Theoretical Investigation for Two-state Reactivity of CO_2 Hydrogenation Catalyzed by Ru in Gas Phase

Gas-phase CO_2 catalyzed activation hydrogenation by Ru atoms was studied with density functional theory. Based on the structure optimization of different potential energy surfaces,there are two crossing points between singlet and triplet potential energy surfaces and there is a crossing point between quintet and triplet potential energy surfaces in the whole catalytic cycle. Spin transition probabilities in the vicinity of the intersections have been calculated by the Landau-Zener model theory. There are three minimum energy crossing points（MECPs） with strong spin-orbital coupling effect and higher spin transition probability,and all spin inversion occurred in s orbital and different d orbitals of ruthenium,indicating this is a typical two-state reactivity（TSR） reaction. Finally,the lowest energy reaction path is ensured.

Correction to:Assembly-level analysis on temperature coefficient of reactivity in a graphite-moderated fuel salt reactor fueled with low-enriched uranium

Following publication of the original article,the authors observed that both Fig.5 and Fig.4 depict the same image.Figure 5 was inaccurately referenced and displayed.The correct Fig.5 is copied below:The original article has been updated.

Pericytes protect rats and mice from sepsis-induced injuries by maintaining vascular reactivity and barrier function:implication of miRNAs and microvesicles

Background Vascular hyporeactivity and leakage are key pathophysiologic features that produce multi-organ damage upon sepsis.We hypothesized that pericytes,a group of pluripotent cells that maintain vascular integrity and tension,are protective against sepsis via regulating vascular reactivity and permeability.Methods We conducted a series of in vivo experiments using wild-type(WT),platelet-derived growth factor receptor-β(PDGFR-β)-Cre+mT/mG transgenic mice and Tie2-Cre+Cx43^(flox/flox)mice to examine the relative contribution of pericytes in sepsis,either induced by cecal ligation and puncture(CLP)or lipopolysaccharide(LPS)challenge.In a separate set of experiments with Sprague-Dawley(SD)rats,pericytes were depleted using CP-673451,a selective PDGFR-βinhibitor,at a dosage of 40 mg/(kg·d)for 7 consecutive days.Cultured pericytes,vascular endothelial cells(VECs)and vascular smooth muscle cells(VSMCs)were used for mechanistic investigations.The effects of pericytes and pericyte-derived microvesicles(PCMVs)and candidate miRNAs on vascular reactivity and barrier function were also examined.Results CLP and LPS induced severe injury/loss of pericytes,vascular hyporeactivity and leakage(P<0.05).Transplantation with exogenous pericytes protected vascular reactivity and barrier function via microvessel colonization(P<0.05).Cx43 knockout in either pericytes or VECs reduced pericyte colonization in microvessels(P<0.05).Additionally,PCMVs transferred miR-145 and miR-132 to VSMCs and VECs,respectively,exerting a protective effect on vascular reactivity and barrier function after sepsis(P<0.05).miR-145 primarily improved the contractile response of VSMCs by activating the sphingosine kinase 2(Sphk2)/sphingosine-1-phosphate receptor(S1PR)1/phosphorylation of myosin light chain 20 pathway,whereas miR-132 effectively improved the barrier function of VECs by activating the Sphk2/S1PR2/zonula occludens-1 and vascular endothelial-cadherin pathways.Conclusions Pericytes are protective against sepsis through regulating vascular reactivity and barrier function.Possible mechanisms include both direct colonization of microvasculature and secretion of PCMVs.

Tuning the reactivity of TiO_(2)layer with uniform distribution of Sub-5 nm Fe_(2)O_(3)particles via in situ voltage-assisted oxidation for robust catalytic reduction

The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.

