Investigation of additive effects in enantioselective copper-catalysed C-H insertion and aromatic addition reactions of α-diazocarbonyl compounds

Significant enhancements in enantioselectivities and reaction efficiencies in asymmetric copper-catalysed C-H insertion and aromatic addition reactions of α-diazocarbonyl compounds in the presence of various group I salts are reported. For the first time in carbenoid chemistry, evidence for the critical role of the metal cation is described.

Efficient Computation of Electromagnetic Waves in Hydrocarbon Exploration Using the Improved Numerical Mode Matching (NMM) Method

In this study, we developed and improved the numerical mode matching (NMM) method which has previously been shown to be a fast and robust semi-analytical solver to investigate the propagation of electromagnetic (EM) waves in an isotropic layered medium. The applicable models, such as cylindrical waveguide, optical fiber, and borehole with earth geological formation, are generally modeled as an axisymmetric structure which is an orthogonal-plano-cylindrically layered (OPCL) medium consisting of materials stratified planarly and layered concentrically in the orthogonal directions.

In this report, several important improvements have been made to extend applications of this efficient solver to the anisotropic OCPL medium. The formulas for anisotropic media with three different diagonal elements in the cylindrical coordinate system are deduced to expand its application to more general materials. The perfectly matched layer (PML) is incorporated along the radial direction as an absorbing boundary condition (ABC) to make the NMM method more accurate and efficient for wave diffusion problems in unbounded media and applicable to scattering problems with lossless media. We manipulate the weak form of Maxwell's equations and impose the correct boundary conditions at the cylindrical axis to solve the singularity problem which is ignored by all previous researchers. The spectral element method (SEM) is introduced to more efficiently compute the eigenmodes of higher accuracy with less unknowns, achieving a faster mode matching procedure between different horizontal layers. We also prove the relationship of the field between opposite mode indices for different types of excitations, which can reduce the computational time by half. The formulas for computing EM fields excited by an electric or magnetic dipole located at any position with an arbitrary orientation are deduced. And the excitation are generalized to line and surface current sources which can extend the application of NMM to the simulations of controlled source electromagnetic techniques. Numerical simulations have demonstrated the efficiency and accuracy of this method.

Finally, the improved numerical mode matching (NMM) method is introduced to efficiently compute the electromagnetic response of the induction tool from orthogonal transverse hydraulic fractures in open or cased boreholes in hydrocarbon exploration. The hydraulic fracture is modeled as a slim circular disk which is symmetric with respect to the borehole axis and filled with electrically conductive or magnetic proppant. The NMM solver is first validated by comparing the normalized secondary field with experimental measurements and a commercial software. Then we analyze quantitatively the induction response sensitivity of the fracture with different parameters, such as length, conductivity and permeability of the filled proppant, to evaluate the effectiveness of the induction logging tool for fracture detection and mapping. Casings with different thicknesses, conductivities and permeabilities are modeled together with the fractures in boreholes to investigate their effects for fracture detection. It reveals that the normalized secondary field will not be weakened at low frequencies, ensuring the induction tool is still applicable for fracture detection, though the attenuation of electromagnetic field through the casing is significant. A hybrid approach combining the NMM method and BCGS-FFT solver based integral equation has been proposed to efficiently simulate the open or cased borehole with tilted fractures which is a non-axisymmetric model.

(Table 1) Organic carbon, hydrogen and oxygen index and hydrocarbons at DSDP Hole 93-603B

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 27 shipboard-sealed, deep-frozen core samples of DSDP Hole 603B off the east coast of North America were determined by a gas-stripping/thermovaporization method. Total yields representing the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediments vary from 22 to 2400 ng/g of dryweight sediment. Highest yields are measured in the two black shale samples of Core 603B-34 (hydrogen index of 360 and 320 mg/g Corg, respectively). In organic-carbon-normalized units these samples have hydrocarbon contents of 12,700 and 21,500 ng/g Corg, respectively, indicating the immaturity of their kerogens. Unusually high organic-carbonnormalized yields are associated with samples that are extremely lean in organic carbon. It is most likely that they are enriched by small amounts of migrated light hydrocarbons. This applies even to those samples with high organic-carbon contents (1.3-2.2%) of Sections 603B-28-4, 603B-29-1, 603B-49-2, and 603B-49-3, because they have an extremely low hydrocarbon potential (hydrogen index between 40 and 60 mg/g Corg). Nearly all samples were found to be contaminated by varying amounts of acetone that is used routinely in large quantities on board ship during core-cutting procedures. Therefore, 48 samples from the original set of 75 collected had to be excluded from the present study.

