Implication of Water-Rock Interaction for Enhancing Shale Gas Production

Horizontal well drilling and multi-stage hydraulic fracturing technologies are at the root of commercial shale gas development and exploitation.During these processes,typically,a large amount of working fluid enters the formation,resulting in widespread water-rock interaction.Deeply understanding such effects is required to optimize the production system.In this study,the mechanisms of water-rock interaction and the associated responses of shale fabric are systematically reviewed for working fluids such as neutral fluids,acid fluids,alkali fluids and oxidative fluids.It is shown that shale is generally rich in water-sensitive components such as clay minerals,acidsensitive components(like carbonate minerals),alkali-sensitive components(like quartz),oxidative-sensitive components(like organic matter and pyrite),which easily lead to change of rock fabric and mechanical properties owing to water-rock interaction.According to the results,oxidizing acid fluids and oxidizing fracturing fluids should be used to enhance shale gas recovery.This study also indicates that an aspect playing an important role in increasing cumulative gas production is the optimization of the maximum shut-in time based on the change point of the wellhead pressure drop rate.Another important influential factor to be considered is the control of the wellhead pressure considering the stress sensitivity and creep characteristics of the fracture network.

Dissolution and Deformation Characteristics of Limestones Containing Different Calcite and Dolomite Content Induced by CO_(2)-Water-Rock Interaction

To investigate the impacts of mineral composition on physical and mechanical properties of carbonate rocks,limestone specimens containing different contents in calcite and dolomite are selected to perform CO_(2)-water-rock reaction experiments.The X-ray Diffraction(XRD) and Nuclear Magnetic Resonance(NMR) are carried out to examine the change characteristics of mineral dissolution and pore structure after reaction.The core flooding experiments with Fiber Bragg gratings are implemented to examine the stress sensitivity of carbonate rocks.The results show that the limestones containing pure calcite are more susceptible to acid dissolution compared to limestone containing impure dolomite.The calcite content in pure limestone decreases as the reaction undergoes.The dissolution of dolomite leads to the formation of calcite in impure limestone.Calcite dissolution leads to the formation of macropore and flow channels in pure limestone,while the effects of impure dolomite in impure limestone results in mesopore formation.When confining pressure is lower than 12 MPa,pure limestones demonstrate higher strain sensitivity coefficients compared to impure limestone containing dolomite after reaction.When confining pressure exceeds 12 MPa,the strain sensitivity coefficients of both pure and impure limestones become almost equal.

Test of subcritical crack growth and fracture toughness under water-rock interaction in three types of rocks

The subcritical crack growth and fracture toughness in peridotite, lherzolite and amphibolite were investigated with double torsion test. The results show that water-rock interaction has a significant influence on subcritical crack growth. With water-rock interaction, the crack velocity increases, while the stress intensity factor declines, which illustrates that water-rock interaction can decrease the strength of rocks and accelerate the subcritical crack growth. Based on Charlse theory and Hilling & Charlse theory, the test data were analyzed by regression and the correlation coefficients were all higher than 0.7, which shows the correlation is significant. This illustrates that both theories can explain the results of tests very well. Therefore, it is believed that the subcritical crack growth attributes to the breaking of chemical bond, which is caused by the combined effect of the tensile stress and the chemical reaction between the material at crack tip and the corrosive agent. Meanwhile, water-rock interaction has a vital effect on fracture toughness. The fracture toughness of samples under atmospheric environment is higher than that of samples immersed in water. And water-rock interaction has larger influence on fracture toughness in amphibolite than that in peridotite and lherzolite.

Groundwater monitoring of an open-pit limestone quarry:Water-rock interaction and mixing estimation within the rock layers by geochemical and statistical analyses

