Triterpenols from sediments of Santa Monica Basin, Southern California Bight, U.S.A.

The triterpenol geochemistry of the Santa Monica Basin from the Southern California Borderland, off the U.S.A., is described from the study of two sets of trap deployments, five box cores (≈30 cm) and a hydroplastic core (≈1 m). The biogenic sources and diagenetic stability of the triterpenols are discussed.The 17β(H), 21β(H)-hopanols (22R isomer) occur in the carbon number range from 30 to 32 and their abundance is nearly uniform in the shallow sediment sections. However, the three hopanols follow the order of abundance, C₃₂ > C₃₁ C₃₀, in deeper sections. Their concentrations spans from trace levels to 156 μg/g organic carbon (<15 ng to 7 μg/g dry sediment). Tetrahymanol (gammaceran-3β-ol) has been identified in all the samples except in one set of trap particles collected at 100 m water depth, from trace level (<1 μg) to 215 μg/g organic carbon (<20 ng to 9 μg/g dry sediment). Diplopterol is also detected in trace amounts in some samples. The triterpenols in the trap material generally increase with the water column depth and decrease with the subbottom depth in the sediment cores.The extended hopanols are either degradation products of polyhydroxybacteriohopanes or are biosynthesized by bacteria. Tetrahymanol is probably the only suggested biological precursor of gammacerane (the reduced counterpart of tetrahymanol), which has been recognized in numerous crude oils and lithified sediments. Although it has been reported earlier from Green River Shale and from a residual Pleistocene lake sediment, tetrahymanol has so far been positively identified from recent marine sediments only in two recent studies. The decreasing content of tetrahymanol in sedimentary depth profiles in the Santa Monica Basin would favor an origin for this compound in the water column or at the sediment surface. The ubiquitous occurrence of this compound throughout the study area suggests that this triterpenol most probably originates from primitive organisms (protozoa, bacteria?), hitherto not identified or, more likely, not yet analyzed for their lipid composition.     

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.     

Mono- and dicyclic unsaturated triterpenoid hydrocarbons in sediments from Lake Masoko (Tanzania) widely extend the botryococcene family

A mixture of C₃₃–C₃₇ botryococcenes and partially reduced derivatives was isolated from ca. 32,000 year old sediment from Lake Masoko, a freshwater crater lake in the Rungwe Range area (Tanzania). Botryococcenes and derivatives accounted for 246 μg/g dry sediment and for >92% of the hydrocarbon fraction; 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry allowed the structure of the dominant botryococcene (43% of hydrocarbon fraction) to be established, after purification using high performance liquid chromatography (HPLC). The compound is a novel tetraunsaturated dicyclic C₃₄ botryococcene and is named C₃₄ masokocene. Overall, the structures of six other novel botryococcenes and four partially reduced derivatives were tentatively assigned. The structures of the new biomarkers, three dicyclic C₃₄–C₃₆ botryococcenes (or masokocenes) and seven monocyclic C₃₄–C₃₇ analogues are discussed along with their biosynthetic relationship. The high abundance of such polyunsaturated compounds preserved in 32,000 year old sediment from the lake indicates an aquatic ecosystem dominated at the time by the green alga Botryococcus braunii, as well very good preservation of the organic matter.     

Marine and terrigenous lipids in coastal sediments from the Peru upwelling region at 15°S: Sterols and triterpene alcohols

