Sterol Distribution in Sediments from Chaiwobu Lake and Caohai Basin and Its Geochemical Significance

In order to understand the distribution characteristics of biomarkers in source rocks,which may be related to organic input,Quaternary sediments from the Caohai Basin and the Chaiwobu Lake were analyzed for sterols,As a result,various sterols,have been found in the sediments.The composition of sterols in the sediments revealed that cholesterols and cholestadienols are more abundant than their C29 counterparts in the Chaiwobu Lake sediments and that C29 sterols are more abundant in the peats from the Caohai Basin,It is also found that stanol/sterol ratios in clays are higher than in peats.Studies show that organic input to the Chaiwobu Lake is mainly plankton and zooplankton and to the Caohai Basin is mainly terrestrial high plant.The authors have proposed that the relative abundance of C27 or C29 sterane in source rocks may reflect input characteristics to some extent and the stanol/sterol ratios may reflect the redox conditions of the depositional environments.     

Sterol diagenesis in Recent sediments from Buzzards Bay,Massachusetts

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.     

Sterols in the western North Atlantic Ocean

The sterol concentrations in fourteen surface and nine deep water samples collected from the continental shelf and slope waters of the western North Atlantic and Sargasso Sea ranged from 0.1 to 1.3μ/l seawater. Isolation and structural elucidation by gas chromatography and combined gas chromatography-mass spectrometry show that cholesterol and β-sitosterol (or clionasterol) are the major free sterols in both the surface and deep water. Fucosterol, brassicasterol, 22-dehydrocholesterol, campesterol (or 22,23-dihydrobrassicasterol), 22-methylenecholesterol, norcholestadienol, and stigmasterol (or poriferasterol) are found in lower concentrations at the surface and in the deep sea. Cholesterol is the major sterol ester in both the surface and deep water, while very low concentrations of other sterol esters were found. The ratio of total free sterols to total esterified sterols is approximately two in both the surface and deep water.Marine sources of sterols in seawater include phytoplankton, yeasts, and marine animals such as Crustacea and molluscs. Terrestrial plants also may contribute. Sterol transport to the deep sea may occur by convective overturn and vertical diffusion or from vertical fluxes of large particles from the surface.     

Sterols as ecological indicators

Plots of the C-27, C-28 and C-29 sterol contents of marine plankton, higher plants, soils, and lacustrine and marine sediments form discrete areas in a triangular diagram. Because the positions of these plots of the various samples are relatable to biological sources, sterol analyses may be used to define ecological systems.     

A study of oxic/anoxic effects on degradation of sterols at the simulated sediment–water interface of coastal sediments

Laboratory incubation experiments were conducted to determine the behavior of sterols at the sediment–water interface in oxic and anoxic sediments. Both plankton and 4- -cholesterol were used as tracers. Cholesterol was rapidly degraded at the sediment–water interface: 55% of -cholesterol was lost from sediments under anoxic conditions and 78% under oxic conditions over three and one-half months. About 3% of initially-added free radiolabel was incorporated into a bound pool that was released only by saponification of solvent-extracted sediment. Less than 1% of initially-added radiolabel remained in pore waters after three and one-half months. Rate constants for degradation of cholesterol in oxic and anoxic surficial sediments were estimated by tracking variations in radioactivity and sterol concentration as a function of time. We discuss our results in terms of factors affecting sterol degradation in coastal marine sediments, including molecular structure, sediment matrix effect, and redox conditions.     

Comparison of lipid character of sediments from the Great Lakes and the Northwestern Atlantic

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.     

Quantitative measurement of the sea ice diatom biomarker IP25 and sterols in Arctic sea ice and underlying sediments: Further considerations for palaeo sea ice reconstruction

