Discovery of nano organo-clay complex pore-fractures in shale and its scientific significance:A case study of Cretaceous Qingshankou Formation shale,Songliao Basin,NE China

A new pore type,nano-scale organo-clay complex pore-fracture was first discovered based on argon ion polishing-field emission scanning electron microscopy,energy dispersive spectroscopy and three-dimensional reconstruction by focused ion-scanning electron in combination with analysis of TOC,R_(o)values,X-ray diffraction etc.in the Cretaceous Qingshankou Formation shale in the Songliao Basin,NE China.Such pore characteristics and evolution study show that:(1)Organo-clay complex pore-fractures are developed in the shale matrix and in the form of spongy and reticular aggregates.Different from circular or oval organic pores discovered in other shales,a single organo-clay complex pore is square,rectangular,rhombic or slaty,with the pore diameter generally less than 200 nm.(2)With thermal maturity increasing,the elements(C,Si,Al,O,Mg,Fe,etc.)in organo-clay complex change accordingly,showing that organic matter shrinkage due to hydrocarbon generation and clay mineral transformation both affect organo-clay complex pore-fracture formation.(3)At high thermal maturity,the Qingshankou Formation shale is dominated by nano-scale organo-clay complex pore-fractures with the percentage reaching more than 70%of total pore space.The spatial connectivity of organo-clay complex pore-fractures is significantly better than that of organic pores.It is suggested that organo-complex pore-fractures are the main pore space of laminar shale at high thermal maturity and are the main oil and gas accumulation space in the core area of continental shale oil.The discovery of nano-scale organo-clay complex pore-fractures changes the conventional view that inorganic pores are the main reservoir space and has scientific significance for the study of shale oil formation and accumulation laws.

In-situ hydrocarbon formation and accumulation mechanisms of micro- and nano-scale pore-fracture in Gulong shale, Songliao Basin, NE China

By conducting experimental analyses, including thermal pyrolysis, micro-/nano-CT, argon-ion polishing field emission scanning electron microscopy (FE-SEM), confocal laser scanning microscopy (CLSM), and two-dimensional nuclear magnetic resonance (2D NMR), the Gulong shale oil in the Songliao Basin was investigated with respect to formation model, pore structure and accumulation mechanism. First, in the Gulong shale, there are a large number of pico-algae, nano-algae and dinoflagellates, which were formed in brackish water environment and constituted the hydrogen-rich oil source materials of shale. Second, most of the oil-generating materials of the Qingshankou Formation shale exist in the form of organo-clay complex. During organic matter thermal evolution, clay minerals had double effects of suppression and catalytic hydrogenation, which expanded shale oil window and increased light hydrocarbon yield. Third, the formation of storage space in the Gulong Shale was related to dissolution and hydrocarbon generation. With the diagenesis, micro-/nano-pores increased, pore diameter decreased and more bedding fractures appeared, which jointly gave rise to the unique reservoir with dual media (i.e. nano-scale pores and micro-scale bedding fractures) in the Gulong shale. Fourth, the micro-/nano-scale oil storage unit in the Gulong shale exhibits independent oil/gas occurrence phase, and shows that all-size pores contain oils, which occur in condensate state in micropores or in oil-gas two phase (or liquid) state in macropores/mesopores. The understanding about Gulong shale oil formation and accumulation mechanism has theoretical and practical significance for advancing continental shale oil exploration in China.

Structural features and exploration targets of platform margins in Sinian Dengying Formation in Deyang-Anyue Rift, Sichuan Basin, SW China

