Genesis of petroleum hydrocarbons in marine sediments

Distribution patterns of isopentane and normal pentane in marine sediments show a reversal in slope at a subsurface temperature of about 90 degrees C. The data indicate that three types of reactions are involved in pentane formation: (i) biological origin at the sediment surface, (ii) low-temperature (< 90 degrees C) chemical reactions yielding predominately secondary carbon structures, and (iii) high-temperature (> 90 degrees C) cracking reactions at great depth yielding predominately straight carbon chains.     

Ti8C12+-Metallo-Carbohedrenes: A New Class of Molecular Clusters?

During the course of studying the dehydrogenation reactions of hydrocarbons by titanium atoms, ions, and clusters, an exceptionally stable and abundant cluster which contains 8 titaniums and 12 carbons was discovered. "Titration" reactions with ND(3) reveal the uptake of eight molecules, pointing to the fact that the titanium atoms are at exposed positions of similar coordination. A dodecahedral structure of T(h) point group symmetry is proposed to account for the unusual stability of this molecular cluster. The Ti(8)C(12)(+) dodecahedron has 12 pentagonal rings and each of the rings is formed by two titanium and three carbon atoms, where each titanium is bound to three carbons. Based on the model, it is expected that neutral Ti(8)C(12) would be a stable metallo-carbododecahedral molecule and may comprise one member of a new class of molecules, namely metallo-carbohedrenes.     

Solubility in water of normal c9 and c10, alkane hydrocarbons

A new method for equilibrating water containing alkane hydrocarbons with a gas phase and analyzing the gas for hydrocarbon content by gas chromatography extends analytical sensitivity to better than 0.1 part per billion. The solubilities at 25 degrees C of the normal C(9) (220 parts per billion) and C(10) (52 parts per billion) alkanes decrease with increasing carbon number. A discontinuity occurs at the normal C(11), alkane, probably because of a change from true solubility (molecular dispersion) to accommodation (aggregation).     

High-temperature synthesis of aromatic hydrocarbons from methane

Arenes of 1, 2, 3, 4 and more rings have been synthesized in a flow system by passing methane through silica gel at 1000 degrees C. Yields of 4.8 to 7.2 percent have been obtained per single pass. As determined by combined gas chromatography-mass spectrometry, the major compound synthesized that are of less than S rings are benzene, naphthalene, acenaphthylene, phenanthrene, fluoranthene, and pyrene. Under certain conditions ( presence of ammonia and water), small amounts of aliphatic hydrocarbons are also synthesized. Even-carbon-numbered hydrocarbons (aromatic as well as aliphatic) predominate, to the extent that about 97 percent of the total weight of the analyzed arenes have even numbers of carbon atoms.     

Synthesis of Linear Acetylenic Carbon: The "sp" Carbon Allotrope

A carbon allotrope based on "sp" hybridization containing alternating triple and single bonds (an acetylenic or linear carbon allotrope) has been prepared. Studies of small (8 to 28 carbon atoms) acetylenic carbon model compounds show that such species are quite stable (130 degrees to 140 degrees C) provided that nonreactive terminal groups or end caps (such as tert-butyl or trifluoromethyl) are present to stabilize these molecules against further reactions. In the presence of end capping groups, laser-based synthetic techniques similar to those normally used to generate fullerenes, produce thermally stable acetylenic carbon species capped with trifluoromethyl or nitrile groups with chain lengths in excess of 300 carbon atoms. Under these conditions, only a negligible quantity of fullerenes is produced. Acetylenic carbon compounds are not particularly moisture or oxygen sensitive but are moderately light sensitive.     

Bacterial Sulfate Reduction Above 100{degrees}C in Deep-Sea Hydrothermal Vent Sediments

The currently known upper temperature limit for growth of organisms, shared by a number of archaebacteria, is 110 degrees C. However, among the sulfate-reducing bacteria, growth temperatures of greater than 100 degrees C have not been found. A search for high-temperature activity of sulfate-reducing bacteria was done in hot deep-sea sediments at the hydrothermal vents of the Guaymas Basin tectonic spreading center in the Gulf of California. Radiotracer studies revealed that sulfate reduction can occur at temperatures up to 110 degrees C, with an optimum rate at 103 degrees to 106 degrees C. This observation expands the upper temperature limit of this process in deep-ocean sediments by 20 degrees C and indicates the existence of an unknown group of hyperthermophilic bacteria with a potential importance for the biogeochemistry of sulfur above 100 degrees C.     

