Tunneling with dissipation in open quantum systems

ARTICLEOPENReceived8Apr2015|Accepted25Aug2015|Published29Sep2015Entropy-stabilized oxidesChristina M.Rost1,Edward Sachet1,Trent Borman1,Ali Moballegh1,Elizabeth C.Dickey1,Dong Hou1,Jacob L.Jones1,Stefano Curtarolo2&Jon-Paul Maria1Configurational disorder can be compositionally engineered into mixed oxide by populating asingle sublattice with many distinct cations.The formulations promote novel and entropy-stabilized forms of crystalline matter where metal cations are incorporated in new ways.Here,through rigorous experiments,a simple thermodynamic model,and afive-componentoxide formulation,we demonstrate beyond reasonable doubt that entropy predominatesthe thermodynamic landscape,and drives a reversible solid-state transformation betweena multiphase and single-phase state.In the latter,cation distributions are proven tobe random and homogeneous.Thefindings validate the hypothesis that deliberateconfigurational disorder provides an orthogonal strategy to imagine and discover new phasesof crystalline matter and untapped opportunities for property engineering.1Department of Materials Science and Engineering,North Carolina State University,Raleigh,North Carolina27695,USA.2Department of Mechanical Engineering and Materials Science,Center for Materials Genomics,Duke University,Durham,North Carolina27708,USA.Correspondence and requests for materials should be addressed to J.-P.M.(email:jpmaria@)or to S.C.(email:stefano@).A grand challenge facing materials science is the continuoushunt for advanced materials with properties that satisfythe demands of rapidly evolving technology needs.The materials research community has been addressing this problem since the early1900s when Goldschmidt reported the‘the method of chemical substitution’1that combined a tabulation of cationic and anionic radii with geometric principles of ion packing and ion radius ratios.Despite its simplicity,this model enabled a surprising capability to predict stable phases and structures.As early as1926many of the technologically important materials that remain subjects of contemporary research were identified (though their properties were not known);BaTiO3,AlN,GaP, ZnO and GaAs are among that list.These methods are based on overarching natural tendencies for binary,ternary and quaternary structures to minimize polyhedral distortions,maximize spacefilling and adopt polyhedral linkages that preserve electroneutrality1–3.The structure-field maps compiled by Muller and Roy catalogue the crystallographic diversity in the context of these largely geometry-based predictions4.There are,however,limitations to the predictive power,particularly when factors like partial covalency and heterodesmic bonding are considered.To further expand the library of advanced materials and property opportunities,our community explores possibilities based on mechanical strain5,artificial layering6,external fields7,combinatorial screening8,interface engineering9,10and structuring at the nanoscale6,11.In many of these efforts, computation and experiment are important companions.Most recently,high-throughput methods emerged as a power-ful engine to assess huge sections of composition space12–17and identified rapidly new Heusler alloys,extensive ion substitution schemes18,19,new18-electron ABX compounds20and new ferroic semiconductors21.While these methods offer tremendous predictive power and an assessment of composition space intractable to experiment, they often utilize density functional theory calculations conducted at0K.Consequently,the predicted stabilities are based on enthalpies of formation.As such,there remains a potential section of discovery space at elevated temperatures where entropy predominates the free-energy landscape.This landscape was explored recently by incorporating deliberatelyfive or more elemental species into a single lattice with random occupancy.In such crystals,entropic contributions to the free energy,rather than the cohesive energy, promote thermodynamic stability atfinite temperatures.The approach is being explored within the high-entropy-alloy family of materials(HEAs)22,in which extremely attractive properties continue to be found23,24.In HEAs,however,discussion remains regarding the true role of configurational entropy25–28, as samples often contain second phases,and there are uncertainties regarding short-range order.In response to these open discussions,HEAs have been referred to recently as multiple-principle-element alloys29.It is compelling to consider similar phenomena in non-metallic systems,particularly considering existing information from entropy studies in mixed oxides.In1967Navrotsky and Kleppa showed how configurational entropy regulates the normal-to-inverse transformation in spinels,where cations transition between ordered and disordered site occupancy among the available sublattices30,31.These fundamental thermodynamic studies lead one to hypothesize that in principle,sufficient temperature would promote an additional transition to a structure containing only one sublattice with random cation occupancy.From experiment we know that before such transitions,normal materials melt,however,it is conceivable that synthetic formulations exist,which exhibit them.Inspired by research activities in the metal alloy communities and fundamental principles of thermodynamics we extend the entropy concept tofive-component oxides.With unambiguous experiments we demonstrate the existence of a new class of mixed oxides that not only contains high configurational entropy but also is indeed truly entropy stabilized.In addition,we present a hypothesis suggesting that entropy stabilization is particularly effective in a compound with ionic character.ResultsChoosing an appropriate experimental candidate.The candi-date system is an equimolar mixture of MgO,CoO,NiO,CuO and ZnO,(which we label as‘E1’)so chosen to provide the appropriate diversity in structures,coordination and cationic radii to test directly the entropic ansatz.The rationale for selection is as fol-lows:the ensemble of binary oxides should not exhibit uniform crystal structure,electronegativity or cation coordination,and there should exist pairs,for example,MgO–ZnO and CuO–NiO, that do not exhibit extensive solubility.Furthermore,the entire collection should be isovalent such that relative cation ratios can be varied continuously with electroneutrality preserved at the net cation to anion ration of unity.Tabulated reference data for each component,including structure and ionic radius,can be found in Supplementary Table1.Testing reversibility.In thefirst experiment,ceramic pellets of E1are equilibrated in an air furnace and quenched to room temperature.The temperature spanned a range from700to 1,100°C,in50-°C increments.X-ray diffraction patterns showing the phase evolution are depicted in Fig.1.After700°C,two prominent phases are observed,rocksalt and tenorite.The tenorite phase fraction reduces with increasing equilibration temperature.Full conversion to single-phase rocksalt occurs between850and900°C,after which there are no additional peaks,the background is low andflat,and peak widths are narrow in two-theta(2y)space.Reversibility is a requirement of entropy-driven transitions. Consequently,low-temperature equilibration should transform homogeneous1,000°C-equilibrated E1back to its multiphase state(and vice versa on heating).Figure1also shows a sequence of X-ray diffraction patterns for such a thermal excursion;initial equilibration at1,000°C,a second anneal at750°C,andfinally a return to1,000°C.The transformation from single phase,to multiphase,to single phase is evident by the X-ray patterns and demonstrates an enantiotropic(that is,reversible with tempera-ture32)phase transition.Testing entropy though composition variation.A composition experiment is conducted to further characterize this phase tran-sition to the random solid solution state.If the driving force is entropy,altering the relative cation ratios will influence the transition temperature.Any deviation from equimolarity will reduce the number of possible configurations O(S c¼k B log(O)), thus increasing the transition temperature.Because S c(x i)is logarithmically linked to mole fraction via B x i log(x i),the com-positional dependence is substantial.This dependency underpins our gedankenexperiment where the role of entropy can be tested by measuring the dependency of transition temperature as a function of the total number of components present,and of the composition of a single component about the equimolar formulation.The calculated entropy trends for an ideal mixture are illustrated in Fig.2b,which plots configurational entropy for a set of mixtures having N species where the composition of an individual species is changed and the others(NÀ1)are keptequimolar.Two dependencies become apparent:the entropy increases as new species are added and the maximum entropy is achieved when all the species have the same fraction.Both dependencies assume ideal random mixing.Two series of composition-varying experiments investigate the existence of these trends in formulation E1.The first experiment monitors phase evolution in five compounds,each related to the parent E1by the extraction of a single component.The sets are equilibrated at 875°C (the threshold temperature for complete solubility)for 12h.The diffraction patterns in Fig.2a show that removing any component oxide results in material with multiple phases.A four-species set equilibrated under these conditions never yields a single-phase material.The second experiment uses five individual phase diagrams to explore the configurational entropy versus composition trend.In each,the composition of a single component is varied by ±2,±6and ±10%increments about the equimolar composition while the others are kept even.Since any departure from equimolarity reduces the configurational entropy,it should increase transition temperatures to single phase,if thattransitionI n t e n s i t y2030405060702 (°)801.81,100N =5No ZnONo MgON =4No CuON =3No NiONo CoON =21,0501,000950T e m p e r a t u r e (°C )T e m p e r a t u r e (°C )T e m p e r a t u r e (°C )T e m p e r a t u r e (°C )T e m p e r a t u r e (°C )S /k B9008501,1001,0501,0009509008501,1001,0501,0009509008501,1001,0501,0009509008501,1001,0501,0009509008500.0X NX NiOX CuOX ZnOX MgoX CoO0.5 1.00.10.20.30.10.20.30.10.20.30.10.20.30.10.20.31.62223112202001111.41.21.00.80.60.40.20.0J14**********Figure 2|Compositional analysis.(a )X-ray diffraction analysis for a composition series where individual components are removed from the parent composition E1and heat treated to the conditions that would otherwise produce full solid solution.Asterisks identify peaks from rocksalt while carrots identify peaks from other crystal structures.(b )Calculated configurational entropy in an N -component solid solutions as a function of mol%of the N th component,and (c –g )partial phase diagrams showing the transition temperature to single phase as a function of composition (solvus )in the vicinity of the equimolar composition where maximum configurational entropy is expected.Error bars account for uncertainty between temperature intervals.Each phase diagram varies systematically the concentration of one element.L o g i n t e n s i t y750 °C750 °C800 °C850 °C900 °C1,000 °C2001111,000 °C 2 (°)T (200)T (002)T (110)T (200)T (002)T (110)Figure 1|X-ray diffraction patterns for entropy-stabilized oxide formulation E1.E1consists of an equimolar mixture of MgO,NiO,ZnO,CuO and CoO.The patterns were collected from a single pellet.The pellet was equilibrated for 2h at each temperature in air,then air quenched to room temperature by direct extraction from the furnace.X-ray intensity is plotted on a logarthimic scale and arrows indicate peaks associated with non-rocksalt phases,peaks indexed with (T)and with (RS)correspond to tenorite and rocksalt phases,respectively.The two X-ray patterns for 1,000°C annealed samples are offset in 2y for clarity.is in fact entropy driven.The specific formulations used are given in Supplementary Table 2.Figure 2c–g are phase diagrams of composition versus transformation temperature for the five sample sets that varied mole fraction of a single component.The diagrams were produced by equilibrating and quenching individual samples in 25°C intervals between 825and 1,125°C to obtain the T trans -composition solvus .In all cases equimolarity always leads to the lowest transformation temperatures.This is in agreement with entropic promotion,and consistent with the ideal model shown in Fig.2b.One set of raw X-ray patterns used to identify T trans for 10%MgO is given as an example in Supplementary Fig.1.Testing endothermicity .Reversibility and compositionally dependent solvus lines indicate an entropy-driven process.As such,the excursion from polyphase to single phase should be endothermic.An entropy-driven solid–solid transformation is similar to melting,thus requires heat from an external source 33.To test this possibility,the phase transformation in formulation E1can be co-analysed with differential scanning calorimetry and in situ temperature-dependent X-ray diffraction using identical heating rates.The data for both measurements are shown in Fig.3.Figure 3a is a map of diffracted intensity versus diffraction angle (abscissa)as a function of temperature.It covers B 4°of 2y space centred about the 111reflection for E1.At a temperature interval between 825and 875°C,there is a distinct transition to single-phase rocksalt structure—all diffraction events in that range collapse into an intense o 1114rocksalt peak.Figure 3b contains the companion calorimetric result where one finds a pronounced endotherm in the identical temperature window.The endothermic response only occurs when the system adds heat to the sample,uniquely consistent with an entropy-driven transformation 33.We note the small mass loss (B 1.5%)at the endothermic transition.This mass loss results from the conversion of some spinel (an intermediate phase seen by X-ray diffraction)to rocksalt,which requires reduction of 3þto 2þcations and release of oxygen to maintain stoichiometry.To address concerns regarding CuO reduction,Supplementary Fig.2shows a differential scanning calorimetry and thermal gravimetric analysis curve for pure CuO collected under the same conditions.There is no oxygen loss in the vicinity of 875°C.Testing homogeneity .All experimental results shown so far support the entropic stabilization hypothesis.However,all assume that homogeneous cation mixing occurs above the tran-sition temperature.It is conceivable that local composition fluc-tuations produce coherent clustering or phase separation events that are difficult to discern by diffraction using a laboratory sealed tube diffractometer.The solvus lines of Fig.2c–g support random mixing,as the most stable composition is equimolar (a condition only expected for ideal/regular solutions),but it is appropriate to ensure self-consistency with direct measurements.To characterize the cation distributions,extended X-ray absorption fine structure (EXAFS)and scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (STEM EDS)is used to analyse structure and chemistry on the local scale.EXAFS data were collected for Zn,Ni,Cu and Co at the Advanced Photon Source 12-BM-B 34,35.The fitted data are shown in Fig.4,the raw data are given in Supplementary Fig.3.The fitted data for each element provide two conclusions:the cation-to-anion first-near-neighbour distances are identical (within experimental error of ±0.01Å)and the local structures for each element to approximately seven near-neighbour distances are similar.Both observations are only consistent with a random cation distribution.As a corroborating measure of local homogeneity,chemical analysis was conducted using a probe-corrected FEI Titan STEM with EDS detection.Thin film samples of E1,prepared by pulsed laser deposition,are the most suitable samples to make the assessment.Details of preparation are given in the methods,and X-ray and electron diffraction analysis for the film are provided in Supplementary Figs 4and 5.The sample was thinned by mechanical polishing and ion milling.Figure 5shows a collection of images including Fig.5a,the high-angle annular dark-field signal (HAADF).In Fig.5b–f,the EDS signals for the K a emission energies of Mg,Co,Ni,Cu and Zn are shown (additional lower magnification images are included in Supplementary Fig.6).All magnifications reveal chemically and structurally homogeneous material.1,100R 111R 111Mass change (%)510151,000900800700600500400300200DSC –30–20Endo DSC (mW) Exo35.536.537.52θ (°)–10010Mass100T e m p e r a t u r e (°C )T e m p e r a t u r e (°C )Figure 3|Demonstrating endothermicity.