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1.
Investigation of chlorins in the oxic surface sediment of a small eutrophic alpine lake (Motte lake) revealed the presence of a new series of steryl chlorin esters containing the pheophorbide a nucleus, together with their pyropheophorbide a steryl ester counterparts previously observed in the anoxic surface sediment of the same lake. Identification of the pheophorbide a steryl esters was based on comparison of spectroscopic, chromatographic and mass spectrometric characteristics of the compounds with those of a synthetic standard and of pyropheophorbide a steryl esters. Combined liquid chromatography-mass spectrometry analysis confirmed the absence of pheophorbide a steryl esters in the anoxic sediment but allowed their detection in traces in the water column, indicating that pheophorbide a steryl esters are, like their pyropheophorbide a analogs, formed in the water column. The distribution of sterols released by hydrolysis of the pheophorbide a steryl esters shows close similarities to that of the free sterols in the water column and of the sterols of the pyropheophorbide a steryl esters. It appears that, like their pyropheophorbide a counterparts, pheophorbide a steryl esters incorporate mainly sterols of phytoplanktonic origin. Their formation probably involves the same mechanism as for pyropheophorbide a steryl ester formation, i.e. metabolism by zooplankton grazing on phytoplankton. The presence of pheophorbide a steryl esters in the oxic sediment and their absence from the anoxic sediment is probably due to a lower stability of compounds containing a carbomethoxy substituent in the anoxic environment.  相似文献   

2.
Photosynthetic pigments and other indicators of phytoplankton were analyzed in a dated undisturbed sediment core obtained from the southern basin of Lake Baikal to reveal temporal changes in the phytoplankton community in the lake through the last glacial/post-glacial transition. The sedimentation age of the core spans the last 24 14C ka. Chlorophyll a, its derivatives, carotenoids and total organic carbon (TOC) started to increase after 15 14C ka, and the onset of biogenic silica occurred at 10 14C ka. This indicated that the post-glacial growth of diatoms was preceded by that of other phytoplankton groups. In the record of the pigments and TOC, a temporary decrease was observed in the period 11.5–10.5 14C ka, corresponding to the Younger Dryas cold period. The similarity found between the depth profiles of pyropheophytin a and steryl chlorin esters formed through predation of phytoplankton by zooplankton and that of TOC suggested the important contribution of fecal pellets to sedimentary organic matter in the lake.  相似文献   

3.
Bacteriochlorophylls c and d, recovered from two sedimentary sequences, were converted to bacteriophaeophorbide methyl esters by methanolysis and analysed by atmospheric pressure chemical ionisation liquid chromatography-multistage mass spectrometry (APCI LC-MSn). The distributions in both settings, a moderately consolidated sediment from Kirisjes Pond, Antarctica, and in a finely laminated microbial mat from Les Salines de la Trinitat, Spain, show significant variations within a narrow depth interval. The overall bacteriophaeophorbide c to d ratios in the two sediments are different, as are the ratios of particular C-31 diastereoisomers, indicating distinct differences between the bacterial communities that contributed to each sediment. Furthermore, a shift towards more extensive alkylation in homologues within each sediment is consistent either with changing environmental conditions in the depositional environments, or development-related changes in the structure of the bacterial community, leading to increased competition for light or nutrients.  相似文献   

4.
Significant quantities of solvent-inextractable geolipids, obtained by saponification of solvent extracted sediments, were found in various sedimentary samples including soils, river inlet sediment and lake sediments from Lake Suwa.The carbon isotopic composition (δ13C) of extractable and inextractable geolipids from the same sediment sample were similar. Moreover, the carbon number distributions of sterols in the two geolipid fractions from the same sediment were also similar.Whereas the ratios of both lipids and sterols to total organic carbon for the extractable geolipids in the lake sediments decreased with depth, the former ratio for inextractable giolipids tends to increase with depth and the latter remains fairly constant. On the other hand, the stanol to stenol ratio of the extractable fraction increased with depth but that of the inextractable fraction was lower than that of the extractable fraction and was fairly constant irrespective of sediment depth.The transformation of extractable sterols into inextractable ones was not observed during incubation for 1200 days of sterols with Suwa sediments.Thus, the following conclusions were made: (1) the extractable and inextractable geolipids have similar origins, (2) some constituents of the latter may be protected from chemical or microbiological degradation and transformation in the sediments, and (3) the transformation of some constituents of the former into the inextractable ones virtually does not occur after incorporation into Suwa sediments.These results suggest that some constituents of the inextractable geolipid fraction may provide fundamental information on early diagenetic alteration of geolipids in lake sediments and on the relatively recent paleoenvironment.  相似文献   

