高效液相色谱-串联质谱法同时测定食用植物油中多种有机锡化合物

有机锡化合物已广泛应用于食品包装材料及其生产过程中,对人体健康存在着潜在的危害。特别是食用植物油因甘油三酯(脂肪)含量较高,约占植物油的95%以上,给分析检测带来较大的基体干扰。本文采用低温冷冻提取结合固相萃取技术,建立了高效液相色谱-串联质谱法同时测定食用植物油样品中二丁基二氯化锡、二苯基二氯化锡、三丁基氯化锡、三苯基氯化锡同时分析的方法。实验对比了甲醇、乙腈、乙醇三种有机萃取溶剂分别在低温冷冻提取和常规液液振荡提取条件下的提取效率,并考察了PSA、中性氧化铝、弗罗里硅土及活性炭四种净化材料对食用油提取液的净化效果。确定了食用油中有机锡化合物的最佳提取净化方案为:以10 m L甲醇为提取溶剂在低温冷冻条件下充分提取两次,并通过50 mg活性炭净化提取液。为评价该方法的准确性,对食用油样品进行三个不同水平的添加回收实验,各有机锡化合物的平均回收率在74.2%~99.5%之间,接近或优于现行国标及相关研究(70%~120%),可应用于菜籽油、花生油、芝麻油、大豆油、玉米油及调和油等不同基质的食用植物油中有机锡化合物的同时测定。     

Isotopic fractionation associated with biosynthesis of fatty acids by a marine bacterium under oxic and anoxic conditions

Shewanella putrefaciens (Strain MR-4), a gram negative facultative marine bacterium, was grown to stationary phase under both aerobic and anaerobic conditions using lactate as the sole carbon source. Aerobically-produced cells were slightly enriched in ¹³C (+1.5‰) relative to the lactate carbon source, whereas those from anaerobic growth were depleted in ¹³C (−2.2‰). The distribution of fatty acids produced under aerobic conditions was similar to that resulting from anaerobic growth, being dominated by C_16:1 ω7 and C_16:0 fatty acids with a lesser amount of the C_18:1 ω7 component. Low concentrations of saturated even numbered normal fatty acids in the C₁₄ to C₁₈ range, and iso-C_15:0 were synthesized under both conditions. Fatty acids from anaerobic cultures (average δ¹³C=−37.8‰) were considerably depleted in ¹³C relative to their aerobically-synthesized counterparts (−28.8‰). The distinct differences in isotopic composition of both whole cells and individual fatty acid components result from differences in assimilation pathways. Under aerobic conditions, the primary route of assimilation involves the pyruvate dehydrogenase enzyme complex which produces acetyl-CoA, the precursor to lipid synthesis. In contrast, under anaerobic conditions formate, and not acetate, is the central intermediate in carbon assimilation with the precursors to fatty acid synthesis being produced via the serine pathway. Anaerobically-produced bacterial fatty acids were depleted by up to 12‰ relative to the carbon source. Therefore, detection of isotopically depleted fatty acids in sediments may be falsely attributed to a terrestrial origin, when in fact they are the result of bacterial resynthesis.     

Long-chain carboxylic acids in pyrolysates of Green River kerogen

Long-chain fatty acids (C₁₀-C₃₂), as well as C₁₄-C21 isoprenoid acids (except for C₁₈), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C₁₆ followed by lesser amounts of C₁₈ and C₂₂ acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C₁₄, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C₁₈ and C₃₀. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.     

Microbial respiratory quinones as indicator of ecophysiological redox conditions

The bacterial respiratory quinones and membrane phospholipid fatty acids (PLFA) were measured to test the biochemical responses to the redox conditions after the respiration of diverse electron acceptors by microorganisms. Shewanella putrefaciens strain CN32 was examined for its growth with O₂, nitrate, ferrihydrite, ferric citrate, and sulfite as electron acceptors. The same parameters were also measured for Desulfovibrio desulfuricans strain G-20, Geobacter metallireducens strain GS-15, Thioploca spp., two strains of magnetotactic bacteria (Magneteospirilum magnetotactium marine vibrioid strain MV-1 and M. sp. strain AMB-1), and environmental sediments. Microorganisms with aerobic respiratory of oxygen (MV-1 and AMB-1) have high ratios of monounsaturated to saturated straight chain PLFA and ubiquinone to menaquinone ratios; while those that conduct strict anaerobic respirations (G-20 with sulfate and GS-15 with ferric iron) have low ratios of monounsaturated to saturated straight chain PLFA and uniquinone to menaquinone ratios. The facultative respiratory of nitrate (Thioploca) has these parameters in the middle. The ratios of menaquinones to ubiquinones in CN32 cells systematically increase according to the increase of redox potential and bioavalibility of electron acceptors. The correlation between σUQ-n/σMK-n ratios and redox conditions indicates the structure of respiratory quinone responses sensitively to the microbial ecophysiological conditions.     

