record changes in the planktonic community structure, including Botryococcus braunii, bacteriavore ciliates, cyanobacteria, Eustigmatophytes and dinoflagellates. A principal shift occurred in the 1910s when cyanobacteria and dinoflagellates became more abundant at the expense and decline of B. braunii and Eustigmatophytes, likely related to increasing anthropogenic activity around the lake. A second shift (less obvious) occurred in the 1960s when cyanobacteria became the sole predominant planktonic class, coinciding with further deterioration of lake conditions.     

Early diagenetic remineralization of sedimentary organic C in the Gulf of Papua deltaic complex (Papua New Guinea): Net loss of terrestrial C and diagenetic fractionation of C isotopes

Oceania supplies ∼40% of the global riverine flux of organic carbon, approximately half of which is injected onto broad continental shelves and processed in shallow deltaic systems. The Gulf of Papua, on the south coast of the large island of New Guinea, is one such deltaic clinoform complex. It receives ∼4 Mt yr⁻¹ particulate terrestrial organic carbon with initial particle C_org loading ∼0.7 mg m⁻². C_org loading is reduced to ∼0.3 mg m⁻² in the topset-upper foreset zones of the delta despite additional inputs of mangrove and planktonic detritus, and high net sediment accumulation rates of 1-4 cm yr⁻¹. Carbon isotopic analyses (δ¹³C, Δ¹⁴C) of ΣCO₂ and C_org demonstrate rapid (<100 yr) remineralization of both terrestrial (δ¹³C <−28.6) and marine C_org (δ¹³C ∼−20.5) ranging in average age from modern (bomb) (Δ¹⁴C ∼60) to ∼1000 yr (Δ¹⁴C ∼−140). Efficient and rapid remineralization in the topset-upper foreset zone is promoted by frequent physical reworking, bioturbation, exposure, and reoxidation of deposits. The seafloor in these regions, particularly <20 m, apparently functions as a periodically mixed, suboxic batch reactor dominated by microbial biomass. Although terrestrial sources can be the primary metabolic substrates at inshore sites, relatively young marine C_org often preferentially dominates pore water ΣCO₂ relative to bulk C_org in the upper foreset. Thus a small quantity of young, rapidly recycled marine organic material is often superimposed on a generally older, less reactive terrestrial background. Whereas the pore water ΣCO₂ reflects both rapidly cycled marine and terrestrial sources, terrestrial material dominates the slower overall net loss of C_org from particles in the topset-upper foreset zone (i.e. recycled marine C_org leaves little residue). Preferential utilization of C_org subpools and diagenetic fractionation of C isotopes supports the reactive continuum model as a conceptual basis for net decomposition kinetics. Early diagenetic fractionation of C isotopes relative to the bulk sedimentary C_org composition can produce changes in ¹⁴C activity independent of radioactive decay. In the Gulf of Papua topset-upper foreset, Δ¹⁴C of pore water ΣCO₂ averaged ∼ 300‰ greater than C_org sediment between ∼1-3 m depth in deposits. Diagenetic fractionation and decomposition aging of sedimentary C_org compromises simple application of ¹⁴C for determination of sediment accumulation rates in diagenetically reactive deposits.     

Geochemistry of C25 and C30 biogenic alkenes in sediments of the narragansett bay estuary

The distributions of a series of structurally related C₂₅ and C₃₀ biogenic alkenes in sediments of the Narragansett Bay estuary have been determined. The suite of alkenes detected differs both quantitatively and qualitatively from those previously reported in other estuanne and coastal regions. Four C₂₅ mono- and dienes and one C₃₀ diene comprise 73–91% of the total alkenes in all surface (upper 2.5–5 cm) sediments analyzed. However, significant geographic variations exist in the relative abundance of these five compounds throughout the estuary. A comparison of alkene concentrations with δ¹³C of the bulk sedimentary organic matter has shown that the geographic variations of some alkenes reflect the distribution of marine organic matter, suggesting a marine source for these compounds. The distributions of other alkenes are not similarly correlated. In particular, concentrations of the C₃₀ diene are relatively constant and exhibit no dependence on the origin of organic matter in these sediments. This distribution implies an in situ production of this alkene throughout the estuary. Analysis of several sediment cores reveals that alkene concentrations are generally highest at the surface and decrease to low, constant values within the upper 25 cm. An exception is the subsurface concentration of one C₂₅ diene, which exhibits an increase at the same depth in two separate upper bay cores.     

Palaeoceanographic controls on geochemical characteristics of organic-rich Exshaw mudrocks: role of enhanced primary production

Organic-rich source rocks have generally been attributed to enhanced preservation of organic matter under anoxic bottom waters. Here, geochemical analysis of kerogen and whole rock samples of organic-rich (lithofacies B₁) and organic-lean (lithofacies B₂) laminated mudrocks of the Devonian–Carboniferous Exshaw Formation, Alberta, highlight the importance of primary production in governing the quantity and quality of organic matter. Lower Si/Al, K/Al, Ti/Al and quartz/clay ratios in lithofacies B₂, similar maceral types and the laminated fabric of the two lithofacies indicate that the quality and quantity of organic matter are not related to grain size, redox or organic matter source changes. High Total Organic Carbon (TOC) and Hydrogen Index (HI), low Oxidation Index (Ox.I. ratio of oxygen functional groups to aliphatic groups derived by FTIR), lighter δ¹⁵N_tot and heavier δ¹³C_org isotopes indicate that kerogen of lithofacies B₁ accumulated during periods of high organic-carbon production and delivery of relatively fresh, labile, well-preserved organic matter to the sea floor. In contrast, low TOC, HI, high Ox.I., heavier δ¹⁵N_tot and lighter δ¹³C_org isotopes indicate low primary productivity and delivery, high recycling and poor preservation of organic matter during accumulation of lithofacies B₂.     

