Hydrothermal geochemistry of sediments and pore waters in Escanaba Trough—ODP Leg 169

Geochemical studies of pore fluids and solid phases in two Ocean Drilling Program (ODP) drill sites (Sites 1037 and 1038) in the Escanaba Trough off Northern California have provided further data on the hydrothermal processes associated with the spreading of the Gorda Ridge. Previous work in the area of ODP Site 1038 includes the discovery of a hydrothermal system and associated sulfide deposits centered around an uplifted sediment hill in this sedimented extensional environment. This earlier work provided some insights into the present nature of venting; however, only deep drilling investigations can provide the means to fully understand the genesis and evolution of this system and associated hydrothermal deposits. ODP Leg 169 is the third deep drilling operation to explore the magnitude, genesis, and evolution of hydrothermal systems on sedimented ridges. Previous studies centered on the Guaymas Basin in the Gulf of California and the Middle Valley in the NE Pacific Ocean. Pore water studies in the reference ODP Site 1037 and in the hydrothermally active area of ODP Site 1038 have revealed the presence of a complex system of hydrothermally originated fluids. Whereas the data in the reference site indicate recent hydrothermal activity in the basal part of the drill site, the evidence in Site 1038 suggests that fluids of hydrothermal origin spread out at shallow depths around the central hill, causing substantial sediment alteration as well as deposition of hydrothermal sulfides in the near surface zone of the sediments. A second major discovery at Site 1038 was the evidence for fluid phase separation at depth at temperatures possibly in excess of 400 °C. This conclusion is based on the presence of both low Cl and high Cl fluids. The latter appear to be advected rapidly towards the surface, presumably along cracks and faults. The low Cl fluids, however, appear to be transported laterally along sandy horizons in the sediments, thus signifying two very different migration pathways for high Cl and low Cl hydrothermally phase separated fluids. Studies of the organic geochemistry of dissolved gases and matured organic matter corroborate these findings of extensive hydrothermal alteration of the sediments.     

Hydrothermal petroleum in the sediments of the Andaman Backarc Basin,Indian Ocean

Recent sediments of the Andaman Backarc Basin, Indian Ocean, between the Andaman Nicobar islands and the Malay Peninsula have been analyzed for biomarker lipids. Three cores were selected: one each from the fault zone in a deep basin (a graben between two fault systems), another from a location adjacent to the fault, and the third from the topographic high in the rift valley. The molecular composition of the lipid classes (n-alkanes, isoprenoids, alkylbenzenes, alkylcyclohexanes, hopanoids, polycyclic aromatic hydrocarbons, steranes, alcohols, sterols and fatty acids) was examined by gas chromatography (GC) and GC/mass spectrometry to understand the nature and source of the hydrocarbons present and the processes of maturation of organic matter. The data show that the hydrocarbons are of hydrothermal origin, derived from thermal alteration of sedimentary organic matter, consisting of a mixture predominantly of marine-derived components with some terrestrial inputs. Normal alcohols and fatty acids also corroborate the distribution of n-alkanes. The distribution profiles and various parameters computed from the concentration of the target compounds suggest that oxidative reactions and microbial degradation in this environment are insignificant. Triterpane and PAH compositions indicate that the thermal maturity of the bitumen in the samples is comparable to or lower than that found at other hydrothermal regions such as the Northern Juan de Fuca Ridge, Guaymas Basin and Escanaba Trough.     

Turbidite Megabeds in an Oceanic Rift Valley Recording Jökulhlaups of Late Pleistocene Glacial Lakes of the Western United States

Escanaba Trough is the southernmost segment of the Gorda Ridge and is filled by sandy turbidites locally exceeding 500 m in thickness. New results from Ocean Drilling Program (ODP) Sites 1037 and 1038 that include accelerator mass spectrometry (AMS) 14C dates and revised petrographic evaluation of the sediment provenance, combined with high-resolution seismic-reflection profiles, provide a lithostratigraphic framework for the turbidite deposits. Three fining-upward units of sandy turbidites from the upper 365 m at ODP Site 1037 can be correlated with sediment recovered at ODP Site 1038 and Deep Sea Drilling Program (DSDP) Site 35. Six AMS 14C ages in the upper 317 m of the sequence at Site 1037 indicate that average deposition rates exceeded 10 m/k.yr. between 32 and 11 ka, with nearly instantaneous deposition of one approximately 60-m interval of sand. Petrography of the sand beds is consistent with a Columbia River source for the entire sedimentary sequence in Escanaba Trough. High-resolution acoustic stratigraphy shows that the turbidites in the upper 60 m at Site 1037 provide a characteristic sequence of key reflectors that occurs across the floor of the entire Escanaba Trough. Recent mapping of turbidite systems in the northeast Pacific Ocean suggests that the turbidity currents reached the Escanaba Trough along an 1100-km-long pathway from the Columbia River to the west flank of the Gorda Ridge. The age of the upper fining-upward unit of sandy turbidites appears to correspond to the latest Wisconsinan outburst of glacial Lake Missoula. Many of the outbursts, or j?kulhlaups, from the glacial lakes probably continued flowing as hyperpycnally generated turbidity currents on entering the sea at the mouth of the Columbia River.     

