Kerogen based characterization of major gas shales: Effects of kerogen fractionation

Research into the origin and the mode of entrapment and expulsion of natural gas from unconventional plays requires the isolation and separation of kerogen in its purest and most intact form from the rock matrix. This study expands on the comparative analysis of the effects that isolation methods, conservative closed system versus conventional open system, have on kerogen’s elemental, isotopic and physical properties. Four major gas shales, including the Barnett, the Marcellus, the Haynesville and a Polish gas shale, were chosen. In addition, the Monterey shale, though not strictly a gas shale, was included to address the effects on sulfur rich, Type II-S kerogen.Results indicate that the kerogen residues from the conventional open system method showed lower recovery and higher mineral content than those from the conservative closed system method. Differences were manifested in the elemental analysis data, where kerogens isolated using the open system method showed a significant deficit in the organic C, H, O, S and N material balance. Furthermore, the recovered residues show different sulfur content and δ³⁴S composition, most likely attributable to differences in pyrite content. Nevertheless, the relative abundances of the various macerals in the kerogen residues from the same parent shale are not very different; neither was the bulk δ¹³C composition of the recovered residues. This is not particularly surprising, considering that in all the five cases examined in this study, the organic matter was fairly homogeneous.     

Phosphorus in suspended matter and sediments of a hypertrophic lake. A case study: Lake Dianchi,China

From June 2004 to December 2004, Lake Dianchi, which had large scale of cyanobacterial blooms was investigated in order to study P-fractionation in the suspended matter and the sediment. The investigation improves our understanding of phosphorus in Lake Dianchi and the relationship between phosphorus and cyanobacterial blooms. It contributes to the available literature on the behavior of P in hypertrophic lakes. The distribution of P-fractions in Lake Dianchi was not uniform from northwest to south, but was closely related to the trophic status of the whole lake. The concentrations of total phosphorus, labile P (NH₄Cl-P), Organic P (NaOH-NRP) and loss on ignition in suspended matter were positively correlated with the strength of cyanobacterial blooms. Total phosphorus in suspended matter was relatively stable for almost half an year and closely related to Chl. a concentration. The main content of organic phosphorus is in the cyanobacterial blooms. The concentrations of phosphorus bound to metal oxides and carbonates (NaOH-SRP and HCl-P) in sediment were similar to NaOH-SRP and HCl-P in the corresponding suspended matter. The latter two forms of P in suspended matter were not affected by cyanobacterial blooms, indicating that the inorganic phosphorus is derived from the sediment after resuspension from the sediment due to wind and wave action. The contribution of the different P-fractions to TP in sediment and in suspended matter indicates that NH₄Cl-P in the suspended matter is an important buffer for maintaining dissolved phosphorus in water.     

腾冲地块晚白垩世-古近纪富锡花岗岩成因:岩浆源区及分异演化条件SCIEI北大核心CSCD

腾冲地块锡成矿作用主要与晚白垩世-古近纪岩浆活动相关,但仅矿区花岗岩体具有较高的锡含量(平均25×10^(-6)),区域上同时代的非成矿花岗岩体并未发生锡的富集。本文通过搜集分析现有研究数据,总结了富锡成矿岩体和区域非成矿岩体在岩浆源区、演化条件和结晶分异程度的异同:区域非成矿岩体锆石ε_(Hf)(t)值(-15.1~+3.39)表明,自东北向西南幔源物质加入有升高的趋势,但区域玄武岩中低含量的Sn(1.61×10^(-6))表明幔源物质混入不利于岩浆中锡的富集。晚白垩世部分非成矿岩体与成矿岩体具有相同ε_(Hf)(t)(-9.7)值,表明其皆源于古老地壳物质的部分熔融,但岩体均表现为准铝质-弱过铝质特征,且锆石Hf同位素(t_(DM2)=1724Ma)和全岩Nd同位素(t_(DM2)=1836Ma)二阶段模式年龄基本一致,因此其源区可能并非富锡的高黎贡山群变质沉积岩,而可能是其中未经风化的变质花岗岩。根据腾冲地块地层厚度(28km)和莫霍面深度(47~35km)推断岩浆源区至少位于地下30km(8.4kbar),由于仅靠地温梯度(25℃/km)无法达到初始熔融温度(>1066℃),源区部分熔融过程很可能受地幔热的影响。根据Fe_(2)O_(3)/FeO比值,非成矿岩体(0.59)与成矿岩体(0.48)均具有较低的氧逸度,属钛铁矿系列,但成矿岩体的结晶分异程度明显高于非成矿岩体,且成矿岩体富含挥发分,高含量的挥发分降低了岩浆固结温度(650~550℃),延长了结晶分异时间,促进了锡在晚期岩浆中的富集。因此腾冲地块富锡花岗岩主要是普通岩浆在低氧逸度环境下发生高度结晶分异的结果。     