(a )In situ X-ray diffraction intensity map as a function of 2y and temperature;and (b )differential scanning calorimetry trace for formulation ‘E1’.Note that the conversion to single phase is accompanied by an endotherm.Both experiments were conducted at a heating rate of 5°C min À1.04k (Å–1)(k )×k 2 (Å–2)2ZnNiCuCo681012Figure 4|Extended X-ray absorption fine structure.EXAFS measured at Advanced Photon Source beamlime 12-BM after energy normalization and fitting.Note that the oscillations for each element occur with similar relative intensity and at similar reciprocal spacing.This suggests a similar local structural and chemical environment for each.X-ray diffraction,EXAFS and STEM–EDS probes are sensitive to 10s of nm,10s of Åand 1Ålength scales,respectively.While any single technique could be misinterpreted to conclude homogenous mixing,the combination of X-ray diffraction,EXAFS and STEM–EDS provide very strong evidence.We note,in particular,the similarity in EXAFS oscillations (both in amplitude and position)out to 12inverse angstroms.This similarly would be lost if local ordering or clustering were present.Consequently,we conclude with certainty that the cations are uniformly dispersed.DiscussionThe set of experimental outcomes show that the transition from multiple-phase to single phase in E1is driven by configurational entropy.To complete our thermodynamic understanding of this system,it is important to understand and appreciate the enthalpic penalties that establish the transition temperature.In so doing,the data set can be tested for self-consistency,and the present data are brought into the context of prior research on oxide solubility.First,we consider an equation relating the initial and final states of the proposed phase transition:MgO ðRS ÞþNiO ðRS ÞþCoO ðRS ÞþCuO ðT ÞþZnO ðW Þ¼Mg ;Ni ;Co ;Cu ;Zn ðÞO ðRS ÞFor MgO,NiO and CoO,the crystal structures of the initial and final states are identical.If we assume that solution of each into the E1rocksalt phase is ideal,the enthalpy for mixing is zero.For CuO and ZnO,there must be a structural transition to rocksalt on dissolution from tenorite and wurtzite,respectively.If we again assume (for simplicity)that the solution is ideal,the mixing energy is zero,but there is an enthalpic penalty associated with the structure transition.From Davies et al.and Bularzik et al.,we know the reference chemical potential changes for the wurtzite-to-rocksalt and the tenorite-to-rocksalt transitions of ZnO and CuO;they are 25and 22kJ mol À1,respectively 36,37.If we make the assumption that the transition enthalpies of ZnO(wurtzite)to ZnO(rocksalt E1)and CuO(tenorite)to CuO(rocksalt E1)are comparable,then the enthalpic penalty for solution into E1can be estimated.For ZnO and CuO,the transition to solid solution in a rocksalt structure involves an enthalpy change of (0.2)Á(25kJ mol À1)þ(0.2)Á(22kJ mol À1),a total of þ10kJ mol À1.This calculation is based on the productof the mol fraction of each multiplied by the reference transition enthalpy.This assumption is consistent with the report of Davies et al.who showed that the chemical potential of a particular cation in a particular structure is associated with the molar volume of that structure 36.Since the rocksalt phases of ZnO and CuO have molar volumes comparable to E1,their reference transition enthalpy values are considered suitable proxies.In comparison,the maximum theoretically expected config-urational entropy difference at 875°C (the temperature were we observe the transition experimentally)between the single species and the random five-species solid solution is B 15kJ mol À1,5kJ mol À1larger than the calculated enthalpy of transition.It is possible that the origins of this difference are related to mixing energy as the reference energy values for structural transitions to rocksalt do not capture that aspect.While the present phase diagrams that monitor T trans as a function of composition demonstrate rather symmetric behaviour about the temperature minima,it is unlikely that mixing enthalpies are zero for all constituents.Indeed,literature reports show that enthalpies of mixing between the constituent oxides in E1are finite and of mixed sign,and their magnitudes are on the same order as the 5kJ mol À1difference between our calculated predictions 36.This energy difference may be accounted for by finite and positive mixing enthalpies.Following this argument,we can achieve a self-consistent appreciation for the entropic driving force and the enthalpic penalties for solution formation in E1by considering enthalpies of the associated structural transitions and expected entropy values for ideal cation mixing.As a final test,these predictions can be compared with experiment,specifically by calculating the magnitude of the endotherm observed by DSC at the transition from multiple-phase to single-phase states.Doing so we find a value B 12kJ mol À1(with an uncertainty of ±2kJ mol À1).While we acknowledge the challenge of quantitative calorimetry,we note that this experimental result is intermediate to and in close agreement with the predicted values.Compared with metallic alloys,the pronounced impact of entropy in oxides may be surprising given that on a per-atom basis the total disorder per volume of an oxide seems be lower than in a high-entropy alloy,as the anion sublattice is ordered (apart from point defects).The chemically uniform sublattice is perhaps the key factor that retains cation configurational entropy.As an illustration,consider a comparison between random metal alloys and random metal oxide alloys.Begin by reviewing the case of a two-component metallic mixture A–B.If the mixture is ideal,the energy of interaction E A–B ¼(E A–A þE B–B )/2,there is no enthalpic preference for bonding,and entropy regulates solution formation.In this scenario,all lattice sites are equivalent and configurational entropy is maximized.This situation,however,never occurs as no two elements have identical electronegativity and radii values.Figure 6a illustrates a two-component alloy scenario A–B where species B is more electronegative than A.Consequently,the interaction energies E A–A ,E B–B and E A–B will be different.A random mixture of A–B will produce lattice sites with a distribution of first near neighbours,that is,species A coordinated to 4-B atoms,2-A and 2-B atoms,etc y Different coordinations will have different energy values and the sites are no longer indistinguishable.Reducing the number of equivalent sites reduces the number of possible configurations and S .Now consider the same two metallic ions co-populating a cation sublattice,as in Fig.6b.In this case,there is always an intermediate anion separating neighbouring cation lattice sites.Again,in the limiting case where only first near neighboursareFigure 5|STEM–EDS analysis of E1.(a )HAADF image.Panels labelled as Zn,Ni,Cu,Mg and Co are intensity maps for the respective characteristic X-rays.The individual EDS maps show uniform spatial distributions for each element and are atomically resolved.considered,every cation lattice site is ‘identical’because each has the same immediate surroundings:the interior of an oxygen octahedron.Differentiation between sites is only apparent when the second near neighbours are considered.From the configura-tional disorder perspective,if each cation lattice site is identical,and thus energetically similar to all others,the number of microstates possible within the macrostate will approach the maximum value.This crystallographic argument is based on the limiting case where first-near-neighbour interactions predominate the energy landscape,which is an imperfect approximation.Second and third near neighbours will influence the distribution of lattice site energies and the number of equivalent microstates—but the impact will be the same in both scenarios.A larger number of equivalent sites in a crystal with an intermediate sublattice will increase S and expand the elemental diversity containable in a single solid solution and to lower the temperature at which the transition to entropic stabilization occurs.We acknowledge the hypothesis nature of this model at this time,and the need for a rigorous theoretical exploration.It is presented currently as a possibility and suggestion for future consideration and testing.We demonstrate that configurational disorder can promote reversible transformations between a poly-phase mixture and a homogeneous solid solution of five binary oxides,which do not form solid solutions when any of the constituents are removed provided the same thermal budget.The outcome is representative of a new class of materials called ‘entropy-stabilized oxides’.While entropic effects are known for oxide systems,for example,random cation occupancy in spinels 30,order–disorder transfor-mations in feldspar 38,and oxygen nonstoichiometry in layered perovskites 39,the capacity to actively engineer configurational entropy by composition,to stabilize a quinternary oxide with a single cation sublattice,and to stabilize unusual cation coordination values is new.Furthermore,these systems provide a unique opportunity to explore the thermodynamics and structure–property relationships in systems with extreme configurational disorder.Experimental efforts exploring this composition space are important considering that such compounds will be challenging to characterize with computational approaches minimizing formation energy (for example,genetic algorithms)or with adhoc thermodynamic models (for example,CALPHAD,cluster expansion)6.We expect entropic stabilization in systems where near-neighbour cations are interrupted by a common intermediateanion (or vice versa),which includes broad classes of chalcogenides,nitrides and halides;particularly when covalent character is modest.The entropic driving force—engineered by cation composition—provides a departure from traditional crystal-chemical principles that elegantly predict structural trends in the major ternary and quaternary systems.A companion set of structure–property relationships that predict new entropy-stabilized structures with novel cation incorporation await discovery and exploitation.MethodsSolid-state synthesis of bulk materials .MgO (Alfa Aesar,99.99%),NiO (Sigma Aldrich,99%),CuO (Alfa Aesar,99.9%),CoO (Alfa Aesar,99%)and ZnO (Alfa Aesar 99.9%)are massed and combined using a shaker mill and 3-mm diameter yttrium-stabilized zirconia milling media.To ensure adequate mixing,all batches are milled for at least 2h.Mixed powders are then separated into 0.500-g samples and pressed into 1.27-cm diameter pellets using a uniaxial hydraulic press at 31,000N.The pellets are fired in air using a Protherm PC442tube furnace.Temperature evolution of phases .Ceramic pellets of E1are equilibrated in an air furnace and quenched to room temperature by direct extraction from the hot zone.Phase analysis is monitored by X-ray diffraction using a PANalytical Empyrean X-ray diffractometer with Bragg-Brentano optics including programmable diver-gence and receiving slits to ensure constant illumination area,a Ni filter,and a 1-D 128element strip detector.The equivalent counting time for a conventional point detector would be 30s per point at 0.01°2y increments.Note that all X-ray are collected using substantial counting times and are plotted on a logarithmic scale.To the extent knowable using a laboratory diffractometer,the high-temperature samples are homogeneous and single phase:there are no additional minor peaks,the background is low and flat,and peak widths are sharp in two-theta (2y )space.Temperature-dependent diffraction data are collected with PANalytical Empyrean X-ray diffractometer with Bragg-Brentano optics includingprogrammable divergence and receiving slits to ensure constant illumination area,a Ni filter,and a 1-D 256element strip detector.The samples are placed in a resistively heated HTK-1200N hot stage in air.The samples are ramped at a constant rate of 5°C min À1with a theta–two theta pattern captured every 1.5min.Calorimetry data are collected using a Netzsch STA 449F1Jupiter system in a Pt crucible at 5°C min À1in flowing air.Determining solvus lines .Five series of powders are mixed where the amount of one constituent oxide is varied from the parent mixture E1.Supplementary Table 2lists the full set of samples synthesized for this experiment.Each individual sample is cycled through a heat-soak-quench sequence at 25°C increments from 850°C up to 1,150°C.The soak time for each cycle is 2h,and samples are then quenched to room temperature in o 1min.After the quenching step for each cycle,samples are immediately analysed for phase identification using a PANalytical Empyrean X-ray diffractometer using the conditions identified above.If more than one phase is present,the sample would be put through the next temperature cycle.The temperature at which the structure is determined to be pure rocksalt,with no discernable evidence of peak splitting or secondary phases,is deemed the transition temperature as a function of composition.Supplementary Fig.1shows an example of the collected X-raypatterns after each cycle using the E1L series with þ10%MgO.Once single phase is achieved,the sample is removed from the sequence.Note that this entire experiment is conducted two times.Initially in 50°C increments and longer anneals,and to ensure accuracy of temperature values and reproducibility,a second time using shorter increments and 25°C anneals.Findings in both sets are identical to within experimental error bar values.In the latter case,error bars correspond to the annealing interval value of 25°C.In the main text relating to Fig.2a we note that in addition to small peaks from second phases,X-ray spectra for N ¼4samples with either NiO or MgO removed show anisotropic peak broadening in 2y and skewed relative intensities where I (200)/I (111)is less than unity.This ratio is not possible for the rocksalt structure.Supplementary Table 3shows the result of calculations of structure factors for a random equimolar rocksalt oxide with composition E1.Calculations show that the 200reflection is the strongest,and that the experimentally measured relative intensities of 111/200are consistent with calculations.We use this information as a means too best assess when the transition to single phase occurs since the most likely reason for the skewed relative intensity is an incomplete conversion to the single-phase state.This dependency is highlighted in Supplementary Fig.1.X-ray absorption fine structure .X-ray absorption fine structure (XAFS)is made possible through the general user programme at the Advanced Photon Source in Lemont,IL (GUP-38672).This technique provides a unique way to probe the local environment of a specific element based on the interference between an emitted core electron and the backscattering from surrounding species.XAFS makes no assumption of structure symmetry or elemental periodicity,making it an ideal means to study disordered materials.During the absorption process,coreelectronsBFigure 6|Binary metallic compared with a ternary oxide.A schematic representation of two lattices illustrating how the first-near-neighbour environments between species having different electronegativity (the darker the more negative charge localized)for (a )a random binary metal alloy and (b )a random pseudo-binary mixed oxide.In the latter,near-neighbour cations are interrupted by intermediate common anions.。

