Influence of physiology and climate on δD of leaf wax n-alkanes from C3 and C4 grasses

We measured hydrogen isotope compositions (δD) of high-molecular-weight n-alkanes (C₂₇-C₃₃) from grasses grown in greenhouses and collected from the US Great Plains. In both cases, n-alkanes from C₄ grasses are enriched in D by more than 20‰ relative to those from C₃ grasses. The apparent enrichment factor (ε_C29-GW) between C₂₉n-alkane and greenhouse water is −165 ± 12‰ for C₃ grasses and −140 ± 15‰ for C₄ grasses. For samples from the Great Plains, δD values of C₂₉n-alkanes range from −280 to −136‰, with values for C₄ grasses ca. 21‰ more positive than those for C₃ grasses from the same site. Differences in C₃ and C₄ grass n-alkane δD values are consistent with the shorter interveinal distance in C₄ grass leaves, and greater back-diffusion of enriched water from stomata to veins, than in C₃ grass leaves. Great Plains’ grass n-alkane isotopic ratios largely reflect precipitation δD values. However, the offset or apparent fractionation between n-alkanes and precipitation is not uniform and varies with annual precipitation and relative humidity, suggesting climatic controls on lipid δD values. The dryer sites exhibit smaller absolute apparent fractionation indicative of D-enrichment of source waters through transpiration and/or soil evaporation. To explore the relationship between climate and n-alkane δD values, we develop three models. (1) The ‘direct analog’ model estimates δD_C29 values simply by applying the apparent enrichment factors, ε_C29-GW, observed in greenhouse grasses to precipitation δD values from the Great Plains. (2) The ‘leaf-water’ model uses a Craig-Gordon model to estimate transpirational D-enrichment for both greenhouse and field sites. The transpiration-corrected enrichment factors between C₂₉ and bulk leaf-water, ε_C29-GW, calculated from the greenhouse samples (−181‰ for C₃ and −157‰ for C₄) are applied to estimate δD_C29 values relative to modeled bulk leaf-water δD values. (3) The ‘soil- and leaf-water’ model estimates the combined effects of soil evaporation, modeled by analogy with a flow-through lake, and transpiration on δD_C29 values. Predictions improve with the addition of the explicit consideration of transpiration and soil evaporation, indicating that they are both important processes in determining plant lipid δD values. D-enrichment caused by these evaporative processes is controlled by relative humidity, suggesting that important climatic information is recorded in leaf wax n-alkane δD values. Calibration studies such as this one provide a baseline for future studies of plant-water-deuterium systematics and form the foundation for interpretation of plant wax hydrogen isotope ratios as a paleo-aridity proxy.     

Carboxylic acid distribution patterns of temperate C3 and C4 crops

Agricultural grasses cover a major part of the land surface in temperate agro-ecosystems and contribute significantly to the formation of soil organic matter. Crop-derived lipids are assumed to be responsible for fast carbon turnover in soils. Differences in lipid distribution patterns between crops following C₃ and C₄ photosynthesis pathways have rarely been described, but could be useful for source apportionment of crop-derived input into soils or sediments. The distribution of long chain n-carboxylic acids (C₂₂, C₂₄, C₂₆) reveals significant differences between crop plants following either the C₃ or the C₄ photosynthetic carbon fixation pathway. The plant compartments leaves, stems and roots of C₄ plants contain relatively large proportions (> 40%) of n-C₂₄ carboxylic acid when compared to C₃ plants. These reveal larger relative proportions of n-C₂₂ and n-C₂₆ acids, whose relative abundance is subject to change between different plant compartments and during the growing season. The carboxylic acid ratio [CAR = n-C₂₄/(n-C₂₂ + n-C₂₆) carboxylic acids] provides distinct ratios for C₄ (> 0.67) and C₃ crops (< 0.67) and can thus be used as a molecular marker for the differentiation of crop plant biomass. In combination with the bulk stable carbon isotopic composition (δ¹³C) the CAR can be used as a tool for the estimation of the C₄ derived carbon proportion in soils or sediments.     

