Problems with argon: K-Ar ages in Gulf Coast shales

K-Ar ages of Gulf Coast shales do not correspond to diagenetic ‘events’, but are a combination of inherited detrital ages and authigenic overprints. The key to understanding K-Ar ages of shales is the fate of the ⁴⁰Ar when the host minerals dissolve or react during the illitisation reaction: is ⁴⁰Ar incorporated within the illite, or is it lost to the porewaters? Ages are modelled as due to a single illitisation reaction, assuming a uniform precursor sediment and open-system import of K. Both whole-rock and clay mineral fraction data can be reproduced by modelling. The ⁴⁰Ar incorporated into illite is a surprisingly high proportion (75-100%) of that produced within detrital phases (smectite, K-feldspar, mica), perhaps implying that the illitisation reaction is a solid-state transformation, or that ⁴⁰Ar is imported into the shales along with incoming K. The model does not provide a good fit to the data below 4000 m, when the illitisation reaction is apparently complete, but shales lose ⁴⁰Ar by solid-state diffusion or recrystallisation.     

Chemical, Isotopic, and Fluid Inclusion Evidence for the Hydrothermal Alteration of the Footwall Rocks of the BIF-Hosted Iron Ore Deposits in the Hamersley District, Western Australia

Abstract. The petrography, chemical, fluid inclusion and isotope analyses (O, Rb-Sr) were conducted for the shale samples of the Mount McRae Shale collected from the Tom Price, Newman, and Paraburdoo mines in the Hamersley Basin, Western Australia. The Mount McRae Shale at these mines occurs as a footwall unit of the secondary, hematite-rich iron ores derived from the Brockman Iron Formation, one of the largest banded iron formations (BIFs) in the world. Unusually low contents of Na, Ca, and Sr in the shales suggest that these elements were leached away from the shale after deposition. The δ¹⁸O (SMOW) values fall in the range of + 15.0 to +17.9 per mil and show the positive correlation with calculated quartz/sericite ratios of the shale samples. This suggests that the oxygen isotopic compositions of shale samples were homogenized and equilibrated by postdepositional event. The pyrite nodules hosted by shales are often rimmed by thin layers of silica of varying crystallinity. Fluid inclusions in quartz crystals rimming a pyrite nodule show homogenization temperatures ranging from 100 to 240C for 47 inclusions and salinities ranging from 0.4 to 12.3 wt% NaCl equivalent for 18 inclusions. These fluid inclusion data give direct evidence for the hydrothermal activity and are comparable to those of the vein quartz collected from the BIF-derived secondary iron ores (Taylor et al, 2001). The Rb-Sr age for the Mount McRae Shale is 1,952 ± 289 Ma and at least 200 million years younger than the depositional age of the Brockman Iron Formation of ∼ 2.5 Ga in age. All the data obtained in this study are consistent with the suggestion that high temperature hydrothermal fluids were responsible for both the secondary iron ore formation and the alteration of the Mount McRae Shale.     

Hydrous pyrolysis of a Type III source: fractionation effects during primary migration in natural and artificially matured samples

A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.     

Hesperornis escapes plesiosaur attack

Evidence from the Pierre Shale (Late Cretaceous) of South Dakota is presented for an attack on a juvenile Hesperornis by a polycotylid plesiosaur. The wound healed and the Hesperornis grew to maturity. Evidence of survival provides our best information about predator prey interactions in the fossil record but are rare for birds where survival is an unlikely outcome.     

渝东南下古生界页岩构造裂缝形成及分布控制因素

天然裂缝对页岩气储集和渗流有重要影响,但目前对页岩构造裂缝研究不够深入。本文通过露头、岩心裂缝观察和分析,探讨了渝东南下古生界页岩构造裂缝类型、形成机理及分布控制因素。基于裂缝特征及力学成因,将剪切裂缝分为高角度剪切裂缝、倾斜滑脱裂缝和水平滑脱裂缝。倾斜滑脱裂缝是在上覆岩层重力和水平构造应力共同作用下沿应力集中的软弱面发生剪切滑动形成,水平滑脱裂缝是在构造挤压应力作用条件下主要沿页理面方向的剪切或层间滑动形成;页理发育程度及岩层曲率是控制水平滑脱裂缝形成的关键因素,岩石矿物组成、构造作用及岩层厚度是控制其它类型构造裂缝形成和分布的主要因素,页岩岩石力学层的划分需要根据裂缝特征、岩性变化特征、岩石力学参数及沉积界面等综合确定,岩层厚度与层间构造裂缝密度呈负相关关系。     

昭通示范区黄金坝气田五峰—龙马溪组页岩气储层地质特征

昭通国家级页岩气示范区黄金坝气田是继礁石坝和长宁—威远之后中国又一个在页岩气勘探、开发领域实现重大突破的地区,为了系统地展示黄金坝气田页岩气资源富集的储层条件,为未来的勘探工作提供参考,以五峰—龙马溪组页岩气储层为研究对象,从区域地质条件、储层岩石学、物性和地球化学4个方面对该页岩气储层进行了综合研究。结果表明稳定的区域构造和良好的顶底板条件是黄金坝地区页岩气资源富集的关键,良好的保存条件使储层维持了较高的压力(压力系数1);较高的孔隙度(平均4%)和TOC含量(目的层2%)提供了良好的储集空间,使储层具有较高的含气量(1.35~3.48 cm3/g,平均2.50 cm3/g);天然气地球化学数据表明,区内天然气主要成分为CH4(97%),其次还含有少量的C2H6、C3H8和CO2;天然气同位素数据表明烃类C同位素组成发生了倒转,表明储层具有良好的封闭性。但储层孔隙系统较为复杂,且非均质性极强,从而导致渗透率较低,在储层改造施工过程中应予以充分考虑。总体上,黄金坝气田具有较好的开发前景,生产测试表明,区内直井压裂产量为0.5×104~3.5×104m3/d/井,水平井压裂产量可达12×104~40×104m3/d/井。     