钻探工程Drilling Engineering第50卷第5期2023年9月Vol. 50 No. 5Sep. 2023：116-124坑道定向钻进系统在隧洞水平勘探工程中的适应性分析胡郁乐1，赵海滨*1，2，姚震桐1（1.中国地质大学（武汉），湖北 武汉 430074； 2.山东省第一地质矿产勘查院，山东 济南 250007）摘要：随着城市地铁隧洞、铁路隧道等工程建设的推进，水平孔定向地质勘探法已成为一种新的勘探手段，相较于传统的竖向孔施工，其能回避复杂的施工环境，节省大量钻探工作量，技术经济优势明显。

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针对高效取心作业和可变轨钻探作业的要求，明确了水平勘探钻机大扭矩强给进能力、多工艺适应能力、高效钻进能力、高效起下钻能力、取心能力和动力头结构的改造方向。

分析了在轨迹变化频繁的定向孔中应用绳索取心钻具的不足和限制，并探索了钻探信息化进程中的信息参数类别和传输路径。

关键词：坑道定向钻进系统；隧洞水平勘探；水平定向勘察；钻探信息化中图分类号：P634；U452.1 文献标识码：A 文章编号：2096-9686（2023）05-0116-09Adaptability analysis of tunnel directional drilling system in tunnelhorizontal exploration engineeringHU Yule 1，ZHAO Haibin *1,2，YAO Zhentong 1(1.China University of Geosciences, Wuhan Hubei 430074, China ；2.The First Geological Team of Shandong Provincial Bureau of Geology and Mineral Resources,Jinan Shandong 250007, China )Abstract ： With the advancement of engineering construction such as urban subway tunnels and railway tunnels ， the horizontal directional geological exploration method has become a new exploration method. Compared to traditional vertical hole construction ， it can avoid complex construction environments ， save a lot of drilling workload ， and have obvious technical and economic advantages. The tunnel directional drilling system has traditional advantages for surface or tunnel exploration ， but the horizontal exploration mainly based on coring has higher requirements. The tunnel directional drilling technology needs targeted improvement and upgrading in aspects such as coring process adaptability and drill function module. Focusing on the technical characteristics of horizontal directional exploration ， this paper compares and analyzes the adaptability of typical tunnel directional drilling systems in aspects of drill pipe system ， horizontal exploration rig ， drill assembly and coring tool ， directional drilling instrument and drilling informatization ， and summarizes the technical integration that must be relied on to build the tunnel horizontal exploration engineering technical system. In response to the requirements for efficient coring operations and variable track drilling operations ， the direction for the transformation of the horizontal exploration drilling rig ’s high torque and strong feeding capacity ，收稿日期：2023-02-28； 修回日期：2023-05-27 DOI ：10.12143/j.ztgc.2023.05.017基金项目：国家自然科学基金重点项目（编号：61733016）；山东省第一地质矿产勘查院2020年对外开放基金项目（编号：2020DW01）第一作者：胡郁乐，男，汉族，1970年生，教授，博士生导师，研究方向为钻探（井）工艺技术、井下工具及钻井仪表，湖北省武汉市洪山区鲁磨路388号，************.cn 。

水工建筑物专业词汇岸墙land wall坝顶dam crest，dam top坝踵dam heel坝趾dam toe板桩sheet pile边墩side pier，land pier变形模量deformation modulus鼻坎bucket lip毕肖普法Bishop method冰压力ice pressure剥离desquamation侧槽式溢洪道side channel Spillway沉降settlement齿墙cut-off trench冲沙闸（排沙闸）silt-releasing Sluice纯拱法independent arch method刺墙key-wall大头坝massive-head buttress dam*buttress 是扶壁的意思单宽流量discharge per unit width单曲拱坝single-curvature arch dam挡潮闸tidal sluice导流隧洞river diversion tunnel倒悬度Overhang degree底流消能energy dissipation by underflow地震作用earthquake action垫座cushion abutment动水压力hydrodynamic pressure断层fault堆石坝rock-fill dam多拱梁法multi-arch beam method阀门valve gate防浪墙wave wall防渗铺盖impervious blanket非常溢洪道emergency spillway分洪闸flood diversion sluice副坝auxiliary dam刚体极限平衡法limit equilibrium method for rigid block 拱坝arch dam拱冠梁crown cantilever拱冠粱法crown cantilever method工作桥service bridge固结灌浆consolidation grouting灌溉隧洞irrigation tunnel灌浆帷幕grout curtain管涌piping海漫apron extension横缝transverse joint虹吸式溢洪道siphon spillway蝴蝶阀butterfly valve护坡slope protection护坦apron弧形闸门radial gate滑雪道式溢洪道ski-jump spillway化学管涌chemical piping混凝土防渗墙concrete cut-off wall混凝土面板堆石坝concrete faced rock-fill dam 基本断面primary section简化毕肖普法simplified Bishop method浆砌石拱坝stone masonry arch dam浆砌石重力坝stone masonry gravity dam交通桥traffic bridge接触冲刷contact scouring接触灌浆contact grouting接缝灌浆joint grouting截水槽cut-off trench节制闸check sluice进水口water inlet进水闸inlet sluice井式溢洪道shaft spillway静水压力hydrostatic pressure均质坝homogeneous earth dam抗滑稳定分析analysis of stability against sliding 抗滑稳定性stability against sliding空腹重力坝hollow gravity dam空化cavitation空蚀cavitation erosion空注阀hollow jet valve宽缝重力坝slotted gravity dam宽尾墩flaring pier廊道gallery浪压力wave force理论计算theoretical computation拦河闸river sluice沥青混凝土asphalt concrete连拱坝multiple-arch dam流土soil flow流网法flow net method锚杆anchor rod面板face slab面流消能energy dissipation by surface flow模型试验model experiment泥沙压力silt pressure碾压混凝土坝Roller Compacted Concrete Dam 牛腿Corbel排沙隧洞silt-releasing tunnel排水drainage排水闸outlet sluice喷混凝土sprayed concrete平板坝flat slab buttress dam平面闸门plane gate破碎带crushed zone铺盖blanket砌石护坡stone pitching人工材料面板坝artificial material faced dam 人工材料心墙坝artificial material-core dam溶洞solution cavern软基重力坝gravity dam on soft foundation软弱夹层soft intercalated layer实用断面practical section试载法trial-load method双曲拱坝double-curvature arch dam水工建筑物hydraulic structure水工隧洞hydraulic tunnel，waterway tunnel 水力发电隧洞hydropower tunnel水利枢纽hydro-complex水力学方法hydraulics method水平施工缝horizontal joint水闸sluice弹性模量elastic modulus挑流消能energy dissipation by trajectory jet土工膜geomembrane土石坝earth-rock dam土质斜墙坝earth dam with inclined soil wall 土质斜心墙坝earth dam with inclined soil core 土质心墙坝earth dam with soil core帷幕灌浆curtain grouting温度荷载temperature load温度控制temperature control温度应力temperature stress温度作用temperature action无压隧洞free level tunnel消力池stilling pool消力戽roller bucket消能工energy dissipater泄洪隧洞spillway tunnel泄水建筑物discharge structure泄水孔outlet hole新奥法NATM（New Austrian Tunneling Method）胸墙breast wall扬压力uplift溢洪道spillway水垫塘plunge pool溢流坝overflow dam、翼墙wing wall应力分析stress analysis优化设计optimization design有限单元法finite element method有压隧洞pressure tunnel闸墩pier闸门gate闸门槽gate slot正槽式溢洪道normal channel spillway整体式重力坝monolithic gravity dam趾板toe slab支墩坝buttress dam重力坝gravity dam重力墩gravity abutment 周边缝peripheral joint 驻波standing wave锥形阀cone valve自由跌流free drop自重dead weight纵缝longitudinal joint键槽key strench伸缩缝contraction joint 施工缝construction joint 反弧段flip bucket拦污栅trash rack渐变段transition泄槽chute发电进水口power intake 通气管air vent检修门bulkhead gate事故门emergency gate 工作门service gate堰weir通气管air vent胸墙breast wall梁beam柱column回填混凝土backfill concrete 接地earth一期混凝土primary concrete 二期混凝土secondary concrete 叠梁门stoplog门机gantry crane止水waterstop钢筋reinforcement模板formwork围堰cofferdam马道bench；berm蜗壳volute水轮机turbine电站power house车间workshop发电机generator变电站transformer station副厂房auxiliary power house安装间erection bay尾水闸门tail lock尾水渠tailrace引水渠approach channel前池fore bay导墙lead wall隔墙partition wall接触灌浆contact grouting回填混凝土backfill concrete帷幕灌浆curtain grouting挡墙retaining wall港口harbour港口建筑物port structure船闸navigation lock船闸充水lock filling船闸充水和泄水系统locking filling and emptying system 船闸前池upper pool船闸上下游水位差lock lift船闸闸首lock head升船机ship elevator；ship lift鱼道fish canal旁通管by-pass 齿槽cut-off wall。