Based on the seismic, logging, drilling and other data, the distribution, structural types and mound-shoal hydrocarbon accumulation characteristics of platform margins of the Sinian Dengying Formation in the Deyang-Anyue Rift and its periphery were analyzed. Four types of platform margins are developed in the Dengying Formation, i.e., single-stage fault-controlled platform margin, multi-stage fault-controlled platform margin, gentle slope platform margin, and overlapping platform margin. In the Gaoshiti West-Weiyuan East area, single-stage fault controlled platform margins are developed in the Deng 2 Member, which trend in nearly NEE direction and are shielded by faults and mudstones, forming fault-controlled–lithologic traps. In the Lezhi-Penglai area, independent and multi-stage fault controlled platform margins are developed in the Deng 2 Member, which trend in NE direction and are controlled by synsedimentary faults;the mound-shoal complexes are aggraded and built on the hanging walls of the faults, and they are shielded by tight intertidal belts and the Lower Cambrian source rocks in multiple directions, forming fault-controlled–lithologic and other composite traps. In the Weiyuan-Ziyang area, gentle slope platform margins are developed in the Deng 2 Member, which trend in NW direction;the mound-shoal complexes are mostly thin interbeds as continuous bands and shielded by tight intertidal belts in the updip direction, forming lithologic traps. In the Gaoshiti-Moxi-Yanting area, overlapping platform margins are developed in the Deng 2 and Deng 4 members;the mound-shoal complexes are aggraded and overlaid to create platform margin buildup with a huge thickness and sealed by tight intertidal belts and the Lower Cambrian mudstones in the updip direction, forming large-scale lithologic traps on the north slope of the Central Sichuan Paleouplift. To summarize, the mound-shoal complexes on the platform margins in the Dengying Formation in the Penglai-Zhongjiang area, Moxi North-Yanting area and Weiyuan-Ziyang area are large in scale, with estimated resources of 1.58×1012 m3, and they will be the key targets for the future exploration of the Dengying Formation in the Sichuan Basin.

Application of General Shear Theory to the Study of Formation Mechanism of the Metamorphic Core Complex:A Case Study of Xiaoqinling in Central China

: The kinematic vorticity number and strain of the mylonitic zone related to the detachment fault increase from ESE to WNW along the moving direction of the upper plate of the Xiaoqinling metamorphic core complex (XMCC) and the geometry of quartz c-axis fabrics changes progressively from crossed girdles to single girdles in the same direction. Therefore, pure shear is dominant in the ESE part of the XMCC while simple shear becomes increasingly important towards WNW. However, the shear type does not change with the strain across the shear zone, thus the variation of shear type is of significance in indicating the formation mechanism. The granitic plutons within the XMCC came from the deep source and their emplacement was an active and forceful upwelling prior to the detachment faulting. The PTt path demonstrates that magmatism is an important cause for the formation of the XMCC. The formation mechanism of the XMCC is supposed to be active plutonism and passive detachment. Crustal thickening and magmatic doming caused necking extension with pure shear, and magmatic heating and doming resulted in detachment extension with simple shear and formed the XMCC.

A local f-x Cadzow method for noise reduction of seismic data obtained in complex formations

A noise-reduction method with sliding called the local f-x Cadzow noise-reduction method, windows in the frequency-space （f-x） domain, is presented in this paper. This method is based on the assumption that the signal in each window is linearly predictable in the spatial direction while the random noise is not. For each Toeplitz matrix constructed by constant frequency slice, a singular value decomposition （SVD） is applied to separate signal from noise. To avoid edge artifacts caused by zero percent overlap between windows and to remove more noise, an appropriate overlap is adopted. Besides flat and dipping events, this method can enhance curved and conflicting events. However, it is not suitable for seismic data that contains big spikes or null traces. It is also compared with the SVD, f-x deconvolution, and Cadzow method without windows. The comparison results show that the local Cadzow method performs well in removing random noise and preserving signal. In addition, a real data example proves that it is a potential noise-reduction technique for seismic data obtained in areas of complex formations.

Formation mechanism of a rainfall triggered complex landslide in southwest China

This case study is about a landslide that occurred after 4 days of heavy rainfall,in the morning of June 29,2012,in Cengong County,Guizhou Province of China,geographical coordinated 108°20′-109°03′E,27°09′-27°32′N,with an estimated volume of 3.3×106 m3.To fully investigate the landslide process and formation mechanism,detailed geotechnical and geophysical investigations were performed including borehole drilling,sampling,and laboratory tests coupled with monitoring of displacement.Also,a combined seepage-slope stability modeling was performed to study the behavior of the landslide.After the heavy rainfall event,the sliding process started in this area.The landslide development can be divided into different parts.The man-made fill area,spatially distributed in the south side of the landslide area with low elevations,slid first along the interface between the slope debris and the strongly weathered bedrock roughly in the EW direction.Consequently,due to severe lateral shear disturbance,the slope in the main sliding zone slid next towards the SW direction,along the sliding surface developed within the strongly weathered calcareous shale formation located at a depth of 25-35 m.This means it was a rainfall triggered deep-seated landslide.Finally,retrogressive failure of a number of upstream blocks occurred,which moved in more than one direction.The initial failure of the man-made fill area was the‘engine’of the whole instability framework.This artificial material with low permeability,piled up in the accumulation area of surface and sub-surface and destroyed the drainage capacity of the groundwater.The numerical modeling results agreed with the analysis results obtained from the laboratory and field investigations.A conceptual model is given to illustrate the formation mechanism and development process of the landslide.