Abiogenic hydrocarbon production at lost city hydrothermal field

Low-molecular-weight hydrocarbons in natural hydrothermal fluids have been attributed to abiogenic production by Fischer-Tropsch type (FTT) reactions, although clear evidence for such a process has been elusive. Here, we present concentration, and stable and radiocarbon isotope, data from hydrocarbons dissolved in hydrogen-rich fluids venting at the ultramafic-hosted Lost City Hydrothermal Field. A distinct "inverse" trend in the stable carbon and hydrogen isotopic composition of C1 to C4 hydrocarbons is compatible with FTT genesis. Radiocarbon evidence rules out seawater bicarbonate as the carbon source for FTT reactions, suggesting that a mantle-derived inorganic carbon source is leached from the host rocks. Our findings illustrate that the abiotic synthesis of hydrocarbons in nature may occur in the presence of ultramafic rocks, water, and moderate amounts of heat.     

An episode of steep geomagnetic inclination 120,000 years ago

The mean inclinations of three sections of 120,000-year-old fine-grained sediments from northern California range from 62 degrees to 66 degrees . These inclinations are significantly steeper than the inclination of the geocentric axial dipole at this site. Because these sediments have probably recorded an actual episode of steep inclination lasting several thousand years, they provide new insights into the significance of mean inclinations shallower than the geocentric axial dipole. Such inclinations are characteristic of fine-grained sediments younger than 35,000 years. The results raise questions about the time-averaged geomagnetic field and about the determination of plate motions from paleomagnetic data.     

Functional characteristics of the blood of the deep-sea hydrothermal vent brachyuran crab

Hemocyanin in the whole blood of the hydrothermal vent brachyuran crab, Bythograea thermydron, has a moderate oxygen affinity (P(50) = 6.6 millimeters of mercury at 2.6 degrees C; pH 7.5), which unlike that of other hemocyanins is independent of temperature over the range 2 degrees to 30 degrees C; carbon dioxide and pH have independent effects on the oxygen affinity of this pigment. The pH effect on affinity is moderate (Deltalog P(50)/DeltapH = -0.34), whereas increased carbon dioxide, which can act both directly and by changing pH, has a much larger effect (Deltalog P(50)/DeltapH = -0.81). This blood has a moderately high degree of cooperativity (Hill cooperativity coefficient, n, was 2.8) and a large oxygen-carrying capacity for a crustacean (4.5 milliliters of oxygen per 100 milliliters of blood). These properties characterize an oxygen transport system whose function appears to be largely independent of the wide range of environmental conditions encountered around the vents.     

Implantation in interplanetary dust of rare-gas ions from solar flares

Measurements of excess Ar(36) + Ar(38) ( released mainly at 1200 degrees C) in magnetic concentrates of Pacific sediments and in a dense concentrate of Greenland dust agree within an order of magnitude with expected concentrations implanted by solar-flare ion streams of energy less than 10 Mev per atomic-mass unit. The agreement implies that more than 10 percent of each concentrate may be extraterrestrial, depending on size distribution and flare spectra. Rare-gas measurements on fine-grained dust can provide data on: solar-flare "paleo-ion" fluxes, energy spectra, and isotopic abundances; identification, mineralogy, and chemistry of interplanetary dust; influx rates to Earth and sedimentation rates of oceanic cores; and lunar-surface residence and mixing times.     

Hemoglobin Kinetics of the Galapagos Rift Vent Tube Worm Riftia pachyptila Jones (Pogonophora; Vestimentifera)

Kinetics of the reactions of Riftia pachyptila hemoglobin with oxygen were followed spectrophotometrically by stopped-flow and laser flash photolysis techniques. The rate of oxygen dissociation increases eightfold over the range of 5 degrees to 20 degrees C (k = 2.2 sec(-1)at 10 degrees C). Oxygen recombination after flash photolysis was biphasic. The rates of both slow and fast phases of the reaction were independent of temperature from 0 degrees to 20 degrees C(k'fast = 7 x 10(6); k'slow = 1 x 16(6) liter mole (-1) sec(-1)). As the oxygen affinity is relatively temperature independent, analysis in terms of the two-state model of cooperativity requires that the conformational equilibrium constant L decrease by about 50-fold between 3 degrees and 15 degrees C.     

