江西九江红土生物标志化合物的分布特征及其古气候环境意义

为了探求江西九江红土地层中所记录的古气候环境信息,论文在对江西九江红土剖面的野外地貌、岩性和相关沉积环境调查分析基础上,利用气相色谱-质谱联用仪对正构烷烃、一元正脂肪酸等生物标志化合物进行了研究,着重分析了正构烷烃和一元正脂肪酸的来源及其碳数分布特征。结果显示:江西九江红土剖面上部均质红土中正构烷烃的CPI、∑C_(21)~–/∑C_(22)~+及一元正脂肪酸的CPI_L值均大于其下部的网纹红土,且波动较为明显,表明网纹红土的形成气候比其上的均质红土形成时期气候暖湿,反映了中更新世中期(600～300kaBP)的极端暖湿期;正构烷烃的∑C_(21)~–/∑C_(22)~+、(C_(15)+C_(17)+C_(19))/(C_(27)+C_(29)+C_(31))、(C_(16)+C_(17)+C_(18))/(C_(29)+C_(31)+C_(33))、C_(17)/C_(31)在剖面上表现出一致的旋回性变化,反应了江西九江中更新世以来气候的冷暖旋回变化。结果表明红土地层中的生物标志化合物具有很好的古气候环境意义。     

东营凹陷古近系升藿烷生物标志物参数分布及演变规律

为研究实际地质体或地质剖面中的C31到C3517α(H), 21β(H)升藿烷生物标志物构型转化参数22S/(22S+22R)及升藿烷指数C35/∑（C31—C35)等的分布、演化特征,对东营凹陷主要烃源岩层系古近系沙河街组三段（淡水—微咸水层系）和沙河街组四段（咸水层系）的系列样品进行了研究,分析样品来源于1 300~4 000的暗色泥岩,其中2 800~4 000 m的样品对应于东营凹陷古近系烃源岩的生油初期到生油晚期。研究结果表明,C31、C32、C33、C34、C35升藿烷（17α(H), 21β(H)）构型转化参数的分布除与异构体之间的手性碳立体构型转化作用有关外,不同异构体之间降解或裂解速率和新生成速率的差异也是其主要控制因素,沉积环境（如高盐环境）也在一定程度上影响了其分布;从未熟—低熟状态到成熟状态,相关升藿烷构型转化参数22S/(22S+22R)总体均表现出随埋藏深度增大而加大的特点,并从离散状态聚集到热演化的平衡状态附近;在到达成熟状态后,相关升藿烷的构型转化参数22S/(22S+22R)从缓慢增大过渡到一个持续的热演化平衡状态,并且该构型转化参数的热演化平衡状态对应于生油门限附近;在高盐环境中除C33升藿烷保持不变的热演化平衡状态外,其它升藿烷均呈现不同幅度的逆转特征,表明高含量的盐类矿物对升藿烷成熟度参数亦具有抑制作用或迟缓效应;C31、C32、C33、C34、C3517α升藿烷之间的22S/(22S+22R)分布型式复杂多变,其中对于成熟源岩样品,C35升藿烷22S/(22S+22R)值变化强烈,表现出“翘尾”状的上升型特征和“坠尾”状的下降型特征,而对于低熟—未熟样品, C32升藿烷的22S/(22S+22R)显示相对高值,并且多数样品显示为C31C33C35的偶数碳优势的特征;研究显示C31到C33升藿烷的构型转化参数S/(S+R)热演化平衡值均为0.6,而C34 S/(S+R)及C35S/(S+R)热演化平衡值相对较高,沙三段、沙四段的C34 S/(S+R)及沙四段的C35S/(S+R)分别达到0.63、0.62、0.65;升藿烷指数C35/∑（C31—C35)受热演化影响也比较明显,在生油期间随着埋藏深度增加而减小,在高盐环境中表现出相对高值,研究表明该指数的变化与其22R异构体演化有关,并且参数C31/∑（C31—C35）、C32/∑（C31—C35）、C33/∑（C31—C35）、C34/∑（C31—C35）、C35/∑（C31—C35)演化特征截然不同。     