Latitudinal distribution of terrestrial lipid biomarkers and n-alkane compound-specific stable carbon isotope ratios in the atmosphere over the western Pacific and Southern Ocean

We investigated the latitudinal changes in atmospheric transport of organic matter to the western Pacific and Southern Ocean (27.58°N-64.70°S). Molecular distributions of lipid compound classes (homologous series of C₁₅ to C₃₅n-alkanes, C₈ to C₃₄n-alkanoic acids, C₁₂ to C₃₀n-alkanols) and compound-specific stable isotopes (δ¹³C of C₂₉ and C₃₁n-alkanes) were measured in marine aerosol filter samples collected during a cruise by the R/V Hakuho Maru. The geographical source areas for each sample were estimated from air-mass back-trajectory computations. Concentrations of TC and lipid compound classes were several orders of magnitude lower than observations from urban sites in Asia. A stronger signature of terrestrial higher plant inputs was apparent in three samples collected under conditions of strong terrestrial winds. Unresolved complex mixtures (UCM) showed increasing values in the North Pacific, highlighting the influence of the plume of polluted air exported from East Asia. n-Alkane average chain length (ACL) distribution had two clusters, with samples showing a relation to latitude between 28°N and 47°S (highest ACL values in the tropics), whilst a subset of southern samples had anomalously high ACL values. Compound-specific carbon isotopic analysis of the C₂₉ (−25.6‰ to −34.5‰) and C₃₁n-alkanes (−28.3‰ to −37‰) revealed heavier δ¹³C values in the northern latitudes with a transition to lighter values in the Southern Ocean. By comparing the isotopic measurements with back-trajectory analysis it was generally possible to discriminate between different source areas. The terrestrial vegetation source for a subset of the southernmost Southern Ocean is enigmatic; the back-trajectories indicate eastern Antarctica as the only intercepted terrestrial source area. These samples may represent a southern hemisphere background of well mixed and very long range transported higher plant organic material.     

Highly isotopically depleted isoprenoids: molecular markers for ancient methane venting

We propose that organic compounds found in a Miocene limestone from Marmorito (Northern Italy) are source markers for organic matter present in ancient methane vent systems (cold seeps). The limestone contains high concentrations of the tail-to-tail linked, acyclic C₂₀ isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), a C₂₅ homolog 2,6,10,15,19-pentamethylicosane (PME), and a distinctive glycerol ether lipid containing 3,7,11,15-tetramethylhexadecyl (phytanyl-) moieties. The chemical structures of these biomarkers indicate a common origin from archaea. Their extremely ¹³C-depleted isotope compositions (δ¹³C ≈ −108 to −115.6‰ PDB) suggest that the respective archaea have directly or indirectly introduced isotopically depleted, methane-derived carbon into their biomass. We postulate that a second major cluster of biomarkers showing heavier isotope values (δ¹³C ≈ −88‰) is derived from sulfate-reducing bacteria (SRB). The observed biomarkers sustain the idea that methanogenic bacteria, in a syntrophic community with SRB, are responsible for the anaerobic oxidation of methane in marine sediments. Marmorito may thus represent a conceivable ancient scenario for methane consumption performed by a defined, two-membered bacterial consortium: (1) archaea that perform reversed methanogenesis by oxidizing methane and producing CO₂ and H₂; and (2) SRB that consume the resulting H₂. Furthermore, the respective organic molecules are, unlike other compounds, tightly bound to the crystalline carbonate phase. The Marmorito carbonates can thus be regarded as “cold seep microbialites” rather than mere “authigenic” carbonates.     

Bulk organic δ13C and C/N ratios as palaeosalinity indicators within a Scottish isolation basin

Microfossils in isolation basin sediments are frequently used to reconstruct sea‐level change, but preservation problems and non‐analogue situations can limit their usefulness. Here we investigate the potential of stable carbon isotopes (δ¹³C) and C/N ratios from bulk organic matter, as an alternative proxy of salinity within isolation basin sediments from a basin in northwest Scotland. Within the Holocene sediment δ¹³C and C/N are determined largely by the mean weighted values of the predominant source of the organic material. Analysis of modern materials and comparison with the diatom record shows that the marine parts of the sequence are dominated by high δ¹³C and variable C/N. In the fresh water sequences the organic material is a mixture of both freshwater aquatic and terrestrial plant input that have relatively low δ¹³C and high C/N. The application of δ¹³C and C/N ratios in the studied basin in general follow the environmental change recorded by the diatoms and shows the potential of bulk organic matter in the investigation of salinity change in isolation basins. Copyright © 2005 John Wiley & Sons, Ltd.