Evaluation of the Oxidation Reactivity and Behavior of Exhaust Soot Particles from Diesel Engines with Different Emission Levels

The aim of this study was to investigate the oxidation reactivity and behavior of exhaust particulate matter(PM)from diesel engines.PM samples from two diesel engines(1K,CY4102)with different emission levels were collected by a thermophoretic system and a quartz filter.The oxidation reactivity,oxidation behaviors,and physicochemical properties of the PM samples were analyzed using thermogravimetric analysis(TGA),high-resolution transmission electron microscopy(HRTEM),Fourier-transform infrared spectrometry(FTIR),and Raman spectroscopy.The results showed that there was a great difference in the oxidation reactivity of soot particles emitted by the two different diesel engines.A qualitative analysis of the factors influencing oxidation reactivity showed that the nanostructure,degree of graphitization,and relative concentration of aliphatic C—H functional groups were the most important factors,whereas no significant correlation was found between the primary particle size and activation energy of the diesel soot.Based on the oxidation behavior analysis,the diesel soot particles exhibited both internal and surface oxidation modes during the oxidation process.Surface oxidation was dominant during the initial stage,and as oxidation progressed,the mode gradually changed to internal oxidation.Internal oxidation mode of soot particles from the 1K engine was significantly higher than that of CY4102.

Wettability,reactivity,and interface structure in Mg/Ni system

The sessile drop method was applied to the experimental investigation of the wetting and spreading behaviors of liquid Mg drops on pure Ni substrates.For comparison,the experiments were performed in two variants:(1)using the Capillary Purification(CP)procedure,which allows the non-contact heating and squeezing of a pure oxide-free Mg drop;(2)by classical Contact Heating(CH)procedure.The high-temperature tests were performed under isothermal conditions(CP:760℃for 30 s;CH:715℃for 300 s)using Ar+5 wt%H_(2) atmosphere.During the sessile drop tests,images of the Mg/Ni couples were recorded by CCD cameras(57 fps),which were then applied to calculate the contact angles of metal/substrate couples.Scanning and transmission electron microscopy analyses,both coupled with energy-dispersive X-ray spectroscopy,were used for detailed structural characterization of the solidified couples.It was found that an oxide-free Mg drop obtained by the CP procedure showed a wetting phenomenon on the Ni substrate(an average contact angleθ<90°in<1 s),followed by fast spreading and good wetting over the Ni substrate(θ_((CP))~20°in 5 s)to form a final contact angle ofθ_(f(CP))~18°.In contrast,a different wetting behavior was observed for the CH procedure,where the unavoidable primary oxide film on the Mg surface blocked the spreading of liquid Mg showing apparently non-wetting behavior after 300 s contact at the test temperature.However,in both cases,the deep craters formed in the Ni substrates under the Mg drops and significant change in the structure of initially pure Mg drops to Mg-Ni alloys suggest a strong dissolution of Ni in liquid Mg and apparent values of the final contact angles measured for the Mg/Ni system.

Experimental Study of the Influence of Intrinsic Parameters on the Thermal Reactivity of Sawdust, Polyethylene Terephthalate and Composite

Several works have been based on the study of thermal variations in biomass to derive more valuable products such as fuels capable of replacing oil in the event of a crisis or activated carbon used as an adsorbent material, widely used in industry for the elimination of unwanted materials, both in liquid and gaseous environments. A study of thermal parameters such as: heating speed, retention time, drying temperature, carbonization temperature, particle size, was carried out with the aim of determining the characteristic factors of the carbonization of Polyethylene terephthalate (PET), sawdust (SC) and sawdust/polyethylene terephthalate (CPS) mixture. The results of the immediate analysis revealed a very low level of ash in PET (0.013%) compared to the level of ash in sawdust (2.9%), as well as a high level of fixed carbon (82.960%), which suggests the presence of mineral oxides and a significant carbon matrix unlike PET, which indicates a very significant organic matrix (essentially made up of organic matter) with the absence of mineral oxides. The study of thermal parameters showed the water loss from Sawdust (SC) and the Sawdust/Polyethylene terephthalate (CPS) mixture, an increase with temperature, unlike that of PET whose variation is essentially zero. Without heat treatment, sawdust alone contains approximately 7% water. The optimal drying temperature for this study is 110˚C for a stay of 24 hours. It appears that the largest mass losses for the PET samples are between 87.19% and 96.05%, followed by that of the mixture, between 47.33% and 64.37%. And the lowest are observed, those of sawdust (from 24.02% to 62.6%). However, here we can say that the influence of the mass is not great, given the slight difference between the losses by temperature. The results of the study of the influence of grain size showed that the differences are insignificant, even if we vary the diameter of the grains from simple to triple. To better minimize physical constraints such as the intragranular diffusibility of the volatile matter and the homogeneity of the temperature in the grains, 75 μm particles are found to be optimal for our study. It can be noted when studying the heating rate that the mass loss at the end of the reaction is approximately the same depending on each precursor material. However, it has been demonstrated that the heating rate strongly influences the nature of the reaction products both for volatile materials and for the solid residue as well as on the kinetic parameters of the chemical reaction. Furthermore, the variation in apparent density shows a decrease as a function of the increase in the residence time of the materials in the reactor. As the carbonization time increases, the apparent density decreases. We note, for the lignocellulosic material, that the apparent density stabilizes after 60 minutes.

