Time Scale Research Articles

Reconciling Roles of External Forcing and Internal Variability in Arctic Sea Ice Change on Different Time Scales

Abstract Two large ensemble simulations are adopted to investigate the relative contribution of external forcing and internal variability to Arctic sea ice variability on different time scales since 1960 by correcting the response error of models to external forcing using observational datasets. Our study suggests that previous approaches might overestimate the real impact of internal variability on Arctic sea ice change especially on long time scales. Our results indicate that in both March and September, internal variability plays a dominant role on all time scales over the twentieth century, while the anthropogenic signal on sea ice change can be steadily and consistently detected on a time scale of more than 20 years after the 2000s. We also reveal that the dominant mode of internal variability in March shows consistency across different time scales. On the contrary, the pattern of internal variability in September is highly nonuniform over the Arctic and varies across different time scales, indicating that sea ice internal variability in September at different time scales is driven by different factors.

Zonal Wavenumber 3 Forces Extreme Precipitation in South America

Abstract The Southern Hemisphere climate and weather are affected by several modes of variability and climate phenomena across different time and spatial scales. An additional key component of the atmosphere dynamics that greatly influences weather is quasi-stationary Rossby waves, which attract particular interest as they are often associated with synoptic-scale extreme events. In the Southern Hemisphere extratropical circulation, the most prominent quasi-stationary Rossby wave pattern is the zonal wavenumber 3 (ZW3), which has been shown to have impacts on meridional heat and momentum transport in mid- to high latitudes and on the Antarctic sea ice extent. However, little is known about its impacts outside of polar regions. In this work, we use ERA5 reanalysis data on monthly time scales to explore the influence of phase and amplitude of ZW3 on temperature and precipitation across the Southern Hemisphere midlatitudes. Our results show a significant impact in various regions for all seasons. One of the most substantial effects is observed in precipitation over southeastern Brazil during austral summer, where different phases of the ZW3 force opposite anomalies. When using the ZW3 phase and amplitude as prior information, the probability of occurrence of precipitation extremes in this region increases up to three times. Additionally, we find that this ZW3 weather signature is largely independent of the zonally symmetric Southern Annular Mode (SAM); neither does it seem to be linked to El Niño–Southern Oscillation (ENSO) or Indian Ocean dipole (IOD) signal.

Association between changes in cardiovascular health and the risk of multimorbidity: community-based cohort studies in the UK and Finland

Better cardiovascular health is associated with lower risk of various chronic diseases, but its association with multimorbidity is poorly understood. We aimed to examine whether change in cardiovascular health is associated with multimorbidity risk. The primary analysis was conducted in the Whitehall II multiwave prospective cohort study (UK) and the validation analysis in the Finnish Public Sector cohort study (Finland). Change in cardiovascular health was assessed using the American Heart Association Life's Simple 7 (LS7) and Life's Essential 8 (LE8) at baseline and re-assessments, using objective measures in Whitehall II and self-reports and pharmacy claims in the Finnish Public Sector cohort study, respectively. Multimorbidity was defined as the presence of two or more of 12 chronic diseases during follow-up. We estimated hazard ratios (HR) and 95% confidence intervals (CI) using Cox's proportional hazard models with age as time scale, adjusting for sex, education, occupation, marital status, and ethnicity. In the primary analysis among 9715 participants, mean age was 44.8 (standard deviation 6.0) years and 67.6% participants were men at baseline. During the median follow-up of 31.4 (interquartile range 26.8-32.3) years, 2751 participants developed multimorbidity. The hazard of multimorbidity decreased by 8% (HR 0.92, 95% CI 0.88-0.96) per ideal LS7 metric increment over 5 years and by 14% (HR 0.86, 95% CI 0.80-0.93) per ten points increase in LE8 score over 10 years. These findings were replicated in the validation analysis among 75,377 participants in terms of 4-year change in cardiovascular health. Improvement in cardiovascular health was associated with lower multimorbidity risk in two community-based cohort studies. Interventions improving cardiovascular health of the community may contribute to multimorbidity prevention. None.