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5–116 hr) and temperatures (150°–410°C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid <1%. Whereas n-alkanes produced from lipid show a CPI > 1.0, those produced by thermal alteration of kerogen display a CPI < 1.0. The volatiles produced by heating the lipid and humic acid fractions were largely CO₂ and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C₂–C₄ hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.     

Dissolved organic carbon in interstitial waters from sediments of Middle Valley and Escanaba Trough,Northeast Pacific,ODP Legs 139 and 169

Oxidation measurements of nonvolatile dissolved organic carbon (DOC) have been determined by high temperature combustion for pore waters from sediments of Middle Valley and Escanaba Trough, Northeastern Pacific, sampled by the Ocean Drilling Program (ODP) Legs 139 and 169, as well as for overlying and near bottom seawater. The DOC values in the interstitial waters are generally greater than those in the overlying water column, ranging from 0.1 to 158 mg of C per liter (mg C/L). Some of the profiles of DOC in the pore waters are similar to total organic C and total inorganic C profiles. DOC maxima at shallow depths of Site 858 are probably enriched due to higher temperature alteration of organic matter. At Sites 856 and 1035, the DOC increases at greather depths due to the hydrothermal activity. The DOC values correlate with MnO and MgO profiles in Hole 856B. The changes below 30 mbsf in the DOC depth profiles of Sites 858 and 1036 parallel those of the volatile hydrocarbon gases. The reference Site 1037 in Escanaba Trough has DOC values that increase with depth according to the increase in thermal stress.     

Organic Composition of Sulphide Ores in the Okinawa Trough and Its Implications

A preliminary organic geochemical study shows that the sulphide ores from the hydrothermal deposit of the Okinawa Trough are generally low in the total organic carbon and extremely low in the soluble organic matter. In the aliphatic hydrocarbon fraction, the n-alkanes range from C15 to C35, with usual maxima in the middle n-C20 region and strong odd-carbon number predominance when n > C25 (CPI = 1.2). The dominant analog in the aromatic fraction is phenanthrene, a polynuclear aromatic hydrocarbon, which provides evidence for hydrothermal activity. The organic matter derived mainly from marine planktonic and terrigenous vascular plants is entrapped in a high-temperature regime such as an active chimney and cooled quickly in the sulphide ores on the seafloor. Organic matter and sulphides are definitely products of a high-temperature alteration. The biomarker compounds indicate that the ores are formed under low Eh and pH conditions-a reducing to anoxic environment, which is favourable for sulphates to be     

Hydrothermal petroleum of Lake Chapala,Citala Rift,western Mexico: Bitumen compositions from source sediments and application of hydrous pyrolysis

Hydrothermal simulation experiments were performed with contemporary sediments from Lake Chapala to assess the source of the lake tars. The precursor-product relationships of the organic compounds were determined for the source sediments and their hydrous pyrolysis products. The pyrolysis products contained major unresolved complex mixtures of branched and cyclic hydrocarbons, low amounts of n-alkanes, dinosterane, gammacerane, and immature and mature hopane biomarkers derived from lacustrine biomass sources. The results support the proposal that the tar manifestations in the lake are not biodegraded petroleum, but were hydrothermally generated from lacustrine organic matter at temperatures not exceeding about 250 °C over brief geological times.     