Biomarker in Heinrich event layers

There are controversies regarding the origin of Heinrich layer 3 (H3), the massive ice-rafting and meltwater event in the North Atlantic during the last glacial cycle spanning a time window between 29 and 30 kyr B.P. Some argue in favor of a Laurentide Ice Sheet source similar to other Heinrich layers, while a contending view argues for the European ice sheet source. Existing geochemical proxies such as 40Ar/39Ar, 206Pb/204Pb, or epsilon-Nd, etc., could not be used to distinguish among various sources of ice-rafted debris in H3 because of their low abundances, suggesting a background glacial sediment signal. In order to circumvent this problem a biomarker-based approach is used to characterize the provenance of H layers 2, 3, and 4 and other non-Heinrich layers. The presence of hopanes and steranes and their aromatic counterparts in the H layers is incompatible with Recent sediments and is attributed to the transportation of organic matter because of the glacial erosion of source rocks. The most diagnostic and useful signatures of this ancient organic matter in the H layers are the dominance of C34 hopanoids over C33 and the occurrence of isorenieratane along with palaerenieratane. Biomarkers signatures in H layers 2 and 3 of the Labrador Sea suggest no difference in their source. Hydrocarbon distributions suggest that these sediments were derived from the Middle to Late Ordovician and Silurian source rocks of the Hudson Bay of eastern Canada. Biomarker data of the H layer 4 from the northwest Atlantic reveal that the sediments of this layer have a similar source to the H layers in the Labrador Sea.

(Table 1) Low molecular weight hydrocarbon concentrations and organic carbon contents at DSDP Hole 71-511

C2-C8 hydrocarbons (36 compounds identified) from 56 shipboard sealed, deep-frozen core samples of DSDP Leg 71, Site 511, Falkland Plateau, South Atlantic, were analyzed by a combined hydrogen stripping-thermovaporization method. Concentrations, which represent hydrocarbons dissolved in the pore water and adsorbed to the mineral surfaces of the sediment, vary from 24 ng/g of dry weight sediment in Lithologic Unit 4 to 17,400 ng/g in Lithologic Unit 6 ("black shale" unit). Likewise, the organic carbon normalized C2-C8 hydrocarbon concentrations range from 104 to 3.5 x 105 ng/g Corg. The latter value is more than one order of magnitude lower than expected for petroleum source beds in the main phase of oil generation. The low maturity at 600 meters depth is further supported by light hydrocarbon concentration ratios. The change of the kerogen type from Lithologic Unit 5 (Type III) to 6 (Type II) is evidenced by changes in the C6 and C7 hydrocarbon composition. Redistribution phenomena are observed close to the Tertiary-Cretaceous unconformity and at the contact between the "black shale" unit and the overlying Cretaceous chalks and claystones. Otherwise, the low molecular weight hydrocarbons in Hole 511 are formed in situ and remain at their place of formation. The core samples turned out to be contaminated by large quantities of acetone, which is routinely used as a solvent during sampling procedures onboard Glomar Challenger.

(Table 1) Hydrocarbon gas composition of sediment and gas hydrate collected in video-guided grabs from Chapopote

In the Campeche Knolls, in the southern Gulf of Mexico, lava-like flows of solidified asphalt cover more than 1 square kilometer of the rim of a dissected salt dome at a depth of 3000 meters below sea level. Chemosynthetic tubeworms and bivalves colonize the sea floor near the asphalt, which chilled and contracted after discharge. The site also includes oil seeps, gas hydrate deposits, locally anoxic sediments, and slabs of authigenic carbonate. Asphalt volcanism creates a habitat for chemosynthetic life that may be widespread at great depth in the Gulf of Mexico.