Western North Pacific Monsoon Vorticity Distribution as a Potential Driver of Interannual Meridional Migration of the Boreal Summer Synoptic-Scale Wave Train

Abstract On interannual time scales, there is significant meridional migration of the boreal summer (May–October) synoptic-scale wave (SSW) train relative to the summer monsoon trough line over the western North Pacific (WNP) during 1979–2021. The associated plausible physical reasons for the SSW meridional migration are investigated by comparing analyses between two distinct groups: atypical SSW years where SSWs tend to prevail northward of the summer monsoon trough line and typical SSW years where SSWs largely occur along the summer monsoon trough line. During typical SSW years, SSWs originate primarily from equatorial mixed Rossby-gravity (MRG) waves and then develop into off-equatorial tropical depression (TD) waves in the lower troposphere of the monsoon region. During atypical SSW years, SSWs appear to be sourced from upper-level easterlies, propagating downward to the lower troposphere in the monsoon region, with a prevailing TD wave structure. A budget analysis of barotropic eddy kinetic energy suggests that interannual meridional SSW migration is closely related to changes in the vorticity distribution along the summer monsoon trough over the WNP, especially the western part of the summer monsoon trough. These changes cause low-frequency zonal convergence and shear differences, changing barotropic conversion around the monsoon trough and modulating interannual SSW meridional movement. In response to these changes, there are corresponding differences in SSW sources: a predominate MRG–TD wave pattern in typical SSW years and a predominate TD wave pattern in atypical SSW years. These results improve our understanding of the interannual variability of large-scale circulation and tropical cyclones.

Insights into the Causes and Predictability of the 2022/23 California Flooding

Abstract In late December of 2022 and the first half of January 2023, an unprecedented series of atmospheric rivers (ARs) produced near-record heavy rains and flooding over much of California. Here, we employ the NASA GEOS AGCM run in a “replay” mode, together with more idealized simulations with a stationary wave model, to identify the remote forcing regions, mechanisms, and underlying predictability of this flooding event. In particular, the study addresses the underlying causes of a persistent positive Pacific–North American (PNA)-like circulation pattern that facilitated the development of the ARs. We show that the pattern developed in late December as a result of vorticity forcing in the North Pacific jet exit region. We further provide evidence that this vorticity forcing was the result of a chain of events initiated in mid-December with the development of a Rossby wave (as a result of forcing linked to the MJO) that propagated from the northern Indian Ocean into the North Pacific. As such, both the initiation of the event and the eventual development of the PNA depended critically on internally generated Rossby wave forcings, with the North Pacific jet playing a key role. This, combined with contemporaneous SST (La Niña) forcing that produced a circulation response in the AGCM that was essentially opposite to the positive PNA, underscores the fundamental lack of predictability of the event at seasonal time scales. Forecasts produced with the GEOS-coupled model suggest that useful skill in predicting the PNA and extreme precipitation over California was in fact limited to lead times shorter than about 3 weeks.

The Ring-Closing Reaction of Cyclopentadiene Probed with Ultrafast X-ray Scattering.

The dynamics of cyclopentadiene (CP) following optical excitation at 243 nm was investigated by time-resolved pump-probe X-ray scattering using 16.2 keV X-rays at the Linac Coherent Light Source (LCLS). We present the first ultrafast structural evidence that the reaction leads directly to the formation of bicyclo[2.1.0]pentene (BP), a strained molecule with three- and four-membered rings. The bicyclic compound decays via a thermal backreaction to the vibrationally hot CP with a time constant of 21 ± 3 ps. A minor channel leads to ring-opened structures on a subpicosecond time scale.

Reversions mask the contribution of adaptive evolution in microbiomes.

