Distributions and sources of bulk organic matter and aliphatic hydrocarbons in surface sediments of the Bohai Sea, China

Surface sediment samples from a matrix of fifty-five sites covering virtually the entire Bohai Sea (Bohai), China were analyzed for total organic carbon (TOC), total nitrogen (TN), n-alkanes, unresolved complex mixture (UCM), biomarkers and stable carbon isotopic composition (δ¹³C), and principal component analysis was performed for source identification of organic matter (OM). The distribution of organic carbon correlated well with sediment grain size with the finest sediments having the highest concentration, suggesting the influence of hydrodynamics on the accumulation of sedimentary organic matter (SOM). The corrected TOC/ON (organic nitrogen) ratios and δ¹³C indicated mixed marine and terrestrial sources of SOM. Results suggested that δ¹³C could be used as a potential indicator to observe the dispersion of Huanghe-derived sediments in Bohai. Total n-alkane concentrations varied over 10-fold from 0.39 to 4.94 μg g^− 1 (dry weight) with the maximum terrigenous/aquatic alkane ratio observed at the Huanghe River Estuary (HRE) due to more higher plant OM from riverine inputs. C₁₂–C₂₂ n-alkanes with even-to-odd predominance were observed in several central-eastern Bohai sites. The HRE and its adjacent area is the main sink for the Huanghe river-derived OC. The ubiquitous presence of UCM, biomarkers (hopanes and steranes) and PCA results indicated the presence of petroleum contamination in Bohai, mainly from offshore oil exploration, discharge of pollutants from rivers, shipping activities and atmospheric deposition.     

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.     

Organic tracers from biomass burning in atmospheric particulate matter over the ocean

Particulate matter from the atmosphere over the Atlantic Ocean along the South American and African Continents has been analyzed for organic tracers from natural and biomass burning emissions. The major biomarker compounds characterized are natural products from continental vegetation consisting primarily of epicuticular wax components. For example, n-alkanes ranged from C₂₅ to C₃₅, with an odd carbon number predominance and carbon maxima (C_max) at 29 or 31. Concentrations of n-alkanes varied from 0.3 to 680 ng/m³. Nevertheless, n-alkanols are the dominant terrestrial tracers in almost all samples (concentrations from 0.1 to 780 ng/m³) and ranged from C₂₂ to C₃₄ with an even carbon number predominance. Despite the major presence of the natural tracers, organic components from biomass burning emissions are also present in the particulate matter. The major tracers from this source are thermal degradation products from the biopolymer cellulose, namely the dianhydromonosaccharide derivatives levoglucosan, galactosan, and mannosan. In general, the concentrations of levoglucosan, the major derivative from this source in all samples, varied from 0.0008 to 0.15 ng/m³ in atmospheric samples collected over the ocean and from 0.04 to 4860 ng/m³ in terrestrial particulate matter, used as reference in this study. Dehydroabietic acid, another marker compound emitted from burning of Gymnosperm fuel, is also detectable in most oceanic samples at concentrations ranging from 0.0001 to 0.4 ng/m³, whereas in terrestrial aerosol particulate matter, this component is present at much higher concentrations (0.23–440 ng/m³). The presence of these tracers in atmospheric particulate matter over the ocean confirms the long-range transport of smoke from biomass burning off the continents.     

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (δ¹³C) compositions and n-alkane (nC_16–38) concentrations were measured for Spartina alterniflora, a C₄ marsh grass, Typha latifolia, a C₃ marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. δ¹³C values of organic matter preserved in the upper fresh water site sediment were more negative (−23.0±0.3‰) as affected by the C₃ plants than the values of organic matter preserved in the sediments of middle (−18.9±0.8‰) and mud flat sites (−19.4±0.1‰) as influenced mainly by the C₄ marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC₂₁ to nC₃₃ long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC₂₉ was the most abundant homologue in all samples measured. Both δ¹³C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters.     

