Polyunsaturated fatty acids in a lacustrine sediment as a possible indicator of paleoclimate

Polyunsaturated fatty acids (C_18:2 and C_18:3ω3 were analyzed in the upper 20m layer of a 200 m long sediment core taken from Lake Biwa. Concentration maxima occur in layers at depths of 0.2, 1–5, 11–12, and 16m. The vertical changes in the $\text{(C}{}_{\mathrm{18:2}}\text{C(C}{}_{\mathrm{18:0}}$ ratio appear to correlate with paleoclimatic condition suggested from palynological evidence. On the basis of $\text{C}{}_{\mathrm{18:2}}\text{C}{}_{\mathrm{18:0}}$ ratios, it was suggested that it has been colder at 200, 1000–4000, 15,000 and 20,000 yr BP than at other times.     

Early diagenesis of fatty acids in lacustrine sediments—I. Identification and distribution of fatty acids in recent sediment from a freshwater lake

Fatty acids have been isolated and quantitatively determined from a 1.5 m sediment core of Lake Suwa, a eutrophic lake in the central districts of Japan.The fatty acids identified by combined gas chromatography-mass spectrometry were straight-chain saturated (C₁₂ to C₃₄), monounsaturated with even carbon number (C₁₆ to C₂₄) and branched-chain (iso, anteiso, 10-methyloctadecanoic) acids. The concentrations of the higher molecular weight (? C₂₀) saturated fatty acids remained nearly constant throughout the core, suggesting a high degree of preservation of those acids, whereas the monounsaturated and the lower molecular weight saturated fatty acids indicated a great decrease in concentration with depth to an approximately 20cm level. It is suggested that the microbial activity in sediments causes a significant reconstruction of the fatty acid distribution during early diagenesis.     

The stereochemistry of 2- and 3-hydroxy fatty acids in a Recent lacustrine sediment

Homologous series of 2- and 3-hydroxy fatty acids occur in both the free and the bound lipid fractions of an oligotrophic lacustrine sediment (Loch Clair, N.W. Scotland). The stereochemistry of each constituent was assigned by gas chromatographic separation of diastereoisomeric O-2(S)-phenylpropionyl methyl ester derivatives. Free and bound 2-hydroxyacids above C₂₀ showed the R configuration characteristic of by-products formed during fatty acid metabolism by α-oxidation. In the C₁₄–C₁₈ region, bound 2- and 3-hydroxyacids show the R configuration more dominantly than the corresponding free lipids. These bound 2(R)- and 3(R)-hydroxyacids are attributed to microbial cell wall lipids.     

Early diagenesis of fatty acids in lacustrine sediments—III. Changes in fatty acid composition in the sediments from a brackish water lake

A 3-m sediment core taken from Lake Suigetsu, in which a shift from fresh to brackish water occurred about three hundred years ago, has been examined for variation with depth of organic carbon and fatty acids. From the difference in total amounts of sulphur between sediments under fresh and brackish water environments, the surface sediments above approximately 35 cm depth were deduced to be accumulated under a brackish water environment. The total contents of organic carbon and fatty acids, and percentage composition of fatty acids gave discontinuous profiles above and below the 35–40 cm sediment layer. At a depth of 12.5 cm, the distribution in chain length of the fatty acids changed from a unimodal (the predominance of C₁₂-C₁₈ over C₂₀-C₃₄) to a bimodal pattern, which was mirrored by the composition diversity index (CDI).Although the fatty acids in the surface sediments (0–40 cm) from Lake Suigetsu seemed to suffer milder degradation through microbial activity than those in a core (0–150 cm) from Lake Suwa, a freshwater eutrophic lake, both lacustrine sediments showed similar trends in the alteration of fatty acid composition with depth.     

Sterols of a contemporary lacustrine sediment

C₂₆, C₂₇, C₂₈ and C₂₉ sterols, including Δ⁵-, Δ²²- and Δ^5,22-sterols and both 5α- and 5β-stanols, have been identified in the contemporary lacustrine sediment of Rostherne mere (Cheshire, England). Amounts of total sterols decrease from ca. 400 ppm extracted sediment dry weight for the 0–7 cm sediment section to ca. 40 ppm for the corresponding 18–30 cm section. 5α-stanols are of far greater abundance than the 5α-stanol isomers. The carbon number distributions of unsaturated and saturated sterols and the increase in stanol: Δ⁵-sterol ratio with sediment depth provide indirect evidence for the operation of a sterol hydrogenation process. C₂₉ sterols preponderate at lower sediment depths, suggesting a predominantly higher plant input, whereas C²⁷ sterols are more abundant in the surface sediment.     