When examining bacterial genomes for evidence of past selection, the results obtained depend heavily on the mutational distance between chosen genomes. Even within a bacterial species, genomes separated by larger mutational distances exhibit stronger evidence of purifying selection as assessed by d N /d S , the normalized ratio of nonsynonymous to synonymous mutations. Here, we show that the classical interpretation of this scale-dependence, weak purifying selection, leads to problematic mutation accumulation when applied to available gut microbiome data. We propose an alternative, adaptive reversion model with exactly opposite implications for dynamical intuition and applications of d N /d S . Reversions that occur and sweep within-host populations are nearly guaranteed in microbiomes due to large population sizes, short generation times, and variable environments. Using analytical and simulation approaches, we show that adaptive reversion can explain the d N /d S decay given only dozens of locally-fluctuating selective pressures, which is realistic in the context of Bacteroides genomes. The success of the adaptive reversion model argues for interpreting low values of d N /d S obtained from long-time scales with caution, as they may emerge even when adaptive sweeps are frequent. Our work thus inverts the interpretation of an old observation in bacterial evolution, illustrates the potential of mutational reversions to shape genomic landscapes over time, and highlights the importance of studying bacterial genomic evolution on short time scales.

Photon correlations in the collective emission of hybrid gold-(CdSe/CdS/CdZnS) nanocrystal supraparticles

We investigate the photon statistics of the light emitted by single self-assembled hybrid gold-CdSe/CdS/CdZnS colloidal nanocrystal supraparticles through the detailed analysis of the intensity autocorrelation function g (2)(τ). We first reveal that, despite the large number of nanocrystals involved in the supraparticle emission, antibunching can be observed. We then present a model based on non-coherent Förster energy transfer and Auger recombination that well captures photon antibunching. Finally, we demonstrate that some supraparticles exhibit a bunching effect at short time scales corresponding to coherent collective emission.

Strengthened Combined Impact of the Pacific and Atlantic Meridional Modes on Eastern North Pacific Tropical Cyclones since the 1990s

Abstract There has been increased focus in recent years on the impact of the Pacific meridional mode (PMM) and the Atlantic meridional mode (AMM) on weather and climate events. This study shows an increased synergistic impact of both the PMM and AMM on eastern North Pacific (ENP) extended boreal summer (June–November) tropical cyclone frequency (TCF) since the 1990s. This increase in the combined impact of both the PMM and AMM on ENP TCF is mainly due to a stronger modulation of the AMM on TCF since the early 1990s and of a stronger modulation of the PMM on TCF since the late 1990s. A budget analysis of the genesis potential index highlights the important contribution of changes in vertical wind shear to the recent strengthened AMM–TCF relationship, while potential intensity and vertical wind shear are the two most important drivers of the recent increase in the PMM–TCF relationship. This intensified association is largely explained by changes in the mean state of sea surface temperatures in the tropical Atlantic associated with the Atlantic multidecadal oscillation (AMO) and trade wind magnitude in the subtropical Pacific Ocean associated with the Pacific decadal oscillation (PDO). This study highlights an asymmetric effect of the AMO and PDO on these two meridional modes and ENP TC genesis frequency and provides a better understanding of ENP TC activity on interannual-to-decadal time scales.

Fast ion relaxation in ITER mediated by Alfvén instabilities

We address the critical issue for future burning plasmas of whether high-energy fusion products or auxiliary heating-beam ions will be confined for a sufficiently long time to compensate for thermal plasma energy losses. This issue can be mitigated by one of the most deleterious collective phenomena—the instability of low, sub-cyclotron frequency Alfvén eigenmodes (AEs), such as toroidicity-induced AEs and reversed-shear AEs in the ITER steady-state scenario. Using a revised quasi-linear (QL) theory applied to energetic particle (EP) relaxation in the presence of AEs, we find that the AE instabilities can affect both neutral beam ions and alpha particles, although the resulting fast ion transport is expected to be modest if classical particle slowing down is assumed. On the other hand, the QL theory predicts that the AE amplitudes will be enhanced by the background microturbulence, although this topic remains outside our scope due to the significant numerical effort required to evaluate these effects. We report our results for EP relaxation dynamics obtained utilizing several tools: (i) a comprehensive linear stability study of the sub-cyclotron Alfvénic spectrum as computed by ideal magnetohydrodynamic NOVA simulations for the AE eigenproblem, (ii) drift kinetic NOVA-C calculations for wave–particle interaction and AE growth/damping rates, and (iii) predictive QL modeling coupled with the global transport code TRANSP to assess the EP relaxation on the equilibrium timescale.