Water-rock interaction and groundwater mixing are important phenomena in understanding hydrogeological systems and the stability of rock slopes especially those consisting largely of moderately watersoluble minerals like calcite. In this study, the hydrogeological and geochemical evolutions of groundwater in a limestone quarry composed of three strata: limestone layer(covering), interbedded layer under the covering layer, and slaty greenstone layer(basement) were investigated. Water-rock interaction in the open-pit limestone quarry was evaluated using PHREEQC, while hierarchical cluster analysis(HCA)and principal component analysis(PCA) were used to classify and identify water sources responsible for possible groundwater mixing within rock layers. In addition, Geochemist's Workbench was applied to estimate the mixing fractions to clarify sensitive zones that may affect rock slope stability. The results showed that the changes in Ca2+and HCO3àconcentrations of several groundwater samples along the interbedded layer could be attributed to mixing groundwater from the limestone layer and that from slaty greenstone layer. Based on the HCA and PCA results, groundwaters were classified into several types depending on their origin:(1) groundwater from the limestone layer(LO),(2) mixed groundwater flowing along the interbedded layer(e.g., groundwater samples L-7, L-11, S-3 and S-4), and(3) groundwater originating from the slaty greenstone layer(SO). The mixing fractions of 41% LO: 59% SO, 64% LO: 36% SO, 43%LO: 57% SOand 25% LO: 75% SOon the normal days corresponded to groundwaters L-7, L-11, S-3 and S-4,respectively, while the mixing fractions of groundwaters L-7 and L-11(61% LO: 39% SOand 93% LO: 7% SO,respectively) on rainy days became the majority of groundwater originating from the limestone layer.These indicate that groundwater along the interbedded layer significantly affected the stability of rock slopes by enlarging multi-breaking zones in the layer through calcite dissolution and inducing high water pressure, tension cracks and potential sliding plane along this layer particularly during intense rainfall episodes.

Experiment study on water-rock interaction about gold activation and migration in different solutions

The interactions on gold active and migratory quantities and rates between tuffaceous slate and solu tions with different compositions were experimentally studied at 200 ℃, 20 MPa, in a high pressure apparatus. After reaction, tuffaceous slate became light colored and soft, and its mass density reduced. The amount of gold extracted from tuffaceous slate ranges widely, from 0 027 to 0 234 μg/g. Chlorine solution may activate appreciable amount of gold, and the gold migratory rate is high enough, from 50 70% to 92 30%, which reveals that sulphur and chlorine work together in solutions to accelerate gold activation and migration, and to realize gold mineralization in favorable places.

Hydrogen and Oxygen Isotope Study on the Water-Rock Interaction of the Yinshan (Cu-) Pb-Zn-Ag Ore Deposit, Jiangxi Province

The δ18O values of vein quartz of different stages from the Yinshan ore deposit are constant around 16‰ and the calculated δ18OH2O values attain 8‰± ; the δDH2O values of fluid inclu-sions in vein quartz are constant at about-60‰. From the surface down to 1200 m below the δ18O values of altered rocks gradually decrease from 15‰± to 11‰± . Various water-rock inversion calculations indicate that the ore fluids were formed by the interaction between meteoric water and phyllite at 350℃ and the effective W/ R value of around 0.1. When the water-rock exchange in the upper mineralization system took place, the effective W / R value increased to 5.0 or more. As a result, an evolution and mineralization model of a buffered open system with two-stage water-rock interactions is proposed in this study.

GIS-Hydrogeochemical Model of the YaoundéFractured Rock Aquifer, Cameroon: Aquifer Setting, Seasonal Variations in Groundwater-Rock Interaction and Water Quality

This study of the gneiss-fractured-rock aquifer in Yaoundé capital of Cameroon determines: the aquifer setting-flow systems, the aquifer type, seasonal variations in rock-water interactions, evolution of the hydrogeochemical processes, physicochemical parameters and the suitability for domestic-agro-industrial use of the groundwater. Physicochemical field tests were carried out on 445 wells during four seasons for EC, pH, TDS, Temperature and static water level from July 2016 to May 2017. 90 well samples were analyzed 45 samples per season: wet/dry. 38 borewell logs were used together with structural data to determine the aquifer setting. The field physico-chemical and laboratory analysis data of well samples were mounted unto various GIS software platforms: Global mapper, AqQa, Aquachem, Rockworks, Logplot7, Surfer and ArcGIS, to get indices/parameters/figures, by use of Durov’s, Piper’s and Gibbs diagrams, Water quality index WQI, USSL ratio, Sodium Absorption ratio SAR, Percent sodium %Na, Kelly Ratio KR, Magnesium Absorption Ratio MAR, Total Hardness TH, Residual Sodium Carbonate RSC and Permeability Index PI that were determined. The process of groundwater ions acquisition is three-fold: by recharge through atmospheric precipitation, by ion exchange/simple dissolution between the rock-groundwater and by groundwater mixing in its flow path. Water types are Ca-HCO3, Mg-HCO3 and Mg-Cl while hydrogeochemical facies are Ca-Mg-HCO3 and Ca-Mg-Cl-SO4. Most water samples are fresh, potable and soft all seasons. The hydrogeological conceptual model is that of a three-layered single phreatic fractured-rock-aquifer while other researchers postulated a two-aquifer, phreatic and semi-confined, two-layered model.