Hydrothermal bitumen generated from sedimentary organic matter of rift lakes – Lake Chapala, Citala Rift, western Mexico

Lake Chapala is in the Citala Rift of western Mexico, which in association with the Tepic-Zacoalco and Colima Rifts, form the well-known neotectonic Jalisco continental triple junction. The rifts are characterized by evidence for both paleo- and active hydrothermal activity. At the south shore of the lake, near the Los Gorgos sublacustrine hydrothermal field, there are two tar emanations that appear as small islands composed of solid, viscous and black bitumen. Aliquots of tar were analyzed by GC-MS and the mixtures are comprised of geologically mature biomarkers and an UCM. PAH and n-alkanes are not detectable. The biomarkers consist mainly of hopanes, gammacerane, tricyclic terpanes, carotane and its cracking products, steranes, and drimanes. The biomarker composition and bulk C isotope composition (δ¹³C = −21.4%) indicate an organic matter source from bacteria and algae, typical of lacustrine ecosystems. The overall composition of these tars indicates that they are hydrothermal petroleum formed from lacustrine organic matter in the deeper sediments of Lake Chapala exceeding 40 ka (¹⁴C) in age and then forced to the lakebed by tectonic activity. The absence of alkanes and the presence of an UCM with mature biomarkers are consistent with rapid hydrothermal oil generation and expulsion at temperatures of 200–250 °C. The occurrence of hydrothermal petroleum in continental rift systems is now well known and should be considered in future energy resource exploration in such regions.     

Restricted utility of δC of bulk organic matter as a record of paleovegetation in some loess-paleosol sequences in the Chinese Loess Plateau

Molecular stratigraphic analyses using gas chromatograph-mass spectrometry have been performed in the upper section (S₀, L₁, S₁) of the Yuanbo loess-paleosol sequences in northwest China, with a record extending from the last interglaciation through the present interglaciation. The CPI (Carbon Preference Index) values of both n-alkanols and n-alkan-2-ones display variations between loess deposits and paleosols, showing a correlation with the magnetic susceptibility record, an indicator of the East Asian summer monsoon. The observed variations in the indexes in relation to changes in lithology/paleoclimate are proposed to result from microbial degradation of higher plant lipids in the paleosols. The CPI values of n-alkanes, n-alkanols, and n-alkan-2-ones are negatively correlated with δ¹³C of bulk organic matter. The correlations suggest that the observed glacial-interglacial variations of δ¹³C data in the loess stratigraphy reflect the relative importance of the contribution of paleovegetation compared with microorganisms (including both the degradation and the addition of organic matter) and allochthonous loess/soil parent materials. It is thus necessary to evaluate the contributions of the latter two before the paleovegetation can be reconstructed based on the δ¹³C analysis of bulk organic matter in some loess-paleosol sequences of the Chinese Loess Plateau.     

Helium and carbon gas geochemistry of pore fluids from the sediment-rich hydrothermal system in Escanaba Trough

Ocean Drilling Program (ODP) Leg 169, which was conducted in 1996 provided an opportunity to study the gas geochemistry in the deeper part of the sediment-rich hydrothermal system in Escanaba Trough. Gas void samples obtained from the core liner were analyzed and their results were compared with analytical data of vent fluid samples collected by a submersible dive program in 1988. The gas geochemistry of the pore fluids consisted mostly of a hydrothermal component and was basically the same as that of the vent fluids. The He isotope ratios (R/R_A=5.6–6.6) indicated a significant mantle He contribution and the C isotopic compositions of the hydrocarbons [δ¹³C(CH₄)=−43‰, δ¹³C(C₂H₆)=−20‰] were characterized as a thermogenic origin caused by hydrothermal activity. On the other hand, the pore fluids in sedimentary layers away from the hydrothermal fields showed profiles which reflected lateral migration of the hydrothermal hydrocarbons and abundant biogenic CH₄. Helium and C isotope systematics were shown to represent a hydrothermal component and useful as indicators for their distribution beneath the seafloor. Similarities in He and hydrocarbon signatures to that of the Escanaba Trough hydrothermal system were found in some terrestrial natural gases, which suggested that seafloor hydrothermal activity in sediment-rich environments would be one of the possible petroleum hydrocarbon generation scenarios in unconventional geological settings.     