A multiscale analysis of returns and volatility spillovers in cryptocurrency markets: A post-COVID perspective

ABSTRACT Since the onset of the COVID-19 pandemic, leading cryptocurrencies have undergone significant price fluctuations, prompting widespread interest in the interdependence and spillover effects among cryptocurrency markets, as well as in identifying the key cryptocurrencies that drive market movements. This study contributes to the existing literature by utilising innovative vector wavelet coherence (VWC) and wavelet local multiple correlation (WLMC) frameworks to investigate the time-frequency co-movements among four cryptocurrencies (Bitcoin, Ethereum, Tether, and Binance). By exploring the co-movements across multiple time scales over a period from 01/01/2020 to 10/04/2023 through continuous and discrete wavelet coherency analysis, we identify four key empirical findings. Firstly, the returns connectedness is stronger than the volatility connectedness. Secondly, high-frequency co-movements are more erratic and correspond to positive and negative unexpected news, while low-frequency co-movements vary with changes in US monetary policy. Thirdly, Tether and Binance exhibit the weakest returns and volatility connectedness with other cryptocurrencies. Lastly, Ethereum and Tether (not Bitcoin) are the primary cryptocurrencies that account for returns and volatility movements in the market. We discuss the implications of these findings for various stakeholders in cryptocurrency markets.

Nonthermal plasma removal of CH4-NOx under LNG engine exhaust environment: experiment, mechanism and kinetic analysis

To explore the mechanism underlying the removal of CH4 and NOx, which are typical emissions from LNG engines, through the nonthermal plasma method, a plasma chemistry model of CH4-NOx under the LNG engine exhaust environment was established in this study. Sixty key reactions affecting the conversion of CH4, CO, and NOx were determined through sensitivity analysis, and their pre-exponential factors were optimized using a genetic algorithm. The proposed model shows good performance in predicting the concentrations of CH4, CO, and NOx under the exhaust conditions of LNG engine. Then, reaction path analyses for evolution of CH4, CO, NO, and NO2 were performed under specific conditions. The results showed that CH4 mainly decomposed into CH2 that is subsequently converted into CO and CO2. CH2 is the main source for CO production. The concentration of NOx is determined by the oxidation reactions of N with O2, OH, and HO2. The specific concentration distributions of NO and NO2 were influenced by the oxidation–reduction reactions between them. Analyses of the time scales for the conversion processes of CH4, CO, and NOx were also conducted, and it was found that the reaction time scales of CH4 and CO were approximately 1 × 10−10−1 × 10−5 s, and that was approximately 1 × 10−9−1 × 10−4 s for NOx. Furthermore, during the overlapping period for the conversion of CH4, CO, and NOx, the NOx was dominant in the competition for O. This study provides a basis for the construction of a plasma catalytic chemistry model of CH4-NOx under LNG engine exhaust conditions.

A stochastic framework for rainfall intensity–time scale–return period relationships. Part ΙΙ: point modelling and regionalization over Greece

ABSTRACT In this work, we formulate a regionalization framework for rainfall intensity–time scale–return period relationships which is applied over the Greek territory. The methodology for single-site estimation is based on a stochastic framework for multi-scale modelling of rainfall intensity which is outlined in the companion paper. Five parameters are first fitted independently for each site and the resulting parameter variability is assessed. Following a systematic investigation of uncertainty and variability patterns, two parameters, i.e. the tail-index and a time scale parameter, are identified as constant in space and estimated using data pooling techniques. The other three parameters are regionalized over Greece by means of spatial interpolation and smoothing techniques that are assessed through cross-validation in a multi-model framework. The regionalization scheme is implemented in a sequential order that allows exploiting rainfall information both from rainfall stations with sub-daily resolution and from the more reliable network of daily raingauges.

A stochastic framework for rainfall intensity–time scale–return period relationships. Part I: theory and estimation strategies

ABSTRACT This work presents a stochastic framework for the construction of rainfall intensity–time scale–return period relationships, which was applied in the recent regionalization of design rainfall curves over the Greek territory, described in a companion paper. The methodology outlined herein builds upon a widely-used mathematical framework, which has been recently revisited and upgraded, and incorporates two different versions: (a) a theoretically consistent stochastic model applicable for rainfall intensity over any scale of interest; and (b) a simplified version valid over small scales, which makes parameter estimation easier. Special attention is given to the presentation of the simplified version, which suffices for most engineering tasks. Parameter estimation approaches are presented in detail, including the K-moments framework that allows for reliable high-order moment estimation and handling of bias due to spatiotemporal dependence.