C3、C4植物及其硅酸体研究的古生态意义

本文概述了C₃、C₄植物生理、生态学意义、地理分布及其相应的植物硅酸体形态,进一步讨论了C₃、C₄植物硅酸体形态在我国表层土壤中的分布规律及生态学意义。最后,对洛川黑木沟全新世黄土剖面中C₃、C₄植物硅酸体形态变化特点做了分析,表明地层中典型的C₃、C₄植物硅酸体形态,作为古植物的直接证据,可以较准确地反映古植被、古环境的变化规律。     

NanoSIMS isotopic analysis of small presolar grains: Search for Si3N4 grains from AGB stars and Al and Ti isotopic compositions of rare presolar SiC grains

We report isotopic ratio measurements of small SiC and Si₃N₄ grains, with special emphasis on presolar SiC grains of type Z, and new nucleosynthesis models for ²⁶Al/²⁷Al and the Ti isotopic ratios in asymptotic giant branch (AGB) stars. With the NanoSIMS we analyzed 310 SiC grains from Murchison (carbonaceous CM2 chondrite) separate KJB (diameters 0.25-0.45 μm) and 153 SiC grains from KJG (diameters 1.8-3.7 μm), 154 SiC and 23 Si₃N₄ grains from Indarch (enstatite EH4 chondrite) separate IH6 (diameters 0.25-0.65 μm) for their C and N isotopic compositions, 549 SiC and 142 Si₃N₄ grains from IH6 for their C and Si isotopic compositions, 13 SiC grains from Murchison and 66 from Indarch for their Al-Mg compositions, and eight SiC grains from Murchison and 10 from Indarch for their Ti isotopic compositions. One of the original objectives of this effort was to compare isotopic analyses with the NanoSIMS with analyses previously obtained with the Cameca IMS 3f ion microprobe. Many of the Si₃N₄ grains from Indarch have isotopic anomalies but most of these apparently originate from adjacent SiC grains. Only one Si₃N₄ grain, with ¹³C and ¹⁴N excesses, has a likely AGB origin. The C, N, and Si isotopic data show that the percentage of SiC grains of type Y and Z increase with decreasing grain size (from ∼1% for grains >2 μm to ∼5-7% for grains of 0.5 μm), providing an opportunity for isotopic analyses in these rare grains. Our measurements expand the number of Al-Mg analyses on SiC Z grains from 4 to 23 and the number of Ti analyses on Z grains from 2 to 11. Inferred²⁶Al/²⁷Al ratios of Z grains are in the range found in mainstream and Y grains and do not exceed those predicted by models of AGB nucleosynthesis. Cool bottom processing (CBP) has been invoked to explain the low ¹²C/¹³C ratios of Z grains, but this process apparently does not lead to increased ²⁶Al production in the parent stars of these grains. This finding is in contrast to presolar oxide grains where CBP is needed to explain their high ²⁶Al/²⁷Al ratios. The low ^46,47,49Ti/⁴⁸Ti ratios found in Z grains and their correlation with low ²⁹Si/²⁸Si ratios extend the trend seen in mainstream grains and confirm an origin in low-metallicity AGB stars. The relatively large excesses in ³⁰Si and ⁵⁰Ti in Z grains are predicted by our models to be the result of increased production of these isotopes by neutron-capture nucleosynthesis in low-metallicity AGB stars. However, the predicted excesses in ⁵⁰Ti (and ⁴⁹Ti) are much larger than those found. Even lowering the strength of the ¹³C pocket cannot solve this discrepancy in a consistent way.     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

Reconstructing the response of C3 and C4 plants to decadal-scale climate change during the late Pleistocene in southern Illinois using isotopic analyses of calcified rootlets