Hydrocarbon analyses of submarine mud volcanoes (MV) in the Kumano forearc basin

Twelve submarine mud volcanoes (MV) in the Kumano forearc basin within the Nankai Trough subduction zone were investigated for hydrocarbon origins and fluid dynamics. Gas hydrates diagnostic for methane concentrations exceeding solubilities were recovered from MVs 2, 4, 5, and 10. Molecular ratios (C1/C2<250) and stable carbon isotopic compositions (d13C-CH4 >-40 per mil V-PDB) indicate that hydrate-bound hydrocarbons (HCs) at MVs 2, 4, and 10 are derived from thermal cracking of organic matter. Considering thermal gradients at the nearby IODP Sites C0009 and C0002, the likely formation depth of such HCs ranges between 2300 and 4300 m below seafloor (mbsf). With respect to basin sediment thickness and the minimum distance to the top of the plate boundary thrust we propose that the majority of HCs fueling the MVs is derived from sediments of the Cretaceous to Tertiary Shimanto belt below Pliocene/Pleistocene to recent basin sediments. Considering their sizes and appearances hydrates are suggested to be relicts of higher MV activity in the past, although the sporadic presence of vesicomyid clams at MV 2 showed that fluid migration is sufficient to nourish chemosynthesis-based organisms in places. Distributions of dissolved methane at MVs 3, 4, 5, and 8 pointed at fluid supply through one or few MV conduits and effective methane oxidation in the immediate subsurface. The aged nature of the hydrates suggests that the major portion of methane immediately below the top of the methane-containing sediment interval is fueled by current hydrate dissolution rather than active migration from greater depth.

Analyses of hydrocarbon gases and sulphate in sediments from the King George Basin, Antarctica

Thermogenic hydrocarbons, formed by the thermal alteration of organic matter, are encountered in several piston core stations in the King George Basin, Anatarctica. These hemipelagic sediments are being deposited in an area of active hydrothermalism, associated with the back-arc spreading in the Bransfield Strait. The lateral extent of sediments infiltrated by the hydrothermally influenced interstitial fluids is characterized by basalt diapiric intrusions and is delineated by an acoustically turbid zone in the sediments of the eastern part of the basin. Iron-sulphide-bearing veins and fractures cut across the sediment in several cores; they appear to be conduits for flow of hydrothermally altered fluids. These zones have the highest C2+ and ethene contents. The thermogenic hydrocarbons have molecular C1/(C2 + C3) ratios typically < 50 and delta13CH4 values between -38? and -48?, indicating an organic source which has undergone strong thermal stress. Several sediment cores also have mixed gas signatures, which indicate the presence of substantial amounts of bacterial gas, predominantly methane. Hydrocarbon generation in the King George Basin is thought to be a local phenomenon, resulting from submarine volcanism with temperatures in the range 70-150°C. There are no apparent seepages of hydrocarbons into the water column, and it is not believed that significant accumulation of thermogenic hydrocarbons reside in the basin.

(Table) Content of organic compounds in the bottom sediments of the Volga River estuary

Materials from different spheres of the Earth are ultimately delivered to bottom sediments, which serve as a natural recorder of the functioning of other spheres and originate as a result of the accumulation of their substances. Sedimentary material and species of river-transported elements are subjected to dramatic reworking in marginal filters, where river and sea waters are mixed. These processes are most important for the Caspian Sea, where runoffs of rivers (especially the Volga River) and the intense development and transportation of hydrocarbon fuel by tankers and pipelines (related to the coastal petroleum industry in the Sumgait and Baku ports, Apsheron Peninsula) are potential sources of hydrocarbon pollution. Previously obtained data showed that the total content of hydrocarbon fraction (i.e., the sum of aliphatic hydrocarbons (AHC) and polycyclic aromatic hydrocarbons (PAH)) in bottom sediments varied within 29-1820 µg/g. The content of petroleum hydrocarbons in the northeastern Caspian region varied from 0.052 to 34.09 µg/g with the maximum content in the Tengiz field. The content of six polyarenes in the Volga delta sediments was no more than 40 ng/g. To determine the recent HC pollution of bottom sediments and trends in the functioning of the Volga marginal filter, in summer of 2003 and 2004 we analyzed bottom sediments (58 samples) in the river waterway; Kirovsk channel; Bakhtemir and Ikryanoe branches; tributaries of the Kizan, Chagan, and other rivers; and the Caspian seashore.