Blood function in the hydrothermal vent vestimentiferan tube worm

Extracellular hemoglobin in the whole blood of Riftia pachyptila has a high oxygen affinity (P50 = 1.8 millimeters of mercury at 3 degrees C), a moderate decrease in oxygen affinity at higher temperatures (P50 = 2.7 millimeters of mercury at 14 degrees C), a small effect of carbon dioxide on oxygen affinity (Delta log P50/Delta pH =-0.12), and a high oxygen carrying capacity (up to 11 milliliters of oxygen per 100 milliliters of blood). These characteristics are compatible with the high oxygen demand of chemoautotrophic metabolism in the variable vent environment.     

Hydrocarbons in hydrothermal vent fluids: the role of chromium-bearing catalysts

Fischer-Tropsch type (FTT) synthesis has long been proposed to account for the existence of hydrocarbons in hydrothermal fluids. We show that iron- and chromium-bearing minerals catalyze the abiotic formation of hydrocarbons. In addition to production of methane (CH4aq), we report abiotic generation of ethane (C2H6aq) and propane (C3H8aq) by mineral-catalyzed hydrothermal reactions at 390 degrees C and 400 bars. Results suggest that the chromium component in ultramafic rocks could be an important factor for FTT synthesis during water-rock interaction in mid-ocean ridge hydrothermal systems. This in turn could help to support microbial communities now recognized in the subsurface at deep-sea vents.     

Extending the sub-sea-floor biosphere

Sub-sea-floor sediments may contain two-thirds of Earth's total prokaryotic biomass. However, this has its basis in data extrapolation from ~500-meter to 4-kilometer depths, whereas the deepest documented prokaryotes are from only 842 meters. Here, we provide evidence for low concentrations of living prokaryotic cells in the deepest (1626 meters below the sea floor), oldest (111 million years old), and potentially hottest (~100 degrees C) marine sediments investigated. These Newfoundland margin sediments also have DNA sequences related to thermophilic and/or hyperthermophilic Archaea. These form two unique clusters within Pyrococcus and Thermococcus genera, suggesting unknown, uncultured groups are present in deep, hot, marine sediments (~54 degrees to 100 degrees C). Sequences of anaerobic methane-oxidizing Archaea were also present, suggesting a deep biosphere partly supported by methane. These findings demonstrate that the sub-sea-floor biosphere extends to at least 1600 meters below the sea floor and probably deeper, given an upper temperature limit for prokaryotic life of at least 113 degrees C and increasing thermogenic energy supply with depth.     

Alkanes in fungal spores

The chlamydospores of Ustilago maydis, U. nuda, and Sphacelotheca reiliana were analyzed by gas chromatography and mass spectrometry for their hydrocarbon contents. For the first time we observed that they contain paraffinic hydrocarbons; the average contents were 42, 58, and 146 parts per million, respectively. n-Alkanes having odd numbers of carbon atoms predom-inate, with carbon-chain lengths ranging from C(14) to C(37). The major alkanes are n-C(27) in U. maydis, n-C(27) and n-C(35) in U. nuda, and n-C(29) in S. reiliana. Each type of spore carried a distinctly characteristic population of hydrocarbons.     

High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys

The dimensionless thermoelectric figure of merit (ZT) in bismuth antimony telluride (BiSbTe) bulk alloys has remained around 1 for more than 50 years. We show that a peak ZT of 1.4 at 100 degrees C can be achieved in a p-type nanocrystalline BiSbTe bulk alloy. These nanocrystalline bulk materials were made by hot pressing nanopowders that were ball-milled from crystalline ingots under inert conditions. Electrical transport measurements, coupled with microstructure studies and modeling, show that the ZT improvement is the result of low thermal conductivity caused by the increased phonon scattering by grain boundaries and defects. More importantly, ZT is about 1.2 at room temperature and 0.8 at 250 degrees C, which makes these materials useful for cooling and power generation. Cooling devices that use these materials have produced high-temperature differences of 86 degrees , 106 degrees , and 119 degrees C with hot-side temperatures set at 50 degrees, 100 degrees, and 150 degrees C, respectively. This discovery sets the stage for use of a new nanocomposite approach in developing high-performance low-cost bulk thermoelectric materials.     