The distributions of free 4-desmethyl sterols in sediments from the Peru coastal zone at 15°S have been determined. Major free sterols in the surface sediments include cholesterol, which is mainly derived from zooplankton, and two C₂₈ sterols: 24-methylcholesta-5,24(28)-dien-3β-ol and 24-methylcholesta-5,22E-dien-3β-ol both of which are derived fro diatoms. Their concentrations decrease by almost an order of magnitude in the top 20 cm of sediment depth, indicating that free sterols are rapidly degraded in this sedimentary environment. Lipids from higher plants were also detected: long chain fatty acids and alcohols and various triterpenoid alcohols, including taraxerol, lupeol and α- and β-amyrin. The concentrations of most terrigenous lipids varied by less than a factor of 3 over the same depth, and these changes were not correlated with changes in the concentrations of total organic carbon. Below 3 cm, lipids from higher plants predominated in the extractable lipid distributions due to the more rapid degradation of marine lipids. We postulate that there are significant marine sources of the higher plant sterols 24-ethylcholesterol, 24-ethylcholesta-5,22E-dien-3β-ol and 24-methylcholesterol in these sediments. A high proportion of many of the terrigenous lipids in these sediments are probably transported into the coastal zone by rivers, rather than from the atmosphere, and then redistributed by bottom currents.     

The effects of surface area, grain size and mineralogy on organic matter sedimentation and preservation across the modern Squamish Delta, British Columbia: the potential role of sediment surface area in the formation of petroleum source rocks

Surface sediment samples were collected from the Squamish River Delta, British Columbia, in order to determine the role of sediment surface area in the preservation of organic matter (OM) in a paralic sedimentary environment. The Squamish Delta is an actively prograding delta, located at the head of Howe Sound.Bulk total organic carbon (TOC) values across the Squamish Delta are low, ranging from 0.1 to 1.0 wt.%. The carbon/total nitrogen ratio (C_org/N) ranges from 6 to 17, which is attributed to changes in OM type and facies variations. The <25-μm fraction has TOC concentrations up to 2.0 wt.%, and a C_org/N ratio that ranges from 14 to 16. The 53–106-μm fraction has higher TOC concentrations and C_org/N ratios relative to the 25–53-μm fraction. The C_org/N ratio ranges from 9 to 18 in the 53–106-μm fraction and 5.5–10.5 in the 25–53-μm fraction. Surface area values for bulk sediments are low (0.5–3.0 m²/g) due to the large proportion of silt size material. Good correlation between surface area and TOC in bulk samples suggests that OM is adsorbed to mineral surfaces. Similar relationships between surface area and TOC were observed in size-fractionated samples. Mineralogy and elemental composition did not correlate with TOC concentration.The relationships between surface area, TOC and total nitrogen (TN) can be linked to the hydrodynamic and sedimentological conditions of the Squamish Delta. As a result, the Squamish Delta is a useful modern analogue for the formation of petroleum source rocks in ancient deltaic environments, where TOC concentrations are often significantly lower than those in source rocks formed in other geological settings.     

Distribution of copper, zinc, lead and cadmium concentrations in stream sediments from the Mapocho River in Santiago, Chile

The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S₁ to S₆) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D₁, autumn); August 2001 (D₂, winter); October 2001 (D₃, spring) and January 2002 (D₄, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g^− 1) were found in the northern part of the river (S₁, average D₁–D₄), near the mountains and a copper mine, and then decreased downstream to 209 μg g^− 1 (S₆). Total Zn showed an irregular variation, with higher values at S₁ (1290 μg g^− 1) and high values in some winter sampling (1384 μg g^− 1 S₄, S₅–D₂). Pb showed different trends, increasing from S₁ to S₆ (17 to 61 μg g^− 1), with the highest values in the summer samples (83 μg g^− 1, S₄–S₆, D₄), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g^− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D₁–D₄). The highest values of total organic matter, carbonate and conductivity were found in S₆, which has the smallest size particles, while at S₁ the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g^− 1, S₁) to 16% (32 μg g^− 1, S₆); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S₁) to 34% (S₆), but copper content was lower (214 to 68 μg g^− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g^− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g^− 1, S₁ to S₆). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S₁ were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g^− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S₆ the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g^− 1, respectively).     