英文论文审稿意见汇总之老阳三干创作1、目标和结果不清晰.It is noted that your manuscript needs careful editing by someone with expertise in technical English editing paying particular attention to English grammar, spelling, and sentence structure so that the goals and results of the study are clear to the reader.2、未解释研究方法或解释不充沛.◆ In general, there is a lack of explanation of replicates and statistical methods used in the study.◆ Furthermore, an explanation of why the authors did these various experimentsshould be provided.3、对研究设计的rationale:Also, there are few explanations of the rationale for the study design.4、夸张地陈说结论/夸年夜功效/不严谨：The conclusions are overstated. For example, the study did not showif the side effects from initial copper burst can be avoid with the polymer formulation.5、对hypothesis的清晰界定：A hypothesis needs to be presented.6、对某个概念或工具使用的rationale/界说概念：What was the rationale for the film/SBF volume ratio?7、对研究问题的界说：Try to set the problem discussed in this paper in more clear,write one section to define the problem8、如何凸现原创性以及如何充沛地写literature review:The topic is novel but the application proposed is not so novel.9、对claim,如A＞B的证明,verification:There is no experimental comparison of the algorithmwith previously known work, so it is impossible to judge whether the algorithm is an improvement on previous work.10、严谨度问题：MNQ is easier than the primitive PNQS, how to prove that.11、格式（重视水平）：◆ In addition, the list of references is not in our style. It is close but not completely correct. I have attached a pdf file with "Instructions for Authors" which shows examples.◆ Before submitting a revision be sure that your material is properly prepared and formatted. If you are unsure, please consult the formatting nstructions to authors that are given under the "Instructions and Forms" button in he upper right-hand corner of the screen.12、语言问题（呈现最多的问题）：有关语言的审稿人意见：◆ It is noted that your manuscript needs careful editing by someone with expertise in technical English editing paying particular attention to English grammar, spelling, and sentence structure so that the goals and results ofthe study are clear to the reader.◆ The authors must have their work reviewed by a proper translation/reviewing service before submission; only then can a proper review be performed. Most sentences contain grammatical and/or spelling mistakes or are not complete sentences.◆ As presented, the writing is not acceptable for the journal. There are problems with sentence structure, verb tense, and clause construction.◆ The English of your manuscript must be improved before resubmission. We strongly suggest that you obtain assistance from a colleague who is well-versed in English or whose native language is English.◆ Please have someone competent in the English language and the subject matter of your paper go over the paper and correct it. ?◆ the quality of English needs improving.来自编纂的鼓励：Encouragement from reviewers:◆ I would be very glad to re-review the paper in greaterdepth once it has been edited because the subject is interesting.◆ There is continued interest in your manuscript titled "……" which you submitted to the Journal of Biomedical Materials Research: Part B - Applied Biomaterials.◆ The Submission has been greatly improved and is worthy of publication.老外写的英文综述文章的审稿意见Ms. Ref. No.: ******Title: ******Materials Science and EngineeringDear Dr. ******,Reviewers have now commented on your paper. You will see that they are advising that you revise your manuscript. If you are prepared to undertake the work required, I would be pleased to reconsider my decision.For your guidance, reviewers&#39; comments are appended below.Reviewer #1: This work proposes an extensive review onmicromulsion-based methods for the synthesis of Ag nanoparticles. As such, the matter is of interest, however the paper suffers for two serious limits:1) the overall quality of the English language is rather poor;2) some Figures must be selected from previous literature to discuss also the synthesis of anisotropically shaped Ag nanoparticles (there are several examples published), which has been largely overlooked throughout the paper. ;Once the above concerns are fully addressed, the manuscript could be accepted for publication in this journal这是一篇全过程我均比力了解的投稿,稿件的内容我认为是相当不错的,中文版投稿于业内有较高影响的某核心期刊,并很快获得发表.其时我作为审稿人之一,除提出一些修改建议外,还特建议了5篇应增加的参考文献,该文正式发表时共计有参考文献25篇.作者或许看到审稿意见还不错,因此决意检验考试向美国某学会主办的一份英文刊投稿.几经修改和弥补后,请一位英文“功底"较好的中国人翻译,投稿后约3周,便返回了三份审稿意见.从英文刊的反馈意见看,这篇稿件中最严重的问题是文献综述和引用不够,其次是语言表达方面的欠缺,另外是论证过程和结果展示形式方面的缺乏.感想：一篇好的论文,从内容到形式都需要精雕细琢.附1：中译审稿意见审稿意见—1(1) 英文表达太差,尽管意思年夜致能表达清楚,但文法毛病太多.(2) 文献综述较差,观点或论断应有文献支持.(3) 论文读起来像是XXX的广告,不知道作者与XXX是否没有关联.(4) 该模式的立异性其实不是如作者所述,目前有许多XX采用此模式（如美国地球物理学会）,作者应详加调查并分析XXX运作模式的立异点.(5) 该模式也不是作者所说的那样胜利……(审稿人结合论文中的数据具体分析)审稿意见—2(1) 缺少直接相关的文献引用(如…).(2) 写作质量达不到美国学术期刊的标准.审稿意见—3(1) 作者应着重指出指出自己的贡献.(2) 缺少支持作者发现的方法学分析.(3) 需要采纳表格和图件形式展示(数据)资料.Our JPCA paper were peer reviewed by two reviewers, and their comments are as follows:The Comments by the First ReviewerEditor: Michael A. DuncanReviewer: 68Manuscript Number: jp067440iManuscript Title: Restricted Geometry Optimization, a Different Way to Estimate Stabilization Energies for Aromatic Molecules of Various TypesCorresponding Author: YuRecommendation: The paper is probably publishable, but should be reviewed again in revised form before it is accepted.Additional Comments: In the present work the authors introduce a new energy-based aromaticity measure. Referred as restricted geometry optimization, the extra stabilization energy (ESE) is calculated by means of an energy scheme in which the different double bonds are localized. This methodology is applied to different sets of aromatic systems, and the results are compared to previous already existing schemes. This procedure seems to work better than previous ones, however it must be underlined that with a much greater complexity. It avoids having to choose a reference structure, and it is worthnoticing that benzene appears to be the most aromatic system. Thus the method presented might mean a new contribution to the different aromacity criteria, however before acceptance for publication I would recommend important changes to be taken into account in the manuscript.The new method used is not presented in a comprehensible way. In the second paragraph of the Introduction the authors should already describe it, and not first presenting the results for benzene and notgoing into the method till the second section. The formulas used must be described precisely as well. So I would recommend that before acceptance the manuscript should be rewritten in order to make it more comprehensible not only to physical chemists but also to the experimental chemical community, and at the same time to improve the English used.Other minor points are:- First line of Introduction: aromaticity is one of the most important concepts in organic chemistry, but most of organic compounds are not aromatic.- Introduction, line 4:notice that only energetic ways of evaluating aromaticity are mentioned, however geometry-based (HOMA), magnetic-based (NICS) and electronic-based (SCI, PDI) methods are also important, and this point should be pointed out.- Section 3.1, last line of first paragraph: is B3LYP chosen just because it gives similar results to HF and MP2? This should be pointed out in the manuscript.- Enlarge description in point 3.4.1 by going deeper into the data in Figure 8.Review Sent Date: 18-Dec-2006******** *********************************The Comments by the Second ReviewerEditor: Michael A. DuncanReviewer: 67Manuscript Number: jp067440iManuscript Title: Restricted Geometry Optimization, a Different Way to Estimate StabilizationEnergies for Aromatic Molecules of Various Types Corresponding Author: YuRecommendation: The paper is probably publishable, but should be reviewed again in revised form before it is accepted.Additional Comments:Comments on the manuscript "Restricted Geometry Optimization, a Different Way to Estimate Stabilization Energies for Aromatic Molecules of Various Types" by Zhong-Heng Yu, Peng BaoAuthors propose a restricted geometry optimization technique subject to pi orbital interaction constraints as a new measure of aromaticity. The approach is interesting and has certain merits. My main objection is that the manuscript is difficult to read and understand, mainly because of poor English. A substantial revision in this respect would be beneficiary.各位：新的恶战开始了.投往JASA的文章没有被拒,但被批得很凶.尽管如此,审稿人和编纂还是给了我们一个修改和再被审的机会.我们应当珍惜这个机会,不急不火.我们首先要有个修改的指导思想.年夜家先看看审稿意见吧.-----邮件原件----- Manuscript #07-04147: Editor's Comments:This is my personal addition to the automatically generated email displayed above. Your manuscript has now been read by three knowledgeable reviewers, each of whom has provided thoughtful and detailed comments on the paper. The main points of the reviews are self-explanatory and mostly consistent across the reviews. Your presentation needs to be reworked substantially, and thereviews give you many suggestions for doing so. Clearly, the introduction needs to be much more concise and focused on the main questions you propose to answer, and why these questions are important. The rationale forselecting this unusual condition must be clear. Your discussion should focuson how the questions have been answered and what they mean. The resultssection is heavily dependent on statistical analyses that did not satisfythe reviewers. The figures and tables could be improved and perhapsconsolidated. The methods could be shortened. For example, I think readers would take your word thatthesewere nonsense sentences, or perhaps you could simply cite some other workwhere they were used. In general, it is unusual to present the first resultsas late as page 17 of a manuscript.Beyond the issues of presentation, some serious questions are raised by the reviewers about the design. The most notable (but not the only problem) is that there are no conditions where young and olderlisteners can be compared at nearly the same performance level in the baseline condition, and that at least floor effects and potentially ceiling effects are likely to significantly influence the older/younger comparison. The older listeners are tested at only one signal-to-noise ratio, at which performance was extremely poor. This asymmetric design where data for three signal-to-masker ratios are available for the younger listeners but only one for the older listeners is not ideal, but perhaps the comparison could have been salvaged if you had guessed a little better in selecting the signal-to-masker ratio for the older listeners. That didn't work out and you didn't adjust to it. I'm sorry to say that in my opinion this problem is so serious that it precludes publication of t!heolder versus younger data in JASA, as I see no way of making a valid comparison with things as they are. Further, after reading the manuscript and the reviews, it seems to me that even the subjective impressioncomparison is difficult to interpret because of the different sensation levels at which the older and younger groups listened (if the target was fixed at 56 dBA).The Brungart et al. and Rakerd et al. data that you cite where the masker delay was manipulated over the 0 to 64 ms range would seem to have been a nice springboard for your study in older listeners. Would it not have been cleaner to have replicated those conditions with younger subjects in your lab, and then tested older listeners to see whether thepatterns of data were different? There, at least, the target stimulus condition itself is not varying and there are archival data out there for comparison. As the reviews point out, your conditions present brand new complications because the ITI changes the spatial impression of the target, may change the energetic masking of the target, and distorts the target temporally all at the same time. Although the temporal distortions did not impair performancesubstantially in quiet, they may well in noise. Further, the spatial impressions created by the target in quiet are likely to be very different than those when the target is at v! erylow sensation levels in masking. Please investigate the literature on the influence of sensation level and noise on the strength ofthe precedence effect, particularly the perception of "echoes" at the longer delays. Yuan Chuan Chiang did her dissertation on this and published the results in JASA in 1998, but the first observation that noise can influence the breaking apart of a lead-lag stimulus into two images dates back at least to Thurlow and Parks (1961). To be sure, the sounds that we want to listen to are often accompanied by reflections, and I am not questioning the general validity of your conditions. However, it is important that your experimental design allows you separate out the various contributions to your results.I think there are several options for you to consider: (1) If you think it is very important to publish all the data you have right now, you couldwithdraw the manuscript and attempt to publish the data in another journal.