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1.
Tightly bound geolipids were separated from a 200 m sediment core of Lake Biwa by a second saponification of sediments from which unbound and bound lipids had been extracted. Tightly bound fatty acids, β-hydroxy acids, ω-hydroxy acids and α,ω-dicarboxylic acids were released; their concentrations ranged from 4.7–31.5, 5.6–60.5, 3.4–9.5 and 0.2–5.4 μg/g dry sediment, respectively. These geolipids were considered to be incorporated in humic substances.Tightly bound fatty acids showed a unimodal distriution with a peak at C16, suggesting that they originate from algae and bacteria and that they are more stable than unbound and bound fatty acids in the sediments. Most of the total β-hydroxy acids, which probably originate from bacteria, were found in the tightly bound fraction. This suggests that a large portion of tightly bound geolipids are formed in the water column and in surface sediments as a result of microbial alteration dead algae. Each class of tightly bound lipids showed higher concentrations between depths of 3 and 15 m in the sediments, where primary production was thought to be enhanced in the past.  相似文献   

2.
Fatty acids and isoprenoid alcohols were analyzed in river, estuarine, and coastal sediment cores: (1) to investigate the distribution of these lipids among the unbound phase. those bound or closely associated with humic substances, and those bound or closely associated with the huminkerogen and clay mineral matrix. (2) to investigate the diagenetic changes of these lipids with depth in the sediments. and (3) to obtain information on the use of these compounds as organic tracers in marine sediments.Results confirm earlier observations that fatty acids are rapidly altered in marine sediments Both the total and the individual fatty acids decrease in concentration with depth in the sediments: unsaturated acids decrease faster than saturated acids and unbound acids decrease faster than bound acids Approximately 8–62% of the fatty acids were unbound. 2–22% were associated with humic substances. and 38–86% were associated with the residual organic-mineral matrix. Qualitative differences also exist between the fatty acids associated with the unbound, humic, and residual fractions. The ratio of trans/cis geometric isomers of the fatty acids generally increases downcore. with no rearrangement of the double bond positions within the molecules. Either the cis isomer is being preferentially degraded with depth in the sediments, or there is a low temperature, clay catalyzed conversion of the cis isomers to the trans isomers occurring down the cores.Phytol was the major alcohol present in the sediments and does not appear to be altered as rapidly as the fatty acids. Less than 10% of the total phytol (PHY) plus dihydrophytol (DHP) was present as DHP and no trend could be discerned between PHY and DHP with depth or with unbound, humic, and residual material in the cores. All of the isolated DHP appeared to be present as the RRR stereoisomer. Along with the absence of phytane in the cores, this observation suggests that the reduction of phytol to dihydrophytol is microbially mediated in the upper layer of the sediment.  相似文献   

3.
Long-chain fatty acids (C10-C32), as well as C14-C21 isoprenoid acids (except for C18), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C16 followed by lesser amounts of C18 and C22 acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C14, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C18 and C30. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.  相似文献   

4.
Prolonged heating (1–248 days) of a recent sediment was conducted under mild conditions (65 and 83°C) to understand the thermal behavior of extractable (unbound and bound) fatty acids (C12C32). In the course of the heating, the concentrations of saturated and monounsaturated fatty acids first decreased, and then increased. This indicates that extractable fatty acids can be converted to a tightly bound form upon heating, before fatty acids are extensively released from sediment matrices. Changes in molecular distributions of extractable fatty acids upon heating were also observed. The higher molecular weight fatty acids (?C20) are more likely to become tightly bound than are lower molecular weight (<C20). Monounsaturated fatty acids (C16:1 and C18:1) are more easily converted to the tightly bound form than polyunsaturated fatty acids (C18:2 and C18:3). These differences probably reflect their mode of occurrence in sediments, which are closely related to their origin.  相似文献   

