Molecular evidence for recent land use change from a swampy environment to a pond (Lorraine,France)

Evidence of a changing environment in the catchment area of a small pond (Lansquenet, Lorraine, France) during the last millennium was provided by coupling palynology data and organic ratios [terrestrial to aquatic ratio: TAR_(HC); the C₂₉ vs. C₂₇ sterols, C₂₉/C_27(ST); average chain length, ACL and aquatic/macrophytes ratio, P_aq]. The depositional and alteration conditions of organic matter (OM) were provided by the 5α(H)-stanols/Δ⁵-sterols ratio. This study shows that quite simple organic ratios clearly allow identification of the different evolution steps of a watershed, from a swamp to the progressive settlement of a pond. During the swampy period, the C/N_(at) (ca. 11.1), TAR_(HC) (ca. 36.8)_, C₂₉/C_27(ST) (ca. 8.7) and P_aq (<0.3) show a high contribution of allochthonous OM associated with the presence of particular aquatic and mesohygrophilous species. A woody level dated to the XIIIth century reflects the period of the settlement of the pond in a more oxic environment [5α(H)-stanol/Δ⁵sterol ratio <0.2]. Then, the progressive increase in aquatic input and the development of submerged and floating macrophytes are evidenced by low C/N_(at) (<7.6), TAR_(HC) (ca. 2.7), C₂₉/C_27(ST) (ca. 2) and high P_aq (ca. 0.5), suggesting an increase in the water level and eutrophication of the pond. A second oxic event [5α(H)-stanols/Δ⁵sterols ratio averaging 0.16], associated with extensive OM degradation, corresponds to the most recent dredging in 2002 and reflects an important disturbance of sediments due to pond management.     

Sources of neutral lipids in a temperate intertidal sediment

The compositions of sterol, alcohol and ketone fractions from an oxic intertidal surface sediment from Corner Inlet. Victoria, Australia, have been examined by capillary gas chromatographymass spectrometry and related to the lipids of diatoms cultured from the sediment and to lipids of the sea-grass Zostera muelleri. Of the more than thirty sterols in the sediment most appear to derive from diatoms, including the major sterol 24-methylcholesta-5.22E-dien-3β-ol. Small amounts of 24-ethylcholesterol probably derive from Zostera, with a minor diatom contribution. 5α-stanols, both fully saturated and with a side-chain double bond, represented ca. 14% of the total sterols: a significant proportion of these are probably derived from marine invertebrates. These organisms also contribute C₂₆ sterols. most of the cholesterol and possibly small amounts of Δ-sterols. The data suggest that in situ biohydrogenation of stenols was not a major process in sterol transformation in the surface oxic sediment. Alcohols ranged from C₁₂ to C₃₀ and showed an unusual abundance of unsaturated components with Δ⁹-16:1 being the major constituent. The long-chain alcohols probably originate largely from Zostera but the shorter-chain. C₁₂-C₂₀. alcohols are at least partly derived from wax esters of unknown origin. Diatoms do not contribute significant amounts of alcohols. Ketones were not major constituents of the sediment and consisted mainly of 6.10.14-trimethylpentadecan-2-one and a series of n-alkan-2-ones ranging from C₁₆ to C₃₃. The latter showed a similar distribution to that of the n-alkanes but the correspondence was not sufficient to substantiate a product-precursor relationship. Very long-chain C₃- C₃₉ unsaturated methyl and ethyl ketones, which may originate from the marine unicellular alga Emiliania huxleyi. were present in low concentration.     

Sterols in sediments from Baffin Bay,Texas

Laminated sediments in Baffin Bay, Texas, consist of alternate layers of blue-green algal remains and terrigenous muds. These sediments resemble stromatolites and contain stenols and stannols. The relatively rare C-27, C-28 and C-29 Δ²²-5α-stenols and the commonly found Δ⁵ and Δ^5.22 sterols and stannols are present in the Baffin Bay sediments.     