Tracing the inputs and fate of marine and terrigenous organic matter in Arctic Ocean sediments: A multivariate analysis of lipid biomarkers

An understanding of the carbon cycle within arctic sediments requires discrimination between the terrigenous and marine components of organic carbon, insight into the removal mechanisms for labile carbon during burial and appreciation of shelf-to-basin processes. Using a large data set of multiple molecular organic markers (alkanes, alkanols, sterols, saturated and unsaturated fatty acids, dicarboxylic acids), we apply (1) principal components analysis (PCA) to obtain a robust comparison of biomarker compositions in Arctic Ocean sediments, (2) geometric mean (GM) linear regression of the PCA variables to estimate the relative contributions of labile/marine and stable/terrigenous sources to each biomarker and (3) the slope of the GM regression of each biomarker with TOC to provide a novel measure of the removal rate of each biomarker relative to phytol. The PCA- and TOC-based indices generally increase together: biomarkers with very high TOC-based removal rates such as the saturated and unsaturated n-alkanoic acids generally have a high labile/marine content from PCA, while the sterols have low removal rates, but exhibit a range of labile/marine content values and the n-alkanes and n-alkanols have low values for both. A dominant feature of all PCA models examined is a progressive decrease in the autochthonous/marine biomarkers with each increase in sediment core depth, which points to a universal diagenetic alteration of organic carbon with depth in the cores. The PCA model also displays a shelf to basin trend that is non-diagenetic and implies the ongoing (centuries or more) delivery of long-chain n-alkanes, n-alcohols and n-alkanoic acids in a matrix that is pre-formed and well-preserved within the sediments. Terrigenous biomarker distributions within the PCA model suggest that atmospheric transport of plant waxes in aerosols and the water borne transport of very fine plant macerals likely have significant roles in the export of these vascular plant biomarkers to the basins. Biomarker ratios and profiles of the PCA-based labile/marine content with core depth indicate that the PCA model is more strongly influenced by the biomarker lability than the marine content, while increases in the marine content are largely responsible for the shifts in composition for near-surface core sections.     

Terrestrial n-alkane signatures in the middle Okinawa Trough during the post-glacial transgression: control by sea level and paleovegetation confounded by offshore transport

We report records of land plant-derived long-chain n-alkanes since 37 ka b.p. from a sediment core in the middle Okinawa Trough, East China Sea. The data show the content and carbon preference index (CPI; degree of freshness) of n-alkanes generally decreasing as sea level rose, which could be explained by coastline retreat resulting in an increased transport route of n-alkanes toward the study site. The n-alkane CPI returned to higher values during the Holocene highstand, however, suggesting sea-level rise was not the only cause for the decline of freshness of n-alkanes. Paleovegetation changes in terms of C₃ vs. C₄ contributions inferred from n-alkane δ¹³C are overall consistent with published marine and terrestrial records during two distinct intervals: from 37.0 to 15.2 ka b.p., and from 7.6 ka b.p. to the present. However, n-alkane δ¹³C excursions from 15.2 to 7.6 ka b.p. are difficult to reconcile with terrestrial signatures. This disagreement, along with other possible causes for the decline of freshness of n-alkanes, and the higher-energy sedimentary environment inferred from increased mean grain sizes and silt/clay ratios during this time period, is consistent with existing knowledge of offshore transport of materials previously stored on the extensive continental shelf during the post-glacial transgression. We therefore suggest that n-alkane records from the Okinawa Trough should be used only cautiously to infer deglacial vegetation and sea-level changes.     

Potential source and diagenetic signatures of oceanic dissolved and particulate organic matter as distinguished by lipid biomarker distributions