5.
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.  相似文献   

6.
The amino acids in a 56 cm sphincter core (K-19-4-9, Woods Hole Oceanographie Institution) from 30°N latitude, 60°W longitude—approximately 300 miles southeast of Bermuda—at a water depth of 5454m were analyzed by gas and liquid chromatography. Amino acids decreased rapidly with depth with β-alanine and γ-aminobutyric acid predominating in deeper sections. Most of the amino acids are tightly bound in the sediment and are released only upon hydrolysis with 6N HC1. Amino acids accounted for only 0.40% of total nitrogen in the non-carbonate minerals in the top 0–8 cm and 7.9 × 10?4 percent in the bottom 48–56 cm. The remaining nitrogen is removed from the sediment by amino acid extraction.  相似文献   

7.
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.  相似文献   

8.
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.  相似文献   

9.
《Applied Geochemistry》2006,21(9):1455-1468
Cyclic base extraction is a commonly used method for the isolation of humic acids from soils and sediments. However, every extract may differ in chemical composition due to the complex nature of humic acids. To better understand the chemical composition of each extract, the heterogeneous property of humic acids and their speciation in environmental samples, eight fractions of humic acids were obtained in the present work by progressive base-extraction of Pahokee peat, and their chemical composition was characterized using two complementary pyrolytic techniques, namely conventional pyrolysis and methylation pyrolysis (TMAH) GC/MS. These quick and effective procedures provide an insight into the structure of macromolecules. The work shows that the lignin-derived aromatic compounds are major components of pyrolysates in both pyrolytic techniques, while aliphatic compounds originating from microorganisms and plants are minor components. Other compounds derived from proteins and carbohydrates at lower concentrations were also detected. Fatty acids were found in the pyrolysis without methylation, indicating their association with humic acid in a free state. These compounds are different from those formed during pyrolysis with in situ methylation, where fatty acids are generally believed to be the cleavage products of carboxylic groups bound to humic acids. A relative decreasing abundance of aromatic components and increasing abundance of aliphatic components in the pyrolysates as the peat was progressively extracted was also observed in this work, suggesting that the extraction of more hydrophobic aliphatics may be delayed in comparison to the aromatic components. Speciation and origin differences may also be important particularly considering that the contribution from lignin organic matter decreased with extraction number, as the contribution of microbial organic matter increased. The observed change in chemical composition with the extracted fractions indicates again that the humic acid distribution and their speciation are complex, and complete extractions are necessary to obtain a representative humic acid sample.  相似文献   

10.
A rank series of lignites and coals of low to moderate maturation levels (vitrinite reflectance (R0): 0.27–0.8%) from the New Zealand Coal Band were investigated using alkaline ester cleavage experiments to reveal compositional changes of ester bound components (fatty acids and alcohols) during increasing maturation. Ester bound alcohols are found to be present in highest amounts in the very immature lignite samples (R0: 0.27–0.29%), but show a rapid decrease during early diagenesis. Ester bound fatty acids also show an initial exponential decrease during diagenesis, but reveal an intermittent increase during early catagenesis before decreasing again during main catagenesis. This intermittent increase was related to the short chain fatty acids. To obtain a maturity related signal and to eliminate facies related scattering in the amounts of fatty acids in the coal samples, the carbon preference index of fatty acids (CPIFA) parameter is introduced here. For the long chain fatty acids (C20–C32) originating from terrigenous plant debris, the CPIFA decreases with increasing maturity, showing a strong maturation related signal. During diagenesis, the same trend can be observed for the short chain fatty acids, but the intermittent increase in the amounts of short chain fatty acids is also accompanied by high CPIFA values. This indicates less altered organic biomass at this advanced maturation level and is in contrast to the mature CPIFA signal of the long chain fatty acids of the same samples. One possible reason for this discrepancy could be extremely different amounts of short and long chain fatty acids in the original source organic matter of these samples. However, another intriguing explanation could be the incorporation of immature bacterial biomass from deep microbial communities containing C16 and C18 fatty acids as main cell membrane components. Deep microbial life might be stimulated at this interval by the increasing release of thermally generated potential substrates from the organic matrix during early catagenesis. In contrast to the fatty acids, the high amounts of alcohols in the immature lignite samples are also visible in the alkene distribution from the open system pyrolysis experiments of the organic matrix before and after saponification.  相似文献   