Conversion of sedimentary fatty acids from extractable (unbound + bound) to tightly bound form during mild heating

Prolonged heating (1–248 days) of a recent sediment was conducted under mild conditions (65 and 83°C) to understand the thermal behavior of extractable (unbound and bound) fatty acids (C_12C32). In the course of the heating, the concentrations of saturated and monounsaturated fatty acids first decreased, and then increased. This indicates that extractable fatty acids can be converted to a tightly bound form upon heating, before fatty acids are extensively released from sediment matrices. Changes in molecular distributions of extractable fatty acids upon heating were also observed. The higher molecular weight fatty acids (?C₂₀) are more likely to become tightly bound than are lower molecular weight (<C₂₀). Monounsaturated fatty acids (C_16:1 and C_18:1) are more easily converted to the tightly bound form than polyunsaturated fatty acids (C_18:2 and C_18:3). These differences probably reflect their mode of occurrence in sediments, which are closely related to their origin.     

Lipid biomarkers and carbon-isotopes of modern travertine deposits (Yellowstone National Park, USA): Implications for biogeochemical dynamics in hot-spring systems

Lipid biomarkers and ¹³C fractionation patterns were used to understand the dynamics of carbon cycling during microbial metabolisms in different environments of travertine precipitation (called facies) at Spring AT-1 on Angel Terrace in the Mammoth Hot Springs complex of Yellowstone National Park, USA. Microbial mats that encrust travertine deposits were collected for analyses of lipid biomarkers and carbon isotopes along the continuous drainage outflow system of Spring AT-1. The spring water exhibits a continuous temperature drop from 71°C in the vent at top to 24°C in the distal slope at bottom. Phospholipid fatty acids (PLFA) and glycolipid fatty acids (GLFA) exhibit distinctly different compositions in each of the facies, which are consistent with partitioning of the bacterial 16S rRNA gene sequences in the Spring AT-1 travertine facies (Fouke et al., 2003).The δ¹³C composition of total biomass within the microbial mats decreases from −16.1‰ in the vent to −23.5‰ in the distal slope. However, lower values occur in the pond (−26.0‰) and the proximal slope (−28.0‰) between the vent and the distal slope. Isotopic compositions of PLFA and GLFA have variations similar to those of total biomass. The average δ¹³C values of PLFA are −12.4 ± 5.2‰ (n = 10 individual fatty acids, same below) in the vent, −33.0 ± 3.1‰ (n = 11) in the pond, −33.7 ± 3.8‰ (n = 16) in the proximal slope, and −22.4 ± 3.4‰ (n = 10) in the distal slope; the average δ¹³C values of GLFA are −19.6 ± 3.0‰ (n = 3) in the vent, −30.4 ± 4.7‰ (n = 8) in the pond, −36.9 ± 2.8‰ (n = 12) in the proximal slope, and −27.9 ± 3.1‰ (n = 13) in the distal slope. In particular, fatty acids in the vent are enriched in ¹³C relative to the total biomass, which is consistent with the notion that the biosynthetic pathways of the extant microbial community in the vent may be dominated by Aquificales using the reversed tricarboxylic acid cycle. Fractionations between fatty acids and total biomass in the pond, the proximal slope and the distal slope suggest the involvement of other biosynthetic pathways for CO₂ fixation by extant microbial populations. The results indicate that lipid biomarkers provide valuable information on the changing diversity and activity of microbial communities in different depositional environments. Carbon-isotope fractionations, on the other hand, can provide insight into the operating biosynthetic pathways associated with different organisms in the changing environment. This integrated approach may serve as a powerful tool for identifying functional metabolism within a community and identify shifts in microbial community structure in modern hot-spring systems.     