锂同位素地球化学研究进展

锂的两个稳定同位素(6Li和7Li)相对质量差较大,因此锂同位素分馏比较显著。由于分析测量技术的改进和完善,锂同位素地球化学近年来有了长足的发展。研究表明,温度是控制锂同位素分馏的一个重要因素。此外,锂在不同矿物中配位结构和化学键强度的差异也会影响共存相之间的锂同位素分馏。由于锂同位素存在较大的分馏和不同地质体中截然不同的δ7Li值,锂同位素地质应用范围十分广泛。目前,锂同位素在地表风化、海底热液和洋壳蚀变、板块俯冲、示踪卤水来源和演化等方面的研究中成效显著,并且开始应用到矿床学中。     

Preliminary15N studies on atmospheric nitrogenous trace gases

Preliminary nitrogen isotope data for ammonia from animal urine, fuel combustion, fertilizer use and fertilizer factories have been measured or estimated. It turns out that direct nitrogen isotope measurements of atmospheric ammonia at Jülich are in the expected range calculated from the ranges of different sources. For deposition of atmospheric ammonium in Jülich-rain a depletion in¹⁵N with respect to atmospheric ammonia has been found which is explained by isotope fractionations during rainout and washout. In correspondence with this fractionation model are nitrogen isotope data of rain-ammonium from coastal areas, which are enriched in¹⁵N due to the fact that sea water acts as a sink for atmospheric ammonia.For Jülich rain-nitrate a pronounced seasonal trend has been detected with lower¹⁵N data in spring and summer than in autumn and winter. This trend is interpreted by different nitrogen isotope data of anthropogenic and natural nitric oxides which have been measured or estimated from isotope fractionation effects during nitrification and denitrification reactions in soils. It should be possible to get better global estimations for anthropogenic and natural nitric oxides from nitrogen isotope measurements.     

Dinosterol δD values in stratified tropical lakes (Cameroon) are affected by eutrophication

In freshwater settings, dinosterol (4α,23,24-trimethyl-5α-cholest-22E-en-3β-ol) is produced primarily by dinoflagellates, which encompass various species including autotrophs, mixotrophs and heterotrophs. Due to its source specificity and occurrence in lake and marine sediments, its presence and hydrogen isotopic composition (δD) should be valuable proxies for paleohydrological reconstruction. However, because the purity required for hydrogen isotope measurements is difficult to achieve using standard wet chemical purification methods, their potential as a paleohydrological proxy is rarely exploited. In this study, we tested δD values of dinosterol in both particulate organic matter (POM) and sediments of stratified tropical freshwater lakes (from Cameroon) as a paleohydrological proxy, the lakes being characterized by variable degrees of eutrophication. In POM and sediment samples, the δD values of dinosterol correlated with lake water δD values, confirming a first order influence of source water δD values. However, we observed that sedimentary dinosterol was D enriched from ca. 19 to 54‰ compared with POM dinosterol. The enrichment correlated with lake water column conditions, mainly the redox potential at the oxic–anoxic interface (E_h OAI). The observations suggest that paleohydrologic reconstruction from δD values of dinosterol in the sediments of stratified tropical lakes ought to be sensitive to the depositional environment, in addition to lake water δD values, with more positive dinosterol δD values potentially reflecting increasing lake eutrophication. Furthermore, in lake sediments, the concentration of partially reduced vs. non-reduced C₃₄ botryococcenes, stanols vs. stenols, and bacterial (diploptene, diplopterol and ββ-bishomohopanol) vs. planktonic/terrestrial lipids (cholesterol, campesterol and dinosterol) correlated with E_h OAI. We suggest using such molecular proxies for lake redox conditions in combination with dinosterol δD values to evaluate the effect of lake trophic status on sedimentary dinosterol δD values, as a basis for accurately reconstructing tropical lake water δD values.     

The effect of cadmium on fulvic acid adsorption to Bacillus subtilis

The effects of Cd on the adsorption of an aquatic fulvic acid (FA) to the surface of Bacillus subtilis were investigated from pH 2.5 to 7.0, at fixed ionic strength (0.1 M NaClO₄) and at ambient temperature (22 °C). Cd (14 mg/l) had no effect on FA adsorption at pH<5 but increased FA adsorption at pH>6. The effects of Cd (0, 14 mg/l) on FA adsorption to B. subtilis were further examined as a function of initial FA concentration (0–45 mg C/l) at pH 6.5. FA adsorption isotherms also were measured at pH 6.5 as a function of dissolved Cd concentration (0–14 mg/l) at three initial FA concentrations (4, 8, 22 mg C/l). At all FA concentrations studied at pH 6.5, FA adsorption increased with increasing initial total Cd concentration.

Under all studied conditions, preferential adsorption of high- to intermediate-molecular-weight FA components to B. subtilis resulted in a fractionation of the FA pool, with lower-molecular-weight components remaining in solution. At pH>6, Cd further enhanced the adsorption of high- to intermediate-molecular-weight FA components but did not significantly enhance the adsorption of lower-molecular-weight components. Hence, the overall process of adsorptive fractionation was not altered significantly by the presence of Cd.