11.
Geolipid compositions of surficial sediments from Lake Michigan, Lake Huron, and from three locations in the Northwestern Atlantic were determined to compare source inputs and alteration processes in different sedimentary environments. Fatty acids, sterols, fatty alcohols, and alkanes were examined in both unbound and bound extracts of these samples. Significant amounts of long chain fatty acids, alcohols, and hydrocarbons are present in the deep ocean station, yet this location contains a proportionally larger amount of short chain geolipids than do marine stations closer to shore. Larger proportions of long chain lipids present in the Lake Michigan, Lake Huron, and Gulf of Maine samples relative to the open ocean samples reflect larger inputs of land-derived lipids to sediments closer to terrigenous sources. Marine samples contain a more complex mixture of sterols than is found in lake sediments, suggesting that sterol inputs and alteration processes in the marine environment are more complex than in lacustrine settings. Ratios of 16:1/16:0 and 18:1/18:0 fatty acids decrease with increasing distance from land, which suggests that fatty acid degradation before and during deposition becomes more extensive in the open deeper ocean stations.  相似文献   

12.
Certain factors influencing the incorporation, transport and release of fatty acids by clay minerals, calcite and marine sediments have been investigated.Salinity was found to be an important factor. The adsorption of heptadecanoic acid by bentonite clay at 4%. was nearly triple that at 0%.. However, from 4%. to 35%., only a minor adsorption increase occurred. This behavior is believed to be related to flocculation of the clay at the lower salinity range. The pH over the range of 6.0–8.5 has a small influence on fatty acid-clay association, depressing it somewhat as the basicity increases.When the temperature of the fatty acid solution was increased from 0°C to 50°C, a decrease in adsorption on to clay was found. This effect may be due to increased water solubility of the acid at higher temperatures, since solubility is very important in controlling the degree of fatty acid-mineral interaction. Furthermore, apparent solubilization of fatty acids by indigenous dissolved organic matter in sea water reduces adsorption on to clay minerals.Based upon the heat of adsorption of ?14.6 kcal/mole, fatty acids are physically bound to clay minerals by weak van der Waals forces and hydrogen bonds.Bentonite and kaolinite were found to be the most adsorptive minerals investigated, followed in order by illite, montmorillonite and calcite. Sediments from Narragansett Bay were found to lie between illite and montmorillonite in adsorptive capacity after indigenous sediment organic matter had been removed. Sediment organic matter reduced fatty acid uptake by a factor of 1.6.  相似文献   

13.
Speciation of Cr in geochemical reference materials was characterised by sequential extraction and X‐ray absorption near‐edge structure (XANES) spectroscopy to identify Cr(III) resulting from the reduction of pollutant Cr(VI). Sequential extraction suggested that the amount of Cr associated with an acetic acid soluble fraction was low; Cr associated with a reducible phase and an oxidisable phase was extracted at 5–10% of the total Cr concentration, and the residual phase was found to be the dominant Cr‐containing fraction. Cr speciation in soil artificially doped with Cr(VI) and sediment samples collected from highly populated and industrialised areas was different from that in naturally occurring materials. Substantial Cr was extracted as a reducible phase (15–30%) and an oxidisable phase (30–60%) for these samples. Through subsequent XANES spectroscopy analysis, the reducible phase was explained by Cr bound to Fe hydroxide, while the oxidisable phase was a mixture of Cr bound to humic substances and Cr hydroxides. That is, Cr(VI) present as a contaminant in sediments and soils was reduced to Cr(III), which then bound to Fe hydroxide and humic substances, precipitating as a hydroxide. Thus, a combination of sequential extraction and XANES spectroscopy allows for effective identification and quantification of the chemical forms of Cr in sediments and soils.  相似文献   

14.
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.  相似文献   

15.
A method of extraction for amino acids from soils and sediments involving superheated water has been investigated. About 75–97 per cent of the amino acids contained in four soils of a soil profile from Illinois were extracted by this method. Deep penetration of water into soil aggregates and partial hydrolysis of peptide bonds during this extraction by water at high temperature are likely mechanisms responsible for the release of amino acids from samples. This extraction method does not require subsequent desalting treatments when analyses are carried out with an ion-exchange amino acid analyzer.  相似文献   