The δ¹³C and δ¹⁸O values of well-preserved carbonate rhizoliths (CRs) provide detailed insights into changes in the abundance of C₃ and C₄ plants in response to approximately decadal-scale changes in growing-season climate. We performed stable isotope analyses on 35-40 CRs sampled at 1-cm intervals from an 18-cm-thick paleosol formed in southern Illinois during Wisconsin interstadial 2. Minimum δ¹³C values show little variation with depth, whereas maximum values vary dramatically, and average values show noticeable variability; maximum δ¹⁸O values vary less than the minimum δ¹⁸O values. These findings indicate that a diverse and stable C₃ flora with a limited number of C₄ grass species prevailed during this interval, and suggest that the maximum growing-season temperatures were relatively stable, but minimum growing-season temperatures varied considerably. Two general patterns characterize the relationships between the δ¹³C and δ¹⁸O values obtained from the 1-cm samples. In some cases, low δ¹³C values correspond to low δ¹⁸O values and high δ¹³C values correspond to high δ¹⁸O values, suggesting that cooler growing-season temperatures favored C₃ and warmer growing-season temperatures favored C₄ plants. In other cases, low δ¹³C values correspond to high δ¹⁸O values, likely suggesting that wetter growing-season conditions were favorable to C₃ plants. The high density of well-preserved CRs in this paleosol provides a unique opportunity to study detailed ecological responses to high-resolution variability in growing-season climate.     

南黄海黑碳记录的中国东部晚上新世以来C3/C4植被演化

陆地植被是全球生态系统的重要组成部分,其C₃/C₄组成类型及演化进程对于理解过去生态系统对全球变化的响应及适应机制具有重要科学意义。晚上新世以来东亚C₄植被扩张的时间、过程和机制等仍存很大争议,尤其缺少长江流域C₃/C₄植被相对丰度演化的地质记录及不同纬度植被演化的时空综合对比。本研究利用大陆架科学钻探计划在南黄海钻取的CSDP-1孔约300.10m长的岩芯沉积物的黑碳含量、通量及碳同位素组成,重建了晚上新世以来中国东部地区C₃/C₄植被演化历史。研究发现,在晚上新世（约3.0~2.6Ma）,黑碳碳同位素组成发生明显正偏,指示沉积物源区长江流域的C₄植被相对丰度的增加,可能受到了中低纬度地区干旱化增强及大气CO₂浓度下降的共同影响;而中高纬度如黄土高原地区的C₄植被则相对减少,推测更低的温度可能成为了C₄植被生长的限制因素。中更新世（约1.0Ma）以来,黑碳碳同位素比值整体负偏,表明源区C₄植被相对丰度减少。尽管沉积物源区在0.8Ma左右转变为纬度更高的黄河流域,但东亚不同纬度地区记录均显示了碳同位素负偏,表明这是一区域现象,分析认为全球气候变冷是影响中更新世以来C₄植被演化的重要因素。本研究揭示出,除了全球性的因素（大气CO₂浓度）外,区域气候（温度和干旱度）在东亚地区C₃/C₄植被长期演化中具有重要影响。

     

Unusual C35 and C36 alkenones in a paleoceanographic benchmark strain of Emiliania huxleyi

Our specimen of the cultured Emiliania huxleyi strain (CCMP1742, also known as NEPCC55a) that provides the benchmark for -based paleothermometry has started producing, for reasons yet unclear, major amounts of three new alkenones identified as ω15,22-C₃₅ methyl ketone, ω15,22-C₃₆ ethyl ketone and ω16,23-C₃₆ methyl ketone. Comparison of these structures with those established now by the same OsO₄ derivatization method applied to the di-unsaturated C₃₇, C₃₈ and C₃₉ alkenones typically found in this organism provides insight into the possible pathway for their biosynthesis. Isothermal batch culture experiments also show the content and composition of these new compounds change systematically and quite significantly in cells when subjected to environmental conditions such as nutrient depletion, variation in light availability and prolonged darkness. Alkenones of similarly unusual short-chain length are evident in suspended particulate materials from present day surface waters in the Ligurian Sea (Mediterranean) and in two different Holocene time horizons (Unit I and Unit II deposits) in Black Sea sediments. However, the positions of the double bonds are different from those that we now report in our culture, implying a different biosynthetic sequence. These alkenones are most likely derived from another, as yet unknown, haptophyte species. If this other organism accounts for all documented occurrences of these compounds in natural samples, then either it has a capacity for growth over a remarkably wide salinity range or surface water salinity in the early Holocene Black Sea may not have been as low as is currently believed.     