New U-Pb Geochronological Constraints on Formation and Evolution of the Susong Complex Zone in the Dabie Orogen

Objective The Susong complex zone（SCZ）is a relatively lowgrade metamorphic unit mostly with an epidoteamphibolite facies,located in the southernmost part of the Dabie orogen.However,its rock compositions,ages,

Determination of Formation Constants of Co￣(2+), Ni￣(2+),Cu￣(2+) and Zn￣(2+) Complexes with Humic and Fulvic Acidsby Potentiometric Titration Method

The formation constants of Co￣(2+), Ni￣(2+), Cu￣(2+) and Zn￣(2+) complexes with humic acid (HA) and fulvicacid (FA) in red soil were determined by the potentiometric titration method. The constants as a functionof composition of the complexation solutions were obtained by two graphical approaches respectively Theformation constants decreased with increasing concentration of metal in the solution. The results provideunambiguous evidence for the heterogeneity of the function groups of humic substances. The formationconstants of FA were much smaller than those of HA, and the formation constants of Cu￣(2+) were muchgreater than those of Co￣(2+) , Ni￣(2+) and Zn￣(2+) . The potentiometric titration method for determining formationconstants are also discussed in the article.

Hydrocarbon accumulation and exploration prospect of mound-shoal complexes on the platform margin of the fourth member of Sinian Dengying Formation in the east of Mianzhu-Changning intracratonic rift, Sichuan Basin, SW China

Drilling,seismic and logging data were used to evaluate the hydrocarbon accumulation conditions of the mound-shoal complexes in the platform margin of the fourth member of Sinian Dengying Formation in the east side of the Mianzhu-Changning intracratonic rift in the Sichuan Basin.The four understandings are:(1)The platform margin belt of the Deng 4 Member can be divided into three sections,northern,middle and southern;the middle section is at the core of the Gaoshiti-Moxi paleouplift and the structural high now,while the southern and northern sections are at the slope of the paleouplift and the structural lows now;the three sections have similar development characteristics and reservoir features of platform margin mound-shoal complex.(2)In the margin of the east side of the rift,there are several faults nearly perpendicular to the platform margin belt,the faults divide the platform margin belt into rugged paleo-landform,and the high part developed platform margin mound-shoal complexes and the reservoirs are good in physical properties,while the low part developed inter-beach depression and no mound-shoal complexes,where the reservoirs are poor in physical properties.(3)The six groups of faults nearly perpendicular to the platform margin belt divide the platform margin belt into seven large mound-shoal complexes which have similar hydrocarbon accumulation conditions and accumulation evolution process and are rich in petroleum.(4)The inter shoal depressions between the mound-shoal complexes are characterized by tighter lithology,which can block the updip direction of the mounds and shoals at the lower part of the slope of the paleouplift and are favorable for the later preservation of mound-shoal gas reservoirs.This has been proved by Well Jiaotan 1 and Heshen 2 drilled successfully.The mound-shoal complexes on the platform margin of the structural slope area have a good exploration prospect.

Sedimentary characteristics and model of gravity flow channel-lobe complex in a depression lake basin:A case study of Chang 7 Member of Triassic Yanchang Formation in southwestern Ordos Basin,NW China

To reveal the development characteristics and distribution of gravity flow sedimentary system under micro-paleogeomorphologic units of the Chang 7 Member of Triassic Yanchang Formation in the southwestern Ordos Basin,on the basis of the restoration of the paleogeomorphological form of the Chang 7 depositional period by the impression method,each micro-paleogeomorphologic unit was depicted in-depth,and the characteristics and development models of gravity flow deposits in the study area were studied in combination with outcrop,core,mud logging and log data.The results show that:(1)The paleogeomorphology in the Chang 7 depositional period was an asymmetrical depression,wide and gentle in the northeast and steep and narrow in the southwest.Three sub-paleogeomorphologic units were developed in the basin,including gentle paleo-slope,paleo-slope and paleo-depression,and they can be further subdivided into eight micro-paleogeomorphologic units:bulge,groove,slope break belt,plain of lake bottom,deep depression of lake bottom,paleo-channel,paleo-ridge of lake bottom,and paleo-uplift of lake bottom.(2)There are 9 types of lithofacies and 4 types of lithofacies assemblages of Chang 7 Member.According to lithofacies composition and lithofacies vertical combination,the gravity flow deposit is further divided into 5 types of microfacies:restricted channel,unrestricted channel,natural levee,inter-channel,lobe.(3)Paleogeomorphology plays an important role in controlling sediment source direction,type and spatial distribution of sedimentary microfacies,genetic types and distribution of sand bodies in Chang 7 Member.