Organic matter from a sediment trap experiment in the equatorial north Atlantic: wax esters,steryl esters,triacylglycerols and alkyldiacylglycerols

The vertical flux and composition of wax esters, steryl esters, triacylglycerols, and alkyldiacylglycerols in particulate matter was determined in the equatorial Atlantic Ocean by deploying sediment traps at 389, 988, 3,755 and 5,068 m. Detailed compositional analyses of these lipids were carried out by high temperature glass capillary gas chromatography and gas chromatography/mass spectrometry.The distributions of these lipids are discussed in terms of potential biological sources. Zooplankton fecal matter and intact zooplankters may represent the most important input of these compounds to the shallower two traps, while the material in the deeper two traps appears to have been biogeochemically altered. The finding of these biochemically important compounds, often unsaturated, indicates that particle transit through the water column must be relatively fast.Wax esters were most abundant in the 389 m sediment trap and decreased with increasing trap depth. Compounds ranging from C₂₈–C₄₄ were present at all depths. The major homologs were C₃₂, C₃₄ and C₃₆, most often monounsaturated. The dominant alcohol/acid combinations in the 389 m trap were $\text{C}{}_{\mathrm{18:1}}\text{C}{}_{\mathrm{14:0}}$ and $\text{C}{}_{\mathrm{18:1}}\text{C}{}_{\mathrm{16:0}}$, but in the 988 m sample, $\text{C}{}_{\mathrm{16:0}}\text{C}{}_{\mathrm{18:1}}$ was the major wax ester. A flux maximum was observed for steryl esters at 988 m. Cholesteryl esters of C_14:0, C_16:1 and C_16:0, and $\text{C}{}_{\mathrm{18:1}}\text{C}{}_{\mathrm{18:0}}$ fatty acids were the dominant steryl esters. For triacylglycerols, fluxes in the 389 and 988 m traps were similar, while the deeper pair of traps contained much less triacylglycerol. C₄₆, C₄₈, C₅₀ and C₅₂ compounds were the major triacylglycerols. Constituent fatty acids in the 389 m and 988 m samples were mainly C_14:0, C_16:1, C_16:0, C_18:1 and C_18:0. In the 988 m material, C_20:5 and C_22:6 were also dominant. A homologous series of alkyldiacylglycerols was abundant in the 389 m trap material. The alkyldiacylglycerols consisted of C₄₆–C₅₆ compounds composed of C_16:0 alkyl moieties and C_14:0, C_16:0, C_18:1, and C_18:0 fatty acids.     

Fatty acids and sterols of particulate matter in a brackish and seasonally anoxic coastal salt pond

Particulate matter and interfacial sediment from a seasonally anoxic coastal salt pond were analyzed for fatty acids and sterols to examine variations in organic sources, and compositional changes across the oxic-anoxic interface in the water column and at the sediment-water interface. Fatty acid distributions in suspended particles varied seasonally and as a function of depth. Fatty acids of algal origin (e.g. 16:3, 16:4, 18:3, 18:4) were abundant in particles in oxic surface waters, but these labile components were depleted in particles from the anoxic zone which instead were enriched in bacterial fatty acids (e.g. 16:1Δ⁹, 18:1Δ¹¹, anteiso-C₁₅). Sterol distributionsvaried less than fatty acid distributions and particles throughout the water column reflected an upper water algal source with little in situ alteration. There was evidence for an in situ conversion of Δ⁵-stenols to 5(α)H-stanols in suspended particles in the anoxic zone. Sinking particles and the interfacial sediment were compositionally similar to each other, but different from suspended particles. These data reflect differences in particle source, transport and transformation processes occuring in the water column.     

Carbon isotope fractionation in phospholipid fatty acid biomarkers of bacteria and fungi native to an acid mine drainage lake