Primary processes of the archetypal model complex azido(porphinato)iron(III) from ultrafast vibrational-electronic spectroscopy.

Azidoiron complexes serve as valuable photochemical precursors for catalytically active species containing high-valent iron. In bioinorganic chemistry, azido(tetraphenylporphinato)iron(III), i.e., [FeIII(tpp)(N3)] with tpp = 5, 10, 15, 20-tetraphenylporphyrin-21, 23-diido, constitutes the archetypal model system that was used to access for the first time the terminal nitridoiron core, FeV ≡ N, in the biomimetic redox-non-innocent ligand environment. So far, the light-induced dynamics leading to the oxidation of the metal and the release of dinitrogen from the N3-ligand have only been studied for precursors featuring redox-innocent auxiliary ligands that simplify the electronic structure change accompanying the photo-transformation. Here, we monitored the primary events of the above paradigmatic complex, following its optical excitation in the ultraviolet-to-visible spectral range using femtosecond spectroscopy with probing in both the UV-vis and mid-infrared regions. Following ultrafast Soret-excitation at 400nm, the complex relaxes to the lowest excited sextet state by a first internal conversion in less than 200fs. The excited state then undergoes vibrational relaxation on a time scale of roughly 2ps before internally converting yet again to recover the sextet electronic ground state within 19.5ps. Spectroscopic evidence is obtained neither for a transient occupation of the energetically lowest metal-centered state, 41A1, nor for vibrational relaxation in the ground-state. The primary processes seen here are thus in contrast to those previously derived from ultrafast UV-pump/vis-probe and UV-pump/XANES-probe spectroscopies for the halide congener [FeIII(tpp)(Cl)]. Any photochemical transformation of the complex arises from two-photon-induced dynamics.

Kinetics and Mechanism of the Singlet Oxygen Atom Reaction with Dimethyl Ether.

We combine in situ laser spectroscopy, quantum chemistry, and kinetic calculations to study the reaction of a singlet oxygen atom with dimethyl ether. Infrared laser absorption spectroscopy and Faraday rotation spectroscopy are used for the detection and quantification of the reaction products OH, H2O, HO2, and CH2O on submillisecond time scales. Fitting temporal profiles of products with simulations using an in-house reaction mechanism allows product branching to be quantified at 30, 60, and 150 Torr. The experimentally determined product branching agrees well with master equation calculations based on electronic structure data and transition state theory. The calculations demonstrate that the dimethyl peroxide (CH3OOCH3) generated via O-insertion into the C-O bond undergoes subsequent dissociation to CH3O + CH3O through energetically favored reactions without an intrinsic barrier. This O-insertion mechanism can be important for understanding the fate of biofuels leaking into the atmosphere and for plasma-based biofuel processing technologies.

Modulation of Lipid Dynamics in the β-Amyloid Aggregates Induced Membrane Fragmentation.

Nonspecific membrane disruption is considered a plausible mechanism for the cytotoxicity induced by β-amyloid (Aβ) aggregates. In scenarios of high local Aβ concentrations, a two-step membrane fragmentation model has been proposed. Initially, membrane-embedded Aβ oligomeric aggregates form, followed by membrane fragmentation. However, the key molecular-level interactions between Aβ oligomeric aggregates and lipids that drive the second-stage membrane fragmentation remain unclear. This study monitors the time-dependent changes in lipid dynamics and water accessibility of model liposomes during Aβ-induced membrane fragmentation. Our results indicate that lipid dynamics on the nanosecond to microsecond time scale undergo rapid acceleration upon initial incubation with membrane-incorporated Aβ oligomeric aggregates, followed by a slow deceleration process. Concurrently, lipid headgroups become less accessible to water. Both observations suggest a carpet-like mechanism of membrane disruption for the Aβ-induced membrane fragmentation process.

Spatial structure could explain the maintenance of alternative reproductive tactics in tree cricket males.