The lipid content of sea ice samples collected in 2011 and 2012 from Resolute Passage in the Canadian Arctic Archipelago was measured and compared with related samples obtained from the Amundsen Gulf in 2008. The highly branched isoprenoid (HBI) sea ice biomarker, IP₂₅, was found in sea ice samples from each study, consistent with its formation by diatoms during the spring bloom. Our analysis also revealed the occurrence of a number of sterols in Arctic sea ice and these were rigorously identified and quantified for the first time. Concentrations of IP₂₅ and sterols exhibited some variability between sampling studies, with somewhat higher values in samples from Resolute in 2012 than for the other two datasets, consistent with a general increase in biomass; however, major differences in biomarker concentration between sampling studies were not observed. An estimate of the proportion of Arctic sea ice diatoms that produce IP₂₅ (ca. 1–5%) was obtained by comparison of the concentration of IP₂₅ in the samples with those in laboratory cultures of known HBI-producing diatoms and cell enumeration in selected sea ice samples. The estimate is similar to the proportion of Haslea spp. in the same samples, providing further support to the suggestion that at least some species of the Haslea genus may be responsible for the biosynthesis of IP₂₅ and related HBI diatom lipids in Arctic sea ice and that IP₂₅ is made by a relatively small proportion of sea ice diatoms. In contrast, median sterol/IP₂₅ values were all substantially higher than those in cultures of HBI-producing diatoms, suggesting that sterols are made by the majority of sea ice diatoms. The sterol/IP₂₅ ratio was quite variable between locations and samples, likely as a result of differences in diatom assemblage; however, a comparison of individual and median sterol/IP₂₅ values in sea ice with those from surface sediments from different Arctic regions demonstrated that sterols from sea ice diatoms may, in some cases, have a significant impact on the sedimentary budget. This should be considered carefully for quantitative estimates of palaeo sea ice reconstruction using methods such as the PIP₂₅ index, which are based on the relative concentrations of IP₂₅ and sterols in Arctic marine sediment cores.     

δC and δD identification of sources of lipid biomarkers in sediments of Lake Haruna (Japan)

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.     

Aspects of the geochemistry of sedimentary sterols in the Chang Jiang estuary

Sediment samples have been collected during the Donghai 1 cruise in January 1986 in the Chang Jiang estuarine region for which solvent extractable sterols have been analysed by GC and GC/MS and the data examined using Correspondence Factorial Analysis (CFA). The main autochthonous sterols in these sediments were cholesterol, 24-methylcholesta-5,22-dien-3β-ol and 24-methylcholesta-5,24(28)-dien-3β-ol, whereas 24-ethylcholesterol, 24-ethylcholesta-5,22-dien-3β-ol and 24-methylcholesterol were principally allochthonous. Autochthonous sterols prevailed in regions of high primary production observed in summer, and allochthonous ones dominated the sterol distribution in the accumulation region of fine sediments just outside the river mouth and in the reaches of coastal currents. The cholesterol/cholesterol ratio values exhibited higher values close to the river mouth and in the region where the turbidity maximum extends. A comparison between sediment and suspended matter indicated a great difference in the sterol content in regions of high autochthonous production which suggested that sterols have been transformed in the course of sedimentation and at the sediment/water interface. In contrast, sedimentary and suspended sterol concentrations were comparable close to the mouth of the Chang Jiang River and in the region where the turbidity maximum extends, a feature that may be attributable to sediment resuspension episodes and lower production of autochthonous sterols. These results demonstrate the distinct impact of biogeochemical processes on the sediment sterol features in different zones of the estuary.     

Spectroscopic and Chromatographic studies of organic carbon in Recent marine sediments from the Peruvian Upwelling Zone

Early diagenesis of organic matter in sediments from two sites in the Peruvian Upwelling Zone (12°05′S, 77°39′W; 15°17′S, 75°24′W) has been studied by observing changes in the total organic carbon and lipid and humin fractions with depth. Transformations of the total carbon and humin fraction have been characterized by conventional and time-dependent solid state NMR techniques, while lipid diagenesis was monitored by measuring the concentration of sterols in the same sedimentary horizons. Both the quantity of total sterols and the relative abundances of individual sterols vary with sampling location, suggesting a difference in the input of biomass to the sediments at the two sites. Total sterol concentrations decrease with depth at both sites, but the loss of sterols occurs much more slowly at the more anoxic northern site, where sedimentation rates and organic carbon contents are approximately twice those at the southern site. ¹³C-NMR spectra of the total organic carbon and the humin fraction suggest that humin-like compounds are an original component of the sedimentary biomass, and dipolar-dephased spectra of the humin residue indicate that diagenetic alterations of the humin fraction are occurring even in these very young sediments. Conventional and time-dependent spectroscopic data support the hypothesis that humin formation results from selective preservation of microbially-resistant biopolymers which are an original component of the sedimentary biomass combined with loss of certain labile compounds.     