Water-Rock Interaction in Tarim Basin: Constraints from Oilfield Water Geochemistry

Oilfield waters from Cenozoic and Mesozoic terrestrial and Paleozoic marine environments in the Tarim Basin show no obvious difference in water chemistry except Br and isotopic compositions. The Paleozoic marine strata have higher Br concentrations than the terrestrial sediments, and the lack of obvious relationship between Br and Ⅰ suggests that Br is not, for the most part, derived from the degradation of organic matter. The oilfield waters are characterized by high TDS (total dissolved solids), ranging from 120000mg/L to 320000mg/L,relatively low Mg, high Ca, Sr, and CF relative to Br of evaporating seawater, suggestive of enhanced water-rock interaction. (Al (organic acid anions) concentrations are generally lower than 1500 mg/L with high values occurring over the temperature range from 95℃ to 140℃ ,in the Cambrian to Jurassic systems, and nearby unconformities. Organic acids are considered to be generated mainly from thermal maturation of kerogens during progressive burial of the Jurassic-Triassic and Cambrian-Ordovician systems, biodegradation of crude oils nearby unconformities, and thermochemical sulfate reduction in part of the Cambrian and Ordovician strata.High Al concentrations up to 3 mg/L to 5. 5 mg/L tend to occur in the waters of high OAA or petroleum- bearing intervals, suggesting the presence of organic complexing agents. Calculation by SOLMINEQ. 88 with updated database shows that AlAc2+ may account for more than 30%of the total Al. IsotoPic measurements (δD, δ18O) provide evidence for the following types of waters: diagenetically- modified connate meteoric water from the Jurassic and Triassic strata;diagenetically-modified connate marine water from the Cambrian and Ordovician strata; subaerially-evaporated water from the Cenozoic and Cretaceous strata; and mixed meteoric-evaporated or/and diagenetically modified connate water from the Carboniferous strata and reservoirs adjacent to the J/C and T/C unconformities. Those waters with very negativeδD values from -51. 30‰. to - 53. 80‰ (SMOW) and positive δ18 O values from 2. 99‰ to 4. 99‰(SMOW) in the continuous burial of the Cambrian-Ordovician system are explained to have resulted from hydrocarbon-water and water-rock interactions.

Hydrogeochemical Simulation of Water-Rock Interaction Under Water Flood Recovery in Renqiu Oilfield, Hebei Province, China

Hydrogeochemical simulation is an effective method to study water-rock interaction. In this paper, PHREEQM was used for the simulation of water-rock interaction under water flooding in the Renqiu Oilfield. Calculated results revealed that when fresh water was injected into the reservoir, Cl\+- and Na\++ would decrease without involvement in water-rock interaction. Erosion to dolomite will lead to an increase in Ca\+\{2+\}, Mg\+\{2+\} and CaHCO\++\-3. Saturation index of calcite and aragonite decreased first and then increased. With fresh water accounting for up to 70%, mixed water has the strongest erosion ability. Deoiled water has erosion ability under high temperature and high partial pressure of CO\-2. Pyrite and gypsum were sensitive to deoiled water, which can cause the dissolution of pyrite and the precipitation of gypsum. Micrographs revealed a great deal of information about water-rock interaction.

Cross-scale mechanical softening of Marcellus shale induced by CO_(2)-water-rock interactions using nanoindentation and accurate grain-based modeling

Mechanical softening behaviors of shale in CO_(2)-water–rock interaction are critical for shale gas exploitation and CO_(2)sequestration.This work investigated the cross-scale mechanical softening of shale triggered by CO_(2)-water–rock interaction.Initially,the mechanical softening of shale following 30 d of exposure to CO_(2)and water was assessed at the rock-forming mineral scale using nanoindentation.The mechanical alterations of rock-forming minerals,including quartz,muscovite,chlorite,and kaolinite,were analyzed and compared.Subsequently,an accurate grain-based modeling(AGBM)was proposed to upscale the nanoindentation results.Numerical models were generated based on the real microstructure of shale derived from TESCAN integrated minerals analyzer(TIMA)digital images.Mechanical parameters of shale minerals determined by nanoindentation served as input material properties for AGBMs.Finally,numerical simulations of uniaxial compression tests were conducted to investigate the impact of mineral softening on the macroscopic Young’s modulus and uniaxial compressive strength(UCS)of shale.The results present direct evidence of shale mineral softening during CO_(2)-water–rock interaction and explore its influence on the upscale mechanical properties of shale.This paper offers a microscopic perspective for comprehending CO_(2)-water-shale interactions and contributes to the development of a cross-scale mechanical model for shale.