Identification of Cu and Ni indicator plants from mineralised locations in Botswana

Plant species that accumulate high levels of metals in proportion to the metal content in the soil are of considerable interest in biogeochemical and biogeobotanical prospecting. This study was aimed at investigating copper and nickel accumulation in the plants Helichrysum candolleanum and Blepharis diversispina, to assess their potential use as mineral indicators in biogeochemical prospecting. Soils and plants were collected from copper–nickel mineralised areas in Botswana. Analyses of the soils and the respective plant parts (roots, stem, leaves and flowers) were carried out using ultrasonic slurry sampling electrothermal atomic absorption spectrometry (ETAAS), which allowed rapid determination of copper and nickel in small amounts of the samples.The metal concentration in the soil was in the range ≈ 40 μg/g–4% (w/w) for Cu and ≈ 60 μg/g–0.3% (w/w) for Ni. The concentration ranges of the elements in the plant parts were ≈ 6 μg/g–0.2% Cu and ≈ 3–210 μg/g Ni. At high soil metal content (greater than 2.5% (w/w) Cu and 0.1% (w/w) Ni), high levels of both nickel and copper were found in the shoots (leaves and flowers) of H. candolleanum. Concentrations as high as 0.2% (w/w) Cu were found in the leaves and flowers of H. candolleanum, indicating hyperaccumulation for this plant. For B. diversispina, the metal concentrations did not exceed 100 μg/g for any plant part, for both metals. Both plant species tolerate high concentrations of metals and should therefore be categorized as metallophytes. In order to evaluate metal translocation from the soil to the shoots, metal leaf transfer coefficients (ratio of metal concentration in the leaf to metal concentration in the soil) were calculated. Our data suggest that the two plant species have different metal uptake and transport mechanisms, which needs to be investigated further. The present work also suggests that H. candolleanum may be used as a copper/nickel indicator plant in biogeochemical or biogeobotanical prospecting.     

青海湖沉积物中的甾醇及其演化

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

The use of model compounds to investigate the release of covalently bound biomarkers via hydropyrolysis

This study describes the reduction of functionalised model compounds to their corresponding hydrocarbons by catalytic hydropyrolysis to provide information on the release of biomarkers from kerogens and asphaltenes covalently bound through the functional groups investigated. Five model compounds were investigated, the n-C₁₈ carboxylic acids, stearic and oleic acids; the C₂₄ steroidal acid, 5β-cholanic acid; and the saturated and unsaturated C₂₇ sterols, 5α-cholestanol and cholesterol. The yield and distribution of the hydrocarbons generated were assessed for the model compounds adsorbed to silica and carbon substrates, and unsupported on a bed of catalyst. The n-C₁₈ acids are shown to be reduced to the n-C₁₈ alkane, with a selectivity of >95% for stearic acid, although due to its unsaturated structure, oleic acid is prone to cracking, with shorter chained n-alkanes also being formed. The conversion of these compounds, adsorbed to either silica or carbon is relatively low, even at hydropyrolysis temperatures significantly above their boiling point, suggesting that interactions between the acids and substrate leading to the formation of stable entities (Si–O–C linkages in the case of silica) significantly retard volatilisation. The yield can be increased by placing the compounds directly onto a bed of catalyst, but for low boiling compounds such as stearic acid this can result in volatilisation and cracking at temperatures below that of the activation point of the catalyst. This method produced improved yields of >95% pure product for higher boiling compounds such as 5β-cholanic acid. The presence of the functional group attached to the ring system of compounds such as 5α-cholestanol does not diminish the selectivity of the technique. The double bond in cholesterol resulted in more incomplete hydrogenation with sterenes being generated, and in addition to 5α and 5β-cholestane, diasteranes were also generated via migration of the double bond.     