The role of zooplankton fecal pellets in the sedimentation of polycyclic aromatic hydrocarbons in Dabob Bay,Washington

Polycyclic aromatic hydrocarbon (PAH) compositions were determined in plankton, sediment-trap-collected particulate material and sediment cores from Dabob Bay using a high performance liquid Chromatographie (HPLC)/fluorescence technique. The annual flux of individual PAH measured in a series of sediment traps was compared with the flux of corresponding compounds determined from ²¹⁰Pb dated bottom sediments. Systematic seasonal variations in the fluxes and concentrations of PAH, Al and organic carbon in the trap-collected particulates and seasonally collected plankton were also investigated to determine whether or not PAH are associated with either terrestrial or marine-derived materials.Concentrations of all PAH studied increased tenfold within the last 80–100 yr of sediment deposition, except for perylene which displayed a reasonably constant concentration profile. This suggests at least two sources contribute to the observed sedimentary PAH compositions in Dabob Bay, i.e., anthropogenic combustion and a natural source. Plankton and sediment trap-collected particulates contained PAH mixtures qualitatively similar to underlying surface sediments. Microscopic examination indicated fecal pellets were the major form of particulate material in the sediment traps. The fecal pellets collected in the sediment trap time series quantitatively account for essentially 100% of the PAH fluxes measured in the ²¹⁰Pb dated sediments, implying Zooplankton fecal pellets control the removal of PAH to Dabob Bay sediments. These measurements provide clear evidence that the PAH studied are not produced after sediment deposition. The observed seasonal covariations of PAH and Al in both sediment trap and plankton samples further indicate that PAH originate from terrestrially-based sources, are introduced into the marine environment by runoff and erosion or atmospheric deposition and are not produced by marine plankton.     

Geochemistry of sterols in sediments from Black Sea and the southwest African shelf and slope

Surface sediment samples from the shelf and continental slope off southwest Africa and sediment cores from the deepest part of the Black Sea were analyzed for sterols. Because the organic matter in these anoxic sediments is relatively well-preserved, the input from source organisms in the water column is important in controlling sterol distribution patterns. The sterol distribution on the Namibian shelf is complex, probably because of the great spatial and temporal variability of biological productivity caused by seasonal upwelling and changes in oxygen concentration. The Black Sea, perhaps because of greater physical stability of the water column, has sterol distributions which can be explained by microbial activity or chemical processes acting on a constant input of organic carbon from surface production.     

广东汕头市内海湾沉积物重金属环境质量调查与评价

内海湾底泥沉积物的环境质量状况与水生生物的生存和人体健康关系密切。在广东汕头市内海湾两岸23个点位采集了表层(0~20 cm)和深层(100~120 cm)底泥沉积物样品46件,对其pH值和Cd、Hg、As、Pb、Cr、Cu、Zn计7项重金属及K含量进行测试分析,调查底泥中这些重金属的含量特征,并参照农用地水田土壤污染风险管控标准对重金属环境污染质量进行评价。结果表明汕头内海湾底泥沉积物的pH介于7.00~8.82之间,平均值为7.83,在46件样品中41件样品的pH值大于7.5。内海湾底泥中7项重金属元素的含量均明显低于环境污染风险管制值,即对该区底泥重金属环境污染不需要管制。Cd、As、Pb、Cr这4项重金属含量均低于污染风险筛选值,其污染风险可以忽略。2件表层样品的Hg含量值高于污染风险筛选值,18件样品的Cu和Zn含量值高于污染风险筛选值,因此建议对底泥中Cu、Zn、Hg含量进行环境质量监测。K含量介于0.70%~2.59%,平均值为1.54%。基于表层底泥和深层底泥元素含量对比分析,认为该区Hg污染来源应为人为源;Cu、Zn的污染来源一部分为人为源,另一部分可能为人为源、自然源或二者的混合源。     

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.     

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.     