Free and bound lipids in recent (1835–1987) sediments from Santa Barbara Basin

In order to study the first steps of incorporation of lipids in recent organic-rich sediments into free and bound fractions, we have selected the Santa Barbara Basin, off California. This basin with a maximum of 590 m water depth is characterized by high phytoplankton production in surface waters and a low oxygen content in bottom waters. Sediments show the following features: high sedimentation rate ≈ 4 mm/yr, no bioturbation, and development of a bacterial mat community at the surface with predominance of sulphur-oxidizing bacteria trapping particles, thus preventing re-distribution of sediment, which permit a unique observations of organic sedimentation on a new few years basis.A sediment core has been divided into 2 cm thick slices corresponding to a time resolution of ≈5 years, from 1835 up to 1987. Samples have been analyzed using a multi-parameter approach, such as for plankton species identification, carbon stable isotope ratios and, as reported here, for lipid organic tracers. Organic tracers have been analyzed in the sterol and fatty series for both free and bound compounds by gas chromatography and gas chromatography/mass spectrometry.The incorporation processes of sterols with depth appear different for free and bound compounds. Total free sterol concentrations show high values in surface sediments (≈ 100 μg/g dry sediment), rapidly decrease up to ≈ 10 cm depth and remain at a constant value of 30–40 μg/g. Total bound sterol concentrations show low values in surface sediment (13.6 μg/g), and vary irregularly with depth up to a value of 55 μg/g at 7.3 m, and then remain constant at 25–26 μg/g.Profiles of evolution with depth of free C₂₇, C₂₈ sterols show a regular decrease, whereas C₂₉ sterols show an irregular decrease with anomalies at 7.3 cm (approximately age: 1977–1978) and at 14.1 cm (1962–1964). Profiles of bound compounds are rather different, very regular for C₂₈ sterols, irregular with oscillations for C₂₇ and C₂₉ sterols at 7.3, 12.2 and 18.0 cm (1954–1956), suggesting a different mode of incorporation and probably different inputs for C₂₇, C₂₉ and C₂₈ sterols.The study of the kinetics of degradation of sterols between surface (1987) and 10.5 cm (1968–1972) shows that C₂₇ compounds are degraded at a slight higher rate (0.53 μg/μg of initial C₂₇ concentration/ year) than are C₂₈ and C₂₉ compounds (0.047 μg/μg of initial concentration/year). An intermediate value is found for brassicasterol: 0.049 μg/μg/year.     

Thermal alteration experiments on organic matter in recent marine sediment—III. Aliphatic and steroidal alcohols

Recent sediments from Tanner Basin (off southern California) and Bandaras Bay (in Gulf of California) have been analyzed for normal, isoprenoid and steroidal alcohols using chromatographic (column, GLC, TLC), and spectroscopic (u.v., i.r., MS) methods, prior to and after heat-treatment (from 65 to 150°C). Normal saturated alcohols (C₁₄-C₂₄) and monounsaturated alcohols (C₂₂-C₂₄) were identified, as well as the isoprenoid alcohols, phytol and dihydrophytol.Two series of sterols (Δ⁵ and Δ⁷) were found in Tanner Basin, and Δ⁵-sterols and triterpenes, in Bandaras Bay sediment. Sterols from both sediments contained the corresponding stanols.     

青海湖沉积物中的甾醇及其演化

Ｃ_２７，Ｃ_２８和Ｃ_２９甾醇（△５.２２，△２２，△５和△５.２４（２８）和５α－甾烷醇）在青海湖三孔近代沉积物（ＱＨ，ＱＥ和ＱＯ）中被检出。其中以Ｃ_２９甾醇占优势。在ＱＥ和ＱＧ孔沉积物中还检出了低浓度的三个Ｃ_３０甾醇（４α，２３，２４－三甲基－５α－胆甾－２２Ｅ－烯醇（甲藻甾醇），４α－甲基－２４－乙基－５α－胆甾－２２Ｅ－烯醇和４α－甲基－２４－乙基－５α－胆甾烷醇］。在ＱＨ和ＱＧ孔上部层段沉积物中，Ｃ_２７，Ｃ_２９.饱和的和不饱和的甾醇的碳数分布的平行性，甾烷醇/△５－甾醇及△２２－/△５.２２－甾醇的比值随沉积物埋深而增加提供了甾酸氢化作用的间接证据。青海湖沉积物中的甾醇主要来自湖区丰富的高等植物和湖中的藻类等。在ＱＧ孔８０～１００ｃｍ和１２０～１４０ｃｍ层段沉积物中，５ａ－胆甾烷醇浓度迅速增加可能反映特殊的生物（介形类）对该二层段沉积物中高浓度的胆甾烷醇的贡献。     