Hydrochemical Assessment of Groundwater and Dominant Water-Rock Interactions in Ooeides Aquifer System, North Greece

This paper deals with the assessment of main controls on groundwater chemistry in the aquifer system of Ooeides, Orestiada Region, NE Greece, contributing to the assessment of groundwater and surface water interaction, as well as water-rock interactions in the study area. Statistical analysis and relevant hydrochemical plots were employed in the analysis of groundwater samples from the study area during sampling campaigns for the years 2018, 2019 and 2020. The process included the collection and analysis of hydrochemical, hydrological and hydrogeological information and data regarding the aquifer system of the study area. Based on the statistical processing and the spatial analysis of the relevant results of the research, interesting and useful information emerged regarding: i) the recharge procedure of the aquifer from surface water of rivers and streams in the study area;ii) the relationship of groundwater composition with the type of rock through which water flows;iii) the impact on groundwater quality from anthropogenic activities (cultivation activities, municipal waste). From the elaboration of all the above, interesting findings and suggestions came out, which are considered useful for the optimal management of the hydrogeological regime of the study area.

Machine learning with active pharmaceutical ingredient/polymer interaction mechanism:Prediction for complex phase behaviors of pharmaceuticals and formulations

The high throughput prediction of the thermodynamic phase behavior of active pharmaceutical ingredients(APIs)with pharmaceutically relevant excipients remains a major scientific challenge in the screening of pharmaceutical formulations.In this work,a developed machine-learning model efficiently predicts the solubility of APIs in polymers by learning the phase equilibrium principle and using a few molecular descriptors.Under the few-shot learning framework,thermodynamic theory(perturbed-chain statistical associating fluid theory)was used for data augmentation,and computational chemistry was applied for molecular descriptors'screening.The results showed that the developed machine-learning model can predict the API-polymer phase diagram accurately,broaden the solubility data of APIs in polymers,and reproduce the relationship between API solubility and the interaction mechanisms between API and polymer successfully,which provided efficient guidance for the development of pharmaceutical formulations.

Strong metal–support interaction boosts the electrocatalytic hydrogen evolution capability of Ru nanoparticles supported on titanium nitride

Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-group metal.Herein,based on the idea of strong metal–support interaction(SMSI)regulation,Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated,which were applied to the alkaline electrolytic water.Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased.Further study shows that the exposed Ru–TiN interfaces greatly promote the H_(2) desorption capacity.Thus,the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance,with an overpotential of 38 mV at 10 mA cm^(−2).Also,due to the encapsulation role of TiN overlayer on Ru nanoparticles,it displays super long-term stability with a very slight potential change after 24 h.This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.

Electrostatic Interaction-directed Construction of Hierarchical Nanostructured Carbon Composite with Dual Electrical Conductive Networks for Zinc-ion Hybrid Capacitors with Ultrastability

Metal-organic framework(MOF)-derived carbon composites have been considered as the promising materials for energy storage.However,the construction of MOF-based composites with highly controllable mode via the liquid-liquid synthesis method has a great challenge because of the simultaneous heterogeneous nucleation on substrates and the self-nucleation of individual MOF nanocrystals in the liquid phase.Herein,we report a bidirectional electrostatic generated self-assembly strategy to achieve the precisely controlled coatings of single-layer nanoscale MOFs on a range of substrates,including carbon nanotubes(CNTs),graphene oxide(GO),MXene,layered double hydroxides(LDHs),MOFs,and SiO_(2).The obtained MOF-based nanostructured carbon composite exhibits the hierarchical porosity(V_(meso)/V_(micro)∶2.4),ultrahigh N content of 12.4 at.%and"dual electrical conductive networks."The assembled aqueous zinc-ion hybrid capacitor(ZIC)with the prepared nanocarbon composite as a cathode shows a high specific capacitance of 236 F g^(-1)at 0.5 A g^(-1),great rate performance of 98 F g^(-1)at 100 A g^(-1),and especially,an ultralong cycling stability up to 230000 cycles with the capacitance retention of 90.1%.This work develops a repeatable and general method for the controlled construction of MOF coatings on various functional substrates and further fabricates carbon composites for ZICs with ultrastability.