(2) You could argue that the reviewers and I are wrong about the seriousness of the floor effect with the older listeners and submit a revision that includes the same data while making a convincing case for the validity of the older/younger comparison. Although this option is open to you, I don't think this is a promising alternative. (3) You could collect more data on older listeners under more favorable conditions where performance is better. With the added data this could either be a new manuscript, or, if such data were collected and the paper rewritten in a reasonable amount of time, it could be considered a revision of the current manuscript. The revision would be sent back to the reviewers. Of course, I cannot promise in advance that amanuscript evenwith these newdata would be judged favorably by the reviewers. (4) You could drop the older/younger comparison from the manuscript and submit a much shorter version that includes only the younger data and focuses on the noise masker/speech masker distinction, perhaps analyzing your data to draw inferences about release from energetic versus informational masking from the data. Here too, it will be important to provide a clear rationale for what your specific question is about release from masking, why your conditions were chosen, and what new insights your data offer. I still worry about how spatial effects and the effects of temporal distortions are to be distinguished. (5) You could simply withdraw the manuscript and consider a more straightforward design for asking the questions you want to ask with older listeners.Thank your for submitting your manuscript to JASA. I hope the alternatives described will help guide you on how you should proceed from here. Whatever you decide to do, please consider the reviewers' comments very carefully as they have gone out of their way to provide you with suggestions on improving the presentation.Sincerely yours, Richard L. FreymanReviewer Comments: Reviewer #1 Evaluations:Reviewer #1 (Good Scientific Quality):No. See attached Reviewer #1 (Appropriate Journal): YesReviewer #1 (Satisfactory English/References): No.Reviewer #1 (Tables/Figures Adequate): No.Reviewer #1 (Concise): No.Reviewer #1 (Appropriate Title and Abstract): No, because the term "interval-target interval" in thetitle required further explanation.MS#: 07-04147 Huang et al. "Effect of changing the inter-target interval on informational masking and energetic masking of speech in young adults and older adults." This paper investigates the benefits of release from masking in younger and older listeners, as a function of inter-target interval (ITI) in two masker conditions (speech masking and noise masker). The same target speech was presented from two different locations simultaneously in two different maskers, one from each location (L or R). Results show that release from informational masking is evident in both younger and older listeners when the ITI was reduced from 64 ms to 0 ms.General comments:1. Introduction needs to be rewritten:&#x2022; The general impression is that the introduction section is unnecessarily lengthy. There is too much unnecessary information, while some important terms and information are left unexplained. &#x2022; The organization is poor and concepts are disjointed, jumping from place to place. For example, the authors spent 1.5 pages on reverberation and the difference between older and younger adults, than spent a full-page to talk about masking, and then came back to reverberation.&#x2022; In addition, the authors did not clearly present the purpose of the study and the core of the issues under investigation. The authors mentioned that "the present study investigated whether changing theITI over the whole precedence-operation range...can induce a release of target speech from speech masking or noise masking." However, they did not explain how and why manipulating ITI can address their questions, questions that were not clearly stated anywhere inthe paper. No hypothesis was provided in the paper and no explanation was given regarding how the experimental conditions or contrast of results in different conditions can answer the questions under investigation.2. Report of results and statistical analyses needs to be accurate and precise:&#x2022; Authors failed to provide results of statistical analyses in many occasions.&#x2022; At the beginning of the result section for both the younger andolder groups, the authors should clearly present the number of factors included in the analysis and which one was a between-subject factor and which ones were within-subject factors. Main effects and interaction (3-way and 2-way) should also be reported clearly. &#x2022; Bonferroni correction was mentioned in the post-hoc analyses; however, no pvalue was reported. &#x2022; The authors should not use the term "marginally significant". It is either"significant" or "nonsignificant". I don't see p=0.084 is "marginallysignificant."&#x2022; When you say percent release, do you mean percentage point difference between the 64 ms ITI and other ITI values? For example, in the statement "...the releaseamount was 31.9% under the speech-masking condition,...", do you mean "31.9 percentage points"?3. Baseline condition is questionable:&#x2022; The authors failed to provide clear explanation of the results. For example, the authors finally provided the definition of release from masking (on p.19) as "...the release of speech from masking at each ITI is defined as the percent difference between the speech-identification at the ITI and the speech identification at the ITI of 64 ms (the longest ITI in this study)." &#x2022; It took me a while to understand what this means, and finally came up with the interpretation (if my interpretation is correct) of the data for the authors. It seems that when ITI was at 0 ms, theperceived spatial location is between the two maskers (spatial separation). But when the ITI was 32 and/or 64 ms, listeners heard two images (one from each side) and there was no spatial separation between the target speech and the masker on either side. Therefore, according to the authors, the release from masking is the performance difference between the ITI conditions when listeners heard only one image in a location different from the maskers', and the ITI conditions where two images from the masker locations were heard. However, I have a problem with the baseline condition (64 ms ITI in which two images were perceived). If the listeners could not fuse the image, did they hear a delay (echo) between the two targets? If so, the poor performance in the 64 ms condition can be partially due to theconfusion/disruption induced by the echo in noise conditions inaddition to the lack of spatial separation between the target and themasker.4. Subject recruitment criteria were unclear:&#x2022; The authors recruited both young and older adults in the study and claimed that both groups had "clinically normal hearing." However, reading the fine details of their hearing thresholds (< 45 dB HL between 125 and 4k Hz), it is hard to accept that the hearing thresholds are within normal limits in the older group. There is at least a mild hearing loss below 4k Hz and mild-to-moderate hearing loss above 4k Hz (see Fig. 1) in these subjects. The authors should explain the differences in the results in relation to the threshold differences between the two groups.&#x2022; The threshold data provided in Fig. 1 is average data. It is necessary to provide individual threshold data (at least for the older group) in a table format.5. Language problem:&#x2022; I understand that English is not the authors' native language. It is recommended that the authors seek assistance in proof-reading the manuscript before submission.6. Tables and Figures:&#x2022; Table 1 and 2 are not necessary since the information is presented in Fig. 7 &#x2022; The authors should provide legends in the figures.&#x2022; The authors should provide error bars in thegraphs in Fig 1. &#x2022; It is hard to see the short ITI data in Fig. 2 &#x2022; The authors should consider changing the scale on the y-axis in Fig. 4 to provide better visualization of the data. &#x2022; Fig. 6 should be deleted. Results could be clearly described in the text.Specific comments (this is by no means a complete list):p.3 first par: The quote from Knudsen (1929) is not necessary.p.4 first & second par. The authors provided an exhaustive list of references in various place. I recommend they only cite the ones that are most relevant and representative. p.4 last sentence. "A listener subject to informational masking a target speech feels it difficult to segregate audible components of the targetspeech from those of masking speech." This sentence is incomprehensible,please rewrite. p.5 first line, first par. "Masking (particularly information masking) of target speech can be reduced if the listener can use certain cues (perceived spatial location, acoustical features, lexical information, etc) to facilitate his/her selective attention to the target speech." References are needed for each cue listed in this sentence. p.5 line 5. "Age-related deficits...inhibition of goal-irrelevantinformation..., therefore may cause more speech-recognition difficulties" This sentence is coming out of the blue without further explanation.p. 8-10. Please explain the terms "inter-loudspeaker interval","inter-masker interval", "inter-target interval" before using them.p.11 line 11 "Moreover, if the recognition of target speech under either the speech masking condition or noise masking condition is significantlyinfluenced by the ITI in younger adults, the present study further investigated whether there is an age-related deficit in the releasing effect of changing the ITI." This sentence is incomprehensible. p.11 line 2 "The 36 young university students all had normal and balanced...." Change "balance" to "symmetrical." p. 12 line 8 "Direct English translations of the sentences are similar but not identical to the English nonsense sentences that were developed by Helfer (1997) and also used in studies by Freyman et al. (1999, 2001, 2004) and Li et al. (2004)." I thought the sentences were created by the authors. So, are they a direct translation from the English version or created by theauthors?p.13 last par "For the two-source target presentation,...." This came out of the blue. The experimental conditions should be described clearly in a separate section. Schematic representation of the conditions could be included.p.15 line 8 "During a session, the target-speech sounds were presented at a level such that each loudspeaker, playing alone, would produce a sound pressure of 56 dBA." Is this the rms level of speech? The level at 56 dBA seems a little low to me. It may sound very soft for the older listeners given that they have mild to moderate hearing loss. Can you explain why you chose such a low presentation level? p.15 last line "There were 36 ((17+1)x2) testing condition for younger participants, and there were 32 ((15+1)x2) testingconditions for older participants." The number of conditions for each group is not apparent to me. Could you explain further in the manuscript? p.16 line 9 "...participated in additional speech-recognition experiments under the condition without masker presentation." Where did the target speech come from? Front? Right? Or left? p.17-27. See comments on reporting results and statistical analysis under "General comments" point #2. p.23 line 12-13 "A 2 (masker type) by 15 (ITI) within-subject ANOVA confirms that the interaction between masker type and ITI was significant..." Since the interaction is significant, the authors should not simply interpret the main effects. p.29 line 9 Explain "self-masking" effect. Would the author expect a "self-masking" effect in noise?p.30 last par first line "Specifically, when the SNR was -4 dB, changing the ITI (absolute value) from 64 to 0 ms led to only a small improvement in target-speech intelligibility, and the improvement was similar between the speech masking condition and the noise masking condition." The amount of release from masking in the speech masker condition at -4 dB SNR may be limited by the ceiling effect. p.31 line 5 "In older participants, the reduction of the ITI also improved speech recognition under both the speech masking condition and the noise masking condition..." It is hard to tell if there is a significant difference among the ITI conditions with the noise masker due to the floor effect. p.31 line 7 from bottom. "The results suggest a faster decay of temporal storage of the fine details of speech sound in olderadults than in younger adults. Thus at long it is (16 ms or 32 ms), cues induced by the integration of leading and lagging target signals were weaker and/or not be well used in older participants." First, the author should take into account the hearing loss in the older group. Second, this conclusion seems somewhatcontradictory to what the authors reported regarding the perceived image(s) of the target signal under various ITI conditions. All except for one younger subject perceived two separate images at 32 ms ITI, but most of the older subjects still perceived the target as one image. p.32 2nd par. The discussion on the effect of inter-sound delay on ear channel acoustics came out of nowhere.Reviewer #2 Evaluations:Reviewer #2 (Good Scientific Quality): Generally yes - see general remarks below. Reviewer #2 (Appropriate Journal): YesReviewer #2 (Satisfactory English/References):Clarity and conciseness could be improved - see general remarks.The referencing is occasionally excessive, e.g. the 17 references provided to back up the existence of informational masking on page 4, lines 13-17, or p28 lines 15-16. Some choice examples would generally suffice instead of。