Sources of neutral lipids in a temperate intertidal sediment

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

Bacterial and algal hydrocarbons in sediments from a saline Antarctic lake, Ace Lake

Capillary gas chromatography-mass spectrometry (C-GC-MS) and Iatroscan thin layer chromatography-flame ionisation detection (TLC-FID) were used to study hydrocarbon distributions in a sediment core from Ace Lake, a saline, meromictic lake in the Vestfold Hills of Antarctica. Hydrocarbons were abundant in most core sections (up to 125/μg/g dry wt), particularly in near-surface samples, and the distributions were very complex. Major constituents were identified as phytane, 2,6,10,15,19-pentamethyleicosane, tetrahydrosqualene, a mixture of phytenes, cholesta-3,5-diene and fern-7-ene. Smaller amounts of sterenes and hopenes were also present. The predominance of the first 3 acyclic isoprenoids in sediments buried less than 30 cm is consistent with high populations of methanogenic bacteria known to be present.Phytenes were abundant in all core sections, and there was no relationship between their abundance and that of phytane which suggests that they were not derived from methanogenic bacteria. Phytadienes were minor constituents at all depths studied. An unusual feature of some distributions was the high concentrations of fern-7-ene which was the major hydrocarbon in the 20–25 cm core section. This alkene was only abundant in sediments which contained high concentrations of methanogen markers suggesting that it may also be indicative of anoxic depositional environments. A possible source might be from purple non-sulphur bacteria. High concentrations of straight-chain C₂₉ and C₃₄ alkenes were also found in these sediments but their origin has not been determined. Major changes in the hydrocarbon distributions with depth indicate that the depositional environment in the lake has altered dramatically since the lake was formed less than 8000 years ago. The present condition of permanent anoxic bottom waters probably developed only in the last 1000 years.     

Nature of sedimentary organic matter in the lower reaches of the Godavari River basin, India

The distribution and nature of sedimentary organic matter (OM) have been examined in sediment cores collected from the lower reaches, including estuary, of the Godavari River in order to understand sedimentation patterns, sources, and diagenesis of OM. The samples were analyzed for organic carbon (Corg), total nitrogen, amino acids and hexosamines. The observed irregular trends in Corg distribution with depth indicate the unstable nature of bed sediment in the lower reaches of the river. Yet, in the lower estuarine region, regular trends in Corg distribution with depth reflect the deposition of sediment. The atomic ratio of Corg and total nitrogen (C/N; 10.5–16.1) also supported this observation. The distribution of amino acids and diagenetic indicators (β-ala+γ-aba mol.%, AA/HA and Glc-NH₂/Gal-NH₂) in individual cores revealed the post-depositional changes in the OM. In the core sediment from the lower reaches, there was no clear cut trend in amino acid content with depth. In the estuarine region, however, amino acid content was very low (50.5 and 186.5 μg g⁻¹) in the upper layers compared to that in the lower layers (558.5 and 1099.3 μg g⁻¹). Reactivity index (range 0.3–3.7) revealed that OM in the upper few centimeters, especially in the lower estuarine region, was more reactive relative to that in the deeper layers.     

A natural pyrolysis experiment — hopanes from hopanoic acids?

The formation or generation of hopanes are important processes during both the natural heating of organic-rich sediments and laboratory pyrolysis experiments. Molecular maturity parameters as well as the amounts (ng/g rock) of the C₃₁ hopanes and C₃₀–C₃₂ hopanoic acids were quantified in a Jurassic silty shale horizon (Isle of Skye, Scotland) as a function of distance from an igneous intrusion. The maturity profiles of the homohopanes and the hopanoic acids are comparable. There is also a correlation between the decreasing amounts of C₃₀–C₃₂ hopanoic acids and concomitant increases in C₂₉–C₃₁ hopanes suggesting that free hopanoic acids could be one potential source of hopanes in this particular horizon. Other possible sources could include hopanoic acids that are bound into the macromolecular fraction.     

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.     

