A molecular and carbon isotopic study towards the origin and diagenetic fate of diaromatic carotenoids

Pyrolysates of high-molecular-weight sedimentary fractions of the Duvernay Formation (Western Canada Basin) are dominated by 1,2,3,4- and 1,2,3,5-tetramethylbenzene, which, generated via beta-cleavage, indicate the presence of diaromatic carotenoids in the macromolecular aggregates. This was substantiated by desulphurization of sulphur-rich aggregates of the polar fraction, which released (partly) hydrogenated carotenoids. Furthermore, these components were important constituents of the aromatic hydrocarbon fractions and related oils. Apart from renieratane and isorenieratane, 1H NMR analysis established the aromatic substitution pattern of the most abundant component present, which was identified as a diaromatic compound with an unprecedented 2,3,6-/3,4,5-trimethyl aromatic substitution pattern. Molecular and isotopic analyses of both soluble and insoluble fractions of organic matter revealed relationships between diagenetically-derived carotenoids found in bitumen and related oils and their precursors incorporated into high-molecular-weight fractions. Aryl isoprenoids, important components in extracts and oils, were apparently derived from thermal cracking of bound diaromatic carotenoids rather than cleavage of free carotenoids as previously suggested. Furthermore, products derived from diaromatic carotenoids were substantially enriched in 13C relative to n-alkanes of algal origin. Together with the characteristic carotenoids, this isotopic enrichment provides evidence of significant contributions from photosynthetic green sulphur bacteria (Chlorobiaceae), which fix carbon via the reversed tricarboxylic acid (TCA) cycle. In spite of the prominence of these molecular signals, the overall isotopic composition of the organic matter indicated that only a very small portion of the preserved organic carbon was derived from the biomass of photosynthetic green sulphur bacteria.     

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.     

火星的火山作用特征与演化历史

天体的吸集增生和热演化模式支持火星早期演化阶段存在岩浆洋事件,以及火星地壳的形成与岩浆洋事件密切相关的观点.火山作用是火星地质演化历史中热演化过程最直接的表现,它与火星地壳的二分性、全球化学成分的分布及大气的演化过程有直接联系.     

The combined application of organic sulphur and isotope geochemistry to assess multiple sources of palaeobiochemicals with identical carbon skeletons

Five immature sediments from a Messinian evaporitic basin, representing one evaporitic cycle, were studied using molecular organic sulphur and isotope geochemistry. It is shown that a specific carbon skeleton which is present in different "modes of occurrence" ("free" hydrocarbon, alkylthiophene, alkylthiolane, alkyldithiane, alkylthiane, and sulphur-bound in macromolecules) may have different biosynthetic precursors which are possibly derived from different biota. It is demonstrated that the mode of occurrence and the carbon isotopic composition of a sedimentary lipid can be used to "reconstruct" its biochemical precursor. This novel approach of recognition of the suite of palaeobiochemicals present during the time of deposition allows for identification of the biological sources with an unprecedented specificity.     

An isotopic biogeochemical study of the Green River oil shale

Thirty-five different samples from three different sulfur cycles were examined in this stratigraphically oriented study of the Shell 22x-l well (U.S.G.S. C177 core) in the Piceance Basin, Colorado. Carbon isotopic compositions of constituents of Green River bitumens indicate mixing of three main components: products of primary photoautotrophs and their immediate consumers (delta approximately -30% vs PDB), products of methanotrophic bacteria (delta approximately -85%), and products of unknown bacteria (delta approximately -40%). For individual compounds synthesized by primary producers, delta-values ranged from -28 to -32%. 13C contents of individual primary products (beta-carotane, steranes, acyclic isoprenoids, tricyclic triterpenoids) were not closely correlated, suggesting diverse origins for these materials. 13C contents of numerous hopanoids were inversely related to sulfur abundance, indicating that they derived both from methanotrophs and from other bacteria, with abundances of methanotrophs depressed when sulfur was plentiful in the paleoenvironment. gamma-Cerane coeluted with 3 beta(CH3),17 alpha(H),21 beta(H)-hopane, but delta-values could be determined after deconvolution. gamma-Cerane (delta approximately -25%) probably derives from a eukaryotic heterotroph grazing on primary materials, the latter compound (delta approximately -90%) must derive from methanotrophic organisms. 13C contents of n-alkanes in bitumen differed markedly from those of paraffins generated pyrolytically. Isotopic and quantitative relationships suggest that alkanes released by pyrolysis derived from a resistant biopolymer of eukaryotic origin and that this was a dominant constituent of total organic carbon.     