Potential biogenic sources of ultrafiltered dissolved and suspended particulate organic matter (UDOM and POM, respectively) from the Sargasso Sea (SS) and North Central Pacific (NCP) Ocean were investigated using lipid biomarker compounds. Organic carbon (OC) concentrations were ~ 20–40 times greater in UDOM than POM and decreased with depth. However, total OC-normalized lipid concentrations were 2–3 orders of magnitude higher in POM than in UDOM. Particulate total lipids decreased 3–10-fold with depth, compared to 10–20% for dissolved total lipids. Total fatty acids (FA), the most abundant lipids, showed similar patterns as total lipids, comprising ~ 62–88% of the total lipids analyzed in UDOM and ~ 57–84% in POM.FA were dominated by straight-chain saturated compounds followed by monounsaturated, polyunsaturated, and branched FA. Polyunsaturated FA were enriched in POM vs. UDOM and in surface vs. deep waters for both UDOM and POM, likely reflecting the algal origins and greater reactivity of surface-derived materials. In both UDOM and POM, sterols of planktonic origin dominated, including cholest-5-en-3β-ol (C₂₇Δ⁵), 24-methylcholesta-5,24(28)E-dien-3β-ol (C₂₈Δ^5,24(28)) and 24-ethylcholest-5-3β-ol (C₂₉Δ⁵), with varying contributions from cholesta-5,22E-3β-ol (C₂₇Δ^5,22), 24-methylcholesta-5,22E-3β-ol (C₂₈Δ^5,22) and 24-ethylcholesta-5,22E-3β-ol (C₂₉Δ^5,22).Factor analysis of lipid biomarkers showed major differences between the UDOM and POM pools and for each pool as a function of depth, but not between the SS and NCP. While UDOM and POM biomarkers were both dominated by autochthonous sources, differences between the two pools suggest potential effects from some combination of source and diagenetic factors. The lipid biomarker data are further evaluated relative to previous studies of radiocarbon (¹⁴C) and elemental (C:N:P) characteristics of UDOM and POM in the SS and NCP.     

Biomarker records from core GH02-1030 off Tokachi in the northwestern Pacific over the last 23,000 years: Environmental changes during the last deglaciation

We investigated marine and terrestrial environmental changes at the northern Japan margin in the northwestern Pacific during the last 23,000 years by analyzing biomarkers (alkenones, long-chain n-alkanes, long-chain n-fatty acids, and lignin-derived materials) in Core GH02-1030. The U ₃₇^K′-derived temperature in the last glacial maximum (LGM) centered at 21 ka was ∼10°C, which was 2°C lower than the core-top temperature (∼12°C). This small temperature drop does not agree with pollen evidence of a large air temperature drop (more than 4°C) in the Tokachi area. This disagreement might be attributed to a bias of U ₃₇^K′-derived temperature within 2.5°C by a seasonal shift in alkenone production. The U ₃₇^K′-derived temperature was significantly low during the last deglaciation. Because this cooling was significant in the Kuroshio-Oyashio transition zone, the temperature drops are attributable to the southward displacement of the Kuroshio-Oyashio boundary. Abundant lignin-derived materials, long-chain n-alkanes and long-chain n-fatty acids indicate a higher contribution of terrigenous organic matter from 17 to 12 ka. This phenomenon might have resulted from an enhanced coastal erosion of terrestrial soils due to marine transgression and/or an efficient inflow of higher plant debris to river waters from 17 to 12 ka.     

Higher plant n-alkane average chain length as an indicator of petrogenic hydrocarbon contamination in marine sediments

The n-alkane average chain length (ACL) is the weight-averaged number of carbon atoms of the higher plant C₂₅–C₃₃ n-alkanes. The abundance of individual n-alkanes from higher plant sources generally increases with increasing carbon number in coastal marine sediments around Taiwan, but this trend is reversed for petrogenic hydrocarbons. The ACL would potentially be lowered if petrogenic hydrocarbons were added to sediments containing biogenic hydrocarbons alone. To test this idea, a marine environment off southwestern Taiwan known to contain both biogenic and petrogenic hydrocarbons and two nearby rivers were selected for investigating possible difference in ACL values between their sediments. The average CPI of C₂₅–C₃₃ n-alkanes was 4.08 ± 2.04 (range 1.90–8.96, n = 15) for the river sediments and 1.70 ± 0.16 (range 1.43–1.97, n = 15) for the marine sediments. The ACL of C₂₅–C₃₃ n-alkanes for river sediments ranged from 29.2 to 30.5 (average 29.9 ± 0.4), and for marine sediments from 28.4 to 29.3 (average 28.9 ± 0.3). The ACL difference between marine and river sediments was significant (Student's t test at 99% confidence) although it appeared small. It is suggested that the ACL can be an additional indicator for detection of petrogenic hydrocarbons in coastal marine sediments.     

