Thermal cracking of oil under water pressure up to 900 bar at high thermal maturities. 1. gas compositions and carbon isotopes

In this study, a C9+ fraction of saturate-rich Tertiary source rock-derived oil from the South China Sea basin was pyrolyzed in normal and supercritical water using a 25 mL vessel at a range of temperature from 350 to 425 °C for 24 h, to probe pressure effects up to 900 bar on gas yields and their stable carbon isotopic compositions during thermal cracking. Pressure generally retards oil cracking, as evidenced by reduced gas yields, but the trends depend upon the level of thermal evolution. In the early stages of cracking (350 and 373 °C, equivalent vitrinite reflectance of 1.3% R0), pressure still has a strong suppression effect from 200 to 470 bar, which then levels off or is reversed as the pressure is increased further to 750 and 900 bar. Interestingly, the stable carbon isotopic composition of the generated methane becomes enriched in 13C as the pressure increases from 200 to 900 bar. A maximum fractionation effect of ∼3‰ is observed over this pressure range. Due to pressure retardation, the isotopically heaviest methane signature does not coincide with the maximum gas yield, contrary to what might be expected. In contrast, pressure has little effect on ethane, propane, and butane carbon isotope ratios, which show a maximum variation of ∼1‰. The results suggest that the rates of methane-forming reactions affected by pressure control methane carbon isotope fractionation. Based on distinctive carbon isotope patterns of methane and wet gases from pressurized oil cracking, a conceptual model using “natural gas plot” is constructed to identify pressure effect on in situ oil cracking providing other factors excluded. The transition in going from dry conditions to normal and supercritical water does not have a significant effect on oil-cracking reactions as evidenced by gold bag hydrous and anhydrous pyrolysis results at the same temperatures as used in the pressure vessel

Low content of highly reactive iron in sediments from Prydz Bay and the adjacent Southern Ocean: Controlling factors and implications for sedimentary organic carbon preservation

Examining iron (Fe) speciation in marine sediments is critical to understand Fe and carbon biogeochemical cycling in polar regions. In this study, we investigated the speciation of Fe in sediments from Prydz Bay and the adjacent Southern Ocean, and examined the factors controlling Fe speciation and its relationship with total organic carbon (TOC). Our results reveal that unreactive silicate Fe (FeU) is the dominant pool of total Fe (FeT), followed by poorly reactive sheet silicate Fe (FePRS), reducible crystalline Fe oxides (Feox2), easily reducible amorphous/poorly crystalline Fe oxides (Feox1), and magnetite (Femag), with carbonate-associated ferrous Fe (Fecarb) being the smallest pool. The highly reactive Fe (FeHR)/FeT ratios (0.13 ± 0.06) in our study area are among the lowest end-member globally, primarily due to weak bedrock weathering and slow glacier melting. The Feox1/FeT ratios are similar to those in continental shelf and marginal seas containing highly weathered materials, while the Feox2/FeT ratios are significantly lower. This result implicates that low temperature inhibits the aging of iceberg melting-sourced Feox1 potentially, and accordingly the regulation of weathering on the FeHR/FeT ratio is mainly reflected in Feox2/FeT ratio. There are no significant correlations between TOC and FeHR, Fecarb, Feox1 or Feox2 in the research region. Four distinct patterns of TOC/FeHR ratio can be discerned by summarizing the global data set: (a) high TOC/FeHR ratios (> 2.5) are likely the result of high marine primary productivity and low chemically weathered source materials; (b) low TOC/FeHR ratios (< 0.6) are caused by high rates of FeHR inputs and OC remineralization; (c) mid-range TOC/FeHR ratios (0.6 – 2.5) typical of most river particulates and marginal sea sediments indicate the same FeHR and OC sources and/or interactions between each other; (d) both low TOC and FeHR content is the result of low marine primary productivity and weak chemical weathering. Our findings provide new insights into the relationship between FeHR and TOC in polar sediments

Determining the lower limit of Liangzhu culture based on black carbon purification with hydropyrolysis technique

Located in the middle and lower reaches of the Yangtze River, the Liangzhu Culture was one of the most important Neolithic cultures at the dawn of Chinese civilization. However, uncertainty over the lower age limit ending the Liangzhu Culture has resulted in a lack of consensus in defining its timespan. In order to establish the lower age limit, a representative site of late Liangzhu Culture, the Bianjiashan wharf, located in Hangzhou City, Zhejiang Province, Eastern China, was selected for investigation. Wooden stakes in the wharf and charcoals in the sediment profile near to the wharf site were collected for 14C AMS dating. To remove any contaminants, the charcoals were pre-treated by catalytic hydropyrolysis (HyPy) to isolate black carbon fractions (BCHyPy). The continuous charcoal age distribution along the vertical profile of the silt core suggests the continual occupation of the Bianjiashan Site and that the site was developed soon after the river formed. The end of river sedimentation indicates that the demise of the Bianjiashan Site occurred no later than Cal BC 2470 (95% probability). The mean age of the more recent calendar calibrated age range BC 2525 for the BCHyPy residue is consistent with earlier evidence. The wharf, as a typical structure of the late Liangzhu Culture, was established between Cal BC 2635 and 2890 (95% probability). The start of the river charcoal sedimentation was found to have a very similar overall age span and, therefore, the river existed at the Bianjiasha Site for no more than a maximum of just over 400 years, which is taken as the maximum period, it was occupied by the Liangzhu population. In comparison to the fresh charcoal samples, the BCHyPy fractions and products were generally found to have similar probability age distributions. GC-MS analysis of the products (non-BCHyPy fractions) released by HyPy indicated that . Tthe exogenous carbon from plants in the charcoal is present as both covalently bonded and adsorbed species, and was deposited at the same time as the charcoal, suggesting that the sediments have been preserved in a closed environment without disturbance as soon as the river ceased to exist. Thus, HyPy has confirms that there was no significant bias in the charcoal radiocarbon ages from more recent sedimentary organic matter