GC-MS characterisation of C27 and C28 triterpanes in sediments and petroleum

Earlier studies have shown that an unusual C₂₇ triterpane is abundant in sediments from the Norwegian Continental Shelf and the North Sea. This compound was assigned the tentative structures 24,28,30-trisnormoretane or 25,28,30-trisnormoretane, but we have now shown from detailed retention time measurements and a reinterpretation of the mass spectral data that its correct structure is 17α(H),18α (H),21β(H)-25,28,30-trisnorhopane. Two other triterpanes, 25,28,30-trisnormoretane and 28,30-bisnormoretane, have also been identified as minor constituents of extracts of sediments from the North Sea. Possible origins for these compounds are discussed.     

末次冰盛期以来东北地区霍拉盆地湖泊沉积物记录的C3/C4植被演化

利用气相色谱-质谱（GC-MS）联用技术对我国大兴安岭北部霍拉盆地湖泊沉积物进行了有机分子地球化学分析,检测出了丰富的正构烷烃。本研究主要讨论了正构烷烃的分布特征及其长链正构烷烃的单体碳同位素组成,结合AMS ¹⁴C年代数据,重建中国东北大兴安岭地区末次冰盛期以来的古植被及古气候变化。正构烷烃分布特征表明,末次冰盛期以来,霍拉盆地湖沼沉积物长链正构烷烃呈现明显的奇碳优势,主峰碳主要为nC₃₁,指示有机质主要来源于陆生高等植物,且草本植物输入占优势,木本植物输入丰富。陆生高等植物来源的长链正构烷烃单体稳定碳同位素的记录显示,末次冰盛期晚期以来古莲剖面沉积物长链正构烷烃（nC₂₇、nC₂₉和nC₃₁）稳定碳同位素整体偏负;此外,利用二元模式估算了C₃/C₄植物相对生物量,结果表明,自末次冰盛期以来我国东北大兴安岭地区C₃植物占绝对优势,然而在全新世大暖期C₄植物生物量呈现明显扩张趋势,这表明气候变暖对C₄植物量的增加有重要影响。

     

Phosphoinnelite, Ba4Na3Ti3Si4O14(PO4,SO4)2(O,F)3, a new mineral species from peralkaline pegmatite of the Kovdor pluton, Kola Peninsula

Phosphoinnelite, an analogue of innelite with P > S, has been found in a peralkaline pegmatite vein crosscutting calcite carbonatite at the phlogopite deposit, Kovdor pluton, Kola Peninsula. Cancrinite (partly replaced with thomsonite-Ca), orthoclase, aegirine-augite, pectolite, magnesioarfvedsonite, golyshevite, and fluorapatite are associated minerals. Phosphoinnelite occurs as lath-shaped crystals up to 0.2 × 1 × 6 mm in size, which are combined typically in bunch-, sheaf-, and rosettelike segregations. The color is yellow-brown, with vitreous luster on crystal faces and greasy luster on broken surfaces. The mineral is transparent. The streak is pale yellowish. Phosphoinnelite is brittle, with perfect cleavage parallel to the {010} and good cleavage parallel to the {100}; the fracture is stepped. The Mohs hardness is 4.5 to 5. Density is 3.82 g/cm³ (meas.) and 3.92 g/cm³ (calc.). Phosphoinnelite is biaxial (+), α = 1.730, β = 1.745, and γ = 1.764, 2V (meas.) is close to 90°. Optical orientation is Z^c ∼ 5°. Chemical composition determined by electron microprobe is as follows (wt %): 6.06 Na₂O, 0.04 K₂O, 0.15 CaO, 0.99 SrO, 41.60 BaO, 0.64 MgO, 1.07 MnO, 1.55 Fe₂O₃, 0.27 Al₂O₃, 17.83 SiO₂, 16.88 TiO₂, 0.74 Nb₂O₅, 5.93 P₂O₅, 5.29 SO₃, 0.14 F, −O=F₂ = −0.06, total is 99.12. The empirical formula calculated on the basis of (Si,Al)₄O₁₄ is (Ba_3.59Sr_0.13K_0.01)_Σ3.73(Na_2.59Mg_0.21Ca_0.04)_Σ3.04(Ti_2.80Fe _0.26 ³⁺ Nb_0.07)_Σ3.13[(Si_3.93Al_0.07)_Σ4O₁₄(P_1.11S_0.87)_Σ1.98O_7.96](O_2.975F_0.10)_Σ3.075. The simplified formula is Ba₄Na₃Ti₃Si₄O₁₄(PO₄,SO₄)₂(O,F)₃. The mineral is triclinic, space group P or P1. The unit cell dimensions are a = 5.38, b = 7.10, c = 14.76 ?; α = 99.00°, β = 94.94°, γ = 90.14°; and V = 555 ?³, Z = 1. The strongest lines of the X-ray powder pattern [d, ? in (I)(hkl)] are: 14.5(100)(001), 3.455(40)(103), 3.382(35)(0 2), 2.921(35)(005), 2.810(40)(1 4), 2.683(90)(200, 01), 2.133(80)( 2), 2.059(40)(204, 1 3, 221), 1.772(30)(0 1, 1 7, 2 2, 2 3). The infrared spectrum is demonstrated. An admixture of P substituting S has been detected in the innelite samples from the Inagli pluton (South Yakutia, Russia). An innelite-phosphoinnelite series with a variable S/P ratio has been discovered. The type material of phosphoinnelite has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? I.V. Pekov, N.V. Chukanov, I.M. Kulikova, D.I. Belakovsky, 2006, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2006, No. 3, pp. 52–60. Considered and recommended by the Commission on New Minerals and Mineral Names, Russian Mineralogical Society, May 9, 2005. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, July 4, 2005 (proposal 2005-022).     