Differential transport and degradation of bulk organic carbon and specific terrestrial biomarkers in the surface waters of a sub-arctic brackish bay mixing zone

Detailed organic geochemical analyses were performed on surface water particulate samples of the lower Kalix River and northern Bothnian Bay collected during the spring flood of 2005. Both bulk geochemical and molecular biomarker analyses indicated a predominance of terrestrially-derived particulate organic matter (POM), both of higher plant and Sphagnum origin in the low salinity zone (LSZ) of the Kalix River estuary, with an increasing contribution of marine-derived POM in the offshore Bothnian Bay basin.Two-dimensional box modeling of the mixed surface layer in the LSZ indicated that 65% of the particulate organic carbon (POC) and between 73 and 93% of the terrestrial biomarker classes analyzed (high molecular weight n-alkanes, n-alkanoic acids and n-alkanols as well as sitosterol) were degraded in the course of their weeklong transit through the inner LSZ during the spring flood. This corresponds to field-based degradation rate constants for the biomarkers of 0.5 and 2.5 day^− 1, which are similar to results reported from mesocosm experiments for related compounds. The degradation rate constant for terrestrial POC of 0.38 day^− 1 was about 20 times larger than for DOC and suggests that POC mineralization stands for 44% of the total mineralization, which is much larger than previously considered.This sub-arctic river-export regime has a geochemistry resembling that of neighboring western Russian Arctic Rivers, suggesting that a large part of the OM coastally exported from northernmost Eurasian soils may be degraded within the vicinity of the river mouths and putatively be released as carbon dioxide. The 65% degradation of terrestrial POC in the coastal surface water of this sub-arctic recipient is substantially larger than a global-average of 35% used in recent budget estimates of the fate of terrestrially-exported POC on the pan-arctic shelves. Considering ongoing and predicted changes in the Arctic Region due to global warming a more efficient degradation of river-exported terrestrial POC may have far-reaching consequences for the large-scale biogeochemical cycling of carbon in the pan-arctic region and beyond.     

Sources and transport of lipids on Amazon continental shelf

Dissolved material and recent sediment from the Amazon continental shelf have been analyzed for hydrocarbons to study the sources and potential fate of the transported organic matter. Dissolvedn-alkanes are present at low concentrations (ppb level) and are dominated by lipids from marine phytoplankton with carbon number maxima (C_max) at C₁₈/C₂₂ and an even-to-odd carbon predominance < C₃₀ (CPI_17–27 from 0.18 to 0.54). In the sediments, bimodal distributions ofn-alkane chain length suggest a mixed input of terrestrial (C_max at C₂₇/C₂₉/C₃₁ and CPI_25–33 from 0.75 to 1.82) and phytoplanktonic/microbial (C_max at C₂₀ and CPI_15–25 from 0.38 to 0.62) organic matter. Sesquiterpenes were the most significant cyclic compounds in all the dissolved samples analyzed reflecting a contribution from resinous trees to the terrestrial organic pool. On the other hand, enhanced concentrations of these compounds in the dissolved phase on the northwest portion of the Amazon shelf, contrasting with decreased concentrations in the sediment samples, suggest that dissolved lipids are released from solid phase in the intensely stirred seabed. Structured organic matter in the sediment has been characterized as being composed of, on average: 19% plant cuticles, 25% woody tissue, 13% pollens and spores, 24% amorphous material, 7% bituminite and 12% altered organic material.     

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.     

Evaluation of anthropogenic and biogenic inputs into the western Mediterranean using molecular markers

Aliphatic hydrocarbons (AHs), sterols (ST), and lipid classes were determined in suspended particles collected in the Catalan Sea, northwestern Mediterranean. Principal Component Analysis of the data set revealed a clustering of samples depending on the sources of organic matter, i.e., coastal influenced, open sea and frontal zone. Terrestrial inputs were recognized in particles collected in the surface waters, at the vicinities of river outflow (i.e., Rhône and Ebro), by a predominance of C₂₉ and C₃₁ n-alkanes, 24-ethylcholest-5-en-3β-ol (S12), and the anthropogenic 5β(H)-cholestan-3β-ol, coprostanol (S1). Phytoplanktonic molecular markers (n-C₁₇, 27-nor-24-methylcholesta-5,22E-dien-3β-ol, cholesta-5,22-dien-3β-ol and 24-methylcholest-5-en-3β-ol) were widespread but relatively more apparent in the open sea and frontal zones. A similar distribution was observed for lipid classes, with higher concentrations of phospholipids, and an enrichment in free fatty acids in the areas influenced by river discharges. Total sterol, the unresolved complex mixture of hydrocarbons and the pristane–phytane ratio were highest at a persistent frontal zone, possibly reflecting the combination of a higher primary productivity and fossil hydrocarbon absorption on to suspended particles. Moreover, vertical profiles exhibited a subsurface concentration maximum at 20–30 m water depth, concurrently with the chlorophyll.     