Early diagenesis of phytyl esters in a contemporary temperate intertidal sediment

Analysis of a sediment core for hydrolysed chlorins (acidic chlorins e.g. pheophorbide a) and non-acidic chlorins, and free, bound and esterified alcohols have been performed and the results have been interpreted in terms of input and sedimentary interconversions. There is an association of the acidic chlorin input with an input of unesterified aliphatic n-alkanols (> C₂₀), and subsequent degradation of the chlorins with depth. Input of phytol to the anoxic region of the sediment is not associated with the n-alkanols:phytol in the sediment is derived largely from chlorophyll-a input to the surface layers as intact microalgae. Degradation with depth involves conversion of the chlorophyll-a to non-chlorin, colourless phytyl esters prior to incorporation of the phytol into a bound fraction. At depth this bound phytol is hydrolysed resulting in release of free phytol.     

Mineralogy and geochemistry of boehmite-rich coals: New insights from the Haerwusu Surface Mine, Jungar Coalfield, Inner Mongolia, China

Boehmite-rich coal of Pennsylvanian age was discovered earlier at the Heidaigou Surface Mine, Jungar Coalfield, Inner Mongolia, China. This paper reports new results on 29 bench samples of the no. 6 coal from a drill core from the adjacent Haerwusu Surface Mine, and provides new insights into the origin of the minerals and elements present. The results show that the proportion of inertinite in the no. 6 coal is higher than in other Late Paleozoic coals in northern China. Based on mineral proportions (boehmite to kaolinite ratio) and major element concentrations in the coal benches of the drill core, the no. 6 coal may be divided into five sections (I to V). Major minerals in Sections I and V are kaolinite. Sections II and IV are mainly kaolinite with a trace of boehmite, and Section III is high in boehmite. The boehmite is derived from bauxite in the weathered surface (Benxi Formation) in the sediment-source region. The no. 6 coal is rich in Al₂O₃ (8.89%), TiO₂ (0.47%), Li (116 μg/g), F (286 μg/g), Ga (18 μg/g), Se (6.1 μg/g), Sr (350 μg/g), Zr (268 μg/g), REEs (172 μg/g), Pb (30 μg/g), and Th (17 μg/g). The elements are classified into five associations by cluster analysis, i.e. Groups A, B, C, D, and E. Group A (ash–SiO₂–Al₂O₃–Na₂O–Li) and Group B (REE–Sc–In–Y–K₂O–Rb–Zr–Hf–Cs–U–P₂O₅–Sr–Ba–Ge) are strongly correlated with ash yield and mainly have an inorganic affinity. The elements that are negatively or less strongly correlated with ash yield (with exceptions of Fe₂O₃, Be, V, and Ni) are grouped in the remaining three associations: Group C, Se–Pb–Hg–Th–TiO₂–Bi–Nb–Ta–Cd–Sn; Group D, Co–Mo–Tl–Be–Ni–Sb–MgO–Re–Ga–W–Zn–V–Cr–F–Cu; and Group E, S–As–CaO–MnO–Fe₂O₃. Aluminum is mainly distributed in boehmite, followed by kaolinite. The high correlation coefficients of the Li–ash, Li–Al₂O₃, and Li–SiO₂ pairs indicate that Li is related to the aluminosilicates in the coal. The boehmite-rich coal is high in gallium and F, which occur in boehmite and the organic matter. Selenium and Pb are mainly in epigenetic clausthalite fillings in fractures. The abundant rare earth elements in the coal benches were supplied from two sources: the bauxite on the weathered surface of the Benxi Formation and from adjacent partings by groundwater leaching during diagenesis. The light rare earth elements (LREEs) are more easily leached from the partings and incorporated into the organic matter than the heavy REEs, leading to a higher ratio of LREEs to HREEs in the coal benches than in the overlying partings.     

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.     

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.     