Trait polymorphisms are widespread in nature, and explaining their stable co-existence is a central problem in ecology and evolution. Alternative reproductive tactics, in which individuals of one or more sex exhibit discrete, discontinuous traits in response to reproductive competition, represent a special case of trait polymorphism in which the traits are often complex, behavioural, and dynamic. Thus, studying how alternative reproductive tactics are maintained may provide general insights into how complex trait polymorphisms are maintained in populations. We construct a spatially explicit individual-based model inspired from extensively collected empirical data to address the mechanisms behind the co-existence of three behavioural alternative reproductive tactics in males of a tree cricket (Oecanthus henryi). Our results show that the co-existence of these tactics over ecological time scales is facilitated by the spatial structure of the landscape they inhabit, which serves to equalise the otherwise unequal mating benefits of the three tactics. We also show that this co-existence is unlikely if spatial aspects of the system are not considered. Our findings highlight the importance of spatial dynamics in understanding ecological and evolutionary processes and underscore the power of integrative approaches that combine models with empirical data.

Nanoparticle Superlattices with Nonequilibrium Crystal Shapes.

Nanoparticle assembly is a material synthesis strategy that enables precise control of nanoscale structural features. Concepts from traditional crystal growth research have been tremendously useful in predicting and programming the unit cell symmetries of these assemblies, as their thermodynamically favored structures are often identical to atomic crystal analogues. However, these analogies have not yielded similar levels of influence in programming crystallite shapes, which are a consequence of both the thermodynamics and kinetics of crystal growth. Here, we demonstrate kinetic control of the colloidal crystal shape using nanoparticle building blocks that rapidly assemble over a broad range of concentrations, thereby producing well-defined crystal habits with symmetrically oriented dendritic protrusions and providing insight into the crystals' morphological evolution. Counterintuitively, these nonequilibrium crystal shapes actually become more common for colloidal crystals synthesized closer to equilibrium growth conditions. This deviation from typical crystal growth processes observed in atomic or molecular crystals is shown to be a function of the drastically different time scales of atomic and colloidal mass transport. Moreover, the particles are spherical with isotropic ligand grafts, and these kinetic crystal habits are achieved without the need for specifically shaped particle building blocks or external templating or shape-directing agents. Thus, this work provides generalizable design principles to expand the morphological diversity of nanoparticle superlattice crystal habits beyond the anhedral or equilibrium polyhedral shapes synthesized to date. Finally, we use this insight to synthesize crystallite shapes that have never before been observed, demonstrating the ability to both predict and program kinetically controlled superlattice morphologies.

Peptide Drug Design Using Alchemical Free Energy Calculation: An Application and Validation on Agonists of Ghrelin Receptor.

With recent large-scale applications and validations, the relative binding free energy (RBFE) calculated using alchemical free energy methods has been proven to be an accurate measure to probe the binding of small-molecule drug candidates. On the other hand, given the flexibility of peptides, it is of great interest to find out whether sufficient sampling could be achieved within the typical time scale of such calculation, and a similar level of accuracy could be reached for peptide drugs. However, the systematic evaluation of such calculations on protein-peptide systems has been less reported. Most reported studies of peptides were restricted to a limited number of data points or lacking experimental support. To demonstrate the applicability of the alchemical free energy method for protein-peptide systems in a typical real-world drug discovery project, we report an application of the thermodynamic integration (TI) method to the RBFE calculation of ghrelin receptor and its peptide agonists. Along with the calculation, the synthesis and in vitro EC50 activity of relamorelin and 17 new peptide derivatives were also reported. A cost-effective criterion to determine the data collection time was proposed for peptides in the TI simulation. The average of three TI repeats yielded a mean absolute error of 0.98 kcal/mol and Pearson's correlation coefficient (R) of 0.77 against the experimental free energy derived from the in vitro EC50 activity, showing good repeatability of the proposed method and a slightly better agreement than the results obtained from the arbitrary time frames up to 20 ns. Although it is limited by having one target and a deduced binding pose, we hope that this study can add some insights into alchemical free energy calculation of protein-peptide systems, providing theoretical assistance to the development of peptide drugs.