Free,esterified and residual bound sterols in Black Sea Unit I sediments

Detailed compositional data for the sterols isolated from a surface, Unit I, sediment from the Black Sea are reported. A procedure based on digitonin precipitation has been used to separate the more abundant free sterols from those occurring in esterified forms. Saponification of the solvent extracted sediment residue liberated only a small quantity of residual bound sterols in contrast to studies of other sediments. 4-Methylsterols are much more abundant than 4-desmethylsterols in both the free and esterified sterol fractions which we attribute to a major dinoflagellate input, as in deeper Unit II sediment. The desmethylsterol fraction appears to derive from a variety of sources including dinoflagellates, coccolithophores, diatoms, terrigenous detritus and perhaps invertebrates. 5α(H)-Stanols are particularly abundant in the free sterol fraction. An analysis of the stanol/stenol ratios suggests that the 4-desmethyl-5α(H)-stanols are the result of specific microbial reductions of Δ⁵-sterols and/or the reflection of a contribution of stanol containing source organisms.     

Constraints on the structure and dynamics of the β-cristobalite polymorphs of SiO2 and AlPO4 from 31P, 27Al and 29Si NMR spectroscopy to 770 K

Nuclear magnetic resonance spectroscopic data are presented for the cristobalite polymorphs of AlPO₄ and SiO₂ from RT to 770 K, through their respective α-β transitions. The nuclear magnetic resonance (NMR) data include chemical shifts for ³¹P, ²⁷Al, and ²⁹Si, ²⁷Al quadrupole coupling parameters, and ³¹P and ²⁷Al spin-lattice relaxation rates. Also presented are electron diffraction patterns of β-cristobalite AlPO₄ that show diffuse scattering similar to that reported previously for SiO₂. For the α-phases of both AlPO₄ and SiO₂, the chemical shifts decrease approximately linearly with increasing temperature from RT to T_c and discontinuously by -2 to -3 ppm from α to β. This result is consistent with a small, continuous increase in the mean T-O-T angle (〈θ〉) of the α-phases with increasing T and an increase of 〈θ〉 by about 4° across the α-β transition for both cristobalite and its AlPO₄ analogue. Based on the ²⁹Si chemical shifts, the mean Si-O-Si angle for β-cristobalite is 152.7±1° near T_c. For AlPO₄-cristobalite, the ²⁷Al nuclear quadrupole coupling constant (C_Q) decreases approximately linearly from 1.2 MHz at RT to 0.94 MHz near T_c (493±10 K). At the α-β transition the ²⁷Al C_Q approaches zero, in agreement with the cubic average structure observed by diffraction. The satellite transitions retain a small frequency distribution above the α-β transition from electric field gradients attributed to defects. The short-range cubic symmetry of the Al-site and non-linear Al-O-P angle support a dynamically disordered model of the β-cristobalite structure. Complete averaging of the ²⁷Al quadrupole coupling in the β-phase indicates that the lifetime of any short-range ordered domains must be shorter than about 1 μs.     