Contamination of harbor sediments in the eastern Gulf of Finland (Neva Bay), Baltic Sea

 The areal distribution of oil products and various trace metals have been studied in bottom surface deposits from the harbors of Neva Bay. The data of contents were normalized to natural background concentrations. Also the size and biomass of benthos groups were analyzed. The results show clearly that industrial discharges have elevated levels of contamination in the sediments. Few efficient measures against environmental contamination have been taken. The sediments contain very high concentrations of oil products and such heavy metals as Hg, Pb, Cu, and Zn. The benthic organisms most sensitive to heavy metal contamination are Chironomidae. The dredging and dumping of the contaminated deposits can lead to secondary contamination of the Gulf of Finland and the Baltic proper. Received: 18 November 1996 · Accepted: 17 March 1997     

Gulf of Mexico hydrocarbon seep communities—IX. Sterol biosynthesis of seep mussels and its implications for host-symbiont association

The sterol analysis of six hydrocarbon seep mussels (mytilid II and mytilid Ib) from the Alaminos Canyon in the Gulf of Mexico is reported. The sterol composition of the mussel-symbiotic bacteria complex reflects a preponderant synthesis of 4α-methyl sterols (seep mytilid II), and a predominant biosynthesis of 4-desmethyl sterols with some amounts of 4α-methyl sterols (seep mytilid Ib). This suggests a methane-based symbiotic relationship between the mussels and methanotrophic bacteria. It also suggests that the biosynthesis of sterols in the mussel-bacteria complex is completed to the level of cholest-5-en-3ß-ol (mytilid II) or 5α-cholestan-3ß-ol (mytilid Ib).     

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.     

北部湾东部海域表层沉积物稀土元素组成及物源指示意义

对北部湾东部海域70个表层沉积物样品的稀土元素(REE)分析结果表明,研究区沉积物 REE 呈现轻稀土元素(LREE)富集、重稀土元素(HREE)平坦以及中等程度的 Eu 异常等特征.REE 组成受沉积物粒度和生物碳酸盐含量的制约,具有典型风化上陆壳 REE 特征,其源岩以上陆壳的长英质岩石为主.根据研究区沉积物 REE 分布规律,研究区可划分为4个地球化学分区,各区域上陆壳标准化曲线明显的不同.物源判别显示研究区的西部、海南岛西南侧(Ⅰ区)呈多源沉积特征,来自以下几个物源区:(1)海南岛西南侧河流沉积物和沿岸侵蚀物;(2)由南向北输入的外海沉积物(冬季);(3)夏季或冬季由北部湾西北部和西部搬运来的沉积物.研究区中部粗粒沉积区(Ⅱ区)与北部湾西部沉积物来源是相同的,主要来源于红河输砂.东北部砂质区(Ⅲ区)沉积物可能来源于雷州半岛西北部近岸基岩侵蚀.研究区东北部(Ⅳ区)沉积物主要来自北部湾北部沿岸侵蚀、琼州海峡和雷州半岛西部的沿岸侵蚀.此外,部分沉积物还可能来自珠江流域以及南海北部陆架区和北部湾西北部     

The geochemistry of iodine in oxidised and reduced recent marine sediments

Surface sediments from the South West Africa shelf and the Gulf of California have been analysed for iodine and organic carbon. The iodine contents range from 96 to 1990 ppm. While iodine and organic carbon show certain anomalies on the South West Africa shelf, the trend of the $\text{I}\text{C}$ ratios is smooth and decreases from the shelf edge, an area of oxidising surface sediment, shorewards to reducing sediments, formed as a result of intense water upwelling. In the Gulf of California, a similar distribution of $\text{I}\text{C}$ ratios with surface sediment type occurs; lowest values occur in the reduced sediments and highest in oxidised sediments. Values of the $\text{I}\text{C}\text{(× 10}{}^4\text{)}$ ratio of the oxidised sediments (~250) are more than an order of magnitude higher than in reduced sediments, and are similar to some other surface oxidised sediments.The high I content of oxidised sediments is mostly due to uptake of I on to plankton seston on the seabed. In reduced sediments, I contained in planktonic matter originating in surface waters forms the bulk of iodine in the sediment.With sediment burial, oxidised sediments lose most of the iodine through degradation of unspecified organic constituents. This does not happen to the same extent in reduced sediments. The geological implications of these reactions are briefly discussed.