Seasonal variations of alkenones and U37 in the Chesapeake Bay water column

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.     

Polar constituents of organic matter rich marls from evaporitic series of the Mulhouse basin

A suite of marl samples from the evaporitic series of the Mulhouse basin (France; Lower Oligocene) was studied for its biomarker content, in particular its polar constituents. Novel series of 3-carboxyalkyl steranes and 15-oxo triaromatic ketones were identified by synthesis. The 3-carboxyalkyl steranes probably originate from highly polar precursors yet unreported in living organisms. Our data suggest that micro-algae could be the major source of these compounds which seem to be indicators of high algal input rather than characteristic of evaporitic environments. The 15-oxo triaromatic ketones could be oxidation products of triaromatic steroid hydrocarbons formed during diagenesis, although their formation during work-up procedure could not be excluded.     

Evaluation of the liquid hydrocarbon potential of coal by artificial maturation techniques

In certain areas, relatively large accumulations of liquid hydrocarbons have been attributed to coals. Evaluating the source rock potential of coal requires definition of both the generative potential (quantity and composition of generated hydrocarbons), and expulsion efficiency. Hydrous pyrolysis experiments were completed using Tertiary lignites (R_o < 0.35%) from North Dakota and the Far East to evaluate the source rock potential of coal. The North Dakota lignite is vitrinite-rich (93%) and liptinite-poor (3%); the Far East lignite is liptinite-rich (32% of total maceral content). These lignites have Hydrogen Index values of 123 and 483 mg HC/g OC, respectively. Differences in oil-pyrolysate yield, composition, and temperature of maximum pyrolysate yield from hydrous pyrolysis experiments for these two lignites are related to the type and amount of liptinite and vitrinite macerals. A maximum of 48 and 158 mg oil-pyrolysate/g OC is generated and expelled from the North Dakota and Far East lignites, respectively. Although these lignites consist predominantly of gas-prone vitrinitic components, their organic-rich nature can compensate for their poor convertibility to liquid hydrocarbons. The composition of these artificially generated oil-pyrolysates are similar to some non-marine oils, suggesting that this type of organic matter can be a significant contributor to many oils. Although the overall composition of the generated products from the two lignites is similar, the distribution of these products is significantly different. Homologous series of methyl ketones and alkyl benzenes have been identified in both oil-pyrolysates. Their presence and characteristic distribution suggest that microbial degradation occurred during the formation of these lignites. Although many coals generate significate amounts of liquid hydrocarbons that are similar to naturally occurring oils, poor explusion efficiency limits their source rock potential. Significant amounts of liquid products are assimilated by the vitrinitic matrix of most coals prior to expulsion, severely limiting the amount of petroleum available for migration and reservoir accumulation. However, adequate expulsion may occur in certain liptinite-rich coals or coals occurring in unique depositional settings.     

古海洋、古气候研究的新工具

“分子温度计”是通过有机地球化学方法获得的沉积物中烯酮化合物的相对丰度来估算古海水表面温度的。烯酮化合物的不饱和度（Ｕｋ３７）与其生物母源Ｅｍｉｌｉａｎｉａｈｕｘｌｅｙｉ的生长温度密切相关，同时这种信息不受有机质溶解与成岩作用影响，而能较完整地保存于海洋沉积物中，因而通过它能很好地反映古海洋与古气候的演变。这种方法不受盐度、上升流与极地冰盖变化等因素影响，尤其适用于碳酸盐贫乏海区的古海洋与古气候研究     

Organic matter of the troposphere — V: Application of molecular marker analysis to biogenic emissions into the troposphere for source reconciliations

Organic matter in tropospheric aerosols is derived from two major sources and is admixed depending on the geographic area. These sources are biogenic detritus and anthropogenic emissions. The biogenic materials in the solvent-extractable organic matter are comprised predominantly of higher plant waxes, with lesser amounts of resin and microbial detritus and the anthropogenic components are primarily vehicular emissions (e.g. oils, soot, etc.) and input from combustion (e.g. charcoal, thermally-altered biogenic matter, etc.). Both biogenic detritus and anthropogenic emissions contain organic compounds (C₁₂–C₄₀₊), which can be identified with unique and distinguishable distribution patterns. Molecular composition analysis has been applied to such extracts after suitable chemical separation into subfractions (i.e. hydrocarbons, ketones, aldehydes, carboxylic acids, alcohols, and wax esters). Both homologous compound series and specific natural products (e.g. phytosterols, terpenes, etc.) are identified as molecular markers.Aerosols from rural and remote areas in the western United States, South America, Nigeria and Australia have been analyzed and all contained predominantly plant waxes. The loadings of hydrocarbons ranged approximately from 10–1400 ng/m³ of air, of fatty acids from 10–450 ng/m³ and of fatty alcohols from 10–1650 ng/m³. These higher molecular weight lipids primarily from flora comprise a major component of the organic carbon in rural and remote aerosols. They are thus important indicators for regional biogenic sources in the global cycling of organic carbon.Presented in part at the International Symposium on Biosphere-Atmosphere Exchange, Mainz, E.R. Germany, March 16–22, 1986, for Part IV see Simoneit et al. (1988) Atmos. Environ. 22, 983–1004.     

Mechanistic and Kinetic Study of the Gas-Phase Reaction of Atomic Chlorine with Cyclohexanone using an Absolute and a Relative Technique; Influence of Temperature

The reaction of Cl with cyclohexanone (1) was investigated, for the first time, as a function of temperature (273–333 K) and at a low total pressure (1 Torr) with helium as a carrier gas using a discharge flow-mass spectrometry technique (DF-MS). The resulting Arrhenius expression is proposed, k ₁= (7.7 ± 4.1) × 10^–10 exp[–(540 ± 169)/T]. We also report a mechanistic study with the quantitative determination of the products of the reaction of Cl with cyclohexanone. The absolute rate constant derived from this study at 1 Torr of total pressure and room temperature is (1.3 ± 0.2) × 10^–10 cm³ molecule^–1 s^–1. A yield of 0.94 ± 0.10 was found for the H-abstraction channel giving HCl. In relative studies, using a newly constructed relative rate system, the decay of cyclohexanone was followed by gas chromatography coupled with flame-ionisation detection. These relative measurements were performed at atmospheric pressure with synthetic air and room temperature. Rate constant measured using the relative method for reaction (1) is: (1.7 ± 0.3) × 10^–10 cm³ molecule^–1 s^–1. Finally, results and atmospheric implications are discussed and compared with the reactivity with OH radicals.