Occurrence of Different Forms and Implications of Compound Specific Sterols in Continental Sediments of the Northeast South China Sea

The South China Sea(SCS) is one of the most productive and accumulative marginal shelves of organic carbon in the world. To expound the transformation and preservation of organic carbon in the Northeast SCS, where abundant oil and gas resources have been reported, compound specific sterols in free(FR), base hydrolytic(BH), and acid hydrolytic(AH) forms were analyzed in surface and columnar sediments in May, 2016. The results showed that the total contents of sterols detected ranged from 0.15 to 3.74 ppm dry weight in the surface sediments, and gradually decreased from 3.41 to0.17 ppm dry weight from surface to deep sediments, in which cholesterol(27~(△5)) was the most abundant component. Sterols mainly existed in the BH form(54.51%-74.20%), followed by the FR form(25.50%-45.49%) and then the AH form(0-3.77%) in turn, in the surface sediments. BH and FR sterols accounted for 0-49.08% and 50.92%-100% in the columnar sediments, while AH sterols were undetectable. The contents of specific sterols indicated that, the primary source of marine organic carbon was about 5 times as much as that from terrestrial input. More and more FR sterols transformed into BH sterols with increasing sedimentary depth, and BH sterols absolutely dominated in sediment depths under 25 cm. The forms of Sterols C27 were maintained at a relative consistence state, but Sterols C28 to C30 degraded gradually during the sedimentation process. It was suggested that the stability of sterols, based on the chemical structures, might be the primary factor controlling their degradation and preservation in deeper sediments. These results would help to understand the organic carbon(OC) transformation in a hydrate formation area in a marginal sea.     

Selective enrichment of steroid and triterpenoid hydrocarbons from crude oil using gel permeation chromatography for stable carbon isotope analysis

Gel permeation chromatography (GPC) using a high performance liquid chromatography (HPLC) system was studied for the separation and enrichment of steroid and hopanoid hydrocarbons from crude oil for stable carbon isotope analysis. A crude oil sample was pretreated using silica gel chromatography and 5A molecular sieve to remove polycyclic aromatic hydrocarbons and n-alkanes. The GPC behavior of both the pretreated saturated hydrocarbon fraction of the oil and standard steroid [5α(H), 14α(H), 17α(H) C₂₇–C₂₉ steranes], hopanoid [17α(H) C₂₇ trisnorhopane, 17α(H), 21β(H) C₂₉–C₃₂ hopanes] and triterpenoid [18α(H)-oleanane, gammacerane] mixtures were examined. The results indicate that 17α(H), 21β(H) hopanes as well as steranes could be enriched efficiently using GPC and that they could be obtained without removing n-alkanes from the oil saturated hydrocarbon fraction. The GPC behavior of steroid and triterpenoid hydrocarbons was controlled by molecular size and shape.     

Chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100°C to 550°C: Case study in the Liassic black shale formation of Central Swiss Alps

Hydrocarbon distributions and stable isotope ratios of carbonates (δ¹³C_car, δ¹⁸O_car), kerogen (δ¹³C_ker), extractable organic matter (δ¹³C_EOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C_<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C₁₂ and C₁₃n-alkanes, C₁₄, C₁₆ and C₁₈n-alkylcyclopentanes and to a lesser extend C₁₅, C₁₇ and C₂₁n-alkylcyclohexanes. The progressive ¹³C-enrichment (up to 3.9‰) with metamorphism of the C_>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C_<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C₁ and C₂ radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C_>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C₂₉ to C₃₁ range and 5α(H),14α(H),17α(H)-20R C₂₇, C₂₉ steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C₂₉Ts) vs. 17α(H),21β(H)-30-norhopane [C₂₉Ts/(C₂₉Ts + C₂₉)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.     

Typification of oils in the Timan-Pechora province according to the composition of hydrocarbon biomarkers (steranes and terpanes)

Distinctive compositional features of cyclic saturated hydrocarbon biomarkers have been established in oils from the main petroliferous lithostratigraphic complexes of various structural zones in the Timan-Pechora petroliferous province (TPPP). Four geochemical families (types) of oils in TPPP are recognized based on the variations in the geochemical parameters of steranes and terpanes including sterane ratios C₂₇/C₂₉ and C₂₈/C₂₉, K¹ mat and K² mat, diasterane/regular sterane, pregnane (C_21–22)/sterane (C_21–22 + C_27–29), as well as terpane Ts/Tm parameters, adiantane C₂₉/hopane C₃₀, neoadiantane/adiantane, tryciclic terpane/pentacyclic terpane, hopane/sum of C₂₉ steranes, etc. The distribution of various types of oil in the sedimentary sequence of TPPP makes it possible to infer source rocks for each of the four selected types.     