ABSORPTION吸收Relaxation processes are the primary mechanisms of energy dissipation for an ultrasound beam transversing tissue.弛豫过程是超声束经过组织时最主要的损失机制。

These processes involve (a) removal of energy from the ultrasound beam and (b) eventual dissipationof this energy primarily as heat.这些过程包括（1）能量从超声束中的转移（2）这些能量最终主要转化为热量消散。

As discussed earlier, ultrasound is propagated by displacement of molecules of a medium into regions of compression and rarefaction.正如我们之前讨论过的，超声通过分子在介质位移进入压缩和稀薄的区域传播.This displacement requires energy that is provided to the medium by the source of ultrasound.位移要求超声源向介质提供能量As the molecules attain maximum displacement from an equilibrium position, their motion stops, and their energy is transformed from kinetic energy associated with motion to potential energy associated with position in the compression zone.分子从平衡位置到达最大位移时，运动停止，能量由动能转化为势能。

纳米金属颗粒物原位催化英文In-situ Catalysis of Nanometal Particles.Nanometal particles, with their unique physicochemical properties, have emerged as promising catalysts in various chemical reactions. The concept of in-situ catalysis, which involves the utilization of these nanoparticles directly at the reaction site, offers significant advantages such as improved activity, selectivity, and efficiency. In this article, we delve into the principles, applications, and challenges associated with in-situ catalysis using nanometal particles.Principles of In-situ Catalysis.In-situ catalysis refers to the use of catalysts that are generated or activated directly within the reaction mixture, rather than being added as preformed entities. In the context of nanometal particles, this approach allowsfor a more intimate interaction between the catalyst andthe reactants, leading to enhanced catalytic activity. The small size of these nanoparticles ensures a high surface-to-volume ratio, which in turn results in a greater numberof active sites available for catalysis.The catalytic activity of nanometal particles isfurther enhanced by their unique electronic and structural properties. The quantum size effects observed in nanoparticles lead to changes in their electronic structure, which can significantly alter their catalytic behavior. Additionally, the high surface energy of nanoparticles promotes their stability and prevents sintering, even at elevated temperatures, maintaining their catalytic activity over extended periods.Applications of In-situ Catalysis.The applications of in-situ catalysis using nanometal particles are diverse and span across various fields of chemistry and engineering. Some of the key applications include:1. Organic Synthesis: Nanometal particles, especially those of platinum, palladium, and gold, have found widespread use in organic synthesis reactions such as hydrogenation, carbon-carbon bond formation, and oxidation reactions. Their use in in-situ catalysis allows for more efficient and selective transformations.2. Fuel Cells: Nanometal particles, particularly those of platinum and palladium, are key components in the electrodes of fuel cells. Their in-situ catalysis promotes the efficient oxidation of fuels such as hydrogen, leading to improved fuel cell performance.3. Photocatalysis: The combination of nanometal particles with photocatalysts such as titanium dioxide offers a powerful tool for solar-driven reactions. The in-situ generation of reactive species at the interface of these materials enhances photocatalytic activity and selectivity.Challenges and Future Directions.While the potential of in-situ catalysis using nanometal particles is immense, there are several challenges that need to be addressed. One of the key challenges is the stability of these nanoparticles under reaction conditions. The aggregation and sintering of nanoparticles can lead to a decrease in their catalytic activity. To address this, strategies such as stabilization by ligands or supports, and the use of bimetallic or core-shell structures have been explored.Another challenge lies in the scale-up of these processes for industrial applications. While laboratory-scale experiments often demonstrate promising results, translating these findings to large-scale operations can be challenging due to factors such as mass transport limitations and heat management.Future research in in-situ catalysis with nanometal particles could focus on developing more robust and stable catalyst systems. The exploration of new nanomaterials with enhanced catalytic properties, as well as the optimization of reaction conditions and reactor designs, are likely tobe key areas of interest. Additionally, the integration ofin-situ catalysis with other technologies such as microfluidics and nanoreactors could lead to more efficient and sustainable catalytic processes.In conclusion, the field of in-situ catalysis using nanometal particles offers significant potential for enhancing the efficiency and selectivity of chemical reactions. While there are still challenges to be addressed, the ongoing research in this area is likely to lead to transformative advancements in catalysis and beyond.。

第42 卷第 5 期2023 年5 月Vol.42 No.5559~567分析测试学报FENXI CESHI XUEBAO（Journal of Instrumental Analysis）超分子溶剂萃取/超高效液相色谱－串联质谱法测定血浆中他克莫司含量谢以清1，2，吕悦广2，孟宪双2，雷海民1*，马强2*（1．北京中医药大学中药学院，北京102488；2．中国检验检疫科学研究院，北京100176）摘要：该文建立了血浆中免疫抑制剂他克莫司（TAC）的超分子溶剂（SUPRAS）萃取/超高效液相色谱－串联质谱分析方法。

通过单因素实验结合响应面设计对超分子溶剂组成、用量及涡旋萃取时间等关键因素进行优化后，血浆样本以正戊醇、四氢呋喃和水形成的超分子溶剂进行高效萃取。

萃取液经Waters ACQUITY UPLC BEH C18（50 mm × 2.1 mm，1.7 μm）色谱柱分离后，在电喷雾质谱正离子模式下，以多反应监测（MRM）模式对他克莫司进行测定，内标法定量。

结果表明，他克莫司在0.5 ~ 30 ng/mL质量浓度范围内的线性关系良好，相关系数（r）为0.998 6；方法检出限和定量下限分别为0.1、0.5 ng/mL；在低、中、高3个加标水平下，平均回收率（n = 3）为91.9% ~ 99.9%，相对标准偏差（RSD）为1.7% ~ 5.7%。

所建立的方法快速、灵敏、稳定，适用于血浆中他克莫司的准确测定。

关键词：他克莫司；免疫抑制剂；超分子溶剂；血浆；超高效液相色谱－串联质谱中图分类号：O657.7；R917文献标识码：A 文章编号：1004-4957（2023）05-0559-09Determination of Tacrolimus in Plasma by Supramolecular Solvent Extraction/Ultra-high Performance Liquid Chromatography－Tandem Mass SpectrometryXIE Yi-qing1，2，LÜ Yue-guang2，MENG Xian-shuang2，LEI Hai-min1*，MA Qiang2*（1．School of Chinese Materia Medica，Beijing University of Chinese Medicine，Beijing 102488，China；2．Chinese Academy of Inspection and Quarantine，Beijing 100176，China）Abstract：An analytical method for the determination of tacrolimus（TAC） in blood plasma was estab⁃lished by supramolecular solvent（SUPRAS）extraction combined with ultra-high performance liquid chromatography－tandem mass spectrometry．After optimizing the key factors such as the composition and amount of SUPRAS，and vortex extraction time through single factor experiment and response sur⁃face design，blood plasma samples were extracted efficiently with SUPRAS formed by pentanol，tetra⁃hydrofuran and water．The extract was separated on a Waters ACQUITY UPLC BEH C18column （50 mm × 2.1 mm，1.7 μm），analyzed by electrospray ionization mass spectrometry in positive ion mode under multiple reaction monitoring（MRM） mode，and quantified by internal standard method．Experimental results demonstrated that there was a good linear relationship for TAC in the concentration range of 0.5－30 ng/mL，with a correlation coefficient（r） of 0.998 6．The limit of detection（LOD）and quantitation（LOQ） were 0.1 ng/mL and 0.5 ng/mL，respectively．The average recoveries（n = 3）at low，medium and high spiked concentration levels ranged from 91.9% to 99.9%，with relative stan⁃dard deviations（RSDs） of 1.7%－5.7%．The proposed method is rapid，sensitive and stable，and it was suitable for the accurate determination of TAC in blood plasma.Key words：tacrolimus；immunosuppresive agent；supramolecular solvent；plasma；ultra-high performance liquid chromatography－tandem mass spectrometry免疫抑制剂是用于抑制机体免疫力的药物，多用于抑制肝肾移植术后的免疫反应，以及治疗变态反应性和自身免疫性疾病，如类风湿关节炎、红斑狼疮等［1－3］。

化工进展Chemical Industry and Engineering Progress2023 年第 42 卷第 S1 期液态金属绕流管束流动传热进展肖辉，张显均，兰治科，王苏豪，王盛（中国核动力研究设计院，四川 成都 610213）摘要：基于液态金属的螺旋管式换热器具有紧凑、换热能力强的特点，在热化学制氢、第四代核能、太阳能高温热发电、余热回收等能源化工系统极具价值，液态金属绕流管束流动传热问题越来越受到重视。

然而，绕流管束湍流传热较复杂，实验和数值模拟难度较大，目前尚未有相关可靠文献综述，阻碍了该类换热器设计与技术进步。

本文回顾了液态金属绕流管束相关研究，首先指出了液态金属流动传热特性与其他流体的异同，然后简述并比较了液态金属流动传热经验关系式，推荐了该类型换热器设计的流动传热经验公式，紧接着应用经验关系式分别对比了不同工质绕流管束、液态金属流经不同流道的流动传热性能。