5.
Past changes in phytoplankton assemblages in Lake Baikal over the last 4.5 Ma, both in population and composition, are inferred from the downcore profiles of the relatively stable chlorophyll derivatives steryl esters of pyropheophorbides a and b (steryl chlorine esters; SCEs) in the 0–200 m section of the BDP-98 drill core, supplemented by the data on biogenic silica (BSi) and total organic carbon (TOC) contents. SCEs-a and -b dominate among sedimentary chlorophyll derivatives in the BDP-98 sediments except for the upper few meters, indicating their high stability during diagenetic alteration of sediments. The depth (age) profiles of SCEs-a are consistent with BSi and TOC profiles and are interpreted as reflecting primary productivity of the lake in the past. Baikal proxies reveal close correlation with marine oxygen isotope records (MIS stratigraphy). These observations confirm that climate change in the northern hemisphere has been a primary factor controlling the total phytoplankton productivity in Lake Baikal during the last several million years.Among SCEs-a, C30 (dinostanol)-SCE-a, a marker of dinoflagellates was identified by GC–MS analysis. SCE-b, a marker of green algae, was identified by its UV–vis spectrum. The ratio of C30-SCE-a to total SCEs-a (TSCEs-a) was higher during 4.5–4.2 and 1.7–1.3 Ma, suggesting that dinoflagellates proliferated preferentially in those periods. The early Pleistocene maximum of this ratio corresponds to the broad minimum of diatom abundance previously suggested to have recorded a prolonged regional cooling. An abrupt increase in the SCE-b/TSCEs-a ratio was observed at 2.5–2.6 Ma, indicating that green algae containing chlorophyll b have proliferated in Lake Baikal during this period. This interval has also been suggested to contain evidence for a significant regional cooling based on minima of diatom abundance and BSi in sediments. The depth profile of C27Δ5 (cholesterol)-SCE-a relative to TSCEs-a showed a trend similar to that of BSi, suggesting that C27Δ5-SCE-a/TSCEs-a ratio is a potential marker of diatoms in Lake Baikal.Certain mismatches between the Lake Baikal profiles of biological indicators and the marine oxygen isotope records, as well as the slight temporal offsets between different Lake Baikal biological marker signals suggest that the regional component of climatic and/or lacustrine environmental changes also have played a role in determining the composition of the Lake Baikal Plio-Pleistocene phytoplankton assemblage.  相似文献   

6.
Organic materials in lacustrine sediments are from multiple terrestrial and aquatic sources. In this study, carbon (δ13C) and hydrogen isotopic compositions (δD) of phytol, various sterols, and major n-fatty acids in sediments at Lake Haruna, Japan, were determined in their solvent-extractable (free) and saponification-released forms (bound). The δ13C-δD distributions of these lipid molecules in sediments are compared with those of terrestrial C3 and C4 plants, aquatic C3 plants, and plankton to evaluate their relative contributions. δ13C-δD of free phytol in sediments is very close to that of phytol in plankton samples, whereas δ13C-δD of bound phytol in sediments is on a mixing line between terrestrial C3 plant and plankton material. Unlike phytol, no significant δ13C-δD difference between free and bound forms was found in sterols and n-fatty acids. δ13C-δD values of algal sterols such as 24-methylcholesta-5,22-dien-3β-ol in sediments are close to those of plankton, whereas δ13C-δD of multiple-source sterols such as 24-ethylcholest-5-en-3β-ol and of major n-fatty acids such as n-hexadecanoic acid in sediments are between those of terrestrial C3 plants and plankton samples. Thus, δ13C-δD distributions clearly indicate the specific source contributions of biomarkers preserved in a lacustrine environment. Free phytol and algal sterols can be attributed to phytoplankton, and bound phytol, multiple source sterols, and major n-fatty acids are contributed by both terrestrial C3 plants and phytoplankton.  相似文献   

