Pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) analysis of Neolithic (4900-3800 BC) archeological rice grains (husked rice fruit) from the Tianluoshan site (Zhejiang Province, eastern China) revealed no polysaccharide products from starch present in the original rice fruit; however, benzene, toluene, dimethyl benzene, phenol, dimethyl phenol and n-alkanes > C-30 were detected, indicating their aromatic nature, plus some aliphatic components. On the contrary, polysaccharides were observed in husk material but in significantly lower concentration than in the modern equivalent. The molecular composition was supported by C-13 nuclear magnetic resonance spectroscopy (NMR) data. Variation in preservation quality was also detected in persimmon seeds, oak acorns and amanranthaceous seeds from the site. This variation in molecular preservation, which could also be observed at the micro-morphological level, was tracked with scanning electron microscopy (SEM). Variation in bulk tissue carbon isotopic values (delta C-13) was apparent among archeological samples, a net 1-2 parts per thousand positive shift in bulk tissue delta C-13 being found in most of the Tianloushan plant remains. Our data suggest the importance of post-excavation storage conditions and illustrate the power of the application of multiple analytical methods for the study of archeological plant remains. (c) 2013 Elsevier Ltd. All rights reserved.

Pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) analysis of Neolithic (4900-3800 BC) archeological rice grains (husked rice fruit) from the Tianluoshan site (Zhejiang Province, eastern China) revealed no polysaccharide products from starch present in the original rice fruit; however, benzene, toluene, dimethyl benzene, phenol, dimethyl phenol and n-alkanes > C-30 were detected, indicating their aromatic nature, plus some aliphatic components. On the contrary, polysaccharides were observed in husk material but in significantly lower concentration than in the modern equivalent. The molecular composition was supported by C-13 nuclear magnetic resonance spectroscopy (NMR) data. Variation in preservation quality was also detected in persimmon seeds, oak acorns and amanranthaceous seeds from the site. This variation in molecular preservation, which could also be observed at the micro-morphological level, was tracked with scanning electron microscopy (SEM). Variation in bulk tissue carbon isotopic values (delta C-13) was apparent among archeological samples, a net 1-2 parts per thousand positive shift in bulk tissue delta C-13 being found in most of the Tianloushan plant remains. Our data suggest the importance of post-excavation storage conditions and illustrate the power of the application of multiple analytical methods for the study of archeological plant remains. (c) 2013 Elsevier Ltd. All rights reserved.

Purple sulfur bacteria (PSB) are important photoautotrophs inhabiting chemoclines in euxinic and meromictic lakes. These organisms are the only producers of the carotenoid, okenone, a compound that has been targeted as a biomarker for photic zone euxinia, particularly in ancient sedimentary environments. Although the natural occurrence and geochemistry of this compound has been studied previously, this is the first systematic and comprehensive report on the microbial physiology of okenone production in pure cultures. Four strains/species: Marichromatium purpuratum DSMZ 1591, Marichromatium purpuratum DSMZ 1711, Thiocapsa marina DSMZ 5653, and FGL21 (isolated from Fayetteville Green Lake, New York) were chosen because they produce okenone and Bacteriochlorophyll a (Bchl a). We developed a new, in vivo technique for the quantification of okenone allowing for more rapid and accurate quantification. The ratio of okenone to Bchl a differs among species and strains of PSB, varying from 0.463 +/- 0.002 to 0.864 +/- 0.002. Photoheterotrophically grown PSB have statistically significant, lowered okenone:Bchl a ratios, decreasing from 0.784 +/- 0.009 under autotrophic metabolism to 0.681 +/- 0.002, which we interpret to indicate a decreased requirement for okenone when PSB are provided with a complex (> C1) carbon source. The variation in okenone production raises the question on whether okenone expression is constitutive or inducible. The broader implication is that concentrations of okenone in sediments are dependent on metabolism and species composition, and not solely on PSB cell density.

Purple sulfur bacteria (PSB) are important photoautotrophs inhabiting chemoclines in euxinic and meromictic lakes. These organisms are the only producers of the carotenoid, okenone, a compound that has been targeted as a biomarker for photic zone euxinia, particularly in ancient sedimentary environments. Although the natural occurrence and geochemistry of this compound has been studied previously, this is the first systematic and comprehensive report on the microbial physiology of okenone production in pure cultures. Four strains/species: Marichromatium purpuratum DSMZ 1591, Marichromatium purpuratum DSMZ 1711, Thiocapsa marina DSMZ 5653, and FGL21 (isolated from Fayetteville Green Lake, New York) were chosen because they produce okenone and Bacteriochlorophyll a (Bchl a). We developed a new, in vivo technique for the quantification of okenone allowing for more rapid and accurate quantification. The ratio of okenone to Bchl a differs among species and strains of PSB, varying from 0.463 +/- 0.002 to 0.864 +/- 0.002. Photoheterotrophically grown PSB have statistically significant, lowered okenone:Bchl a ratios, decreasing from 0.784 +/- 0.009 under autotrophic metabolism to 0.681 +/- 0.002, which we interpret to indicate a decreased requirement for okenone when PSB are provided with a complex (> C1) carbon source. The variation in okenone production raises the question on whether okenone expression is constitutive or inducible. The broader implication is that concentrations of okenone in sediments are dependent on metabolism and species composition, and not solely on PSB cell density.

