Widespread changes in surface temperature persistence under climate change.

Climate change has been and will be accompanied by widespread changes in surface temperature. It is clear that these changes include global-wide increases in mean surface temperature and changes in temperature variance that are more regionally-dependent1-3. It is less clear whether they also include changes in the persistence of surface temperature. This is important as the effects of weather events on ecosystems and society depend critically on the length of the event. Here we provide an extensive survey of the response of surface temperature persistence to climate change over the twenty-first century from the output of 150 simulations run on four different Earth system models, and from simulations run on simplified models with varying representations of radiative processes and large-scale dynamics. Together, the results indicate that climate change simulations are marked by widespread changes in surface temperature persistence that are generally most robust over ocean areas and arise due to a seemingly broad range of physical processes. The findings point to both the robustness of widespread changes in persistence under climate change, and the critical need to better understand, simulate and constrain such changes.

Exceptional stratospheric contribution to human fingerprints on atmospheric temperature.

In 1967, scientists used a simple climate model to predict that human-caused increases in atmospheric CO2 should warm Earth's troposphere and cool the stratosphere. This important signature of anthropogenic climate change has been documented in weather balloon and satellite temperature measurements extending from near-surface to the lower stratosphere. Stratospheric cooling has also been confirmed in the mid to upper stratosphere, a layer extending from roughly 25 to 50 km above the Earth's surface (S25 - 50). To date, however, S25 - 50 temperatures have not been used in pattern-based attribution studies of anthropogenic climate change. Here, we perform such a "fingerprint" study with satellite-derived patterns of temperature change that extend from the lower troposphere to the upper stratosphere. Including S25 - 50 information increases signal-to-noise ratios by a factor of five, markedly enhancing fingerprint detectability. Key features of this global-scale human fingerprint include stratospheric cooling and tropospheric warming at all latitudes, with stratospheric cooling amplifying with height. In contrast, the dominant modes of internal variability in S25 - 50 have smaller-scale temperature changes and lack uniform sign. These pronounced spatial differences between S25 - 50 signal and noise patterns are accompanied by large cooling of S25 - 50 (1 to 2[Formula: see text]C over 1986 to 2022) and low S25 - 50 noise levels. Our results explain why extending "vertical fingerprinting" to the mid to upper stratosphere yields incontrovertible evidence of human effects on the thermal structure of Earth's atmosphere.

On the effects of the ocean on atmospheric CFC-11 lifetimes and emissions.

The ocean is a reservoir for CFC-11, a major ozone-depleting chemical. Anthropogenic production of CFC-11 dramatically decreased in the 1990s under the Montreal Protocol, which stipulated a global phase out of production by 2010. However, studies raise questions about current overall emission levels and indicate unexpected increases of CFC-11 emissions of about 10 Gg ⋅ yr-1 after 2013 (based upon measured atmospheric concentrations and an assumed atmospheric lifetime). These findings heighten the need to understand processes that could affect the CFC-11 lifetime, including ocean fluxes. We evaluate how ocean uptake and release through 2300 affects CFC-11 lifetimes, emission estimates, and the long-term return of CFC-11 from the ocean reservoir. We show that ocean uptake yields a shorter total lifetime and larger inferred emission of atmospheric CFC-11 from 1930 to 2075 compared to estimates using only atmospheric processes. Ocean flux changes over time result in small but not completely negligible effects on the calculated unexpected emissions change (decreasing it by 0.4 ± 0.3 Gg ⋅ yr-1). Moreover, it is expected that the ocean will eventually become a source of CFC-11, increasing its total lifetime thereafter. Ocean outgassing should produce detectable increases in global atmospheric CFC-11 abundances by the mid-2100s, with emission of around 0.5 Gg ⋅ yr-1; this should not be confused with illicit production at that time. An illustrative model projection suggests that climate change is expected to make the ocean a weaker reservoir for CFC-11, advancing the detectable change in the global atmospheric mixing ratio by about 5 yr.

Thermodynamic constraint on the depth of the global tropospheric circulation.

The troposphere is the region of the atmosphere characterized by low static stability, vigorous diabatic mixing, and widespread condensational heating in clouds. Previous research has argued that in the tropics, the upper bound on tropospheric mixing and clouds is constrained by the rapid decrease with height of the saturation water vapor pressure and hence radiative cooling by water vapor in clear-sky regions. Here the authors contend that the same basic physics play a key role in constraining the vertical structure of tropospheric mixing, tropopause temperature, and cloud-top temperature throughout the globe. It is argued that radiative cooling by water vapor plays an important role in governing the depth and amplitude of large-scale dynamics at extratropical latitudes.