The characteristics of the biomarkers and δ13C of n-alkanes released from thermally altered solid bitumens at various maturities by catalytic hydropyrolysis

Solid bitumen occurs extensively in the paleo-reservoirs of marine sequences in southern China. The fluids in these paleo-reservoirs have usually experienced severe secondary alteration such as biodegradation and/or thermal maturation. The concentrations of extractable organic matter (EOM) in the resulting solid bitumens are too low to satisfy the amount required for instrumental analysis such as GC–MS and GC–IRMS. It is also difficult to get enough biomarkers and n-alkanes by dry pyrolysis or hydrous pyrolysis directly because such solid bitumens are hydrogen poor due to high maturities. Catalytic hydropyrolysis (HyPy) can release much more EOM from solid bitumen at mature to highly over-mature stages than Soxhlet extraction, dry pyrolysis and hydrous pyrolysis. However, whether the biomarkers in hydropyrolysates can be used for bitumen-source or bitumen–bitumen correlations has been questionable. In this study, a soft biodegraded solid bitumen sample of low maturity was thermally altered to various maturities in a closed system. HyPy was then employed to release bound biomarkers and n-alkanes. Our results show that the geochemical parameters for source and maturity based on biomarkers released from these thermally altered bitumen residues by HyPy are insensitive to the degree of thermal alteration. Furthermore, the maturity parameters are indicative of lower maturity than bitumen maturation products at a corresponding temperature. This suggests that biomarker source and maturity parameters, based on the products of HyPy, remain valid for bitumens which have suffered both biodegradation and severe thermal maturation. The distributions of δ¹³C of n-alkanes in hydropyrolysates are also insensitive to the temperature used for bitumen artificial maturation. Hence, the δ¹³C values of n-alkanes in hydropyrolysates may also provide useful information in bitumen–bitumen correlation for paleo-reservoir solid bitumens.     

Carbon isotope systematics of individual hydrocarbons in hydrothermal petroleum from Escanaba Trough, northeastern Pacific Ocean

We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba Trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7%, respectively) reflect a primarily terrestrial organic matter source.     

Variscan and post-Variscan lead–zinc mineralization, Rhenish Massif, Germany: evidence for sulfide precipitation via thermochemical sulfate reduction

A mechanical decrepitation device coupled with a gas chromatograph has been used to characterize the molecular composition of gaseous and liquid hydrocarbons contained in minerals. Application of this technique allows the identification of low-molecular-weight n-alkanes and some aromatic hydrocarbons in sulfides and gangue minerals from epigenetic Variscan and post-Variscan lead–zinc deposits in the Rhenish Massif, Germany. Based on the analysis of 200 samples, Variscan and post-Variscan mineralization can be distinguished by the composition of associated hydrocarbons. Variscan sulfides and gangue minerals contain high abundancies of methane. In contrast, n-alkanes in the C₂–C₉ range and aromatic hydrocarbons (benzene, toluene) are dominant in post-Variscan mineralization. The absence of high-molecular-weight hydrocarbons in ore minerals suggests highly mature gas associated with hydrothermal activity, during which hydrothermal fluids caused an increase in thermal maturation of organic matter and the generation of low-molecular-weight hydrocarbons in the adjacent organic-rich rocks. The hydrocarbon compositions contained in fluid inclusions of Variscan and post-Variscan minerals are probably governed by the maturation level of the potential source rocks. In Variscan time tectonic brines (T > 175 °C) generated predominantly methane, whereas basement brines (T < 175 °C) expelled higher-molecular-weight hydrocarbons (wet gases, condensates, aromatic hydrocarbons) from adjacent rocks during the Mesozoic event. The specific role of hydrocarbons in sulfide precipitation via thermochemical sulfate reduction is indicated by geochemical characteristics of organic matter associated with the Plombières Pb–Zn deposit, in eastern Belgium. Intense alteration phenomena were observed in near-ore kerogens, compared with unaltered kerogens far from the ore body, as well as by a very high maturity (5.40% R_o), a systematic depletion in ¹²C towards the vein-type mineralization, high atomic S/C ratios (0.49), and by low atomic H/C ratios (0.29). The data suggest that hydrothermal solutions caused a drastic increase in the thermal maturation of organic matter within the adjacent wall rock. Increased thermal maturation resulted in increased δ¹³C-values of organic carbon due to the preferential release of ¹²C. The change in the organic matter to a H-depleted and S-enriched bulk composition in association with sulfide ores strongly suggests that thermochemical sulfate reduction was responsible for organic degradation. Thus, thermochemical sulfate reduction probably triggered base metal sulfide precipitation in Variscan and post-Variscan ore deposits of the Rhenish Massif. Finally, based on data from this study and previous investigations, new genetic models are presented for both Variscan and post-Variscan mineralization in the Rhenish Massif. Received: 15 September 1999 / Accepted: 2 December 1999     