The mechanism leading to the formation of aliphatic components in sedimentary rocks and petroleum products has been the subject of debate. Recent research has concluded that algaenan is not as widespread ecologically or phylogenetically, so may contribute less to the resistant aliphatic content of kerogens where such algae are source organisms. We conducted experiments with the non-algaenan producing alga, Chlamydomonas reinhardtii, at 260 and 350 degrees C and 700 bar to simulate fossilization of the microorganism under confined pyrolysis conditions. Pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) analysis revealed that the unheated alga consisted of biopolymers primarily related to proteins and lipids, including C-16 and C-18 fatty acids (FAs). However, heating at 260 and 350 degrees C resulted in macromolecules with a significant aliphatic component similar to high hydrogen content kerogen, derived from lipids in the alga, primarily from saturated and unsaturated C-16 and C-18 FAs, as determined from experiments with model compounds. The presence of amides, nitriles and oximes in the heated alga was likely due to the reaction of the lipids with the abundant N-containing proteinaceous compounds. Py-GC-MS of the residue of Scenedesmus quadricauda at 350 degrees C (a green alga containing algaenan as a control) demonstrated survival of algaenan at that temperature. The solvent insoluble residue of a cyanobacterium (Oscillatoria sp.) and a purple non S containing bacterium Rhodopseudomonas palustris subjected to similar high temperature and pressure, resulted in a residue with significant aliphatic content. The results reveal that algaenan survived the P/T conditions of the experiments, which additionally suggest an alternative mechanism that may lead to aliphatic geopolymers. Since this mechanism seems to be valid for organisms that are phylogenetically wide apart, it may be valid for organism cells in general. Thus, bacterial biomass may also contribute to the insoluble organic inventory of ancient sediments. (C) 2013 Elsevier Ltd. All rights reserved.

Organic nanoglobules are microscopic spherical carbon-rich objects present in chondritic meteorites and other astromaterials. We performed a survey of the morphology, organic functional chemistry, and isotopic composition of 184 nanoglobules in insoluble organic matter (IOM) residues from seven primitive carbonaceous chondrites. Hollow and solid nanoglobules occur in each IOM residue, as well as globules with unusual shapes and structures. Most nanoglobules have an organic functional chemistry similar to, but slightly more carboxyl-rich than, the surrounding IOM, while a subset of nanoglobules have a distinct, highly aromatic functionality. The range of nanoglobule N isotopic compositions was similar to that of nonglobular 15N-rich hotspots in each IOM residue, but nanoglobules account for only about one third of the total 15N-rich hotspots in each sample. Furthermore, many nanoglobules in each residue contained no 15N enrichment above that of bulk IOM. No morphological indicators were found to robustly distinguish the highly aromatic nanoglobules from those that have a more IOM-like functional chemistry, or to distinguish 15N-rich nanoglobules from those that are isotopically normal. The relative abundance of aromatic nanoglobules was lower, and nanoglobule diameters were greater, in more altered meteorites, suggesting the creation/modification of IOM-like nanoglobules during parent-body processing. However, 15N-rich nanoglobules, including many with highly aromatic functional chemistry, likely reflect preaccretionary isotopic fractionation in cold molecular cloud or protostellar environments. These data indicate that no single formation mechanism can explain all of the observed characteristics of nanoglobules, and their properties are likely a result of multiple processes occurring in a variety of environments.

Organic nanoglobules are microscopic spherical carbon-rich objects present in chondritic meteorites and other astromaterials. We performed a survey of the morphology, organic functional chemistry, and isotopic composition of 184 nanoglobules in insoluble organic matter (IOM) residues from seven primitive carbonaceous chondrites. Hollow and solid nanoglobules occur in each IOM residue, as well as globules with unusual shapes and structures. Most nanoglobules have an organic functional chemistry similar to, but slightly more carboxyl-rich than, the surrounding IOM, while a subset of nanoglobules have a distinct, highly aromatic functionality. The range of nanoglobule N isotopic compositions was similar to that of nonglobular 15N-rich hotspots in each IOM residue, but nanoglobules account for only about one third of the total 15N-rich hotspots in each sample. Furthermore, many nanoglobules in each residue contained no 15N enrichment above that of bulk IOM. No morphological indicators were found to robustly distinguish the highly aromatic nanoglobules from those that have a more IOM-like functional chemistry, or to distinguish 15N-rich nanoglobules from those that are isotopically normal. The relative abundance of aromatic nanoglobules was lower, and nanoglobule diameters were greater, in more altered meteorites, suggesting the creation/modification of IOM-like nanoglobules during parent-body processing. However, 15N-rich nanoglobules, including many with highly aromatic functional chemistry, likely reflect preaccretionary isotopic fractionation in cold molecular cloud or protostellar environments. These data indicate that no single formation mechanism can explain all of the observed characteristics of nanoglobules, and their properties are likely a result of multiple processes occurring in a variety of environments.

The interaction of hydrogen and deuterium with dimethylamine borane (Me2NHBH3) was studied at pressures from 0 to 10 GPa. Me2NHBH3 is stable to isothermal compression in noble gas pressure media up to 16 GPa. During these compressions a strong positive pressure dependence of the frequencies of BN and BH stretching fundamentals was observed. The opposite trend was observed with NH modes. Me2NHBH3 + He mixtures remain phase separated over the entire 0-16 GPa range. During the isothermal compression of Me2NHBH3 + H-2 mixtures two separate phases are observed at low pressure which subsequently collapse into one phase above 3 GPa. Prior to the formation of the Me2NHBH3/H-2 phase loss of the H-2 vibron was observed concurrently with the growth of broad features in the 3600-4000 region. Further compression of the Me2NHBH3:H-2 results in the growth of new Raman-active BN, BH, and NH modes not present in noble gas compressions. These modes are assigned to the new high pressure solid: [(Me2NH)(2)BH2+][BH4-] similar called diammoniate of diborane often observed in experiments with ammonia and diborane at ambient pressure.