This study identifies isotope signatures associated with autotrophic and heterotrophic microbial communities that may provide a means to determine carbon cycling relationships in situ for acid mine drainage (AMD) sites. Stable carbon isotope ratios (δ¹³C) of carbon sources, bulk cells, and membrane phospholipids (PLFA) were measured for autotrophic and heterotrophic microbial enrichment cultures from a mine tailings impoundment in northern Ontario, Canada, and for pure strains of the sulfur oxidizing bacteria Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. The autotrophic enrichments had indistinguishable PLFA distributions from the pure cultures, and the PLFA cyc-C_19:0 was determined to be a unique biomarker in this system for these sulfur oxidizing bacteria. The PLFA distributions produced by the heterotrophic enrichments were distinct from the autotrophic distributions and the C_18:2 PLFA was identified as a biomarker for these heterotrophic enrichments. Genetic analysis (16S, 18S rRNA) of the heterotrophic cultures indicated that these communities were primarily composed of Acremonium fungi.Stable carbon isotope analysis revealed that bulk cellular material in all autotrophic cultures was depleted in δ¹³C by 5.6–10.9‰ relative to their atmospheric CO₂ derived carbon source, suggesting that inorganic carbon fixation in these cultures is carbon limited. Individual PLFA from these autotrophs were further depleted by 8.2–14.6‰ compared to the bulk cell δ¹³C, which are among the largest biosynthetic isotope fractionation factors between bulk cell and PLFA reported in the literature. In contrast, the heterotrophic bulk cells were not significantly fractionated in δ¹³C relative to their carbon source and heterotrophic PLFA ranged from 3‰ enriched to 4‰ depleted relative to the isotopic composition of their total biomass. These distinct PLFA biomarkers and isotopic fractionations associated with autotrophic and heterotrophic activity in this laboratory study provide potential biomarkers for delineating autotrophic and heterotrophic carbon cycling in AMD environments.     

Anoxygenic phototrophic bacterial diversity within wastewater stabilization plant during ‘red water’ phenomenon

The molecular diversity of the purple photosynthetic bacteria was assessed during temporal pigmentation changes in four interconnected wastewater stabilization ponds treating domestic wastewater by denaturant gel gradient electrophoresis method applying pufM gene. Results revealed high phylogenetic diversity of the purple phototrophic anoxygenic bacteria community characterized by the presence of the purple non-sulfur, purple sulfur, and purple aerobic photosynthetic anoxygenic bacteria. This phototrophic bacterial assemblage was dominated by the purple non-sulfur bacteria group (59.3 %) with six different genera followed by the purple sulfur community (27.8 %) with four genera and finally 12.9 % of the pufM gene sequences were assigned throughout the aerobic anoxygenic phototrophic bacterial group. The purple phototrophic bacterial community was characterized by the presence of salt-dependant bacterial species belonging to the genus Marichromatium, Thiorhodococcus, Erythrobacter, and Roseobacter. The wastewater treatment plant performances were unsatisfactory, and the biological and chemical parameters suggested that the purple photosynthetic bloom was correlated with the eutrophic state.     

Lipid Distribution in Marine Sediments from the Northern South China Sea and Association with Gas Hydrate

The distributions of lipids in surface and subsurface sediments from the northern South China Sea were determined. The n-alkanes were in bimodal distribution that is characterized by a centre at n-C16 –n-C20 with maximum at C18(or C19) and n-C27 –n-C31 as well as at C29(or C31). The short-chain alkanes suffered from significant losses due to their slow deposition in the water column, and their presence with a slight even carbon predominance in shallow seafloor sediments was ascribed mainly to the direct input from the benthos. The long-chain alkanes with odd predominance indicate transportion of terrigenous organic matter. Immature hopanoid biomarkers reflect the intense microbial activity for bacteria–derived organic matter and the gradual increase of maturity with burial depth. Abundant n-fatty acid methyl esters(n-FAMEs) that are in distributions coincident with fatty acids were detected in all samples. We proposed that the observed FAMEs originated from the methyl esterification of fatty acids; methanol production by methanotrophs and methanogenic archaea related to the anaerobic oxidation of methane, and sulfate reduction provided an O–methyl donor for methylation of fatty acids. The CH4 released from hydrate dissociation at oxygen isotope stage II of Cores ZD3 and ZS5, which had been confirmed by the occurrence of negative δ13C excursion and spherical pyrite aggregates, could have accelerated the above process and thus maximized the relative content of FAMEs at ZD3-2(400–420 cm depth) and ZS5-2(241–291 cm depth).     