Microbial lipids from a nearshore sediment from Bowling Green Bay,North Queensland: The fatty acid composition of intact lipid fractions

Samples from a sediment core collected in Bowling Green Bay, North Queensland have been analysed for hexane/isopropanol extractable lipids and fatty acids. These data revealed a subsurface lipid abundance maximum at 3–4 cm depth and consistent low total fatty acid abundances (ca 2 μg/g) in the deeper samples ( > 10 cm depth). Lipid phosphate was below the level of detection in all the samples. Bacterial community structure was found to vary markedly in the upper 10 cm of the core, with the 18:1Δ11 bacterial chemotype predominant in the surface sediment and trans-acid chemotypes dominating in the 3–4 cm depth sediment. Based on the fatty acid composition, the bacterial biomass was estimated to vary from 199 μg/g at 3–4 cm depth toca 8 μg/g at 11–13 cm depth, although the fatty acid distributions indicated possible interference from protozoan detritus. In order to test this possibility, a surface sediment sample from a nearby site was extracted and analysed for fatty acids in lipid fractions separated by silica column chromatography. The fatty acid distributions in lipid fractions containing wax/steryl esters, triacylglycerols, glycolipids and phospholipids were markedly different. These analyses were interpreted in terms of fatty acid contributions to the extractable lipids from bacteria, cyanobacteria, protozoan detritus and highly degraded organic matter.     

Water dissolution in albite melts:: Constraints from ab initio NMR calculations

Hartree-Fock and B3LYP NMR calculations were performed at the 6-311+G(2df,p) level on cluster models representing albite glasses using B3LYP/6 to 31G* optimized geometries. Calculation results on several well-known crystalline materials, such as low albite and KHSi₂O_5, were used to check the accuracy of the calculation methods.Calculated ²⁹Si-NMR results on clusters that model protonation of Al-O-Si linkages and the replacement of Na⁺ by H⁺ indicate a major increase in Si-O(H) bond length and a 5 ppm difference in δ_iso for ²⁹Si compared to that for anhydrous albite glass. The calculated δ_iso of ²⁷Al in such linkages agrees with the experimental data, but shows an increase in C_q that cannot be fully diminished by H-bonding to additional water molecules. This protonation model is consistent with both experimental ¹⁷O NMR data and the major peak of ¹H-NMR spectra. It cannot readily explain the existence of the small peak in the experimental ¹H spectra around 1.5 ppm. Production of the depolymerized units Al [Q³]-O-H upon the dissolution of water is not consistent with ²⁷Al, ¹H, or ¹⁷O NMR experimental results. Production of Si [Q³]-O-H is consistent with all of the experimental ¹⁷O and ¹H-NMR data; such units can produce both the major peak at 3.5 ppm and the small peak at 1.5 ppm in ¹H spectra, either with or without hydrogen bonding. This species, however, cannot produce the main features of ²⁹Si spectra.It is concluded that although neither protonation nor the production of Si [Q³]-O-H alone is consistent with the available experimental data, the combination of these two processes is consistent with available experimental NMR data.     

Lipid geochemistry of Lake Kinneret

Lake Kinneret, a relict lake from the Neogene, is characterised by the dominance among its phytoplankton of the dinoflagellate Peridinium cinctum. The lipid geochemistry of Lake Kinneret is discussed herein in terms of the biology, chemistry and hydrology of the lake. Lipids isolated from two sediment sections (surface and 15 cm deep), obtained from the deepest point of Lake Kinneret, include: (1) 4α-methyl-5α (H)-stanols and related derivatives characteristic of P. cinctum, the novel sterol 4a-methylgorgosterol, and peridinosterol and 4α-methylgorgostanol, not previously reported to occur in lacustrine sediments; (2) C₃₀ and C₃₂ alkane-1,15-diols, not previously reported to occur in contemporary lacustrine deposits, and (3) products of early diagenesis. Many similarities were observed with the more widely studied marine dinoflagellates and marine sediments with dinoflagellate input.     