Overall, the results of this study (1) demonstrate that FA adsorption to bacterial surfaces can be altered by the presence of a metal cation, and (2) provide further evidence that microbe–metal–ligand interactions may significantly affect the mobility and fate of natural organic matter in the subsurface.     

Stable Strontium Isotopic Fractionation During Chemical Weathering in Drainage Basins: Mechanisms and Applications

The new non-traditional stable strontium (Sr) isotope has aroused great attention from academic scholars in terms of the continental weathering and marine Sr cycle. The analytical precision of stable Sr isotope using mass spectrometry is better than 0.03‰. The compiled δ⁸⁸/ ⁸⁶Sr values vary from -3.65‰ to 1.68‰ in natural reservoirs. Recent findings indicate that multiple processes can cause stable Sr isotope fractionation in Earth surface, including the incongruent dissolution of primary minerals, the formation and adsorption of secondary minerals, the precipitation of calcium carbonate, and the biological cycling. These processes lead to higher δ⁸⁸/ ⁸⁶Sr in the liquid phase and lower δ⁸⁸/ ⁸⁶Sr in the solid phase, and thus result in different geochemical behavior of stable Sr isotopes in water and sediment during the weathering processes. The δ⁸⁸/ ⁸⁶Sr values of river sediment decrease with the increase of weathering intensity, which has the potential to indicate chemical weathering intensity. Meanwhile, further study on the fractionation mechanisms and constraints of stable Sr isotopes in river water plays an important role in tracing chemical weathering processes within the watershed, which will lead to a better understanding of the global ocean Sr cycle.     

有效全岩成分的计算方法及其在变质相平衡模拟中的应用

变质相平衡模拟是变质岩领域近几十年最重要的进展之一,它已经成为确定变质作用P-T-t轨迹和探索变质演化过程的有力工具。变质岩的矿物组合不但与其形成的温度（T）和压力（P）条件有关,而且受控于岩石的全岩成分（X）。但是变质岩通常是不均匀的并且往往保留两期以上的矿物组合,因此计算不同成分域或不同变质演化期次的有效全岩成分是模拟P-T视剖面图的核心问题之一。在中-低温变质岩中,石榴石变斑晶的生长会不断地将其核部成分"冻结"而不参与后续变质反应,这导致根据实测全岩成分计算的P-T视剖面图无法有效地模拟石榴石幔部或边部生长阶段的变质演化过程。"瑞利分馏法"和"球体积法"利用电子探针实测的石榴石成分环带可以模拟计算石榴石各个生长阶段所对应的有效全岩成分,本文推荐使用这两个方法来处理石榴石变斑晶的分馏效应问题。相比较而言,石榴石在高温变质岩中通常无法保留生长阶段的成分环带特征,这是因为石榴石成分在高温条件下会发生扩散再平衡,并同时与多数基质矿物达到热力学平衡,这时一般不需要考虑石榴石的分馏效应。但是高温变质岩通常会发生部分熔融并伴随熔体的迁移,进而改变岩石的有效全岩成分。因此,通过P-T视剖面图模拟熔体迁移前后的变质演化过程需要使用"相平衡法"计算迁移的熔体成分以及熔体迁移前后岩石的有效全岩成分。此外,后成合晶与反应边是变质岩中最常见的退变质反应结构,但是后成合晶或反应边中的矿物之间并未达到热力学平衡。这种情况需要结合岩相学观察和矿物成分,利用最小二乘法确定后成合晶或反应边中发生的平衡反应方程式,进而获取变质反应发生时的有效全岩成分并通过计算P-T视剖面图来估算退变质的温压条件。除此之外,岩石体系中三价铁（Fe2O3）和H2O含量的估算一直以来都是相平衡模拟研究中的难点,本文推荐使用P/T-X（Fe3+/Fetot,MH2O）视剖面图来确定这两个组分的含量,这是因为P/T-X图可以估算各个变质演化阶段或特定矿物组合的Fe2O3或H2O含量。     

汉诺坝玄武岩化学及其演化趋势

汉诺坝玄武岩于中新世喷出。除了碱性玄武岩以外,夏威夷岩广泛分布,还有苦橄玄武岩和马盖尔岩。有三个岩浆演化趋势:地壳岩浆房内橄榄石和单斜辉石斑晶组合的分离作用产生了从夏威夷岩到马盖尔岩的肯尼迪分异趋势;莫霍面附近的岩浆房内石榴石、普通辉石、歪长石和钛铁矿巨晶组合的分离作用导致了由原生夏威夷岩和碱性玄武岩经过进化的夏威夷岩和碱性玄武岩到拉斑玄武岩的跨式B型分异趋势;原生岩浆演化趋势。