Geochemistry of C25 and C30 biogenic alkenes in sediments of the narragansett bay estuary

The distributions of a series of structurally related C₂₅ and C₃₀ biogenic alkenes in sediments of the Narragansett Bay estuary have been determined. The suite of alkenes detected differs both quantitatively and qualitatively from those previously reported in other estuanne and coastal regions. Four C₂₅ mono- and dienes and one C₃₀ diene comprise 73–91% of the total alkenes in all surface (upper 2.5–5 cm) sediments analyzed. However, significant geographic variations exist in the relative abundance of these five compounds throughout the estuary. A comparison of alkene concentrations with δ¹³C of the bulk sedimentary organic matter has shown that the geographic variations of some alkenes reflect the distribution of marine organic matter, suggesting a marine source for these compounds. The distributions of other alkenes are not similarly correlated. In particular, concentrations of the C₃₀ diene are relatively constant and exhibit no dependence on the origin of organic matter in these sediments. This distribution implies an in situ production of this alkene throughout the estuary. Analysis of several sediment cores reveals that alkene concentrations are generally highest at the surface and decrease to low, constant values within the upper 25 cm. An exception is the subsurface concentration of one C₂₅ diene, which exhibits an increase at the same depth in two separate upper bay cores.     

黄土高原西部地区末次冰期和全新世有机碳同位素变化与C3/C4植被类型转换研究

文章利用黄土高原西缘代表性的塬堡剖面有机碳同位素数据,估算了末次冰期以来地表植被中C₃/C₄植 物的相对丰度,指示出研究区域末次冰期几乎为纯粹的C₃植物,而全新世为C₃植物占优势的C₃和C₄混合植被类 型。温度是控制中国黄土高原C₄植物是否发生的关键性气候因素,末次冰期向全新世转化过程中存在的某“阈值 温度”控制了两种植被类型的存在。全新世土壤有机碳同位素偏正于末次冰期,符合前人研究得到的认识。末次 冰期间冰段(MIS3)至盛冰期,土壤有机碳同位素为偏正变化趋势,符合现代C₃植物本身随气候条件改变的碳同位 素组成变化。研究表明,利用黄土-古土壤有机碳同位素进行古气候变化研究,不能只将有机碳同位素简单的解 释为C₃/C₄植物相对丰度的变化,在单一植被类型下,还需要考虑植物本身碳同位素组成随气候条件的变化;另外, 研究还说明,我国黄土高原不同地区同时段土壤有机碳同位素值可以不同,其变化可以不具有相同的趋势,因此, 简单将有机碳同位素偏正归因于夏季风增强是值得商榷的。     