Standard Enthalpies of Formation of Solid Complexes of Lanthanide Nitrates with Alanine

The combustion energies of fourteen solid complexes of lanthanide nitrate with alanine were determined. The standard enthalpies of combustion, Δ c,coor(s) H °, and standard enthalpies of formation, Δ f,coor(s) H °, were calculated for these complexes. The relationship of Δ c,coor(s) H ° and Δ f,coor(s) H ° with the atomic numbers of the elements in the lanthanide series were examined. The results show that a certain amount of covalence is present in the chemical bond between the lanthanide cations and alanine.

SCIENTIFIC PRINCIPLES FOR MODIFICATION OF WATER-SOLUBLE POLYMERS. FORMATION OF MACROMOLECULAR COMPLEXES

The study of nanosecond dynamics of macromolecules with the lumines-cent methods make it possible to investigate the formation and functioning of polymericcomplexes, polymeric conjugates and macromolecular metal complexes, which are widelyused for solving many practical tasks. The nanosecond dynamics of macromolecules are ahighly sensitive indicator of interpolymer complexes (IPC) formation. It enables us to solvethe problems of studying IPC formation and stability and to investigate the interpolymerreactions of exchange and substitution. The investigation of changes in the rotational mo-bility of globular protein molecules as a whole makes it possible to determine the complexcomposition and its stability, and to control the course of polymer-protein conjugate forma-tion reaction. The nanosecond dynamics of polymers interacting with surfacants' ions (S)are the sensitive indicator of the S-polymer complex formation. A method for determin-ing the equilibrium constants of the S-polymer complex formation was developed on thebasis of the study of polymer chains mobility. It is established that nanosecond dynamicsinfluences the course of chemical reactions in polymer chains. Moreover, the marked effectof the nanosecond dynamics is also revealed in the study of photophysical processes (theformation of excimers and energy migration of electron excitation) in polymers with pho-toactive groups. It was found that the efficiency of both processes increases with increasingthe mobility of side chains, the carriers of photoactive groups.

Samarium(II) Diiodide Induced Polarity Inversion of π-Allyl Palladium Complexes: The Formation of Allylic Selenides

Allylic acetates were reduced with Pd(0)-SmI2 in the presence of ArSeBr to form corresponding allylic selenides in good yields.

Complex Formation between Heptakis(2,3,6-tri-O-butyl)-β-cyclodextrin with p-Nitrophenol in Heptane

Heptakis(2, 3, 6-tri-o-n-butyl)- β-cyclodextrin(TB- β-CD) has been found to form an inclusion compound with p-nitrophenol in heptane. The stability constent of the inclusion compound of p-nitrophenol with TB-β-CD in heptane is an order of magnitude greater than that in water.

Complex Formation of 1,6-Anhydro-<i>β</i>-Maltose and Sodium Ions Using Single-Crystal X-Ray Crystallography and NMR Spectroscopy

Complex formation of 1,6-anhydro-β-maltose and sodium ions was characterized using single-crystal X-ray crystallography and solution- and solid-state NMR spectroscopy. The 7-coordination structure, comprising two 1,6-anhydro-β-maltoses, a thiocyanate ion and a sodium ion, was identified in the crystal of the complex, where a sodium ion was positioned in the center of the pentagon. In the NMR study, the line broadening of 23Na signals and the decrease of the spin-lattice relaxation times (T1) of 23Na were observed in CD3OD in the presence of 1,6-anhydro-β-maltose, indicating complex formation.

Acid-base behavior of cryptand 1, 4, 7, 10, 13, 16, 21, 24-octaaza-bicyclo [8, 8, 8] hexacosan-3, 8, 12, 17, 20, 25-hexone and complex formation

The bicyclic cryptand 1,4,7, 10,13,16,21, 24-octaaza-bigcyclo [8, 8,8] hexacosan-3, 8, 12, 17, 20, 25-hex-one (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of discrete neutral macrobicyclic units; the two cycles share the two tertiary amine nitrogen atoms, which exhibit an endo-cndo conformation. Three identical branches formed by 1, 2-diaminoethane link the two tertiary amine groups. The protonation reactions of cryptand (COBH) and its complex formation with copper (II) were investigated by potentiometry in water and in a DMSO/water (80:20 in mass ratio) mixture as solvents. The cryptand acts as a his-base through its two N-bridgehead and exhibits a strong cooperativity that favors the first protonation and makes the second one difficult (△pK= 5.0). An inward rotation of the amide groups to form hydrogen bonds accounts for this cooperativity. The interaction of COBH with copper (II) leads to several binuclear complex proton contents.