Morphology,Nanostructure,and Oxidation Reactivity of Particulate Matter Emitted by Diesel Blending with Various Aromatics

This study aims to analyze the influence of the polycyclic aromatic hydrocarbon(PAH)content in diesel on the physical and chemical properties of diesel soot particles.Four diesel fuels with different PAH content were tested on a 11.6 L direct-injection diesel engine.The raw particulate matter(PM)before the after-treatment devices was collected using the thermophoresis sampling system and the filter sampling system.A transmission electron microscope and Raman spectrometer are used to analyze the physical properties of the soot particles,including morphology,primary particle size distribution,and graphitization degree.A Fourier transform infrared spectrometer and thermogravimetric analyzer are used to characterize the surface chemical composition and oxidation reactivity of soot particles,respectively.The results show that as the PAH content in the fuel decreases,the size of the primary soot particles decreases from 29.58 to 26.70 nm.The graphitization degree of soot particles first increases and then decreases,and the relative content of the aliphatic hydrocarbon functional groups of soot particles first decreases and then increases.The T_(10),T_(50),and T_(90) of soot from high-PAH fuel are 505.3,589.3,and 623.5℃,while those from low-PAH fuel are 480.1,557.5,and 599.2℃,respectively.This indicates that exhaust PM generated by the low-PAH fuel has poor oxidation reactivity.However,as the PAH content in fuel is further decreased,the excessively high cetane number may cause uneven mixing and incomplete combustion,leading to enhanced oxidation reactivity.

Synergistic activation of smithsonite with copper-ammonium species for enhancing surface reactivity and xanthate adsorption

Copper ions(Cu^(2+))are usually added to activate the sulfidized surface of zinc oxide minerals to enhance xanthate attachment using sulfidization xanthate flotation technology.The adsorption of Cu^(2+)and xanthate on the sulfidized surface was investigated in various systems,and its effect on the surface hydrophobicity and flotation performance was revealed by multiple analytical methods and experiments.X-ray photoelectron spectroscopy(XPS)and time-of-flight secondary ion mass spectrometry(To F-SIMS)characterization demonstrated that the adsorption of Cu^(2+)on sulfidized smithsonite surfaces increased the active Cu—S content,regardless of treatment in any activation system.The sulfidized surface pretreated with NH_(4)^(+)-Cu^(2+)created favorable conditions for the adsorption of more Cu^(2+),significantly enhancing the smithsonite reactivity.Zeta potential determination,ultraviolet(UV)-visible spectroscopy,Fourier transform-infrared(FT-IR)measurements,and contact angle detection showed that xanthate was chemically adsorbed on the sulfidized surface,and its adsorption capacity in various systems was illustrated from qualitative and quantitative aspects.In comparison to the Na2S–Cu^(2+)and Cu^(2+)–Na2S–Cu^(2+)systems,xanthate exhibited a higher adsorption capacity on sulfidized smithsonite surfaces in NH_(4)^(+)-Cu^(2+)–Na2S–Cu^(2+)system.Hence,activation with Cu^(2+)–NH4+synergistic species prior to sulfidization significantly enhanced the mineral surface hydrophobicity,thereby increasing its flotation recovery.