指出液态金属湍流传热具有一定强化潜力，且绕流管束带来形阻较大，建议采取减阻措施。

本文为后续涉及液态金属绕流管束的换热器设计提供了参考。

关键词：传热；对流；管束；液态金属；湍流中图分类号：TK172 文献标志码：A 文章编号：1000-6613（2023）S1-0010-11Advances in flow and heat transfer research of liquid metal flowingacross tube bundlesXIAO Hui ，ZHANG Xianjun ，LAN Zhike ，WANG Suhao ，WANG Sheng(Nuclear Power Institute of China, Chengdu 610213, Sichuan, China)Abstract: The helical coiled tube heat exchanger based on liquid metal has the characteristics of compactness and strong heat exchange capacity. It is valuable in energy and chemical systems such as thermochemical hydrogen production, fourth-generation nuclear energy, high-temperature solar thermal power generation, and waste heat recovery. The convective heat transfer issues of liquid metal flowing across tube bundles are getting more and more attention. However, turbulent heat transfer flowing across tube bundles is complicated, and the experimental and numerical simulation is chanllenging. At present, there is no reliable and relevant literature review, hindering the design and technical development of this type of heat exchanger. This paper reviewed convective heat transfer researches on liquid metal flowing across tube bundles. Firstly, it was pointed out the similarities and differences between liquid metal and other fluids in convective heat transfer characteristics. Then, it was summarized and compared flow and heat transfer empirical relations of liquid metal. It was recommended empirical formulas for the design of this type of heat exchanger. Subsequently, by applying the recommended empirical relations, the flow and heat transfer performance of different working fluid was compared with flowing across tube bundles, and the liquid metal flowing through different flow channels was also compared. The turbulent heat transfer of综述与专论DOI ：10.16085/j.issn.1000-6613.2023-1221收稿日期：2023-07-18；修改稿日期：2023-10-28。