Lipid geochemistry of a post-glacial lacustrine sediment

The post-glacial environmental history of Voua de la Motte, a small pond, was studied by the lipid geochemistry of a 6 m long core. Palynological studies show that the deepest part of the core goes back to 10,000 yr BP corresponding to the time of formation of the lake following the retreat of the Rhodanian glacier. Hydrocarbons, aldehydes, linear alcohols, sterols, monocarboxylic and monohydroxy fatty acids, were determined throughout the core both in the free and bound lipid fractions, as well as in the tightly bound fraction for the carboxylic acids. There is no clear evidence of a transformation from the unbound to the bound form, except perhaps for the α-hydroxy acids.Qualitative as well as quantitative fluctuations in the distributions of these lipid classes were observed upward in the core. An attempt is made to correlate these fluctuations with the bioenvironmental and climatological evolution of the Basin on the basis of information obtained from palynology.     

Early diagenesis of fatty acids in lacustrine sediments—II. A statistical approach to changes in fatty acid composition from recent sediments and some source materials

The percentage composition and total amounts of fatty acids from plankton, live and dead plants (waterweeds and higher plants) and a forest soil, considered as possible origins of autochthonous and allochthonous organic materials in lacustrine sediments, have been determined by gas-liquid chromatography. Statistical analyses were carried out by computing distance index of the fatty acid composition between these source materials and the uppermost sediment from Lake Suwa, and the composition diversity index (CDI) of fatty acids in the recent sediments from Lake Suwa.The distance index indicated that the fatty acid composition in the uppermost sediment is similar to those in diatoms, Zooplankton and forest soil, and the values for dead leaves were smaller than for live ones. It suggests that the autolysis and/or decomposition processes prior to deposition onto the top sediment makes the fatty acid composition of organic debris similar to the uppermost sediment. The CPI in recent sediments varied irregularly, whereas the CDI increased during early diagenesis to yield a value comparable to ancient sediments.     

Porphyrin and chlorin distributions in a Late Pliocene lacustrine sediment

The tetrapyrroles in a highly immature Late Pliocene lacustrine sediment (Willershausen, Germany) show a simple distribution of both chlorin and porphyrin components as the free bases. The major components are C32 desoxophylloerythroaetioporphyrin (DPEP), a C33 bicycloalkano porphyrin, the chlorin analogue of the latter, and desoxophylloerythrin and its chlorin counterpart. The structure of the novel bicycloalkano chlorin was determined using a combination of two-dimensional phase-sensitive COSY NMR and nOe studies. Measurements of delta 13C and other data indicate that DPEP and the bicycloalkano porphyrin were derived from the chlorophyll(s) of photosynthetic organisms utilising a common source of CO2, probably diatoms. The occurrence of DPEP and other minor alkyl porphyrins indicates that the chlorophyll defunctionalisation pathway leading to these components can occur at low temperature and was probably biologically mediated, as was the condensation leading to the fused ring components.     

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.     

Stereochemical studies of acyclic isoprenoid compounds—II The role of chlorophyll in the derivation of isoprenoid-type acids in a lacustrine sediment

The stereochemistries of a series (I)–(IX) of isprenoid-type acids in the lacustrine Green River Shale (Eocene) have been examined. The absolute configurations of five of the acids present in the free-fatty acid fraction have been determined by high resolution gas Chromatographic analysis of the methyl and (?)-menthyl esters and are compatible with an origin from the phytyl moiety of chlorophyll. The results for two other isoprenoid-type acids, 5,9,13-trimethyltetradecanoic acid (IV) and 6,10,14-trimethylpentadecanoic acid (VI), do not at present preclude a chlorophyll derivation. The 4,8,12,16-tetramethylheptadecanoic (VIII) and 5,9,13,17-tetramethyloctadecanoic (IX) acids each comprise two or more stereoisomers. The stereoisomeric composition of the 2,6,10,14-tetramethylpentadecanoic acid (VI) indicates that it is unlikely that 2,6,10,14-tetramethylpentadecane, pristane, is an intermediate in the geochemical pathways presumed to lead from phytol to this acid.     

Dissolved organic carbon and volatile fatty acids in marine sediment pore waters

The results of a study of the contribution of microbial metabolic products to total dissolved organic carbon (DOC) levels in coastal sediments are presented. The data indicate that acidic volatile compounds make up a substantial fraction of pore water DOC's in both oxic and anoxic pore waters of coastal marine sediments. Formic, acetic and butyric acids are the principal volatile species identified at levels exceeding 10 μM. Acid concentrations are up to five times higher in anoxic pore waters than in oxic waters. Volatile organic acids show promise as indicators of diagenetic processes in marine sediments and of the ecological succession of microorganisms, in particular.     