Direct observation of light-driven, concerted electron-proton transfer.

The phenols 4-methylphenol, 4-methoxyphenol, and N-acetyl-tyrosine form hydrogen-bonded adducts with N-methyl-4, 4'-bipyridinium cation (MQ+) in aqueous solution as evidenced by the appearance of low-energy, low-absorptivity features in UV-visible spectra. They are assigned to the known examples of optically induced, concerted electron-proton transfer, photoEPT. The results of ultrafast transient absorption measurements on the assembly MeOPhO-H---MQ+ are consistent with concerted EPT by the instantaneous appearance of spectral features for MeOPhO·---H-MQ+ in the transient spectra at the first observation time of 0.1 ps. The transient decays to MeOPhO-H---MQ+ in 2.5 ps, accompanied by the appearance of oscillations in the decay traces with a period of ∼1 ps, consistent with a vibrational coherence and relaxation from a higher υ(N-H) vibrational level or levels on the timescale for back EPT.

Revisiting the mystery of recent stratospheric temperature trends.

Simulated stratospheric temperatures over the period 1979-2016 in models from the Chemistry-Climate Model Initiative (CCMI) are compared with recently updated and extended satellite observations. The multi-model mean global temperature trends over 1979- 2005 are -0.88 ± 0.23, -0.70 ± 0.16, and -0.50 ± 0.12 K decade-1 for the Stratospheric Sounding Unit (SSU) channels 3 (~40-50 km), 2 (~35-45 km), and 1 (~25-35 km), respectively. These are within the uncertainty bounds of the observed temperature trends from two reprocessed satellite datasets. In the lower stratosphere, the multi-model mean trend in global temperature for the Microwave Sounding Unit channel 4 (~13-22 km) is -0.25 ± 0.12 K decade-1 over 1979-2005, consistent with estimates from three versions of this satellite record. The simulated stratospheric temperature trends in CCMI models over 1979-2005 agree with the previous generation of chemistry-climate models. The models and an extended satellite dataset of SSU with the Advanced Microwave Sounding Unit-A show weaker global stratospheric cooling over 1998-2016 compared to the period of intensive ozone depletion (1979-1997). This is due to the reduction in ozone-induced cooling from the slow-down of ozone trends and the onset of ozone recovery since the late 1990s. In summary, the results show much better consistency between simulated and satellite observed stratospheric temperature trends than was reported by Thompson et al. (2012) for the previous versions of the SSU record and chemistry-climate models. The improved agreement mainly comes from updates to the satellite records; the range of simulated trends is comparable to the previous generation of models.

The mystery of recent stratospheric temperature trends.

A new data set of middle- and upper-stratospheric temperatures based on reprocessing of satellite radiances provides a view of stratospheric climate change during the period 1979-2005 that is strikingly different from that provided by earlier data sets. The new data call into question our understanding of observed stratospheric temperature trends and our ability to test simulations of the stratospheric response to emissions of greenhouse gases and ozone-depleting substances. Here we highlight the important issues raised by the new data and suggest how the climate science community can resolve them.

The Signature of Southern Hemisphere Atmospheric Circulation Patterns in Antarctic Precipitation.

We provide the first comprehensive analysis of the relationships between large-scale patterns of Southern Hemisphere climate variability and the detailed structure of Antarctic precipitation. We examine linkages between the high spatial resolution precipitation from a regional atmospheric model and four patterns of large-scale Southern Hemisphere climate variability: the southern baroclinic annular mode, the southern annular mode, and the two Pacific-South American teleconnection patterns. Variations in all four patterns influence the spatial configuration of precipitation over Antarctica, consistent with their signatures in high-latitude meridional moisture fluxes. They impact not only the mean but also the incidence of extreme precipitation events. Current coupled-climate models are able to reproduce all four patterns of atmospheric variability but struggle to correctly replicate their regional impacts on Antarctic climate. Thus, linking these patterns directly to Antarctic precipitation variability may allow a better estimate of future changes in precipitation than using model output alone.

An abrupt drop in Northern Hemisphere sea surface temperature around 1970.