The ecological implications of a Yakutian mammoth's last meal

Part of a large male woolly mammoth (Mammuthus primigenius) was preserved in permafrost in northern Yakutia. It was radiocarbon dated to ca. 18,500 ¹⁴C yr BP (ca. 22,500 cal yr BP). Dung from the lower intestine was subjected to a multiproxy array of microscopic, chemical, and molecular techniques to reconstruct the diet, the season of death, and the paleoenvironment. Pollen and plant macro-remains showed that grasses and sedges were the main food, with considerable amounts of dwarf willow twigs and a variety of herbs and mosses. Analyses of 110-bp fragments of the plastid rbcL gene amplified from DNA and of organic compounds supplemented the microscopic identifications. Fruit-bodies of dung-inhabiting Ascomycete fungi which develop after at least one week of exposure to air were found inside the intestine. Therefore the mammoth had eaten dung. It was probably mammoth dung as no bile acids were detected among the fecal biomarkers analysed. The plant assemblage and the presence of the first spring vessels of terminal tree-rings of dwarf willows indicated that the animal died in early spring. The mammoth lived in extensive cold treeless grassland vegetation interspersed with wetter, more productive meadows. The study demonstrated the paleoecological potential of several biochemical analytical techniques.     

Sesquiterpenoids in sediments of a hypersaline lagoon: A possible algal origin

Core samples were collected in Lagoa Vermelha, a hypersaline lagoon located about 100 km east of Rio de Janeiro (Brazil). The sediment composition is predominantly carbonate in amounts up to 93%. Analysis of δ¹³C of the total organic matter in the sediments showed that marine organic matter predominates throughout the core (δ¹³C ranges from −15.84 to −22.64‰ vs. PDB). Organic carbon contents (TOC) ranged from 0.81 to 13.28%. A series of cadinane-type sesquiterpenoids can be recognized in the gas chromatography-mass spectrometry data. Essentially the same components are present in all the samples, with variations only in their relative abundances. The most abundant compounds are α- and β-cubebene, α- and β-cedrene, cadinenes (different isomers), α-curcumene and calamenene, with minor amounts of calarene, humulene, calacorene and cadalene. Since this lagoon is surrounded by dunes with only minor vegetation typical of this environment (grasses, small non-resinous shrubs and no forest) with no potential source for sesquiterpenoids, a terrestrial origin for these compounds is excluded and an algal origin is more consistent with the locale and the recognition of sesquiterpenoids (including cadinol) in microbial mats from the lagoon. Only the natural product precursor sesquiterpenoids are present in the microbial mats with no detectable diagenetic derivatives (e.g. calamenene and cadalene). This indicates that the compounds in the mats are from recent input and those found in the sediments are most likely derived from former algal biomass in this lagoon, a fact confirmed by the recognition of a series of diagenetic aromatic components in the sediments. Surface sediments contain n-alkanes with no even-to-odd predominance indicating that microbial activity is higher in shallower sediments. Moreover, mass fragmentograms (m/z 191) of biomarkers revealed the presence of 17α(H),21β(H)-hopanes, the mature isomers, together with their ββ precursors and low amounts of the intermediates with the βα configuration (moretanes). This indicates a contribution of mature organic matter to these immature sediments.     

Geochemistry of shallow sediments in Guaymas Basin, gulf of California: hydrothermal gas and oil migration and effects of mineralogy