Diagenesis of free and bound lipids in terrestrial detritus deposited in a lacustrine sediment

Recent sediments from an oligotrophic lake (Loch Clair) having uniform organic input for 2000 yr show changes in lipid abundance and composition, with increasing depth, attributed to diagenesis. Stability of free lipids decreases in the order n-alkanes, alkan-2-ones, sterols, n-alkanoic acids, n-alkanols, n-alkenoic acids. Diagenetic loss of shorter-chain homologues is complete within 400 yr. Stabilisation of bound relative to free lipids increases the proportion of the former with sediment age and reduces loss of shorter-chain bound homologues.In an eutrophic lake (Cross Mere), shorter-chain free and bound sedimentary lipids show increased abundance compared with Loch Clair. The relative importance of higher input of shorter-chain lipids derived from aquatic detritus, and slower initial diagenesis due to the anoxic hypolimnion, as causative factors for this difference between lake types cannot yet be assessed.     

Elemental composition of sediment cores from a mangrove environment using neutron activation analysis

The geochemistry of Sepetiba Bay was studied in four sediment cores using a multi-element approach. Two cores were sampled in the more contaminated eastern part of the bay and two cores were sampled in the western region. The aim was to determine whether less common elements like the rare earths or the actinides are associated with contaminant metals like zinc in the Bay. Samples were analysed by instrumental neutron activation analysis that permits the quantification of total concentrations of metals (Ba, Co, Cr, Cs, Fe, Hf, Rb, Sc, Zn), rare earth elements (Ce, Eu, La, Lu, Sm and Yb), actinides (Th, U), non-metals and semi-metals (As, Br). Organic carbon and total sulphur were also analysed. The results show very strong zinc contamination in the top layers (more than 1000 μg g⁻¹) and background concentrations in the bottom (15 μg g⁻¹). Elements like chromium which would be expected to be released by the heavy industries of Sepetiba Bay, did not show a contamination profile, and concentrations remained close to those of natural environments. No evidence of any association between the zinc and other potential contaminant elements could be identified in this work.     

Phospholipid ester-linked fatty acids composition of size-fractionated particles at the top ocean surface

Surface microlayer and subsurface water samples were collected at an oligotrophic Mediterranean site during a diel cycle. The composition of phospholipid ester-linked fatty acids (PLFA) was determined in size-fractionated particles (0.2–0.7 μm; 0.7–200 μm) in order to characterize the major contributors of organic matter to different size fractions. GF/F-retained particles (0.7–200 μm) from the surface microlayer were consistently enriched in PLFA relative to the underlying water. Molecular markers revealed a substantial difference in biological assemblages in both particle sizes. The larger particles were dominated by dinoflagellates, cyanobacteria, microzooplankton and attached bacteria, whereas particles filtered through GF/F and collected on 0.2 μm porosity Durapore filters (0.2–0.7 μm) were mostly bacteria and heterotrophic flagellates. Bacterial PLFA associated with 0.7–200 μm particles were more abundant than those in the 0.2–0.7 μm particles. Specific markers in the branched series appeared more representative of bacteria of smaller particle size.     

Environmental changes during the past 13500 cal. a BP deduced from lacustrine sediment records of Lake Qinghai,China

A 475-cm long sediment core (QH-2005) from Lake Qinghai was used to carry out multi-proxy analysis of δ18O and body length of ostracod valves and redness and grain size of sediments, in order to reconstruct environ-mental changes during the past 13500 cal. a BP. The age model was based on 6 14C dates for bulk orgnic carbon (BOC) and 2 14C dates for lignin. The lignin 14C dates are apparently younger than the corresponding layers’ BOC 14C dates, indicating that the reservoir age varied from 728 to 1222 a since the Late Glacial and from 2390 to 2490 a immediately before the pre-bomb era. Hence, the 14C age model for Core QH-2005 was corrected by the changing reservoir age. Ostracod δ18O values were primarily related to dilution and evaporative enrichment of the lake water. The reconstructed salinity based on ostracod body length coincides well with ostracod δ18O values. High redness and mean grain size (MZ) values indicate increased riverine supply to Lake Qinghai associated with increasing monsoon rainfall. Multi-proxy results show that climate during 13500-10900 cal. a BP was relatively cold and dry with fre-quent short-term fluctuations; a warm and wet climate began at about 10900 cal. a BP and culminated around 6500 cal. a BP as a result of monsoon strengthening; the climate became cold and dry afterwards and has remained rela-tively stable since 3400 cal. a BP. Our data also reveal short-term (millennial/centennial timescales) climatic fluctua-tions including: Younger Dryas events, ice-rafting events 8 and 1 (by ～11000 cal. a BP and ～1600 cal. a BP respec-tively), 8200 cal. a BP cold event, Little Ice Age and the Medieval Warm Period.     