7.
Fossil pigments were identified in a sediment core from Kirisjes Pond, a small lake in the Larsemann Hills, east Antarctica, using reversed-phase HPLC and LC–MS/MS. Chlorophyll a- and b-derived components indicate the presence of oxygenic primary producers; steryl chlorin esters provide evidence of grazing, while shifts in their esterifying sterol composition record changes in the primary producer community. Bacteriochlorophyll c- and d-derived components, indicative of photic zone anoxia, were identified with structural variations including extensive alkylation in the macrocycle up to C6. The pigment distribution reveals a change from oxygenated freshwater to a stratified water body with development of photic zone anoxia. This coincides with a marine incursion identified from diatom records and is followed by re-isolation and reversion to oxygenated freshwater conditions.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
C26, C27, C28 and C29 sterols, including Δ5-, Δ22- and Δ5,22-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.  相似文献   

11.
Sterol biomarkers serve as an alternative method for detecting sewage pollution. Sterols were extracted from samples of surface sediment collected in Cubat?o (the Vila dos Pescadores and Vila Esperan?a communities) and quantified using GC–MS after Soxhlet extraction, cleanup, and derivatization. Fecal contamination was evaluated based on the concentration of coprostanol and the ratio of the selected sterols. The most abundant sterol was cholestanol, followed by coprostanol. The concentrations of coprostanol in surface sediments ranged from a minimum of 4.21?μg?g?1 dry sediment (Vila dos Pescadores station) to a maximum of 8.32?μg?g?1 dry sediment (Vila Esperan?a station). A coprostanol concentration of about 10?μg?g?1 was found, indicating areas of high sewage contamination. Coprostanol levels at sewage stations were higher than in other Brazilian coastal areas, which may be attributed to the fraction of the population without sanitation services.  相似文献   

12.
We investigated the molecular inventory of River Danube sediments and identified wax esters with 28–36 carbons, with C30, C31 and C32 homologs the most abundant. They consist of various combinations of n-, iso- and anteiso-aliphatic acid and alcohol moieties, with different isomer distributions for the esters with odd and even carbon numbers. The short chain length (C28–C36), high proportion of methyl moieties and presence of monounsaturated esters together suggest a bacterial origin for the wax esters. The concentration in surface sediments varied from 0 to 741 μg/kg, being significantly enriched at locations with high nutrient concentration and high primary productivity. Cluster analysis of denaturing gradient gel electrophoresis (DGGE) band patterns revealed different bacterial communities in surface sediments from the stream and surface sediments from the reservoir. The concentration in a 70 cm core of rapidly deposited sediments decreased significantly with depth, following first order kinetics, suggesting a loss of the esters within ca. 3 years following burial and hence a low probability for preservation in the geological record. Wax esters in rivers have rarely been investigated; our results suggest that they represent a bacterial response to enhanced primary production, triggered by higher nutrient supply.  相似文献   

13.
An evaluation of the distribution of P concentrations in streamflow, P fractions andthe microbial biomass P pool was made of bed and bank sediments along a lowlandstream in New Zealand. Agricultural intensification increased downstream. However,most P fractions decreased downstream (total P decreased from c. 400 to 250 mg kg-1) in bed sediments, while P in streamflow remained relatively constant (generally < 0.005 mg l-1) and sediment microbial P increased from 2 to 8 mg kg-1. An investigation of P release from dried and rewetted sediments showed that solution P (CaCl2-P) increased, on average > 300%, and proportional to the size of the microbial biomass P pool before drying, except in sediments with much organic carbon (OC). When supplied with a P source (1 mg l-1) and then simultaneously with a C source (glucose, 100 mg l-1), all sediment behaved similarly and biotic sorption accounted for, on average, 27 and 34% of the total sediment uptake, respectively (maximum of 58%). The quantity of P taken up was related to the initial size of the microbial biomass P pool, and the availability of P as influenced by organic P complexes and OC. The sediment microbial biomass represents a transient, but small store of P could be useful to indicate bioavailable P inputs.  相似文献   