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants (aBFRs) in sediments from four bays of the Yellow Sea, North China

The distribution characteristics and potential sources of polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants (aBFRs) were investigated in 54 surface sediment samples from four bays (Taozi Bay, Sishili Bay, Dalian Bay, and Jiaozhou Bay) of North China's Yellow Sea. Of the 54 samples studied, 51 were collected from within the four bays and 3 were from rivers emptying into Jiaozhou Bay. Decabromodiphenylethane (DBDPE) was the predominant flame retardant found, and concentration ranged from 0.16 to 39.7 ng g(-1) dw and 1.13-49.9 ng g(-1) dw in coastal and riverine sediments, respectively; these levels were followed by those of BDE 209, and its concentrations ranged from n.d. to 10.2 ng g(-1) dw and 0.05-7.82 ng g(-1) dw in coastal and riverine sediments, respectively. The levels of DBDPE exceeded those of decabromodiphenyl ether (BDE 209) in most of the samples in the study region, whereas the ratio of DBDPE/BDE 209 varied among the four bays. This is indicative of different usage patterns of brominated flame retardants (BFRs) and also different hydrodynamic conditions among these bay areas. The spatial distribution and composition profile analysis indicated that BFRs in Jiaozhou Bay and Dalian Bay were mainly from local sources, whereas transport from Laizhou Bay by coastal currents was the major source of BFRs in Taozi Bay and Sishili Bay. Both the Sigma PBDEs and Sigma aBFRs (sum of pentabromotoluene (PBT), 2,3-diphenylpropyl-2,4,6-tribromophenyl ether (DPTE), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB)) were at low concentrations in all the sediments. This is probably attributable to a combination of factors such as low regional usage of these products, atmospheric deposition patterns, coastal currents transportation patterns, and degradation processes for higher BDE congeners. This paper is the first study that has investigated the levels of DBDPE in the coastal sediments of China's Yellow Sea. (C) 2016 Elsevier Ltd. All rights reserved

Finishing the euchromatic sequence of the human genome

The sequence of the human genome encodes the genetic instructions for human physiology, as well as rich information about human evolution. In 2001, the International Human Genome Sequencing Consortium reported a draft sequence of the euchromatic portion of the human genome. Since then, the international collaboration has worked to convert this draft into a genome sequence with high accuracy and nearly complete coverage. Here, we report the result of this finishing process. The current genome sequence (Build 35) contains 2.85 billion nucleotides interrupted by only 341 gaps. It covers ∼99% of the euchromatic genome and is accurate to an error rate of ∼1 event per 100,000 bases. Many of the remaining euchromatic gaps are associated with segmental duplications and will require focused work with new methods. The near-complete sequence, the first for a vertebrate, greatly improves the precision of biological analyses of the human genome including studies of gene number, birth and death. Notably, the human enome seems to encode only 20,000-25,000 protein-coding genes. The genome sequence reported here should serve as a firm foundation for biomedical research in the decades ahead

Impacts of different factors on seepage and land uplift due to compressed-air injection

In this study, using an in-situ, air-flow test in Essen, the impacts of different factors on multiphase flow and land uplift during and after compressed-air injection were investigated using numerical simulations. A loosely coupled, two-phase flow and geo-mechanical modeling approach, linking two numerical codes (TOUGH2/EOS3 and FLAC3D) was employed to simulate the in-situ, air-flow test for comparing the simulated and measured results. As the compressed air is injected, it flows upwards and laterally, and the vertical effective stress near and above the injection zones decreases owing to the pore pressure increasing here, causing an expansion of the soil skeleton in the corresponding zones. The land uplift, induced mainly by support actions from lower deformed soils, is relevant to the distribution of the porosity increments in the soil interior, and it increases rapidly during air injection. After the compressed-air injection stops, the land uplift decreases gradually to zero due to the overpressure dissipation. With a combination of intensive rainfall, the land uplift is slightly greater near the borehole, but it is significantly greater at a distance from the borehole than the land uplift with no or low rainfall, but the air-injection rate remains almost unchanged due to the unchangeable pore pressure near the injection region. As the intrinsic permeability increases or the air entry pressure decreases in the injected strata, both the land uplift and the air injection rate increase, but the time required for the land uplift to become zero is slightly advanced with either a small permeability or a high air entry pressure