Assessing the factors controlling high sedimentation rates from the latest Barremian–earliest Aptian in the hemipelagic setting of the restricted Organyà Basin,NE Spain

The Organyà Basin, south–central Spanish Pyrenees, developed as a marginal depocenter during a rapid extensional phase of anticlockwise rotation of the Iberian plate. As a result of increased subsidence, an important change in sedimentation occurred from the late Barremian to the Aptian leading to unusually high sediment accumulation rates. Approximately 1000 m of hemipelagic marls and limestones accumulated during this time interval.Here we studied the basal 85 m of the hemipelagic facies of the El Pui section, Organyà Basin, that are characterized by alternating 15 cm – ∼3 m thick beds of limestone and marls. Geochemical analyses indicate high total inorganic carbon (TIC) values (average 70%) suggesting enhanced CaCO₃ production and deposition. SEM analyses of the samples indicate high abundance of calcareous nannofossils, which together with the absence of shallow water taxa characteristic of the Urgonian Carbonate platform of Organyà, and the lack of sedimentary facies attributable to carbonate platform components point to nannofossils as the main source for the elevated TIC. Organic-rich levels (total organic carbon (TOC) up to 1.74%) concurrent with positive excursions up to 2‰ in δ¹³C_org, imply enhanced preservation of organic matter (OM) in the basin. In addition, pronounced peaks of δ¹³C_org higher than the global average suggest superimposed local factors related to intensified ¹²C removal due to primary productivity. Biomarker analyses and the δ¹³C_org profile suggest an autochthonous origin of the OM from phytoplankton and possible additional contributions from microbial communities.X-ray diffraction (XRD) results attest for sustained terrestrial fluxes as the source of nutrients to the basin because of a 30% average non-carbonate bulk mineral content in the sediment. The non-carbonate fraction is dominated by quartz (average, 14%) whereas the clay mineral assemblages are characterized by high illite content (>73 relative%) with minor concentrations of kaolinite (<5%), illite /smectite mixed layers (<17%) and chlorite (<15%), consistent with a provenance from the Paleozoic metamorphic terranes adjacent to the Organyà Basin.The integrated results suggest a high sediment accumulation rate (5 cm/ky–7.5 cm/ky) and enhanced carbon burial during the latest Barremian–earliest Aptian in the hemipelagic setting of the El Pui section.     

Carbon isotope composition of long chain leaf wax n-alkanes in lake sediments: A dual indicator of paleoenvironment in the Qinghai-Tibet Plateau

The carbon isotope composition (δ¹³C values) of long chain n-alkanes in lake sediments has been considered a reliable means of tracking changes in the terrigenous contribution of plants with C₃ and C₄ photosynthetic pathways. A key premise is that long chain leaf wax components used for isotope analysis are derived primarily from terrigenous higher plants. The role of aquatic plants in affecting δ¹³C values of long chain n-alkanes in lacustrine sediments may, however, have long been underestimated. In this study, we found that a large portion of long chain n-alkanes (C₂₇ and C₂₉) in nearshore sediments of the Lake Qinghai catchment was contributed by submerged aquatic plants, which displayed a relatively positive carbon isotope composition (e.g. −26.7‰ to −15.7‰ for C₂₉) similar to that of terrestrial C₄ plants. Thus, the use of δ¹³C values of sedimentary C₂₇ and C₂₉ n-alkanes for tracing terrigenous vegetation composition may create a bias toward significant overestimation/underestimation of the proportion of terrestrial C₄ plants. For sedimentary C₃₁, however, the contribution from submerged plants was minor, so that the δ¹³C values for C₃₁ n-alkane in surface sediments were in accord with those of the modern terrestrial vegetation in the Lake Qinghai region. Moreover, we found that changes in the δ¹³C values of sedimentary C₂₇ and C₂₉ n-alkanes were closely related to water depth variation. Downcore analysis further demonstrated the significant influence of endogenous lipids in lake sediments for the interpretation of terrestrial C₄ vegetation and associated environment/climate reconstruction. In conclusion, our results suggest that the δ¹³C values of sedimentary long chain n-alkanes (C₂₇, C₂₉ and C₃₁) may carry different environmental signals. While the δ¹³C values of C₃₁ were a reliable proxy for C₄/C₃ terrestrial vegetation composition, the δ¹³C values of C₂₇ and C₂₉ n-alkanes may have recorded lake ecological conditions and sources of organic carbon, which might be affected by lake water depth.     