Geochemical characteristics of the Paleogene shales in the Dongying depression,eastern China

Fluctuations in lacustrine sedimentary environments significantly affect distributions of organic matter (OM), uranium, and other elements in shales. In this study a high-resolution geochemical record of fluctuations in the paleo-depositional environment of a terrestrial lake basin is provided on the basis of extensive samples collected from the Member 3 of the Paleogene Shahejie Formation (Es₃) of the Niu-38 well in the Dongying Depression, Eastern China. These samples were tested for total organic carbon (TOC), element concentrations, and biomarkers to study the evolution and fluctuation in the depositional environments of an ancient lake basin and associated geochemical response. The evolution and fluctuation of the sedimentary environment from a deep lake to a semi-deep lake and then to a shallow lake delta were indicated by geochemical response. During this evolution, the values of TOC, S₁, S₂, Sr, and Ts/(Ts + Tm) remarkably decreased, whereas those of Co, Ni, Rb, Na, Fe/Mn, Fe/(Ca + Mg), and C₂₉ mortane/C₂₉ hopane significantly increased. The deep lake basin shows depositional fluctuations, as indicated by rock lithofacies and their geochemical parameters. A close interrelationship was observed among U concentration, TOC content, and inorganic element content. Uranium concentrations are positively correlated with TOC contents, Ca and Sr concentrations, and Sr/Ba and Ca/Mg ratios but negatively with K, Na, Ba, and Rb contents and Fe/(Ca + Mg) and Fe/Mn ratios. The observed increase in U concentration in the lower Es₃ section is closely related to surface adsorption by clay minerals and OM, together with some replacements of Ca and Sr by U in the shales.     

The evolution of the Huangling uplift and its control on the accumulation and preservation of shale gas

There are plenty of Sinian and Cambrian potential shale gas resources in South China, which is characterized by high thermal evolution degrees, poor drilling performances and only occurs in local areas. Taking the principle “high to find low” is the key issue to achieving a breakthrough in older shale. China Geological Survey drilled in the periphery of the Proterozoic basement, i.e. the Huangling anticline, in the western Hubei, and Hannan paleocontinent in the southern Shanxi. It received high-quality gas-bearing shale with relatively low Ro in the in Lower Cambrian Niutitang formation and Sinian Doushantuo formation. Based on geological conditions of shale gas reservoirs in the Huangling anticline, this paper puts forward the new model named “Control over reservoirs by periphery of basement” about shale gas accumulation, suggesting that the shale deposited in a deepwater continental shelf in the periphery of the basement is characterized by shallow burial, a short burial time, stable tectonics, relatively low thermal evolution degrees, and shale gas reservoirs in a good condition. The shale of the Sinian-Cambrian strata deposited in deepwater continental shelves in the periphery of Chuanzhong paleo-uplift in Sichuan, Hannan paleocontinent in the southern Shanxi, Huangling anticline in western Hubei and Jiangnang-Xuefeng paleo-uplift in Hunan and Guizhou province have good shale gas exploration potential.     

Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China: Their mobilization and inter-connection

Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale.     

川东南丁山地区龙马溪组页岩裂缝特征及对含气性的影响

川东南丁山地区是近年来四川盆地页岩气勘探开发的热点区域,裂缝的发育对页岩含气性及保存条件有重要的影响。综合运用野外露头、岩心、测井资料,结合岩石脆性矿物含量、岩石力学参数等数据,深入分析龙马溪组页岩裂缝发育特征和控制因素,并探讨了裂缝发育对含气性的影响。结果表明,丁山地区龙马溪组页岩裂缝主要以构造成因的剪切缝为主,裂缝优势方位共6组,主要包括4组平面剪切缝和2组剖面剪切缝,其发育主要受2个方向、3个阶段的构造应力场影响而成;裂缝延伸稳定,平均密度小,宽度小,充填程度高,主要被方解石和黄铁矿等充填。裂缝受控因素主要包括古构造应力场、构造部位、脆性矿物组分、岩石力学性质等;断层对裂缝发育具有明显的控制作用,其中断层两盘均存在裂缝发育程度急剧下降的临界范围,临界范围内裂缝发育程度高,超过此临界范围,裂缝发育程度变差且变化趋于平缓;不同期次的裂缝中,形成时间晚、规模过大、充填程度不高、与现今地应力方向一致或呈低角度相交的裂缝易造成页岩气的散失,对提高页岩含气性不利;龙马溪组岩石脆性矿物含量高,脆性指数属中等偏上程度,有利于构造缝发育且可压性较好。随着距齐岳山断裂距离的适当增加,龙马溪组页岩埋藏深度适中,地层压力增大,抗压强度增强高,脆性指数适中,构造保存条件变好,有利于不同方位的裂缝发育和页岩含气量的增加,位于该区域的DY2井与DY4井均位于该有利区域,含气性良好。研究结果对下一步深化页岩气勘探开发具有重要指导作用。