Sources and distribution of allochthonous organic matter in surface sediment from the Seomjin River to the southern inner shelf of Korea

The spatial distributions of δ¹³C, δ¹⁵N, and n-alkanes were investigated to determine the source and transportation of allochthonous organic matter from the mouth of the Seomjin River to the southern inner shelf break of Korea. Total organic carbon (%) ranged from 0.3% to 1.6% (average = 0.80%, n = 81), and the C/N ratio varied from 2.4 to 12.4 (average = 6.76, n = 81). The δ¹³C values ranged from ?25.86 to ?20.26‰ (average = ?21.47‰, n = 81), and δ¹⁵N values ranged from 4.37‰ to 8.57‰ (average = 6.72‰, n = 81). The contribution of the terrestrial fraction of organic matter to the total ranged from 4.4% to 97.7% (average = 24.4%, n = 81), suggesting higher amounts around the catchment area and lower amounts in the offshore area. The concentration of total n-alkanes (nC₂₅ ? nC₃₅) was higher at the boundary between the outer bay and inner shelf break (BOBIS). Average chain length and the carbon preference index both indicated that major leaf wax n-alkanes accounted for the observed distribution of terrestrial organic matter, and were dominant in the inner shelf break (around BOBIS) and outer shelf break. Based on the spatial distribution of the total n-alkanes and the sum of nC₂₇, nC₂₉, and nC₃₁, the terrestrial organic matter distribution was considered to be controlled by local oceanographic conditions, especially at the center of the BOBIS. In addition to enabling the distribution and source of terrestrial organic matter to be identified, the n-alkanes indicated that minor anthropogenic allochthonous organic materials were superimposed on the total organic materials in the central part of Yeosu Bay and the catchment area. The n-alkane indices revealed weathered petroleum contamination, with contamination levels being relatively low at the present time.     

白令海北部陆坡全新世以来长链正构烷烃的古环境意义

本文对白令海北部陆坡B2-9站位沉积物岩芯开展了高分辨率的生物标志物分析,获得了研究区近一万年来陆源长链正构烷烃（简写为烷烃）的输入及其源区植被结构的变化等相关记录。结果表明,nC₂₇是烷烃中最高的主碳峰,对烷烃总量的贡献也最大,这可能与源区木本植物的丰度及其分布有关;nC₂₃的含量也较高,可能主要是来源于北半球沿海地区广泛分布的一类沉水植物。全新世期间,烷烃总量分别在7.8 ka B.P.,6.7 ka B.P.和5.4 ka B.P.经历了三次阶梯状的下降过程,呈现出四个相对稳定的阶段,可能主要受控于早全新世海平面上升以及源区气候环境和植被分布的变化。烷烃的分子组合特征各参数（如CPI、ACL以及nC₃₁/nC₂₇等）的变化则表明,烷烃主要来自陆生高等植物,且全新世期间植被结构较为稳定,木本植物占据优势。此外,在几个较短的时期内,烷烃总量及其分子组合特征等参数的变化具有同步性,表明在这些时期特殊的气候条件下,源区木本植物烷烃对烷烃总量的贡献率的增加可能低于草本植物烷烃和化石烷烃。     

Biogeochemistry of sterols in plankton, settling particles and recent sediments in a cold ocean ecosystem (Trinity Bay, Newfoundland)