Fatty acid geochemistry of a 200 m sediment core from Lake Biwa,Japan. Early diagenesis and paleoenvironmental information

Fatty acids (FAs), β- and ω-hydroxy acids, α,ω-dicarboxylic acids and n-alkanes were studied in a 200 m sediment core taken from Lake Biwa, Japan. FAs showed bimodal distribution with peaks at C₁₆ and C₂₂-C₂₈. Their distribution patterns clearly changed with depth from lower molecular weight (C₁₂-C₁₉) predominance to higher molecular weight (C₂₀-C₃₂) predominance in the upper 20 m interval. Analyses of related compounds (β- and ω-hydroxy acids and α, ω-dicarboxylic acids) suggest that β- and ω-oxidative degradation of C₁₂-C₁₉ FAs has occurred in the sediments.The ratio of bound C₁₂-C₁₉ to unbound FAs increases with depth in the upper 0–1 m sediments, suggesting that unbound FAs are more labile. However, the ratio varies significantly in deeper sections and may be associated with water temperature.In the sediments deeper than 20 m in depth, C₁₂-C₁₉ FAs gradually decrease. On the other hand, higher molecular weight FAs (HFAs: C₂₀-C₃₂), which were probably derived from terrestrial plants, increase in concentration from 20 m to 100 m, suddenly decrease at 100 m and show progressively lower concentration in deeper sediments. These fluctuations are interpreted in relation to paleolimnological changes of the lake and the drainage basin. ω-Hydroxy C₂₀-C₃₀ acids and C₂₀-C₃₀α, ω-dicarboxylic acids show a distribution pattern similar to HFAs. Branched chain FAs, ω-hydroxy acids and C₉-C₁₉α,ω-dicarboxylic acids show a major peak around 3–15 m in depth. This peak is probably caused by increased bacterial activity in the water column and surface sediments in the past, which may be associated with an increase in primary production of the lake.     

Hydrocarbons in 60 northeast Gulf of Mexico shelf sediments: a preliminary survey

Hydrocarbon results from gas chromatography of 60 recent sediment and 10 benthic algae samples delineate two distinct shelf environments in the northeastern Gulf of Mexico.Sediments off Florida (shell hashes and sands) have moderate amounts of lipids/total sediment (average 113ppm ± 80%) but low hydrocarbon levels (average 3.06 ppm ± 41%). Aliphatic hydrocarbons are dominated by a series of branched or cyclic, unsaturated C₂₅ isomers. The major n-alkane is n-C₁₇. The n-alkane and isoprenoid patterns are consistent with a marine hydrocarbon source.Sediments closer to the Mississippi River (silts and clays) contain large amounts of lipids (average 232 ppm ± 53%) and hydrocarbons (average 11.7 ppm ± 55%) to total sediment. Aliphatic hydrocarbons are mainly odd carbon number high molecular weight n-alkanes, indicating a terrigenous hydrocarbon source. Isoprenoids are present in greater abundance than in sediments off Florida (n-C₁₇/ pristane and n-C₁₈/phytane ratios ~2to 3). Relatively large amounts of n-C₁₆, together with an even distribution of n-alkanes in the range C₁₄–C₂₀ and a substantial unresolved envelope all point to a fossil fuel input to the Mississippi samples.Samples off the Alabama coast show intermediate characteristics.