软件定义网络Reactive交换模式IP转发效率研究

现代计算机网络技术发展迅速,SDN具有转发与控制分离、应用灵活多变、适应性强等特点,已逐渐被IT厂商和电信运营商所接纳并采用,但SDN作为一种发展中的技术很多方面还有待完善。本文首先将IP层相关协议的通信过程进行了分析,然后针对SDN的Reactive交换机模式将这些协议的通信效率与以太网进行了对比。实验与分析表明,在地址解析、连通性测试和数据传输等基本网络行为中,SDN的Reactive交换模式效率并不占据优势,需要进一步优化。

Enhanced structural damage behavior of liquid-filled tank by reactive material projectile impact

A series of ballistic experiments were performed to investigate the damage behavior of high velocity reactive material projectiles(RMPs) impacting liquid-filled tanks,and the corresponding hydrodynamic ram(HRAM) was studied in detail.PTFE/Al/W RMPs with steel-like and aluminum-like densities were prepared by a pressing/sintering process.The projectiles impacted a liquid-filled steel tank with front aluminum panel at approximately 1250 m/s.The corresponding cavity evolution characteristics and HRAM pressure were recorded by high-speed camera and pressure acquisition system,and further compared to those of steel and aluminum projectiles.Significantly different from the conical cavity formed by the inert metal projectile,the cavity formed by the RMP appeared as an ellipsoid with a conical front.The RMPs were demonstrated to enhance the radial growth velocity of cavity,the global HRAM pressure amplitude and the front panel damage,indicating the enhanced HRAM and structural damage behavior.Furthermore,combining the impact-induced fragmentation and deflagration characteristics,the cavity evolution of RMPs under the combined effect of kinetic energy impact and chemical energy release was analyzed.The mechanism of enhanced HRAM pressure induced by the RMPs was further revealed based on the theoretical model of the initial impact wave and the impulse analysis.Finally,the linear correlation between the deformation-thickness ratio and the non-dimensional impulse for the front panel was obtained and analyzed.It was determined that the enhanced near-field impulse induced by the RMPs was the dominant reason for the enhanced structural damage behavior.

Overview of the immunological mechanisms in hepatitis B virus reactivation:Implications for disease progression and management strategies

Hepatitis B virus(HBV)reactivation is a clinically significant challenge in disease management.This review explores the immunological mechanisms underlying HBV reactivation,emphasizing disease progression and management.It delves into host immune responses and reactivation’s delicate balance,spanning innate and adaptive immunity.Viral factors’disruption of this balance,as are interac-tions between viral antigens,immune cells,cytokine networks,and immune checkpoint pathways,are examined.Notably,the roles of T cells,natural killer cells,and antigen-presenting cells are discussed,highlighting their influence on disease progression.HBV reactivation’s impact on disease severity,hepatic flares,liver fibrosis progression,and hepatocellular carcinoma is detailed.Management strategies,including anti-viral and immunomodulatory approaches,are critically analyzed.The role of prophylactic anti-viral therapy during immunosuppressive treatments is explored alongside novel immunotherapeutic interventions to restore immune control and prevent reactivation.In conclusion,this compre-hensive review furnishes a holistic view of the immunological mechanisms that propel HBV reactivation.With a dedicated focus on understanding its implic-ations for disease progression and the prospects of efficient management stra-tegies,this article contributes significantly to the knowledge base.The more profound insights into the intricate interactions between viral elements and the immune system will inform evidence-based approaches,ultimately enhancing disease management and elevating patient outcomes.The dynamic landscape of management strategies is critically scrutinized,spanning anti-viral and immunomodulatory approaches.The role of prophylactic anti-viral therapy in preventing reactivation during immunosuppressive treatments and the potential of innovative immunotherapeutic interventions to restore immune control and proactively deter reactivation.