Stream-stage response tests and their joint interpretation with pumping tests

Hydraulic head response to stream-stage variations can be used to explore the hydraulic properties of stream-aquifer systems at a relatively large scale. These stream-stage response tests, also called flooding tests, are typically interpreted using one- or two-dimensional models that assume flow perpendicular to the river. Therefore, they cannot be applied to systems that are both horizontally and vertically heterogeneous. In this work, we use the geostatistical inverse problem to jointly interpret data from stream-stage response and pumping tests. The latter tests provide flow data (which are needed to resolve aquifer diffusivity into transmissivity and storage coefficient) and may supply supplementary small-scale information. Here, we summarize the methodology for the design, execution, and joint numerical interpretation of these tests. Application to the Aznalcóllar case study allows us to demonstrate that the proposed methodology may help in responding to questions such as the continuity of aquitards, the role and continuity of highly permeable paleochannels, or the time evolution of stream-aquifer interaction. These results expand the applicability and scope of stream-stage response tests.     

Spatial and temporal distribution of dissolved/dispersed aromatic hydrocarbons in seawater in the area affected by the Prestige oil spill

Seawater samples collected at three depths from 68 stations along the Northern Spanish coast were analysed for dissolved/dispersed petroleum aromatic hydrocarbons by UV-fluorescence and for 25 individual compounds by GC-MS. Sampling was performed in December 2002, just after the Prestige oil spill, and in February-March and September 2003. Higher concentrations of total aromatic hydrocarbons were found at all depths in the samples collected during December 2002 off the Galicia coast, with levels ranging between 0.19 and 28.8 microg/L eq. oil (0.1-4.8 microg/L chrysene eq.). These values decreased in the following cruises, till <0.05-2.86 microg/L oil eq. (av. 0.23 microg/L chrysene eq.) in September 2003, possibly representing the background levels for the region. However, in the Cantabrian coast they were still high at the surface in the March cruise, probably by the late arrival of the fuel-oil to this area. Some coastal hot spots were also identified, with values up to 29.2 microg/L fuel-oil eq., close to river mouths and urban areas. The individual PAH distributions in the December 2002 sampling off-Galicia were dominated by alkyl-naphthalene derivatives, consistently with the pattern distribution shown by the fuel-oil water accommodated fraction. The higher concentrations were found in the subsurface samples along the Costa da Morte, the area most heavily affected by the spill (av. 0.46 microg/L Sigma16 PAHs). The rest of the samples collected in other areas exhibited lower concentrations and a more even distribution of 2-4 ring PAHs, that ranged from 0.09 to 0.37 microg/L (av. 0.15 microg/L Sigma16 PAHs), with decreasing trends offshore and downward the water column. In September 2003, the values were rather uniform, averaging 0.09 microg/L (Sigma16 PAHs).     

Opportunistic macroalgae metrics for transitional waters. Testing tools to assess ecological quality status in Portugal

Macroalgae communities constitute one of the ecological quality elements for the evaluation of the ecological quality status (EQS) of coastal and transitional waters, required to implement the WFD. While these algae are natural components of estuarine systems and play important roles in several estuarine processes, macroalgal blooms are of ecological concern because they can reduce the habitat quality. Several works are being carried out to set standard methods for monitoring macroalgae blooms, in order to develop tools to derive EQS based upon this biological quality element. The aim of this paper is to apply the methodology described by Scanlan et al. [Scanlan, C.M., Foden, J., Wells, E., Best, M.A., 2007. The monitoring of opportunistic macroalgal blooms for the water framework directive. Marine Pollution Bulletin 55, 162–171] to a series of data assembled in the south arm of the Mondego estuary (Atlantic coast of Portugal) considering two different ecological situations. Additionally, an alternative assessment method intended to be used when no biomass data are available was also tested. In general, both options captured the inter-annual variations in accordance with the system evolution. Option 2, less expensive and time-consuming, allowed an EQS evaluation with accurate results when biomass data were not available. The results suggest that sampling should be carried out from April to June.     

河外射电源变化的观测研究

在本文中评述河外射电源变化的观测进展。首先对几个射电变源的一些专门术语和定义作介绍。然后叙述在整个频谱上各种变化测量的结果，包括流量、频谱和偏振的变化。讨论了ＶＬＢＩ对变化研究的重要影响。简要地触及短时标变化引发的逆康普顿灾变的理论问题，最后，强调指出了多波段同时观测河外射电源在深入了解活动星系核方面的重要作用。