Biological Interaction and Imaging of Ultrasmall Gold Nanoparticles

Ultrasmall gold nanoparticles(AuNPs)typically includes atomically precise gold nanoclusters(AuNCs)and AuNPs with a core size below 3 nm.Serving as a bridge between small molecules and traditional inorganic nanoparticles,the ultrasmall AuNPs show the unique advantages of both small molecules(e.g.,rapid distribution,renal clearance,low non-specific organ accumulation)and nanoparticles(e.g.,long blood circulation and enhanced permeability and retention effect).The emergence of ultrasmall AuNPs creates significant opportunities to address many challenges in the health field including disease diagnosis,monitoring and treatment.Since the nano–bio interaction dictates the overall biological applications of the ultrasmall AuNPs,this review elucidates the recent advances in the biological interactions and imaging of ultrasmall AuNPs.We begin with the introduction of the factors that influence the cellular interactions of ultrasmall AuNPs.We then discuss the organ interactions,especially focus on the interactions of the liver and kidneys.We further present the recent advances in the tumor interactions of ultrasmall AuNPs.In addition,the imaging performance of the ultrasmall AuNPs is summarized and discussed.Finally,we summarize this review and provide some perspective on the future research direction of the ultrasmall AuNPs,aiming to accelerate their clinical translation.

Ecological network analysis reveals complex responses of tree species life stage interactions to stand variables

Tree interactions are essential for the structure,dynamics,and function of forest ecosystems,but variations in the architecture of life-stage interaction networks(LSINs)across forests is unclear.Here,we constructed 16 LSINs in the mountainous forests of northwest Hebei,China based on crown overlap from four mixed forests with two dominant tree species.Our results show that LSINs decrease the complexity of stand densities and basal areas due to the interaction cluster differentiation.In addition,we found that mature trees and saplings play different roles,the first acting as“hub”life stages with high connectivity and the second,as“bridges”controlling information flow with high centrality.Across the forests,life stages with higher importance showed better parameter stability within LSINs.These results reveal that the structure of tree interactions among life stages is highly related to stand variables.Our efforts contribute to the understanding of LSIN complexity and provide a basis for further research on tree interactions in complex forest communities.

Study of the Relationship Between New Ionic Interaction Parameters and Salt Solubility in Electrolyte Solutions Based on Molecular Dynamics Simulation

Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is proposed by using molecular dynamics simulation,and the relationship between ion-to-ion interaction and salt solubility in a simulated seawater water-salt system is investigated.By analyzing the variation of distance and contact time between ions in an electrolyte solution,from both spatial and temporal perspectives,new parameters were proposed to describe the interaction between ions:interaction distance(ID),and interaction time ratio(ITR).The best correlation between characteristic time ratio and solubility was found for a molar ratio of salt-to-water of 10:100 with a correlation coefficient of 0.96.For the same salt,a positive correlation was found between CTR and the molar ratio of salt and water.For type 1-1,type 2-1,type 1-2,and type 2-2 salts,the correlation coefficients between CTR and solubility were 0.93,0.96,0.92,and 0.98 for a salt-to-water molar ratio of 10:100,respectively.The solubility of multiple salts was predicted by simulations and compared with experimental values,yielding an average relative deviation of 12.4%.The new ion-interaction parameters offer significant advantages in describing strongly correlated and strongly hydrated electrolyte solutions.

Interatomic Interaction Models for Magnetic Materials:Recent Advances

Atomistic modeling is a widely employed theoretical method of computational materials science.It has found particular utility in the study of magnetic materials.Initially,magnetic empirical interatomic potentials or spinpolarized density functional theory(DFT)served as the primary models for describing interatomic interactions in atomistic simulations of magnetic systems.Furthermore,in recent years,a new class of interatomic potentials known as magnetic machine-learning interatomic potentials(magnetic MLIPs)has emerged.These MLIPs combine the computational efficiency,in terms of CPU time,of empirical potentials with the accuracy of DFT calculations.In this review,our focus lies on providing a comprehensive summary of the interatomic interaction models developed specifically for investigating magnetic materials.We also delve into the various problem classes to which these models can be applied.Finally,we offer insights into the future prospects of interatomic interaction model development for the exploration of magnetic materials.

Resistive field generation in intense proton beam interaction with solid targets

The Brown-Preston-Singleton(BPS)stopping power model is added to our previously developed hybrid code to model ion beam-plasma interaction.Hybrid simulations show that both resistive field and ion scattering effects are important for proton beam transport in a solid target,in which they compete with each other.When the target is not completely ionized,the self-generated resistive field effect dominates over the ion scattering effect.However,when the target is completely ionized,this situation is reversed.Moreover,it is found that Ohmic heating is important for higher current densities and materials with high resistivity.The energy fraction deposited as Ohmic heating can be as high as 20%-30%.Typical ion divergences with half-angles of about 5°-10°will modify the proton energy deposition substantially and should be taken into account.