In the context of a multidisciplinary study to determine current and past ecosystem health and the relative contributions of sources of organic matter (marine vs. terrestrial and natural vs. anthropogenic input), sterols were determined in plankton, settling particles and sediments from Trinity Bay, Newfoundland, a sub-polar Atlantic Ocean ecosystem. The centric diatoms Chaetoceros spp., Thalassiosira spp. and Leptocylindrus danicus were all prominent in the plankton samples, and centric diatoms predominated in the settling particles. Plankton samples contained 0.4±0.4 mg/g dw (1995) or 1.4±1.3 mg/g dw (1996) total sterols, with cholesta-5,24-dien-3β-ol (mean 26% of total sterols), cholest-5-en-3β-ol (24%) and cholesta-5,22(E)-dien-3β-ol (13%) chief among these, denoting diatom and zooplankton sources. In settling particles, the prominence of cholesta-5,24-dien-3β-ol (24%), cholest-5-en-3β-ol (24%), cholesta-5,22(E)-dien-3β-ol (13%) and 24-methylcholesta-5,22(E)-dien-3β-ol (9%) again suggested mainly marine sources. The sterol composition of plankton and settling particles from different sampling periods showed a high degree of consistency. Higher plant C₂₉ sterols (notably 24-ethylcholest-5-en-3β-ol, 9–26%) were prominent in sediments from both inshore and offshore sites. No decreasing trend in total or individual sterols was observed down the 30-cm sediment cores, suggesting good overall preservation. No 5β-stanols such as 5β-cholestan-3β-ol (coprostanol) were detected in offshore sediments, plankton or settling particles, with only low levels (5β-cholestan-3β-ol max. 4.4%, 5β-cholestan-3α-ol max. 5.1%) in certain inshore sediments. This suggests that raw sewage discharges in rural Newfoundland are being efficiently degraded or dispersed, or that inputs are highly localized. Source apportionation of organic matter in the sediment samples based on sterol composition was attempted. This highlighted the large terrestrial contribution to the sterols in marine sediments (up to 58% of sterols inshore, 24% offshore) and suggests either degradation or effective recycling of marine sterols.     

Hydrocarbons in the Bay of Bengal and Central Indian Basin bottom sediments: indicators of geochemical processes in the lithosphere

A study on the bulk distributions and molecular structures of n-alkanes and polycyclic aromatic hydrocarbons (PAH) in organic matter of the sediments from the Bay of Bengal and the Eastern and Central Indian Basins was undertaken. The former two regions represent areas characterised by “normal” sedimentation while the third one mainly represents a region of “active tectonism”. Content of the hydrocarbons in the sediments of “normal” sedimentation ranges between 4.6 and 10.5 μg/g and aromatic hydrocarbons ranges between 0 and 0.38 μg/g. n-Alkanes in the sediments of the northern deep part of the Bay of Bengal consist mostly of long-chain structures (total C₂₅–C₃₃ up to 70%) with a high carbon preference index (CPI=3.01–3.43), indicating a large contribution of organic matter from terrigenous sources. The sediments from the Eastern Indian Basin have n-alkane distributions in which the long-chain components did not exceed 52.5% and the CPI was 1.7–1.90, indicating that the hydrocarbons are mostly derived from marine sources. Sharp increases of hydrocarbons are found in the vicinity of the tectonically active region of the Central Indian Basin, particularly in the sediments collected from the fracture zone. The total concentration of hydrocarbons increase to 170 μg/g and the aromatic hydrocarbons fraction to 156.3 μg/g. The proportion of short-chain n-alkanes increases up to 70%, CPI decreases to 0.76–1.12, and high concentrations of n-C₁₆ (16–40%) occur, all of which are absent in the other samples. The molecular content of PAH includes the unsubstituted individual structures: biphenyl, fluorene, pyrene, perylene, benzo(ghi)perylene, and the groups of homologues of naphthalene, benzofluorene, phenanthrene and chrysene. The association of the PAH and composition of paraffin hydrocarbons in the surficial sediments of deformation zone indicate that these are the resultant products of hydrothermal processes. It is, therefore, suggested that the association and composition of the hydrocarbons in sediments can be utilised as a paleoceanographic parameter to decipher the history of tectonism of an area.     