14.
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   

15.
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.  相似文献   

16.
Roman cisterns served as rainwater storage devices for centuries and are densely distributed in parts of northern Jordan. A major earthquake hit the region ca. A.D. 750 and in a short time many settlements were abandoned. As a consequence, most cisterns were not maintained, and they filled with sediments that today provide a postabandonment depositional record. In two field surveys, we mapped the locations of more than 100 cisterns in the Wadi Al‐Arab basin and selected two for detailed stratigraphic analysis that included 14C and optically stimulated luminescence dating. Catchment basin area for each cistern was determined by differential GPS. Both cisterns filled with sediments after the great earthquake and consequent abandonment of the region. Calculated sediment volumes are translated to long‐term average sediment export rates of 2.6–6.6 t ha−1a−1, which are comparable to erosion and sediment yield rates from other studies within the Mediterranean region. Our pilot study suggests that this approach can be applied elsewhere to calculate long‐term sediment export rates on hill slopes containing relict cisterns.  相似文献   

17.
The early diagenetic chemical dissolution of skeletal carbonates has previously been documented as taking place within bioturbated, shallow water, tropical carbonate sediments. The diagenetic reactions operating within carbonate sediments that fall under the influence of iron‐rich (terrigenous) sediment input are less clearly understood. Such inputs should modify carbonate diagenetic reactions both by minimizing bacterial sulphate reduction in favour of bacterial iron reduction, and by the reaction of any pore‐water sulphide with iron oxides, thereby minimizing sulphide oxidation and associated acidity. To test this hypothesis sediment cores were taken from sites within Discovery Bay (north Jamaica), which exhibit varying levels of Fe‐rich bauxite sediment contamination. At non‐impacted sites sediments are dominated by CaCO3 (up to 99% by weight). Pore waters from the upper few centimetres of cores show evidence for active sulphate reduction (reduced SO4/Cl? ratios) and minor CaCO3 dissolution (increased Ca2+/Cl? ratios). Petrographic observations of carbonate grains (specifically Halimeda and Amphiroa) show clear morphological evidence for dissolution throughout the sediment column. In contrast, at bauxite‐impacted sites, the sediment is composed of up to 15% non‐carbonate and contains up to 6000 μg g?1 Fe. Pore waters show no evidence for sulphate reduction, but marked levels of Fe(II), suggesting that bacterial Fe(III) reduction is active. Carbonate grains show little evidence for dissolution, often exhibiting pristine surface morphologies. Samples from the deeper sections of these cores, which pre‐date bauxite influence, commonly exhibit morphological evidence for dissolution implying that this was a significant process prior to bauxite input. Previous studies have suggested that dissolution, driven by sulphate reduction and sulphide oxidation, can account for the loss of as much as 50% of primary carbonate production in localized platform environments. The finding that chemical dissolution is minor in a terrigenous‐impacted carbonate environment, therefore, has significant implications for carbonate budgets and cycling, and the preservation of carbonate grains in such sediment systems.  相似文献   

18.
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.  相似文献   

19.
Sedimentary phosphorus (P) composition was investigated in Effingham Inlet, a fjord located on the west coast of Vancouver Island in Barkley Sound. Solid-state 31P nuclear magnetic resonance (NMR) spectroscopy was applied to demineralized sediment samples from sites overlain by oxic and anoxic bottom waters. The two sites were similar in terms of key diagenetic parameters, including the mass accumulation rate, integrated sulfate reduction rate, and bulk sediment organic carbon content. In contrast, P benthic fluxes were much higher at the anoxic site. 31P NMR results show that P esters and phosphonates are the major organic P species present at the surface and at depth in sediments at both sites. Polyphosphates were only found in the surface sediment of the site overlain by oxic waters. The varying stability of polyphosphates in microorganisms under different redox conditions may, in part, explain their distribution as well as differences in P flux between the two sites.  相似文献   

20.
The concentrations of lipids were determined in atmospheric particle, gas and rain samples collected from the tropical North Pacific to assess lipid sources, transport mechanisms and fluxes to the ocean surface. Four lipid compound classes (aliphatic hydrocarbons, fatty alcohols, fatty acid esters, and salts) all unequivocally show a terrestrial vascular plant source. These aerosol lipids originate from wind erosion of Asian and American soils and direct emission from vegetation. The major fluxes result from rain rather than dry deposition. These fluxes are large enough to have a major potential impact on the inventory of terrestrially derived lipid material found in deep-sea sediments. This has been showm for n-alkanes, fatty alcohols, fatty acids, total lipids and for organic carbon. By comparing atmospheric and sediment trap fluxes with sediment accumulation rates, it is suggested that some biogenic terrestrial material is more protected from degradation than marine-derived material.  相似文献   

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