Early diagenesis of organic matter in the water column and sediments: Microbial degradation and resynthesis of lipids in Lake Haruna

Particulate matter, sediment trap, and surface sediment samples collected in freshwater Lake Haruna were studied to understand early diageesis of organic materials in the water column and in bottom sediments. The samples were analyzed for biomarkers, including aliphatic and aromatic hydrocarbons, fatty alcohols, saturated and unsaturated fatty acids, β- and ω-hydroxyacids, and α,ω-dicar☐ylic acids. Decreases in concentrations of autochthonous saturated C₁₂–C₁₉ fatty acids and polyunsaturated C₁₈ acids relative to TOC occured with the settling of organic matter ot the lake bottom, whereas the amounts of terrestial saturated C₂₀–C₃₀ acids remained almost constant. Conversely, the concentrations of monosaturated fatty acids, branched chain fatty acids, and β- and ω-hydroxyacids, which are probably produced by microbial activity, increased. These results indicate that preferential degradation of algal lipids accompanies microbial resynthesis of lipids during settling, however, terrigenous lipids are relatively stable.     

The elastic constants of monoclinic single-crystal chrome-diopside to 1,300 K

Values of the complete adiabatic elastic tensor for single-crystal chrome-diopside (a monoclinic pyroxene mineral) are presented from 298 to 1,300 K. The data were obtained using resonant ultrasound spectroscopy (RUS). They are the first published results for the temperature T dependences of the 13 individual elastic constants C _ij of any clinopyroxene mineral. Each C _ij is appropriately described by a linear function in T throughout the range of T. Values for each (∂C _ij /∂T) _P in GPa K⁻¹ are as follows: C ₁₁, −0.0291; C ₂₂, −0.0248; C ₃₃, −0.0179; C ₄₄, −0.0103; C ₅₅, −0.0077; C ₆₆, −0.0152; C ₁₂, −0.0119; C ₁₃, −0.0064; C ₂₃, 0.0000; C ₁₅, 0.0025; C ₂₅, 0.0022; C ₃₅, −0.0046; and C ₄₆, 0.0026. Values of (∂M/∂T) _P in GPa K⁻¹, where M represents an isotropic bulk property calculated from the C _ij data, are as follows: adiabatic bulk modulus K _S , −0.0123; isothermal bulk modulus K _T , −0.0178; and shear modulus G, −0.00998. Some diopside derivatives, notably (∂K _S /∂T) _P , (∂K _T /∂T) _P , and (∂V _P /∂T) _P , where V _P is the compressional wave velocity, have smaller magnitudes than all other minerals of importance in Earth’s mantle, thus, confirming predictions from systematics studies. We find several dimensionless quantities for this monoclinic mineral have normal values compared to other mantle minerals. Further, αK _T (α is the volume coefficient of thermal expansion) for diopside is approximately independent of both T and volume V at elevated temperature, so its equation of state is accurately expressed in simplified form.     

Occurrence of highly abundant bacterial hopanoids in Dajiuhu peatland, central China

Based on gas chromatography and gas chromatography-mass spectrometry analyses, an amazing amount of hopanoids was detected in the peat deposits in the Dajiuhu National Wetland Park in central China. The hopanoids identified included hopanes (C₂₇-C₃₁ αβ, C₂₇-C₃₂ ββ, C₂₉ βα), hopenes (hop-22(29)-ene, 22,29,30-trinorhop-17(21)-ene, hop-17(21)-ene, hop-13(18)-ene, etc.), hopanoic acids (C₃₁-C₃₄ ββ, C₃₂-C₃₃ βα, C₃₂ αβ), hopanols (C₃₂ ββ and αβ) and hopanone (22,29,30-trinorhop-21-one). C₃₁ αβ-22R hopane was found to be the dominant hopanoid, more abundant than individual nalkanes derived from higher plants. These hopanoids, exclusive of some hopenes, are proposed to be primarily from bacteria. The dominant C₃₁ αβ-22R hopane in young sediments, without any thermal maturation, might be formed through microbial epimerization under acidic conditions in the peatland as suggested before, or directly from aerobic bacteria. This finding highlights the importance of microbes in the formation of peatland as well as in the reconstruction of paleoenvironments.     

n-alkane distribution coupled with organic carbon isotope composition in the shell bar section, Qarhan paleolake, Qaidam basin, NE Tibetan Plateau

Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triterpenoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C₁₅, n-C₁₇, n-C₁₉ alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C₂₁, n-C₂₃, n-C₂₅ homologues from aquatic plants, and the n-C₂₉, n-C₃₁ homologues from vascular plants. In contrast, the n-C₂₇ alkane is not categorized in the n-C₂₉ and n-C₃₁ group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ¹³C_org), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ¹³C_org, excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ¹³C_org, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.     