Fluxes,source and transport of organic matter in the western Sea of Okhotsk: Stable carbon isotopic ratios of n-alkanes and total organic carbon

Settling particles and surface sediments collected from the western region of the Sea of Okhotsk were analyzed for total organic carbon (TOC), long-chain n-alkanes and their stable carbon isotope ratio (δ¹³C) to investigate sources and transport of total and terrestrial organic matter in the western region of the sea. The δ¹³C measurements of TOC in time-series sediment traps indicate lateral transport of resuspended organic matter from the northwestern continental shelf to the area off Sakhalin via the dense shelf water (DSW) flow at intermediate depth. The n-alkanes in the surface sediments showed strong odd carbon number predominance with relatively lighter δ¹³C values (from −33‰ to −30‰). They fall within the typical values of C3-angiosperms, which is the main vegetation in east Russia, including the Amur River basin. On the other hand, the molecular distributions and δ¹³C values of n-alkanes in the settling particles clearly showed two different sources: terrestrial plant and petroleum in the Sea of Okhotsk. We reconstructed seasonal change in the fluxes of terrestrial n-alkanes in settling particles using the mixing model proposed by Lichtfouse and Eglinton [1995. ¹³C and ¹⁴C evidence of a soil by fossil fuel and reconstruction of the composition of the pollutant. Organic Geochemistry 23, 969–973]. Results of the terrestrial n-alkane fluxes indicate that there are two transport pathways of terrestrial plant n-alkanes to sediments off Sakhalin, the Sea of Okhotsk. One is lateral transport of resuspended particles with lithogenic material from the northwestern continental shelf by the DSW flow. Another is the vertical transport of terrestrial plant n-alkanes, which is independent of transport of lithogenic material. The latter may include dry/wet deposition of aerosol particles derived from terrestrial higher plants possibly associated with forest fires in Siberia.     

Sources and transport of organic carbon to shelf,slope, and basin surface sediments of the Arctic Ocean

Lipids in surface sediment transects across the Arctic Ocean were identified to define the sources of organic carbon and the transport of material in the ocean basin. Sterols representing diatoms (24-methylcholesta-5,24(28)-dien-3β-ol, 24-methylcholesta-5,22-dien-3β-ol) and dinoflagellates (4α,23,24-trimethylcholest-22-en-3β-ol) together with algal polyunsaturated fatty acids (20:5, 22:6) demonstrated the importance of primary production to organic matter inputs on the Chukchi Shelf. The presence of terrestrial biomarkers including long-chain n-alkanes and mono- and dicarboxylic acids in shelf sediments indicated that while the fraction of terrestrial biomarkers was small compared to marine material, the transport of allochthonous material impacts carbon cycling on the shelf. Algal biomarkers were found in all surficial sediments from the central Arctic basins, demonstrating that some fraction of primary production reached bottom sediments despite ice cover and light limitation. Marine markers represented a small fraction of the total lipids in central basin sediments. This implies that the basins are less productive than shallow waters, significant degradation occurs before the organic matter reaches the sediment–water interface, and substantial amounts of vascular plant material are exported to the central Arctic. Circulation and topographical features, such as the Transpolar Drift and the Lomonosov Ridge, appear to have an important influence on the transport and focusing of terrestrial material in the Arctic Ocean basins.     

Composition research of <Emphasis Type="Italic">n</Emphasis>-alkanes in the samples of hydrothermal deposits of the Mid-Atlantic Ridge by means of gas chromatography-mass spectrometry

The optimum conditions were selected for the chromatographic separation of model mixtures of C₁₂–C₄₀ n-alkanes. For one of the samples of hydrothermal deposits, the extraction conditions of the hydrocarbons were studied and a sample preparation procedure was selected. A procedure is proposed to determine the n-alkanes in samples of hydrothermal deposits by means of gas chromatography-mass spectrometry (GC-MS). The detection limit for the n-alkanes amounted to 3 × 10⁻⁹ to 10⁻⁸% depending on the components. On the basis of the procedure proposed, the composition of the n-alkanes was studied in the samples of hydrothermal deposits collected at the Mid-Atlantic Ridge (the Broken Spur, Lost City, and Rainbow fields). The analysis performed showed that the samples treated contained C₁₄-C₃₅ n-alkanes. The concentrations of the n-alkanes considered were rather low and varied from 0.002 to 0.038 μg/g. Hypotheses concerning the genesis of the n-alkanes identified were formed.