Branched-chain and cyclopropanoid acids in a recent sediment

From the recent sediments of a small productive lake in the English Lake District 10-methyl and cis-9, 10-methylene C₁₆ acids and also 10-methyl, cis-9, 10-, and cis-11, 12-methylene C₁₈ acids have been identified as constituents of the branched/cyclic acid fraction.     

Characteristics of normal fatty acids from sediments as a function of geologic-geochemical factors

Forty-nine samples from Mesozoic rocks of Northern Bulgaria and from recent marine muds of the Black Sea have been analyzed for fatty acids (FA), using extraction, treatment with ion exchange resin and gas chromatography. There is a higher concentration of normal (n) FA in the recent marine sediments, as well as in their bitumen extracts than in the rocks as a whole. There is twice as much n-FA in the rocks containing dispersed organic matter (DOM) formed mainly by benthonic organisms as compared to ancient sediments with planktonic DOM. The content of n-FA has decreased nine and five times, respectively in planktonic DOM in the sequence: limestones-marls-argillites and clayey siltstones, while the amount of organic carbon has risen four and two times. The n-FA are chiefly represented by C₁₆ and C₁₈ and in the recent sediments also by C₂₂ molecules. However when the level of maturity of DOM corresponds to the katagenetic degrees of MK₃ and MK₄, maximum is in n-FA with 19 and 20 carbon atoms. A gradual decrease in the amount of the n-FA with even-numbered carbon atoms was noted as maturity of the planktonic DOM increases from early diagenesis in recent marine sediments to the katagenetic degrees of MK₃ and MK₄ in ancient rocks. The ratios $\text{FA}\text{HC}$ and $\text{FA}\text{HC}\text{+ FA}$ have also decreased when the katagenetic maturity of DOM changes from PK₃ degree to MK₄ degree. These geochemical features may be used as an additional criterion in determining the principal phase of oil formation.     

Late Holocene monsoon climate as evidenced by proxy records from a lacustrine sediment sequence in western Guangdong,South China

The study of a 300-cm-thick exposed lacustrine sediment section in the Hedong village in Zhaoqing area which is located in sub-tropical west Guangdong Province in South China, demonstrates that the lacustrine sedimentary sequence possibly contains evidence for exploring variation of Asian monsoon climate. Multi-proxy records, including the humification intensity, total organic carbon, and grain size fractions, reveal a general trend towards dry and cold conditions in the late Holocene that this is because of a decrease in solar insolation on an orbital scale. Three intensified Asian summer monsoon (ASM) intervals (∼3300–3000 cal yr BP, ∼2600–1600 cal yr BP, and ∼900–600 cal yr BP), and three weakened ASM intervals (∼4000–3300 cal yr BP, ∼3000–2600 cal yr BP, and ∼1600–900 cal yr BP) are identified. Our humification record (HD_cal) shows a good correlation on multi-centennial scale with the tree ring Δ¹⁴C record, a proxy of solar activity. A spectral analysis of HD_cal reveals four significant cycles, i.e., ∼1250 yr, 300 yr, 110 yr, and 70 yr, and most of these cycles are related to the solar activity. Our findings indicate that solar output and oceanic–atmospheric circulation probably have influenced the late Holocene climate variability in the study region.     

Fatty acids and Pb-210 geochronology of a sediment core from Buzzards Bay,Massachusetts

Four sections of a Pb-210 dated core of 62 cm length from Buzzards Bay, Massachusetts, were analyzed for fatty acids. A comparison of fatty acids extracted by Soxhlet extraction (unbound fatty acids) with fatty acids extracted by subsequent saponification extraction of the same sample (bound fatty acids) showed the former did not undergo diagenetic loss any faster than the latter. However, compositional differences between bound and unbound fatty acids were apparent in the top section of 1–2 cm and were less apparent in the 54–58 cm section. At least 14% of the bound fatty acids are esterified to non-solvent extractable material. The net conversion of fatty acids to other compounds is 32 μ/g dry weight sediment over the first 30 yr after deposition.     

The amino acid composition of a deep-water marine sediment from the upwelling region northwest of Africa

The distribution of amino acids with depth have been described for three samples of a core of recent sediment (< 1000–8000 yr) from the continental slope off N.W. Africa. Basic amino acids are more abundant than acidic amino acids in all samples. The amino acid composition of the oldest sample resembles most closely the amino acid composition of planktonic protein. It is suggested that the differences in amino acid composition of the three samples reflect diagenetic changes which are probably controlled by the environment of deposition.