Maturation related changes in the distribution of ester bound fatty acids and alcohols in a coal series from the New Zealand Coal Band covering diagenetic to catagenetic coalification levels

A rank series of lignites and coals of low to moderate maturation levels (vitrinite reflectance (R₀): 0.27–0.8%) from the New Zealand Coal Band were investigated using alkaline ester cleavage experiments to reveal compositional changes of ester bound components (fatty acids and alcohols) during increasing maturation. Ester bound alcohols are found to be present in highest amounts in the very immature lignite samples (R₀: 0.27–0.29%), but show a rapid decrease during early diagenesis. Ester bound fatty acids also show an initial exponential decrease during diagenesis, but reveal an intermittent increase during early catagenesis before decreasing again during main catagenesis. This intermittent increase was related to the short chain fatty acids. To obtain a maturity related signal and to eliminate facies related scattering in the amounts of fatty acids in the coal samples, the carbon preference index of fatty acids (CPI_FA) parameter is introduced here. For the long chain fatty acids (C₂₀–C₃₂) originating from terrigenous plant debris, the CPI_FA decreases with increasing maturity, showing a strong maturation related signal. During diagenesis, the same trend can be observed for the short chain fatty acids, but the intermittent increase in the amounts of short chain fatty acids is also accompanied by high CPI_FA values. This indicates less altered organic biomass at this advanced maturation level and is in contrast to the mature CPI_FA signal of the long chain fatty acids of the same samples. One possible reason for this discrepancy could be extremely different amounts of short and long chain fatty acids in the original source organic matter of these samples. However, another intriguing explanation could be the incorporation of immature bacterial biomass from deep microbial communities containing C₁₆ and C₁₈ fatty acids as main cell membrane components. Deep microbial life might be stimulated at this interval by the increasing release of thermally generated potential substrates from the organic matrix during early catagenesis. In contrast to the fatty acids, the high amounts of alcohols in the immature lignite samples are also visible in the alkene distribution from the open system pyrolysis experiments of the organic matrix before and after saponification.     

The organic geochemistry of black sedimentary barite: significance and implications of trapped fatty acids

Fatty acids isolated in sedimentary black barite (BaSO₄) from Arkansas and Nevada were identified by gas chromatography-mass spectroscopy. The dominant or major fatty acids found in these beds of barite are C_16:0, C_18:0, and C_18:1. The occurrence and distribution of these acids in this type of rock may serve as “molecular fingerprints” of microbial biogeochemical processes. The organic matter and associated microorganisms are shown to be trapped within the finely crystalline barite, thus forming a closed system for microbial diagenesis.Important differences that occur in the distribution of the lesser or minor fatty acids probably result from: (1) the nature of the progenitor organic detritus in the environment of barite deposition: and (2) the subsequent degree of microbiological alteration of the parent organic debris swept into and trapped in the depositional environment.Three general models of sedimentary environments are proposed in which anoxic conditions may prevail and where barium sulfate (BaSO₄) may precipitate: (1) in a silled basin with semi-restricted circulation; (2) on an outer continental shelf where the slope is encroached upon by water of the oxygen minimum layer; (3) on a low-energy, inner shelf or semi-restricted embayment impinged by a wedge of anoxic water.The major geochemical and geological parameters which are believed to be the significant factors controlling the formation and high grade of these organic-rich, black bedded barites are: (1) a unique source of barium-rich fluid that only contains trace amounts of other elements; (2) the presence of an anoxic bottom environment within the depositional basin; (3) a reflux source of sulfate ion; (4) an adequate source of organic matter.The results of this study may serve as guidelines for future exploration in similar, untested sedimentary basins, especially those with rocks of middle Paleozoic age.     