ENVIRONMENTAL POLLUTIONAUTHOR INFORMATION PACK TABLE OF CONTENTS• Description• Audience• Impact Factor• Abstracting and Indexing • Editorial Board• Guide for Authors p.1p.1p.1p.2p.2p.4ISSN: 0269-7491DESCRIPTIONEnvironmental Pollution is an international journal that focuses on papers that report results from original research on the distribution and ecological effects of pollutants in air, water and soil environments and new techniques for their study and measurement. Findings from re-examination and interpretation of existing data are also included.The editors are focusing on papers that provide new insights into environmental processes and or the effects of pollutants.The editors discourage papers which describe results from routine surveys or routine monitoring programs, which are more local in interest than regional or global. 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Papers focus particularly on the distribution and ecological effects of environmental pollutants, and on new techniques for their study and measurement• review articles by international authorities giving up–to–date critical reviews of particular pollution problems• occasional themed issues on topics of particular interest• the expertise of an active international Editorial Board• a bibliography surveying current available literature compiled with the assistance of Excerpta Medica.AUDIENCEPollution research workers including chemists, toxicologists, environmentalists, conservationists, botanists, marine scientists, ecologists, biologists.IMPACT FACTOR2010: 3.395 © Thomson Reuters Journal Citation Reports 2011ABSTRACTING AND INDEXINGAGRICOLAAir Pollution Control Association JournalBiological and Agricultural IndexCurrent Contents/Agriculture, Biology & Environmental SciencesEMBASEEnergy Information AbstractsEnvironmental Periodicals BibliographyGeoSciTechMEDLINE®SCISEARCHScience Citation IndexScopusEDITORIAL BOARDEditor-in-Chief:W. Manning, Dept. of Plant, Soil and Insect Sciences, University of Massachusetts, Fernald Hall, 270 Stockbridge Road, Amherst, MA 01003-9320, USA, Fax: +1 413 545 2532, Email: environmentalpollution@ Associate Editors:K.C. Jones, Dept. of Environmental Science, Lancaster University, Lancaster, LA1 4YQ, UK, Email: k.c.jones@B. Nowack, , Email: Bernd.Nowack@empa.chC. Wiegand, Inst. of Biology, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark, Email: wiegand-ep@biology.sdu.dkY-G. Zhu, Research Ctr. for Eco-environmental Sciences, Chinese Academy of Sciences (CAS), 18 Shuangqing RD, 100085 Beijing, China, Email: ygzhu@Emeritus Editor:J.P. Dempster, The Limes, Hilton, Huntingdon, UKEditorial Board:M. Agrawal, Banaras Hindu University, Varanasi, India, Email: madhoo@bhu.ac.inR. Altenburger, Umweltforschungszentrum (UFZ) Leipzig-Halle GmbH, Leipzig, Germany, Email: rolf.altenburger@ufz.deD. Amarasiriwardena, Hampshire College, Amherst, MA, USA, Email: dula@W. Arnold, University of Minnesota, Minneapolis, MN, USA, Email: arnol032@A.J. Baker, Felixstowe, Suffolk, England, UK, Email: ajmb@.auA.V. Barker, University of Massachusetts, Amherst, MA, USA, Email: barker@J.N.B. Bell, Imperial College London, Kensington, London, UK, Email: n.bell@J. Bender, Johann Heinrich von Thünen-Institut, Braunschweig, Germany, Email: juergen.bender@fal.deB. Braune, Carleton University, Ottawa, ON, Canada, Email: birgit.braune@ec.gc.caM. Bredemeier, Georg-August Universität Göttingen, Göttingen, Germany, Email: mbredem@gwdg.deK. Breivik, Norwegian Institute for Air Research, Kjeller, Norway, Email: Knut.Breivik@niku.noA. Bytnerowicz, U.S. Department of Agriculture (USDA), Forest Service, Riverside, CA, USA, Email: abytnerowicz@A. Chappelka, Auburn University, Auburn, AL, USA, Email: chappah@P. Christie, Queen's University Belfast, Belfast, UK, Email: p.christie@T.W. Custer, U.S. Geological Survey (USGS), Lacrosse, WI, USA, Email: tom_w_custer@J. 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Hodson, University of Reading, Reading, England, UK, Email: m.e.hodson@S. Huttunen, University of Oulu, Oulu, Finland, Email: satu.huttunen@oulu.fiH. Kankaanpaa, Finnish Institute of Marine Research, Helsinki, Finland, Email: harri.kankaanpaa@fimr.fiJ. Lead, University of Birmingham, Birmingham, UK, Email: j.r.lead@A.H. Legge, Biosphere Solutions, Calgary, AB, Canada, Email: allan.legge@shaw.caN.W. Lepp, Liverpool John Moores University, Liverpool, UK, Email: besnlepp@S. Loppi, Università degli Studi di Siena, Siena, Italy, Email: loppi@unisi.itM. MacLeod, , Email: Macleod@chem.ethz.chB. Markert, Haren-Erika, Germany, Email: markert@schlundmail.deM. McLaughlin, CSIRO (The Commonwealth Scientific and Industrial Research Organization), Glen Osmond, Australia, Email: mike.mclaughlin@csiro.auSt. McNulty, North Carolina State University, Raleigh, NC, USA, Email: sgmcnult@J. Mertens, Universiteit Gent, Gent, Belgium, Email: jan.mertens@hogent.beE. Paoletti, Consiglio Nazionale delle Ricerche (CNR), Firenze, Italy, Email: e.paoletti@r.itW. Peijnenburg, Rijksinstituut voor Volksgezondheid en Milieu (RIVM), Bilthoven, Netherlands, Email: wjgm.peijnenburg@rivm.nlK. Percy, Canadian Forest Service, Fredericton, NB, Canada, Email: kpercy@nrcan.gc.caS. Pflugmacher, Leibniz Institute of Freshwater Ecology, Berlin, Germany, Email: pflugmacher@IGB-Berlin.de S. Pirintsos, University of Crete, Iraklion, Crete, Greece, Email: pirintsos@biology.uoc.grM. Puschenreiter, Universität für Bodenkultur Wien (BOKU), Vienna, Austria, Email: markus.puschenreiter@boku.ac.atF. Páez-Osuna, Universidad Nacional Autónoma de México (UNAM), Mazatlan Sinaloa, Mexico, Email: paezos@servidor.unam.mxP.S. Rainbow, Natural History Museum, London, UK, Email: p.rainbow@B. Reid, University of East Anglia, Norwich, UK, Email: b.reid@D. Sarkar, Montclair State University, Montclair, NJ, USA, Email: sarkard@M. Schaub, Swiss Federal Institute for Forest, Snow, Birmensdorf, Switzerland, Email: marcus.schaub@wsl.ch K. Schirmer, Swiss Federal Institute of Aquatic Science and Technology (EAWAG), Dübendorf, Switzerland, Email: kristin.schirmer@eawag.chH. Segner, Universität Bern, Bern, Switzerland, Email: helmut.segner@itpa.unibe.chW. Shin-Ichiro, Kyushu University, Fukoka, Japan, Email: wadasi@agr.kyushu-u.ac.jpR.F. Shore, Centre for Ecology and Hydrology (CEH), Abbots Ripton, Huntingdon, UK, Email: rfs@ P.N. Smith, Texas Tech University, Lubbock, TX, USA, Email: phil.smith@L. Sonesten, Swedish University of Agricultural Sciences, Uppsala, Sweden, Email: lars.sonesten@ma.slu.se F.M. Tack, Universiteit Gent, Gent, Belgium, Email: filip.tack@rug.ac.beS. Tao, Peking University, Beijing, China, Email: taos@E. Tipping, Centre for Ecology and Hydrology (CEH), Bailrigg, Lancaster, UK, Email: et@H.F. van Dobben, IBN-DLO, Wageningen, Netherlands, Email: Han.vandobben@wur.nlC.A.M. van Gestel, Vrije Universiteit Amsterdam, Amsterdam, Netherlands, Email: kees.van.gestel@falw.vu.nl J.A.C. Verkleij, Vrije Universiteit Amsterdam, Amsterdam, Netherlands, Email: verkleij@bio.vu.nlD. Vetterlein, Umweltforschungszentrum (UFZ) Leipzig-Halle GmbH, Halle/Saale, Germany, Email: doris.vetterlein@ufz.deP. Vikesland, Virginia Polytechnic Institute and State University, Blacksburg, VA, USA, Email: pvikes@ W.-X. Wang, Hong Kong University of Science & Technology, Kowloon, Hong Kong, Email: wwang@ust.hkJ.C. White, Connecticut Agricultural Experimental Station, New Haven, CT, USA, Email: jason.white@P.N. Williams, Chinese Academy of Sciences (CAS), Beijing, China, Email: p.n.williams@H.Th. Wolterbeek, Technische Universiteit Delft, Delft, Netherlands, Email: H.T.Wolterbeek@tudelft.nlF. Wu, Chinese Academy of Sciences (CAS), Guiyang/Guizhou, China, Email: wufengchang@D.A. Wunderlin, Universidad Nacional de Cordoba (Argentina), Cordoba, Argentina, Email: dwunder@.arB. Xing, University of Massachusetts, Amherst, MA, USA, Email: bx@J. Xu, Zhejiang University, Hangzhou, China, Email: jmxu@S.D. Young, University of Nottingham, Nottingham, UK, Email: scott.young@S. Zhang, Chinese Academy of Sciences (CAS), Beijing, China, Email: szzhang@F. Zhao, IACR-Rothamsted Experimental Station, Harpenden, UK, Email: Fangjie.Zhao@GUIDE FOR AUTHORSTypes of paper•Full Research Papers: Full Research Papers should not exceed 5000 words (including abstract but excluding references). If this is not possible, please contact the Editor in Chief. To facilitate the review process line numbers should be inserted into the text of the manuscript.•Short Communications:These follow the same format as full papers, except that Results and Discussion sections should be combined. Manuscripts should not exceed 2000 words.• Rapid Communications: These are Short Communication papers that are submitted for consideration for publication on an accelerated schedule. These papers report highly significant new findings and indicate new directions for research. Authors should fax or E-mail the abstract of their manuscript to the Editor-in-Chief, or appropriate Associate Editor before submitting a Rapid Communication manuscript.•Special Issues: Proposals for Special Issues of Full Research Papers that focus on a specific topic or theme will also be considered.• New Initiatives: Intended as very brief reports of significant new findings indicating new directions in research. Manuscripts should be no more than 6-8 double spaced manuscript pages, including no more than 10 references and 1-3 short tables and/or small figures. An abstract is not required. Include a very brief Introduction, Materials and Methods, and Discussion of Results, including speculation about their meaning and implications. Please submit the name and complete mailing address (including e-mail address) of one appropriate referee who has agreed to review the manuscript. Authors should contact the Editor-in-Chief, or appropriate Associate Editor by e-mail before submitting a New Initiatives manuscript.•Review Papers: Authors may submit manuscripts that provide in-depth critical review of a special subject. These reviews must provide a Synthesis and Critical Evaluation of the state of the knowledge of the subject and indicate research directions. The Editors also periodically invite review articles.•Commentary: Commentary papers may be submitted that express opinions and concerns, suggest research priorities and question conventional methodologies and conclusions. Manuscripts should include an Abstract, Introduction, Presentation of the Concerns or Analysis and Conclusions. References, Tables and Illustrations should be used sparingly. The manuscript should not exceed 12 double-spaced pages. The Editors will evaluate all manuscripts, for suitability of publication.•Letters to Editor: Readers are encouraged to write to any of the Editors and raise issues and concerns about papers published in the journal. Editors or authors will reply to letters.Please note that the word count does not include figures, tables or the reference listBEFORE YOU BEGINEthics in PublishingFor information on Ethics in Publishing and Ethical guidelines for journal publication see /publishingethics and /ethicalguidelines.Conflict of interestAll authors are requested to disclose any actual or potential conflict of interest including any financial, personal or other relationships with other people or organizations within three years of beginning the submitted work that could inappropriately influence, or be perceived to influence, their work. See also /conflictsofinterest.Submission declarationSubmission of an article implies that the work described has not been published previously (except in the form of an abstract or as part of a published lecture or academic thesis), that it is not under consideration for publication elsewhere, that its publication is approved by all authors and tacitly or explicitly by the responsible authorities where the work was carried out, and that, if accepted, it will not be published elsewhere including electronically in the same form, in English or in any other language, without the written consent of the copyright-holder.Changes to authorshipThis policy concerns the addition, deletion, or rearrangement of author names in the authorship of accepted manuscripts:Before the accepted manuscript is published in an online issue: Requests to add or remove an author, or to rearrange the author names, must be sent to the Journal Manager from the corresponding author of the accepted manuscript and must include: (a) the reason the name should be added or removed, or the author names rearranged and (b) written confirmation (e-mail, fax, letter) from all authors that they agree with the addition, removal or rearrangement. In the case of addition or removal of authors, this includes confirmation from the author being added or removed. Requests that are not sent by the corresponding author will be forwarded by the Journal Manager to the corresponding author, who must follow the procedure as described above. Note that: (1) Journal Managers will inform the Journal Editors of any such requests and (2) publication of the accepted manuscript in an online issue is suspended until authorship has been agreed.After the accepted manuscript is published in an online issue: Any requests to add, delete, or rearrange author names in an article published in an online issue will follow the same policies as noted above and result in a corrigendum.CopyrightUpon acceptance of an article, authors will be asked to complete a 'Journal Publishing Agreement' (for more information on this and copyright see /copyright). Acceptance of the agreement will ensure the widest possible dissemination of information. 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Jones, Associate Editor, at k.c.jones@ for environmental fate, behavior, and persistence of organic contaminantsDr. Bernd Nowack, Associate Editor, at nowack@empa.ch for nanomaterials in the environment, chelating agents, soil remediationProfessor Claudia Wiegand, Associate Editor, at wiegand-ep@biology.sdu.dk for aquatic ecosystems, anthropogenic impact, and nutrient loading effectsProfessor Yongguan Zhu, Associate Editor, at ygzhu@ for soil pollution and soil biologyPlease send your abstract and accompanying paragraph within the body of your e-mail message and not in an attachment.Send your abstract to only one editor. Do not cc other editors when you send your abstract.The abstract must be approved by the Editor-in-Chief or an Associate Editor before a manuscript can be submitted via EES.Manuscript SubmissionIf the Editor-in-Chief, or an Associate Editor, approves the abstract, then the complete manuscript can be submitted via EES at /envpol , following all instructions exactly. Complete manuscripts received via EES will be further evaluated by an Editor. This final evaluation will determine whether or not a manuscript will be sent out for review.Submission to this journal proceeds totally online and you will be guided stepwise through the creation and uploading of your files. The system automatically converts source files to a single PDF file of the article, which is used in the peer-review process. Please note that even though manuscript source files are converted to PDF files at submission for the review process, these source files are needed for further processing after acceptance. 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The final decision for publication of all manuscripts is made by the Editor-in-Chief.Additional informationUS National Institutes of Health (NIH) voluntary posting (" Public Access") policy Elsevier facilitates author response to the NIH voluntary posting request (referred to as the NIH "Public Access Policy"; see /about/publicaccess/index.htm) by posting the peer-reviewed author's manuscript directly to PubMed Central on request from the author, 12 months after formal publication. Upon notification from Elsevier of acceptance, we will ask you to confirm via e-mail (by e-mailing us at NIHauthorrequest@) that your work has received NIH funding and that you intend to respond to the NIH policy request, along with your NIH award number to facilitate processing. Upon such confirmation, Elsevier will submit to PubMed Central on your behalf a version of your manuscript that will include peer-review comments, for posting 12 months after formal publication. This will ensure that you will have responded fully to the NIH request policy. There will be no need for you to post your manuscript directly with PubMed Central, and any such posting is prohibited.If excerpts from other copyrighted works are included, the Author(s) must obtain written permission from the copyright owners and credit the source(s) in the article. Elsevier has preprinted forms for use by authors in these cases: contact ES Global Rights Department, P.O. Box 800, Oxford, OX5 1DX, UK; phone: (+44) 1865 843830, fax: (+44) 1865 853333, Elsevier's Rights Department, Oxford, UK: phone (+44) 1865 843830, fax (+44) 1865 853333, e-mail permissions@ . Requests may also be completed on-line via the Elsevier homepage (/locate/permissions ). PREPARATIONUse of wordprocessing softwareIt is important that the file be saved in the native format of the wordprocessor used. The text should be in single-column format. Keep the layout of the text as simple as possible. Most formatting codes will be removed and replaced on processing the article. In particular, do not use the wordprocessor's options to justify text or to hyphenate words. However, do use bold face, italics, subscripts, superscripts etc. Do not embed "graphically designed" equations or tables, but prepare these using the wordprocessor's facility. When preparing tables, if you are using a table grid, use only one grid for each individual table and not a grid for each row. If no grid is used, use tabs, not spaces, to align columns. The electronic text should be prepared in a way very similar to that of conventional manuscripts (see also the Guide to Publishing with Elsevier: /guidepublication). Do not import the figures into the text file but, instead, indicate their approximate locations directly in the electronic text and on the manuscript. See also the section on Electronic illustrations.To avoid unnecessary errors you are strongly advised to use the "spell-check" and "grammar-check" functions of your wordprocessor.General: Please write your text in good English (American or British usage is accepted, but not a mixture of these). Italics are not to be used for expressions of Latin origin, for example, in vivo, et al., per se. Use decimal points (not commas); use a space for thousands (10 000 and above). Double spacing and wide margins (3 cm) should be used (avoid full justification, i.e., do not use a constant right-hand margin). Ensure that each new paragraph is clearly indicated. Present tables and figure captions on separate pages at the end of the manuscript. If possible, consult a recent issue of the journal to become familiar with layout and conventions. Number all pages consecutively. To facilitate the review process line numbers should be inserted into the manuscript file.Cover LetterA cover letter must be sent with the manuscript and must include:•The name of the editor who approved the abstract•The names and valid, current e-mail addresses for five (5) potential reviewers who are well-qualified to review the manuscript if they are asked to review it. Potential reviewers should be from the international scientific community and not from one country or region.•The name and e-mail address of the corresponding authorArticle structureSubdivision - unnumbered headsFull Research Papers should not exceed 5000 words (including abstract but excluding references). If this is not possible, please contact the Editor in Chief.Divide your article into clearly defined sections. Each subsection is given a brief heading. Each heading should appear on its own separate line. Subsections should be used as much as possible when cross-referencing text: refer to the subsection by heading as opposed to simply "the text".IntroductionState the objectives of the work and provide an adequate background, avoiding a detailed literature survey or a summary of the results.Material and methodsProvide sufficient detail to allow the work to be reproduced. Methods already published should be indicated by a reference: only relevant modifications should be described.ResultsResults should be clear and concise.DiscussionThis should explore the significance of the results of the work, not repeat them. A combined Results and Discussion section is often appropriate. Avoid extensive citations and discussion of published literature.ConclusionsThe main conclusions of the study may be presented in a short Conclusions section, which may stand alone or form a subsection of a Discussion or Results and Discussion section.Essential title page informationFull Research Papers: Provide the following data on the title page (in the order given).• Title.Concise and informative. Titles are often used in information-retrieval systems. Avoid abbreviations and formulae where possible.• Author names and affiliations.Where the family name may be ambiguous (e.g., a double name), please indicate this clearly. Present the authors' affiliation addresses (where the actual work was done) below the names. Indicate all affiliations with a lower-case superscript letter immediately after the author's name and in front of the appropriate address. Provide the full postal address of each affiliation, including the country name, and, if available, the e-mail address of each author.• Corresponding author. Clearly indicate who will handle correspondence at all stages of refereeing and publication, also post-publication. Ensure that telephone and fax numbers (with country and area code) are provided in addition to the e-mail address and the complete postal address.• Present/permanent address. If an author has moved since the work described in the article was done, or was visiting at the time, a "Present address" (or "Permanent address") may be indicated as a footnote to that author's name. The address at which the author actually did the work must be retained as the main, affiliation address. Superscript Arabic numerals are used for such footnotes. AbstractA concise and factual abstract is required. (maximum length 100-150 words).The abstract should state briefly the purpose of the research, the principal results and major conclusions. An abstract is often presented separately from the article, so it must be able to stand alone. For this reason, References should be avoided, but if essential, then cite the author(s) and year(s). Also, non-standard or uncommon abbreviations should be avoided, but if essential they must be defined at their first mention in the abstract itself.Capsule: In addition to the abstract for the manuscript, authors are required to submit a one- sentence statement that describes the significance of their work to the rest of the scientific community. When necessary, the capsule may be edited before publication.Graphical abstractA Graphical abstract is optional and should summarize the contents of the article in a concise, pictorial form designed to capture the attention of a wide readership online. Authors must provide images that clearly represent the work described in the article. Graphical abstracts should be submitted as a separate file in the online submission system. Image size: Please provide an image with a minimum of 531 × 1328 pixels (h × w) or proportionally more. The image should be readable at a size of 5 ×13 cm using a regular screen resolution of 96 dpi. Preferred file types: TIFF, EPS, PDF or MS Office files. See /graphicalabstracts for examples.。