Relationships between hydrodynamic parameters and grain size in two contrasting transitional environments: The Lagoons of Venice and Cabras, Italy

A comparison was made of shallow water sediments from the Lagoon of Venice (LV) and the Lagoon of Cabras (LC), comparing depositional environments and exploring the relationships between hydrodynamics and sedimentological parameters. The two water bodies are very different in size (LV: 360 km²; LC: 22 km²), and the sediments predominantly consist of silty-clay (LV: Mz ≈ 26 μm; LC: Mz ≈ 6 μm). However, there are large differences between the two lagoons with respect to sand (LV: mean 19%; LC: mean ~ 3%) and clay (LV: mean 20%; LC: mean 45%) contents. The Lagoon of Venice (mean depth ~ 1 m) can be considered a tidal basin, whereas the Lagoon of Cabras (mean depth ~ 2 m) has the character of a coastal lake in which wind is the main hydrodynamic forcing factor. A comparison of sediment grain-size distributions with water circulation patterns in different parts of the lagoons highlighted some interesting differences. Grain-size analyses of samples reveal a deficiency of particles around 8 μm in the LC, which is interpreted as reflecting the transition between cohesive flocs/aggregates and non-cohesive coarser silt particles, while the transition limit in the LV is ~ 20 μm. Thus, particles are cohesive below 8 μm in the LC and below ~ 20 μm in the LV. This is probably because of the differences in the clay/silt ratio, which is much lower in the LV (~ 0.3) than in LC (~ 1), conferring a “silt-dominated network structure” on most of the LV sediments.The hydrographical data used were root mean square velocity (RMSV) and water residence time (WRT), computed under the main forcing conditions. The results show a general correlation between RMSV and sortable silt in the LC, and between RMSV and coarser sediments (63–105 μm) in the LV. Some significant differences between the lagoons were detected in the degree of correlation between WRT and grain size. Root mean square velocity (~ 7 cm s^− 1 in the LV and ~ 3 cm s^− 1 in the LC) was a greater forcing factor in the LC than in the LV. Conversely, WRT, which is on average ~ 16 days in the LV and ~ 19 days in the LC, has more influence in the LV. This study highlights the usefulness of comparing environments with different hydrodynamic energies, e.g., tidal and/or wind-driven currents, to elucidate and thereby improve our understanding of the processes governing the spatial distribution of sedimentological features, the transport mechanisms of sediments, and the relationship between them. The results demonstrate that the approach outlined in this study has the potential to provide a universal hydro-sedimentological classification scheme.     

Algal pigments in sediments as a measure of eutrophication in the Baltic environment

A method of quantitative comparison of eutrophication of an area is proposed for the Baltic Sea, based on pigment content in sediments. The pigments concerned were chlorins a (i.e. chlorophylls a, b and selected chlorophyll a derivatives) and chlorophylls c. The analyses were performed on 300 samples from different layers of recent (0–10 cm) sediments, collected from about 50 stations, at different sites of the southern Baltic, including the estuaries of the two largest Polish rivers, in different seasons between 1992 and 2001, before and after the great flood of July 1997. The results are related to sampling site, sediment layer and hydrological conditions and also to organic carbon and E_h in sediments, oxygen and salinity in near-bottom waters. Depending on different chlorin a content in 0–1 and 0–10 cm layers, the sampling sites are classified into one of three groups: 1. Szczecin Lagoon and the Deep of Gda sk stations (permanently eutrophic, chl a in 0–1 cm >40 nmol/g, Σchlns a in 0–1 in 0–10 cm layer, Σchlns a_A in Σchlns a=55–65%), 2. Open sea stations (mesotrophic/oligotrophic, chl a in 0–1 cm <10 nmol/g, Σchlns a in 0–1 in 0–10 cm layer, Σchlns a_A in Σchlns a 50%; and 3. Coastal stations (periodically eutrophic, chl a in 0–1 cm 10–40 nmol/g, Σchlns a_A in Σchlns a 40%). The correlation coefficient between chlorophyll a and chlorophylls b and c indicates the classes of algae, which could be the main source of organic matter in the sediments. A high correlation with chlorophylls c is a marker of diatoms; a high correlation with chlorophyll b is a marker of green algae; and low correlation both with chlorophylls b and c—indicates a high blue–green algae input.