Organic geochemical study of Ypresian sediments at Jebel Ousselat,Tunisia

This new study was carried out in order to accurately characterize the geochemical pattern of Ousselat organic-rich facies from the Ypresian basin in central-northern Tunisia. It has been found that the organic matter is located towards the end of diagenesis/beginning of catagenesis. This assumption is supported by the relative low T _max values (429–439°C) and by steranes maturity parameters such as C₂₉ αα 20S/(20S + 20R), and C₂₉ ββ/(ββ + αα). High HI values and the abundance of saturates (1–83%) compared to aromatics (2–27%) are unequivocal evidence of type-II organic matter as indicated by a high abundance of cholestane and the predominance of short-chain n-alkanes centred at n-C₁₈ and at n-C₂₀. Total organic carbon (TOC) content and petroleum potential values suggest that the Ypresian period corresponds to an anoxic event which led to the accumulation and preservation of large quantities of organic matter with high primary production. Due to their geochemical characteristics, the Lower Eocene facies represent a new potential source rocks in central-northern Tunisia.     

Low temperature hydrothermal maturation of organic matter in sediments from the Atlantis II Deep,Red Sea

Hydrocarbons and bulk organic matter of two sediment cores (No. 84 and 126, CHAIN 61 cruise) located within the Atlantis II Deep have been analyzed. Although the brines overlying the coring areas were reported to be sterile, microbial inputs and minor terrestrial sources represent the major sedimentary organic material. This input is derived from the upper water column above the brines.Both steroid and triterpenoid hydrocarbons show that extensive acid-catalyzed reactions are occurring in the sediments. In comparison with other hydrothermal (Guaymas Basin) or intrusive systems (Cape Verde Rise), the Atlantis II Deep exhibits a lower degree of thermal maturation. This is easily deduced from the elemental composition of the kerogens and the absence of polynuclear aromatic hydrocarbons of a pyrolytic origin in the bitumen.The lack of carbon number preference among the n-alkanes suggests, especially in the case of the long chain homologs, that the organic matter of Atlantis II Deep sediments has undergone some degree of catagenesis. However, the yields of hydrocarbons are much lower than those observed in other hydrothermal areas. The effect of lower temperature and poor source-rock characteristics appear to be responsible for the differences.     

Size distributions of hydrocarbons in suspended particles from the Yellow River

Suspended particle samples from the Yellow River estuary were sorted into five grain size fractions to explore the effect of grain size distribution on organic matter content and composition. The n-alkanes and PAHs were determined for each size fraction. PAHs and n-alkanes were more abundant in the finer fractions and the loading decreases steadily with increasing of grain size. However, the total n-alkanes or PAHs normalized to organic C were lower in the smaller size fractions than those in the larger size fractions, suggesting n-alkanes or PAHs may be diluted by the addition of organic matter or gradually decreased by degradation in the smaller size fractions. The particulate n-alkanes in the Yellow River estuary consist of a mixture of compounds from terrigenous and riverine biogenic n-alkanes and more biogenic n-alkanes accumulate in finer particles. Particulate PAHs are related to combustion/pyrolysis processes of coal/wood, and the relative contribution of petrogenic PAHs increase with increasing grain size. The total particulate n-alkane and PAH discharges passing the Lijin Station are about 3.94 t d⁻¹ and 0.52 t d⁻¹, respectively. Fine particles (<32 μm) play a significant role in organic matter transfer.     

Fossil fuel compounds from fly dust in recent organic matter of southern Poland peats

Several samples of peat from 6 bogs located in southern Poland were investigated for occurrence and distribution types of biomarkers present in their extractable organic matter fraction. It was found that there are inputs from two different sources of organic compounds differing in their characteristics and origin: (1) recent immature peat organic matter deposited in situ which is the source of all polar functionalized compounds, most of n-alkanes, and acyclic isoprenoids, and (2) mature fossil fuels, most probably bituminous coals from the Upper Silesia Coal Basin of vitrinite reflectance equivalent values of 0.9–1.1%. The latter compounds were most probably transported with fly ash to bogs from nearby settlements utilizing such fuel in domestic ovens. This group includes pentacyclic triterpenoids (hopanes and moretanes), minor amounts of n-alkanes, and numerous alkyl naphthalenes and alkyl phenanthrenes. All these compounds show distributions and values of geochemical ratios characteristic for mature organic matter confirming there ex situ origin.     