Offset of prograde hydrothermal alterations by retrograde reactions is evident in sediments from a piston core (PC6, 8 m long) from the Guaymas Basin, Gulf of California. Geochemical and mineralogical analyses of sediments and pore fluids show superimposed geochemical signals that indicate currently active reactions are modifying previously formed secondary solids. Hydrothermal barite was formed in a previously active flow channel between 150 and 250 cm depth. Hydrothermal gypsum is presently dissolving at depths > 780 cm, below which hydrothermal fluid flow is channeled by a secondary dolomite layer. Thermal stress of organic matter generates hydrothermal gas and petroleum having wide ranges of compositions and maturities. A significant amount of hydrothermally generated oil has been transported laterally through a porous debris flow (approx. 240 cm subbottom), overwhelming the indigenous bituminous matter. Water soluble petroleum constituents have disseminated throughout the cored sediments. From 400 to 700 cm depth the immature organic matter continues to experience thermally-enhanced diagenesis, and an even higher thermal stress has occurred at the bottom of the core. Enhanced bacterial degradation of organic matter has led to depletion of pore water sulfate and enrichment of ammonium (NH₄⁺) in both pore fluid and sediment, resulting in formation of NH₄⁺ bearing secondary clay minerals at depths below 780 cm.     

Structural investigations of sulphur-rich macromolecular oil fractions and a kerogen by sequential chemical degradation

Structural studies of a sulphur-rich kerogen and macromolecular oil fractions from the Monterey Formation were performed by selective sequential chemical degradation. The method provides low-molecular weight compounds as former building blocks of the network which allow detailed analyses on a molecular level. The degradation sequence is based on three subsequently performed reactions—a selective cleavage of sulphur bonds in the first step carried out with Ni(0)cene/LiAlD₄, an ether and ester bond cleavage (BCl₃), and an oxidation of aromatic entities by ruthenium tetroxide as a final step. Each step of this sequence afforded a considerable amount of low-molecular weight material which was separated chromatographically and studied by GC and GC/MS, while the high-molecular weight or insoluble fractions were subjected to the next reaction step.The chemical degradation products—hydrocarbons and carboxylic acids—are discussed in terms of incorporation into the macromolecular structure, distribution of heteroatomic bridges and the genetic relationships between the different macromolecular crude oil fractions and kerogen.Labelling experiments with deuterium provided evidence for a simultaneous linkage by oxygen and sulphur functionalities or by aromatic units and sulphur bonds of cross-linking macromolecular network constituents.The determination of sulphur positions in the macromolecule suggests early diagenetic sulphur incorporation into the biological precursor compounds and subsequent formation of a cross-linked network.     

An application of Iatroscan thin-layer chromatography with flame ionization detection—lipid classes of microorganisms as biomarkers in the marine environment

Iatroscan TLC-FID combines the separatory capabilities of thin-layer chromatography (TLC) (on silica coated chromarods) with the possibility of quantitation by flame ionization detection (FID). It can be used to separate lipid extracts into classes of compounds ranging from neutral to polar products. The rapidity with which this system provides lipid class profiles from small samples makes it particularly useful in oceanographic studies where routine analyses of large numbers of samples are required. Lipid classes were analysed in 4 marine bacterial strains grown on various substrates and 10 microalgae isolated from the marine environment and grown in batch cultures. Data on lipid composition of these microorganisms were obtained and compared to literature data. Results show that ratios between classes of compounds within the different groups of microorganisms were characteristic enough to constitute a good print of bacterial or phytoplankton sources in organic matter in sea water. In a preliminary study, phospholipid classes from a bacterial strain and a microalga were separated. Results show that the determination of ratios between phospholipid classes in organic matter could represent an improvement in the utilization of lipid classes as biomarkers.     

Assessment of toxicological status of a SW Mediterranean segment population of striped dolphin (Stenella coeruleoalba) using skin biopsy

Various studies have revealed high concentrations of contaminants such as organochlorines (OCs) and heavy metals in Mediterranean cetaceans. A geographical trend of contamination (PCBs and DDTs) has been found for striped dolphin (Stenella coeruleoalba). In this study we used a non-lethal approach (skin biopsy) to investigate bioaccumulation of OCs, including polychlorobiphenyls (PCBs), DDTs, polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), trace elements (Hg, Cd, Pb) and CYP1A activity (BPMO) in nine striped dolphins sampled in the Aeolian area (Sicily – Italy) in summer 2002. The arithmetic mean value of BPMO activity in this group was 43.46 AUF/g tissue/h. This value is approximately 3 times and 5 times lower, respectively, than the value found in the Ionian and in the Ligurian groups. Skin biopsies of striped dolphins emerged as a suitable material for assessing the toxicological status of the various Mediterranean groups.     