Study of Complex Formation Constants for Some Cations With O-Phenylenediamine in Binary Systems Using Square Wave Polarography Technique

The formation of metal cation complexes between o-phenylenediamine with metal ions, Ni2+, Cu2+, Zn2+, Pb2+ and Cr3+ were studied in the dimethylformamide/water(DMF/H2O), acetonitrile/water(AN/H2O) and ethanol/water(EtOH/H2O) binary systems using square wave polarography (SWP) technique. The stoichiometry and stability of the complexes were determined by monitoring the shifts in half-waves or peak potentials of the polarographic waves of metal ions against the ligand concentration. In the most cases, the formation constants of complexes decreased with increasing amounts of H2O, DMF and EtOH in AN/H2O, DMF/H2O and EtOH/H2O binary systems, respectively. The stoichiometry of the complexes was found 1:1. The results obtained show that there is an inverse relationship between the formation constant of the complexes and the donor number of the solvents based on the Gatmann donocity scale. Also, the stability constants show a high sensitivity to the composition of the mixed solvent systems. In most of the systems investigated, Cr3+ cation forms a more stable complex with o-phenylenediamine than other four cations and the order of selectivity of this ligand for cations in pure water is:Cr3+>>Cu2+>Ni2+>Zn2+>Pb2+.

Formation mechanism of MgB_2 in 2LiBH_4+MgH_2 system for reversible hydrogen storage

The formation conditions of MgB2 in 2LiBH4 ＋ MgH2 system during dehydrogenation were investigated and its mechanism was discussed. The results show that direct decomposition of LiBH4 is suppressed under relative higher initial dehydrogenation pressure of 4.0×10^5 Pa, wherein LiBH4 reacts with Mg to yield MgB2, and 9.16% （mass fraction） hydrogen is released within 9.6 h at 450 ℃. However, under relatively lower initial dehydrogenation pressure of 1.0×10^2 Pa, LiBH4 decomposes independently instead of reacting with Mg, resulting in no formation of MgB2, and 7.91% hydrogen is desorbed within 5.2 h at 450 ℃. It is found that the dehydrogenation of 2LiBH4 ＋ MgH2 system proceeds more completely and more hydrogen desorption amount can be obtained within a definite time by forming MgB2. Furthermore, it is proposed that the formation process of MgB2 includes incubation period and nucleus growth process. Experimental results show that the formation process of MgB2, especially the incubation period, is promoted by increasing initial dehydrogenation pressure at constant temperature, and the incubation period is also influenced greatly by dehydrogenation temperature.

O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts

Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.

Reservoir characteristics and genetic differences between the second and fourth members of Sinian Dengying Formation in northern Sichuan Basin and its surrounding areas

This study investigated the characteristics and genesis of reservoirs in the 2^(nd) and 4^(th) members of Sinian Dengying Formation in northern Sichuan and its surrounding areas, on the basis of outcrop, drilling cores and thin section observation and geochemical analysis. The reservoirs of 2^(nd) member are distributed in the middle part of the stratum. The reservoir quality is controlled by supergene karst and the distribution of mound-shoal complex. The bedded elongated isolated algal framework solution-cave and the residual "grape-lace" cave, which are partially filled with multi-stage dolosparite, constituted the main reservoir space of the 2^(nd) member. There is no asphalt distribution in the pores. The pore connectivity is poor, and the porosity and permeability of the reservoir is relatively low. The reservoirs of 4^(th) member were distributed in the upper and top part of the stratum. The reservoir quality is controlled by burial dissolution and the distribution of mound-shoal complex. The bedded algal framework solution-pores or caves, intercrystalline pores and intercrystalline dissolved pores constituted the main reservoir space of the 4^(th) member. It's partially filled with asphalt and quartz, without any dolosparite fillings in the pores and caves. The pore connectivity is good. Most of the 4^(th) member reservoirs had medium-low porosity and low permeability, and, locally, medium-high porosity and medium permeability. Affected by the development of mound-shoal complex and heterogeneous dissolution, the platform margin along Ningqiang, Guangyuan, Jiange and Langzhong is the most favorable region for reservoir development. Deep buried Dengying Formation in the guangyuan and langzhong areas should be the most important hydrocarbon target for the future exploration.