Generation and migration of light hydrocarbons (C2C7) in sedimentary basins

Sixty-five samples from selected source bed-type shale sequences from three exploration wells were analysed for yield and detailed composition of light hydrocarbons(C₂C₇) by a new hydrogen stripping/capillary gas chromatographic technique. In spite of low maturation levels (0.35–0.55% vitrinite reflectance), significant generation of ethane and propane was recognized in a Jurassic source bed sequence bearing hydrogen-poor kerogens. Light hydrocarbon generation in another and mature Jurassic source rock sequence is controlled by kerogen quality. Associated with a change from hydrogen-poor to hydrogen-rich kerogens, yields of total and most individual hydrocarbons exhibit orders-of-magnitude increases. At the same time, iso/n-alkane ratios for butanes, pentanes and heptanes decrease significantly. A study of an interbedded marine/nonmarine coal-bearing sequence of Upper Carboniferous age from the Ruhr area, West Germany, revealed that a marine shale unit in comparison to the adjacent coal seam is more prolific in generating n-alkanes of increasing molecular size.A case history for migration of light hydrocarbons by means of diffusion through shales is presented. In two shallow core holes in Campanian/Maastrichtian shales in West Greenland, upward diffusion of ethane to pentane range hydrocarbons is an active process within the near-surface 3 m interval. Diffusive losses within this interval amount to 99.8% for propane, 85.6% for n-butane and 38.9% for n-pentane.     

Solubility of pyromorphite Pb5(PO4)3Cl-mimetite Pb5(AsO4)3Cl solid solution series

Pyromorphite Pb₅(PO₄)₃Cl and mimetite Pb₅(AsO₄)₃Cl are isostructural minerals with apatite. Due to their high environmental stability, they have gained considerable attention as metals sequestration agents in water treatment and contaminated soil remediation. Pyromorphite and mimetite can form a continuous solid solution series in near-Earth surface environments. Precipitation of the end members and intermediate members of the series is likely to occur in the areas where the cost-effective in situ immobilization reclamation method, based on phosphate amendments, is applied. In contrast to the widely studied thermodynamic parameters of pyromorphite and mimetite, knowledge of the thermodynamics of their solid solutions is sparse. To supplement the data, a number of compounds from the pyromorphite-mimetite series were synthesized at room temperature using a method to simulate the conditions in the near-Earth surface environments. Afterwards, batch dissolution and dissolution-recrystallization experiments of seven synthesized precipitates were conducted at 25 °C, pH = 2 and in a 0.05 M KNO₃ background electrolyte. The experiments were carried out for a period of 6 (dissolution) and 14 (dissolution-recrystallization) months. A plateau in the [Pb] evolution patterns was used to determine equilibrium. All seven dissolutions were congruent, and the ionic activity products (IAP) of the minerals from the pyromorphite-mimetite solid solution series were calculated based on the dissolution reaction: . The IAPs for pyromorphite and mimetite exhibit a significant difference in values over three orders of magnitude between approximately 10⁻⁷⁹ for pyromorphite and approximately 10⁻⁷⁶ for mimetite. The series appeared to be ideal, and Lippmann and Roozboom diagrams were used for better understanding of its thermodynamics. The results indicated a strong tendency of pyromorphite to partition into the solid phase in the series, which explains some of the naturally observed phenomena. The improvement of the lattice stability of the mimetite due to isostructural phosphate substitutions in anionic sites was observed. The thermodynamic data reported in this study supplement existing databases used in geochemical modeling.     

The effect of minor to moderate biodegradation on C5 to C9 hydrocarbons in crude oils