Lipid biomarkers of deep-sea hydrothermal vent polychaetes—Alvinella pompejana, A. caudata, Paralvinella grasslei and Hesiolyra bergii

The lipid composition was determined for 5 species of polychaete annelids collected by the Deep Submergence Vehicle ALVIN from high temperature chimneys at the 2500 m depth hydrothermal vent field of the East Pacific Rise. These are the first lipid biomarker analyses reported for these hydrothermal vent polychaetes. Lipid content was low in all samples (1.6–35.9 mg g^–1 wet mass) and was dominated by polar lipid (78–90% of total lipid) with 8–19% sterol (ST), and very low storage lipid (triacylglycerol and wax ester). Total polyunsaturated fatty acids (PUFA) were moderately high (22–31% of total fatty acids (FA)) with extremely low or no docosahexaenoic acid (DHA, 22:6(n-3)). Eicosapentaenoic acid (EPA, 20:5(n-3)) levels were 5–6% in Alvinella pompejana and A. caudata and 10.3–13.7% in an errantiate polychaete (likely Hesionidae) and Hesiolyra bergii. There were greater PUFA and a greater EPA/AA (AA is arachidonic acid, 20:4(n-6)) ratio in the anterior versus the posterior half of A. pompejana, which may correlate to the strong temperature gradient reported in its tube. Total nonmethylene interrupted diunsaturated fatty acids (NMID) were 4–9% of total FA for most polychaete species and included several 20:2 and 22:2 components. The principal monounsaturated fatty acids (MUFA) included 18:1(n-7)c (14–19%), 16:1(n-7)c (2.6–10%) and 20:1(n-11)c (3–7% of total FA). These polychaete species may desaturate and elongate the bacterial-derived 18:1(n-7)c to obtain the essential FA EPA and AA. The major ST in the polychaetes is cholesterol (89–98% of total ST) with less cholesterol in the gut contents of A. pompejana. Other ST included 24-ethylcholesterol (1.5–5% of total ST) with lesser amounts of 24-methylenecholesterol, desmosterol, lathosterol, 24-methylcholesterol, 24-ethylcholesterol, and the stanols dehydrocholestanol and cholestanol. The high ST levels could play a role in thermal adaptation of membranes at the hydrothermal vent environment. Differences in the FA profiles separated the closely related species A. pompejana and A. caudata from Paralvinella grasslei, H. bergii, and the errantiate polychaete (likely Hesionidae).     

Potential Use of Biomarkers in Zooplankton as Early Warning Signals of Ecotoxicological Risk in the Marine Food Chain

Abstract. Zooplankton is an essential component of the marine and brackish food chains. The ecotoxicological risk of zooplanktonic communities, estimated by the modern methodological approach of biomarkers, can be used as an early warning signal of ecosystem health. The aim of this project is to estimate the potential use of several biomarkers (esterases, mixed function oxidases, porphyrins) in zooplanktonic organisms. Studies were carried out with different zooplanktonic crustaceans: the copepods Acartia margalefi and Acartia latisetosa collected in Ganzirri Lake (Messina); the mysid Siriella clausi collected in Faro Lake (Messina); the mysids Diamysis bahirensis, Siriella armata and Mysidopsis gibbosa collected in Stagnone di Marsala (Palermo); the Antarctic euphausiids Euphausia crystallorophias and Euphausia superba; the am-phipod Streetsia challengeri and the euphausiid Meganycthiphanes norvegica collected after a shore-stranding along Messina's Ionian coast. Moreover, experiments were carried out with the benthic decapods Eriphia verrucosa and Pachygrapsus marmoratus from a rocky shore of Messina's Ionian coast. Acetylcholinesterase activity (AChE) was determined in homogenates of whole organisms. The key result of this project concerns the different AChE activity basal values of different crustacean species. Particular attention should be paid to the difference in basal activity found between the Antarctic and the Mediterranean species.