Triclinic elastic constants for low albite

The full set of elastic constants for plagioclase end-member phase albite (NaAlSi₃O₈) is reported for the first time. Velocities of surface acoustic waves (both Rayleigh and pseudo-surface waves) were measured using impulsively stimulated light scattering on polished surfaces having six different orientations (three normal to the Cartesian axes and three lying on diagonals). Data were inverted and results tested using several non-linear optimization techniques. Compliance moduli determined under hydrostatic compression provided additional constraints and reduced covariance in the reported constants. The Cartesian coordinate system associated with the constants (using the unit cell) has the y-axis parallel to the crystal b axis, the x-axis parallel to a* (perpendicular to b and c) and the z-axis consistent with a right-handed coordinate system. The values of the moduli C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₂₂, C₂₃, C₂₄, C₂₅, C₂₆, C₃₃, C₃₄, C₃₅, C₃₆, C₄₄, C₄₅, C₄₆, C₅₅, C₅₆, C₆₆ and their 2σ uncertainties (in parentheses) are, respectively, 69.1(0.6), 34.0(0.7), 30.8(0.5), 5.1(0.1), −2.4(0.1), −0.9(0.1), 183.5(2.7), 5.5(2.2), −3.9(0.5), −7.7(0.7), −5.8(0.7), 179.5(2.3), −8.7(0.4), 7.1(0.6), −9.8(0.6), 24.9(0.1), −2.4(0.1), −7.2(0.1), 26.8 (0.2), 0.5(0.1), 33.5(0.2). These constants differ significantly from the previously reported pseudo-monoclinic constants that were based on velocity measurements on polysynthetic twinned crystal aggregates. Differences are consistent with systematic errors in the earlier study associated with sparse data and the presence of cracks and other imperfections.     

Lipid geochemistry in a sediment core from Ruoergai Marsh deposit (Eastern Qinghai-Tibet plateau, China)

Peats in a sediment core from Ruoergai bog, which has a cold and moist plateau climate with major source input from herbaceous plants, have been studied by GC–MS in order to understand the composition and diagenetic processes of lipids in this depositional environment. Long chain components (C₂₁–C₃₅) predominate in the n-alkanes, n-alk-1-enes, n-fatty acids, n-alkan-2-ones and n-alkanols with a maximum of C₃₁, C_27, C₂₂ or C_24, C₂₃ or C₂₅ and C₂₂, respectively. A herbaceous origin for these long chain compounds is suggested, and this is supported by their stable carbon isotopic compositions. Diterpenoid hydrocarbons with abietane, pimarane and kaurane skeletons, some of which have not been reported often in modern sediments, are prominent and are derived from higher plants. Several triterpenoid ketones and alcohols with oleanane or lupane skeletons, and a series of des-A-triterpenoid hydrocarbons which have not been reported often in modern sediments are also present, and are assigned to a higher plant source. Hopanoids, including their alkanes, alkenes, ketones, alcohols and esters, are abundant and of bacterial origin. Steroid ketones and alkanols are dominated by C₂₉ homologues. C₂₈ and C₂₉ steroids are derived mainly from higher plants, whereas the C₂₇ component is assigned to a microbial source. The presence of short-chain n-alkanes with no odd-even carbon predominance, bacterially derived fatty acids (C₁₄, C₁₅, iso- and unsaturated acids), n-alkan-2-ones, des-A-triterpenoid hydrocarbons, hopanoids and some steroid ketones indicate that intense microbial reworking of the organic matter has taken place in this depositional environment. The chemical and biochemical conversions of some cyclic alkenes to alkanes, such as tricyclic diterpenoids, tetracyclic terpenoids and steroid ketones, are also evident with depth. The dominance of C₂₀ components in the diterpenoid hydrocarbons may reflect an oxidizing or reducing depositional condition.     

Middle Pleistocene climate and habitat change at Zhoukoudian, China, from the carbon and oxygen isotopic record from herbivore tooth enamel

The Pleistocene deposits at Zhoukoudian, often referred to as the “Peking Man” site, contain dental remains from a diverse group of herbivores, including Equus sanmeniensis, Cervus elaphus, Cervus nippon, Megaloceros pachyosteus, Sus lydekkeri, and Dicerorhinus choukoutienensis. The carbon and oxygen isotopic compositions of structural carbonate within the enamel of these teeth are used to reconstruct the paleodiet and paleoenvironment of the mammals. The δ¹³C values of enamel from Zhoukoudian range from −2.3‰ to −13.0‰, indicating that these mammals consumed between 25% and 100% C₃ plants. The presence of significant amounts of C₄ plants in the diets of some herbivore species indicates that at the onset of the Middle Pleistocene local habitats included mixed C₃/C₄ vegetation. By approximately 470,000 yr ago, C₃ plants dominated the diets of herbivores studied, suggesting that the abundance of C₄ flora had decreased in the area. For all deer analyzed in this study, the values of δ¹³C and δ¹⁸O decrease substantially from about 720,000 to 470,000 yr ago. This trend may be due to a strengthening of the winter monsoon during the Middle Pleistocene.