Qualitative fatty acid and n-alkane stratigraphy of the Lake Turkana Basin,Kenya

In order to improve understanding of the stratigraphy of the Lake Turkana Basin, one of the important sites in the evolution of early man, this study evaluates the usefulness of organic biological marker compounds, n-alkanes and fatty acids, for correlation of isolated sedimentary strata.Eighty-five paleosol samples were collected from well-defined sedimentary horizons in two regions (Area 103 and Area 130) of the Koobi Fora area of Lake Turkana. Results indicate that most of the organic matter present was derived from terrestrial plant waxes. In sediments where extensive diagenesis has occurred, microbial input of organic matter may have been substantial. Algae were either not an important source of organic matter, or their marker compounds have been removed or altered by degradative processes.The fate of the original paleosol organic matter has been governed to some extent by weathering processes, especially in Area 130. Weathering decreased the amount of extractable lipids, particularly fatty acids and the low molecular weight alkanes (C₁₇C₂₀); produced or retained relatively large amounts of alkanes greater than C₂₁ within a unimodal distribution; and lowered CPI values. Consequently, stratigraphic correlation by unique alkane and fatty acid distributions has been confined to short distances (many meters).Both n-alkanes and fatty acids have been retained better by association with clay minerals than by sand matrices. The alkane distribution of sandstones differs from that of clay organics in having a narrower carbon chain length distribution and lower CPI values. In Area 103, where weathering was less severe, compositional variations with stratigraphic position indicate that lipid material has been retained within each of the facies examined.     

Catagenesis and composition of petroleum: Origin of n-alkanes and isoalkanes in petroleum crudes

Distribution of n-alkanes and isoalkanes in ca. 50 petroleum crudes have been examined by the gas chromatography. Molar distributions of n-alkanes with respect to their c atom numbers in the majority of crudes follow the exponential law, which signifies a random, chemical nature of n-alkane-generating processes occurring in the catagenesis stage of petroleum maturation. Similar distributions of n-alkanes were found in the products of mild thermolysis of heavy n-alkanes.Isoalkanes represent a major, 10–25%, petroleum component. The principal types of isoalkanes in crudes are monomethyl-branched, with the branches randomly positioned in the chains, and dimethyl-branched with one of the methyl groups predominantly in the second position in the chains. Thermolysis studies of individual n-alkanes, alkanoic acids, and esters in the presence of various minerals provided an explanation of the n-alkane and isoalkane distributions. Selected heavy n-alkanes are initially formed in decarboxylation reactions of heavy n-alkanoic acids and esters. Extensive thermocracking produces mixtures of lighter n-alkane and α-olefins. The olefins, in the presence of acidic clays, are converted in cationic reactions into mixtures of predominantly mono- and dimethyl-branched isoalkanes.     

Effect of climate change on delivery and degradation of lipid biomarkers in a Holocene peat sequence in the Eastern European Russian Arctic

Lipid biomarkers from a peat plateau profile from the Northeast European Russian Arctic were analyzed. The peat originated as a wet fen ca. 9 ka BP and developed into a peat bog after the onset of permafrost ca. 2.5 ka BP. The distributions and abundances of n-alkanols, n-alkanoic acids, n-alkanes, n-alkan-2-ones and sterols were determined to study the effect of degradation on their paleoclimate proxy information. Plant macrofossil analysis was also used in combination with the lipid distributions. The n-alkanol and n-alkanoic acid distributions in the upper part of the sequence generally correspond to compositions expected from plant macrofossil assemblages. Their carbon preference index (CPI) values increase with depth and age, whereas those of the n-alkanes decrease. The different CPI patterns suggest that n-alkanoic acids and n-alkanols deeper in the sequence may be produced during humification through alteration of other lipids. Excursions in the n-alkanoic acid content also suggest an important contribution of invasive roots to the lipid biomarker composition. The CPIs associated with these compounds show that under permafrost conditions organic material from Sphagnum is better preserved than material from vascular plants. Increasing stanol/stenol ratio values and decreasing n-alkane CPI values indicate progressive degradation of organic matter (OM) with depth. The n-alkan-2-one/n-alkane and n-alkan-2-one/n-alkanoic acid ratios were shown to be useful proxies that can reflect the degree of OM preservation and suggest that both microbial oxidation of n-alkanes and decarboxylation of n-alkanoic acids produce n-alkan-2-ones in this peat sequence.