A suite of 18 oils from the Barrow Island oilfield, Australia, and a non-biodegraded reference oil have been analysed compositionally in order to detail the effect of minor to moderate biodegradation on C₅ to C₉ hydrocarbons. Carbon isotopic data for individual low molecular weight hydrocarbons were also obtained for six of the oils. The Barrow Island oils came from different production wells, reservoir horizons, and compartments, but have a common source (the Upper Jurassic Dingo Claystone Formation), with some organo-facies differences. Hydrocarbon ratios based on hopanes, steranes, alkylnaphthalenes and alkylphenanthrenes indicate thermal maturities of about 0.8% R_c for most of the oils. The co-occurrence in all the oils of relatively high amounts of 25-norhopanes with C₅ to C₉ hydrocarbons, aromatic hydrocarbons and cyclic alkanes implies that the oils are the result of multiple charging, with a heavily biodegraded charge being overprinted by fresher and more pristine oil. The later oil charge was itself variably biodegraded, leading to significant compositional variations across the oilfield, which help delineate compartmentalisation. Biodegradation resulted in strong depletion of n-alkanes (>95%) from most of the oils. Benzene and toluene were partially or completely removed from the Barrow Island oils by water washing. However, hydrocarbons with lower water solubility were either not affected by water washing, or water washing had only a minor effect. There are three main controls on the susceptibility to biodegradation of cyclic, branched and aromatic low molecular weight hydrocarbons: carbon skeleton, degree of alkylation, and position of alkylation. Firstly, ring preference ratios at C₆ and C₇ show that isoalkanes are retained preferentially relative to alkylcyclohexanes, and to some extent alkylcyclopentanes. Dimethylpentanes are substantially more resistant to biodegradation than most dimethylcyclopentanes, but methylhexanes are depleted faster than methylpentanes and dimethylcyclopentanes. For C₈ and C₉ hydrocarbons, alkylcyclohexanes are more resistant to biodegradation than linear alkanes. Secondly, there is a trend of lower susceptibility to biodegradation with greater alkyl substitution for isoalkanes, alkylcyclohexanes, alkylcyclopentanes and alkylbenzenes. Thirdly, the position of alkylation has a strong control, with adjacent methyl groups reducing the susceptibility of an isomer to biodegradation. 1,2,3-Trimethylbenzene is the most resistant of the C₃ alkylbenzene isomers during moderate biodegradation. 2-Methylalkanes are the most susceptible branched alkanes to biodegradation, 3-methylalkanes are the most resistant and 4-methylalkanes have intermediate resistance. Therefore, terminal methyl groups are more prone to bacterial attack compared to mid-chain isomers, and C₃ carbon chains are more readily utilised than C₂ carbon chains. 1,1-Dimethylcyclopentane and 1,1-dimethylcyclohexane are the most resistant of the alkylcyclohexanes and alkylcyclopentanes to biodegradation. The straight-chained and branched C₅–C₉ alkanes are isotopically light (depleted in ¹³C) relative to cycloalkanes and aromatic hydrocarbons. The effects of biodegradation consistently lead to enrichment in ¹³C for each remaining hydrocarbon, due to preferential removal of ¹²C. Differences in the rates of biodegradation of low molecular weight hydrocarbons shown by compositional data are also reflected in the level of enrichment in ¹³C. The carbon isotopic effects of biodegradation show a decreasing level of isotopic enrichments in ¹³C with increasing molecular weight. This suggests that the kinetic isotope effect associated with biodegradation is site-specific and often related to a terminal carbon, where its impact on the isotopic composition becomes progressively ‘diluted’ with increasing carbon number.     

K-H3OFe3(SO4)2(OH)6铁矾的XRD研究

根据X射线衍射(XRD)分析发现: A Fe₃(SO₄)₂(OH)₆(A=K⁺、H₃O⁺)系列铁钒的XRD数据十分相近,难以用XRD区别,需通过能谱(EDS)辅助分析,才能区分此类铁矾。另外,此类铁矾的003和107面网间距d随K⁺含量增大而增大,且呈一元三次方程的关系;而033和220面网间距d随K⁺含量增大而减小,呈一元二次方程的关系。对该现象从铁矾晶体结构方面进行解释:K⁺、H₃O⁺离子位于较大空隙中,且沿着Z轴方向排列,当K⁺、H₃O⁺离子之间相互替换时,会导致该铁矾晶体结构在Z轴方向有较明显的变化。     

Actinide crystal-liquid partitioning for clinopyroxene and Ca3(PO4)2

Using fission and alpha track radiography techniques, we have measured partition coefficients (D) for the actinide elements Th, U and Pu between diopsidic clinopyroxene, whitlockite [β-Ca₃ (PO₄)₂] and silicate liquid at 20kbar. Equilibrium partitioning at the crystal-liquid interface is assumed, and corrections for actinide zoning have been applied to the measured D values. Reproducibility for both actinide and minor element D values is carefully examined as a criterion for crystal-liquid interface equilibrium. The data are mostly compatible with interface equilibrium except for experiments at high cooling rates ( ? 30 deg/hr). Partition coefficients for Th/U/Pu of about 0.002/0.002/0.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. At an oxygen fugacity of 10^?8.5, Pu is much more readily incorporated into the crystalline phases than is U or Th because of the importance of trivalent Pu. The D_Pu(cpx) is similar to D(cpx) of the light rare earths supporting the concept of Pu/(rare earth) dating.     