Contents of hydrocarbons in waters and bottom sediments of the southwestern Amur Bay (Sea of Japan) in April 2005

Abundances and compositions of aliphatic hydrocarbons (AHC) and polyaromatic hydrocarbons (PAH) were investigated in water and bottom sediments of the southwestern Amur Bay, Sea of Japan. Water contained 0-129 ?g/l AHC (average 42.2 ?g/l) and 5-85 ng/l PAH (average 18 ng/l). Bottom sediments contained 168-2098 ?g/g AHC and 7.2-1100 ng/g dry mass PAH. It was shown that input of anthropogenic hydrocarbons is better recorded by molecular markers than by distribution of AHC and PAH concentrations. Discovery of elevated hydrocarbon concentrations in the bottom water layer suggests that bottom sediments induced secondary contamination of the water body.

Modulation of CYP1A1 by PKC Inhibitors and TPA Pre-Treatments in MH1C1 Rat Hepatoma Cells Exposed to 3 -Methylcholanthrene

Cytochrome P4501A1 (CYP1A1), an enzyme known to metabolize polycyclic aromatic hydrocarbons, is regulated by the aryl hydrocarbon receptor (AhR). The involvement of protein kinase C (PKC) in the regulation of AhR signal transduction pathway, has been widely studied but the role of specific PKC isoform(s) involved in this process it is not well clarified. To study which PKC isoform(s) is implicated in the regulation of CYP1A1, in the poorly tumorigenic MH1C1 rat hepatoma cells, we examined the effects of some PKC pharmacological inhibitors, Calphostin C (CAL), Staurosporine (STA) and H7, and of 12-0-tetradecanoyl phorbol 13-acetate (TPA), a PKC activator, on basal and 3- methylcholanthrene (MC)-induced CYP1A1 protein expression and mediated ethoxyresorufin O-deethylation (EROD) activity. In parallel, the activities of PKC-α, -βI, -δ and -ε isoforms, the most expressed in MH1C1 cells, were monitored. After pre-treatment with CAL, STA and H7, the MC-induced CYP1A1 protein and EROD activity were rapidly reduced with temporal profile similar to the profile of the activity of α and β1 PKC isoforms. Moreover, TPA pre-treatment induced a biphasic effect on EROD activity, and a decline of PKC -βI and -α, in first instance, and -δ and -ε activities later on. These findings clearly show that, in MH1C1 cells, PKC is involved in CYP1A1 regulation and that α and βI classic PKC isoforms play an active role in modulating this process.

Exploring hydrocarbonoclastic bacterial communities in the estuarine surface microlayer

Bacteria that degrade polycyclic aromatic hydrocarbons (PAHs) in the estuarine surface microlayer (SML) of the Ria de Aveiro, Portugal—which is chronically polluted with oil hydrocarbons (OH)—were isolated and characterized; Pseudomonas was dominant among the PAH-degrading bacteria. Screening for PAH dioxygenase genes detected almost identical nahAc genes (encoding the alpha subunits of naphthalene dioxygenase) in 2 phylogenetically distinct isolates: Pseudomonas sp. and an unknown species of the family Enterobacteriaceae; this suggested that horizontal transfer of nah genes might be involved in PAH degradation in the SML. We also investigated the effect of PAH contamination on the spatial variability of the bacterioneuston along a gradient of pollution in the estuarine system of the Ria de Aveiro. Culture-independent techniques—fluorescence in situ hy - bridization (FISH) and denaturing-gradient gel electrophoresis (DGGE)—revealed a similar structure among the bacterioneuston communities along the estuary. In contrast, we detected differences in the relative abundance and diversity of organisms of the Gammaproteobacteria, including those of the genus Pseudomonas (which belongs to the Gammaproteobacteria). This is the first insight into the hydrocarbonoclastic bacterial communities in the SML of an estuarine area polluted with hydrocarbons. Our findings highlight the importance of SML-adapted hydrocarbonoclastic bacterioneuston as a potential source of new PAH-degrading bacteria (including new pseudomonads) with potential use in the bioremediation of hydrocarbon-polluted ecosystems.