16.
Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).  相似文献   

17.
The distributions of lipids in surface and subsurface sediments from the northern South China Sea were determined. The n-alkanes were in bimodal distribution that is characterized by a centre at n-C16 –n-C20 with maximum at C18(or C19) and n-C27 –n-C31 as well as at C29(or C31). The short-chain alkanes suffered from significant losses due to their slow deposition in the water column, and their presence with a slight even carbon predominance in shallow seafloor sediments was ascribed mainly to the direct input from the benthos. The long-chain alkanes with odd predominance indicate transportion of terrigenous organic matter. Immature hopanoid biomarkers reflect the intense microbial activity for bacteria–derived organic matter and the gradual increase of maturity with burial depth. Abundant n-fatty acid methyl esters(n-FAMEs) that are in distributions coincident with fatty acids were detected in all samples. We proposed that the observed FAMEs originated from the methyl esterification of fatty acids; methanol production by methanotrophs and methanogenic archaea related to the anaerobic oxidation of methane, and sulfate reduction provided an O–methyl donor for methylation of fatty acids. The CH4 released from hydrate dissociation at oxygen isotope stage II of Cores ZD3 and ZS5, which had been confirmed by the occurrence of negative δ13C excursion and spherical pyrite aggregates, could have accelerated the above process and thus maximized the relative content of FAMEs at ZD3-2(400–420 cm depth) and ZS5-2(241–291 cm depth).  相似文献   

18.
Sections of a 42 cm core from one area and surface sediments from two other areas of Buzzards Bay, Massachusetts were analyzed for sterols. The distribution of sterols in surface sediments appears to be influenced by benthic faunal composition or factors controlling this composition. A comparison of sterols extracted by Soxhlet-extraction with sterols extracted after subsequent saponification of the sediment showed that the former sterols decrease in concentration while the latter saponified sterols increase in concentration with depth. In both fractions, the individual sterol compositions are similar. A transformation between Soxhlet-extractable and non-Soxhlet-extractable saponified sterols appears to be occurring over the 130 yrs sampled by the core. This transformation is probably due to chemical/physical processes rather than biological processes. Comparison with fatty acid data shows that early diagenesis of sterols is slower than early diagenesis of fatty acids.  相似文献   

19.
Two hydrogen-rich lithobodies of highly alipathic character from a coal occurring in southwest Utah, have been studied. Bituminite (>50%), vitrinite (25–30%) and liptodetrinite (7–12%) are the principal macerals. The hexane-soluble products of hydrogenating the lithotypes at 400° with tetralin and hydrogen have been analyzed by GC-MS. Products identified include homologous series of alkylated naphthalenes, phenols, furans, cyclohexenones and hydroxy-pyridines. In the case of furans, the alkyl groups extend beyond C30. Materials released by Soxhlet extraction with pyridine consist chiefly of homologous series of fatty acids and their methyl esters and of methyl alkyl ketones, which were not found in the hydrogenation products. The long alkyl chains in these substances can account for about 75% of the alkanes found in the hydrogenation products but not in the extracts. Most of the compounds mentioned in the foregoing are thought to be physically held or trapped in the coal, rather than chemically combined in its macromolecular network. Except for the fatty acids, the origins of these substances are difficult to identify.  相似文献   

20.
The Fe content of soils and aquifer solids is usually quantified using different extraction solutions performed with homogenized samples in a well-mixed batch experiment. For structured media where preferential flow prevails over the matrix flow, however, the Fe content determined from homogenized samples may not well represent the Fe available for biogeochemical reactions. In this study ammonium oxalate extraction was performed on a core of intact saprolite where physical structure was preserved. An unsaturated flow setup was modified with the intent of allowing the extraction under two pore tensions, 15 and 0 cm of water, although a malfunctioning vacuum regulator made this more difficult than anticipated. Approximately 85% of the oxalate-extractable Fe was contained within the finer pore domain (matrix potential larger than 15 cm). Less than 15.5% of the extracted Fe mass (an upper bound) was present in domains of pore tension less than15 cm. To the extent that Fe(III) oxides play an important role in contaminant biogeochemistry and solute transport, their distribution in structured subsurface media is critical to the understanding of these processes.  相似文献   

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