Identification of C24 and C25 lanostanes in Tertiary sulfur rich crude oils from the Jinxian Sag, Bohai Bay Basin, Northern China

Unusual short chain lanostanes (C₂₄ and C₂₅) and C₃₀ lanostane were identified in sulfur rich crude oils from the Jinxian Sag, Bohai Bay Basin, northern China. Besides the regular steranes (C_27-30), a series of 4-methyl steranes (C₂₂₋₂₃, C₂₇₋₃₀), 4,4-dimethyl steranes (C₂₂₋₂₄, C₂₈₋₃₀), short chain steranes (C₂₃₋₂₆), abundant pregnanes (C₂₁₋₂₂) and androstanes (C₁₉₋₂₀), together with sulfur containing steroids (20-thienylpregnanes and thienylandrostanes) were detected in the aliphatic and branched-cyclic hydrocarbon fraction of these crude oils. A literature survey of some long chain sterane analogues (e.g., A-nor-steranes, norcholestanes, C₃₀ steranes, lanostanes) and pregnanes seems to point to a sponge and/or dinoflagellate source. 4-Methyl, 4,4-dimethyl steroids and lanosterols (4,4,14-trimethyl steroids as the basic skeleton of lanostanes) can be derived from methanotrophic bacteria. Thus, a biological origin from a prokaryotic methylotroph can be used to explain the common source of abundant short chain steranes (C_23-26), 4-methyl (C_22-23) and 4,4-dimethyl steranes (C_22-24), as well as lanostanes (C_24-25 and C₃₀ analogues) in our oil samples. Generally, the steroids appear to have been extensively sulfurized with sulfur substitution at the C-22 position in the side chain during the early stage of diagenesis, which was readily subject to attack by bacterial degradation (enzymatic cleavage) and/or abiotic oxidation. As a consequence, short chain sterane analogues (e.g., abundant pregnanes and androstanes in this study) and short chain lanostanes (C₂₄−C₂₅) might later be released through cleavage of weak C-S bonds at the C-22 carbon in the sulfurized steroids and lanostane sulfides. Finally, the formation of the short chain C₂₄−C₂₅ lanostanes and distinctive occurrence of short chain steranes in this study can be well explained by microbial biodegradation of sulfurized lanostanoids and steroids in the reservoir.     

C25 and C30 biogenic alkenes in a sediment core from the upper anoxic basin of the Pettaquamscutt River (Rhode Island,U.S.A.)

Concentration profiles of five C₂₅ and C₃₀ biogenic alkenes in a sediment core collected from the upper anoxic basin of the Pettaquamscutt River have been determined. The five alkenes were identified usin gas chromatography/mass spectrometry as three isomeric C₂₅ dienes, a C₂₅ triene and a bicyclic C₃₀ diene. All five compounds exhibit subsurface concentration maxima, thought to result from either preservation of a past increase in alkene production or a current bacterial in situ production at depth. Similarities exist in the concentrations of two alkenes common to this core and a core from upper Narragansett Bay, despite significant differences in the origin and content of sedimentary organic matter (as inferred from organic carbon and δ ¹³C measurements) at each location. These observations support the proposed bacterial in situ synthesis of alkenes. Other alkenes, whose concentration in sediments had been previously correlated with the incidence of marine organic matter, were not detected in the upper basin sediments. Their absence is consistent with the range of organic carbon δ ¹³C values measured, which indicate that the component originating from marine sources is small. A comparison of organic carbon and δ ¹³C values in this core with those previously reported from a core collected in an adjoining basin indicate that the sedimentary regimes at the two sites differ despite their close proximity and similar hydrography.