沙颍河流域水环境中多环芳烃污染及风险评价

为了研究沙颍河流域上覆水与表层沉积物中多环芳烃(PAHs)的空间分布、来源与生态风险,2018年7月对沙颍河流域30个采样点的上覆水与表层沉积物中16种PAHs使用气相色谱/质谱技术(GC/MS)进行调查研究。结果表明,在上覆水与表层沉积物中ΣPAHs的浓度范围分别为:356.60～2 275.04 ng·L~(-1)、64.27～11 433.63 ng·g~(-1),平均浓度分别为1 051.23 ng·L~(-1)、965.77 ng·g~(-1);各支流上覆水中PAHs含量呈现贾鲁河颍河沙河澧河趋势,表层沉积物中PAHs含量呈现沙河澧河颍河贾鲁河趋势,上覆水与表层沉积物中均以4～6环高环多环芳烃为主,与国内外其他河流相比沙颍河流域上覆水中PAHs处于较高污染水平,表层沉积物中PAHs污染水平相对较低;来源分析表明沙颍河流域上覆水与沉积物中多环芳烃主要来自高温燃烧源;生态风险评估表明上覆水中荧蒽(Fla)、芘(Pyr)、苯并[a]蒽(BaA)、苯并[b]荧蒽(BbF)、苯并[a]芘(BaP)、茚并[1,2,3-cd]芘(IcdP)和苯并[g,h,i]苝(BghiP)等PAHs单体为高风险多环芳烃单体,高分子量多环芳烃(4～6环)对生态风险贡献最大,沙颍河流域上覆水中PAHs属于高风险水平;沉积物中各PAHs单体的浓度除点位S27外均未超过效应区间中值(ERM)与频繁效应浓度值(FEL),表明沙颍河流域沉积物中PAHs潜在生态风险发生概率并不高。     

不同年龄人工香椿林对土壤理化性质的影响

为弄清不同龄级人工香椿林对土壤的改良效果,采用主成分分析法,按I龄级(8～13年)、Ⅱ龄级(15～25年)和Ⅲ龄级(>25年)对香椿林及无林地土壤肥力的整体水平进行了评价。结果表明:不同林级人工香椿林土壤理化性质较无林地均有不同程度的改良效果,香椿林的土壤含水量高于无林地,含水量随林级增加而增高,土壤容重和pH值相对于无林地均有所减小,土壤毛管孔隙和非毛管孔隙均有不同程度增加;土壤有机质、全氮、碱解氮、全磷、速效磷和速效钾含量均高于无林地,且随林级的增高,均呈不同程度增加的趋势;第Ⅲ龄级香椿林土壤全钾含量显著降低;各龄级香椿林地及无林地的土壤肥力大小由高到低依次为Ⅲ龄级>Ⅱ龄级>Ⅰ龄级>无林地。     

Olefins of high molecular weight in two microscopic algae

The hydrocarbon composition of two algae, a golden-brown (Bot-ryococcus braunii) and a blue-green (Anacystis montana), has been investigated by gas chromatography-mass spectrometry. Both show distributions of aliphatic hydrocarbons of odd carbon numbers in the medium and high ranges of molecular weight, with maxima at n-C(17) and n-C(29) for B. braunii and n-C(17) and n-C(29) for A. montana. With the exception of the n-heptadecane of A. montana all the hydrocarbons are monoenes, dienes, or trienes. Since certain continental sediments and oils show similar distributions of alkanes with respect to carbon number, these organisms may be the precursors of the hydrocarbons in these formations.     

Synthesis and Single-Crystal X-ray Structure of a Highly Symmetrical C60 Derivative, C60Br24

C(60) and liquid bromine react to form C(60)Br(24), a crystalline compound isolated as a bromine solvate, C(60)Br(24)(Br(2))(x), The x-ray crystal structure defines a new pattern of addition to the carbon skeleton that imparts a rare high symmetry. The parent C(60) framework is recognizable in C(60)Br(24), but sp(3) carbons at sites of bromination distort the surface, affecting conformations of all of the hexagonal and pentagonal rings. Twenty-four bromine atoms envelop the carbon core, shielding the 18 remaining double bonds from addition. At 150 degrees to 200 degrees C there is effectively quantitative reversion of C(60)Br(24) to C(60) and Br(2).