Assembly-level analysis on temperature coefficient of reactivity in a graphite-moderated fuel salt reactor fueled with low-enriched uranium

To provide a reliable and comprehensive data reference for core geometry design of graphite-moderated and low-enriched uranium fueled molten salt reactors,the influences of geometric parameters on the temperature coefficient of reactivity(TCR)at an assembly level were characterized.A four-factor formula was introduced to explain how different reactivity coefficients behave in terms of the fuel salt volume fraction and assembly size.The results show that the fuel salt temperature coefficient(FSTC)is always negative owing to a more negative fuel salt density coefficient in the over-moderated region or a more negative Doppler coefficient in the under-moderated region.Depending on the fuel salt channel spacing,the graphite moderator temperature coefficient(MTC)can be negative or positive.Furthermore,an assembly with a smaller fuel salt channel spacing is more likely to exhibit a negative MTC.As the fuel salt volume fraction increases,the negative FSTC first weakens and then increases,owing to the fuel salt density effect gradually weakening from negative to positive feedback and then decreasing.Meanwhile,the MTC weakens as the thermal utilization coefficient caused by the graphite temperature effect deteriorates.Thus,the negative TCR first weakens and then strengthens,mainly because of the change in the fuel salt density coefficient.As the assembly size increases,the magnitude of the FSTC decreases monotonously owing to a monotonously weakened fuel salt Doppler coefficient,whereas the MTC changes from gradually weakened negative feedback to gradually enhanced positive feedback.Then,the negative TCR weakens.Therefore,to achieve a proper negative TCR,particularly a negative MTC,an assembly with a smaller fuel salt channel spacing in the under-moderated region is strongly recommended.

Computational Chemistry and Molecular Modeling Techniques for the Study of Micropeptin EI-964: Insights into Its Chemical Reactivity and Potential Pharmaceutical Properties

Micropeptin EI-964 is a cyclic peptide compound isolated from a marine cyanobacterium with potent inhibitory activity against serine proteases, particularly chymotrypsin and trypsin. It has shown promising activity against various cancer cell lines, making it a candidate for drug development. The unique structure and activity of Micropeptin EI-964 make it a promising lead compound for the development of novel serine protease inhibitors and anti-cancer drugs. Computational Chemistry and Molecular Modeling techniques can provide valuable insights into the chemical reactivity and pharmaceutical properties of Micropeptin EI-964, guiding the design and development of new compounds with enhanced bioactivity and improved drug-like properties.

Molecular Reactivity and Interface Stability Modification in In-Situ Gel Electrolyte for High Performance Quasi-Solid-State Lithium Metal Batteries

Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply.Despite intensive efforts on electrolytes,uncontrolled interfacial reactions on lithium with electrolyte and patchy interfacial contacts still hinder its practical process.Herein,we bring in rationally designed F contained groups into polymer skeleton via in-situ gelation for the first time to establish quasi-solid-state battery.This method achieves a capacity retention of 90%after 1000 cycles at 0.5C with LiFePO_(4)cathodes.The interface constructed by polymer skeleton and reaction with–CF_(3)lead to the predicted solid electrolyte interface species with high stability.Furthermore,we optimize molecular reactivity and interface stability with regulating F contained end groups in the polymer.Comparisons on different structures reveal that high performance solid stable lithium metal batteries rely on chemical modification as well as stable polymer skeleton,which is more critical to construct robust and steady SEI with uniform lithium deposition.New approach with functional groups regulation proposes a more stable cycling process with a capacity retention of 94.2%at 0.5C and 87.6%at 1C after 1000 cycles with LiFePO_(4) cathodes,providing new insights for the practical development of quasi-solid-state lithium metal battery.

Formation behaviors of rod-like reactive shaped charge penetrator and their effects on damage capability

Formation behaviors of rod-like reactive shaped charge penetrator(RRSCP)and their effects on damage capability are investigated by experiments and numerical simulations.The pulsed X-ray technology and a spaced aluminum/steel plate with the thicknesses of 5 mm/100 mm are used.Three types of sphericalsegment aluminum-polytetrafluoroethylene-copper(Al-PTFE-Cu)reactive liners with Cu contents of 0%,46.6%,and 66%are fabricated and tested.The experimental results show that the reactive liners can form excellent rod-shaped penetrators with tail skirts under the shaped charge effect,but the tail skirts disappear over time.Moreover,rupturing damage to the aluminum plate and penetration to the steel plate are caused by the RRSCP impact.From simulation analysis,the RRSCP is formed by a mechanically and chemically coupled response with the reactive liner activated by shock in its outer walls and bottom and then backward overturning,forming a leading reactive penetrator and a following chemical energy cluster.The unique formation structure determines the damage modes of the aluminum plate and the steel plate.Further analysis indicates that the formation behaviors and damage capability of Al-PTFE-Cu RRSCP strongly depend on Cu content.With increasing Cu content,the velocity,activation extent,and reaction extent of Al-PTFE-Cu RRSCP decrease,which contribute to elongation and alleviate the negative effects of chemical reactions on elongation,significantly increasing the length-diameter ratio and thus enhancing the capability of steel plate penetration.However,the lower activation extent and energetic density will weaken the RRSCP's capability of causing rupturing damage to the aluminum plate.

Monomeric C-reactive protein:a link between chronic inflammation and neurodegeneration?

Pre-diabetic insulin resistance is associated with sub-clinical inflammation and concomitant increase in systemic C-reactive protein(CRP)levels.Type 2 diabetes mellitus(T2DM)patients register even higher chronic levels of inflammation,with excess circulating CRP originating from both typical hepatic synthesis,and also visceral white adipose tissue.

Computational investigation on the molecular structure and chemical reactivity of a traditional Chinese medicine extract MK-1 molecule

MK-1 molecule(C_(16)H_(16)O_(2)),the simplest structure of vitamin K(VK)compound family,is an extract from traditional Chinese medicine Cymbopogon distans(Nees ex Steud.)Wats(Chinese name YunXiangCao),which has attracted a great deal of attention in recent years due to its antiasthmatic,antitussives and expectorant effects.To investigate the molecular structure and chemical reactivity of MK-1 molecule,computational investigations on six conformational minima structures were carried out at the MP2/6-311++G(2d,2p)level of theory.Several local reactivity descriptors including condensed Fukui function,average local ionization energy,and molecular electrostatic potential on each individual atom were determined to predict the intrinsic reactivity of MK-1 molecule.

Fabrication and Properties of a New Reactive Diluent for Cationic UV Curing

The reactive diluent prepared by siloxane modified Trimethylene oxide can improve the performance of the UV curing system.Therefore,1,7-bis[(3-ethyl-3-methoxyoxacylobutane)propyl]octadecylosiloxane(BEMOPOMTS)was synthesized from diethyl carbonate,trimethylopropanes,allyl bromide,and 1,1,3,3,5,5,7,7-octadecylosiloxane as the main raw materials.BEMOPOMTS can be used as reactive diluents in the field of cationic UV curing.It has good thermal stability,and the addition of BEMOPOMTS significantly improves the tensile strength and elongation at break of epoxy resin.Compared with the pure epoxy resin,adding 20%BEMOPOMTS increased the elastic modulus by 25%to 677 MPa.

Reactive Transport Process of Earthquake-induced Hydrochemical Changes in Guanding Thermal Spring,Western Sichuan,China

Earthquake-related hydrochemical changes in thermal springs have been widely observed;however,quantitative modeling of the reactive transport process is absent.In the present study,we apply reactive transport simulation to capture the hydrochemical responses in a thermal spring following the Wenchuan Ms 8.0 and Lushan Ms 7.0 earthquakes.We first constrain deep reservoir geothermal fluid compositions and temperature by multicomponent geothermometry,and then a reactive geochemical transport model is constructed to reproduce the hydrochemical evolution process.The results show that the recharge from the shallow aquifer increases gradually until it reaches a peak because of the permeability enhancement caused by the Lushan earthquake,which may be the mechanism to explain the earthquake-related hydrochemical responses.In contrast to the postseismic effect of the Wenchuan earthquake,the chemical evolution can be considered as hydrochemical anomalies related to the Lushan earthquake.This study proves that the efficient simulation of reactive transport processes is useful for investigating earthquake-related signals in hydrochemical time series.