The twentieth-century trend in global-mean surface temperature was not monotonic: temperatures rose from the start of the century to the 1940s, fell slightly during the middle part of the century, and rose rapidly from the mid-1970s onwards. The warming-cooling-warming pattern of twentieth-century temperatures is typically interpreted as the superposition of long-term warming due to increasing greenhouse gases and either cooling due to a mid-twentieth century increase of sulphate aerosols in the troposphere, or changes in the climate of the world's oceans that evolve over decades (oscillatory multidecadal variability). Loadings of sulphate aerosol in the troposphere are thought to have had a particularly important role in the differences in temperature trends between the Northern and Southern hemispheres during the decades following the Second World War. Here we show that the hemispheric differences in temperature trends in the middle of the twentieth century stem largely from a rapid drop in Northern Hemisphere sea surface temperatures of about 0.3 °C between about 1968 and 1972. The timescale of the drop is shorter than that associated with either tropospheric aerosol loadings or previous characterizations of oscillatory multidecadal variability. The drop is evident in all available historical sea surface temperature data sets, is not traceable to changes in the attendant metadata, and is not linked to any known biases in surface temperature measurements. The drop is not concentrated in any discrete region of the Northern Hemisphere oceans, but its amplitude is largest over the northern North Atlantic.

A large discontinuity in the mid-twentieth century in observed global-mean surface temperature.

Data sets used to monitor the Earth's climate indicate that the surface of the Earth warmed from approximately 1910 to 1940, cooled slightly from approximately 1940 to 1970, and then warmed markedly from approximately 1970 onward. The weak cooling apparent in the middle part of the century has been interpreted in the context of a variety of physical factors, such as atmosphere-ocean interactions and anthropogenic emissions of sulphate aerosols. Here we call attention to a previously overlooked discontinuity in the record at 1945, which is a prominent feature of the cooling trend in the mid-twentieth century. The discontinuity is evident in published versions of the global-mean temperature time series, but stands out more clearly after the data are filtered for the effects of internal climate variability. We argue that the abrupt temperature drop of approximately 0.3 degrees C in 1945 is the apparent result of uncorrected instrumental biases in the sea surface temperature record. Corrections for the discontinuity are expected to alter the character of mid-twentieth century temperature variability but not estimates of the century-long trend in global-mean temperatures.

Click synthesized dianthryl-TTFV: an efficient fluorescent turn-on probe for transition metal ions.

Tetrathiafulvalene vinylogue (TTFV) was functionalized with two anthryl fluorophores via Cu(I)-catalyzed alkyne-azide [3 + 2] cycloaddition, forming a dianthryl-TTFV hybrid to show fluorescent turn-on sensing behaviour for Cu(2+), Fe(2+), and Cd(2+) ions in THF with remarkably low detection limit down to the sub-ppm level.

Phase Unlocking and the Modulation of Tropopause-Level Trace Gas Advection by the Quasibiennial Oscillation.

Open questions about the modulation of near-surface trace gas variability by stratosphere-troposphere tracer transport complicate efforts to identify anthropogenic sources of gases such as CFC-11 and N2O and disentangle them from dynamical influences. In this study, we explore one model's modulation of lower stratospheric tracer advection by the quasi-biennial oscillation (QBO) of stratospheric equatorial zonal-mean zonal winds at 50 hPa. We assess instances of coherent modulation versus disruption through phase unlocking with the seasonal cycle in the model and in observations. We quantify modeled advective contributions to the temporal rate of change of stratospheric CFC-11 and N2O at extratropical and high-latitudes by calculating a transformed Eulerian mean (TEM) budget across isentropic surfaces from a 10-member WACCM4 ensemble simulation. We find that positive interannual variability in seasonal tracer advection generally occurs in the easterly QBO phase, as in previous work, and briefly discuss physical mechanisms. Individual simulations of the 10-member ensemble display phase-unlocking disruptions from this general pattern due to seasonally varying synchronizations between the model's repeating 28-month QBO cycle and the 12-month seasonal cycle. We find that phase locking and unlocking patterns of tracer advection calculations inferred from observations fall within the envelope of the ensemble member results. Our study bolsters evidence for variability in the interannual stratospheric dynamical influence of CFC-11 near-surface concentrations by assessing the QBO modulation of lower stratospheric advection via synchronization with the annual cycle. It identifies a likely cause of variations in the QBO influence on tropospheric abundances.

Highly sensitive detection of saccharides under physiological conditions with click synthesized boronic acid-oligomer fluorophores.

Two phenylboronic acid based saccharide sensors bearing conjugated oligomer fluorophores with linear and cruciform π-frameworks were synthesized in a modular approach utilizing a Cu-catalyzed alkyne azide cycloaddition (click) reaction. The cruciform fluorophore showed excellent saccharide sensing function under physiological conditions in the mM range, whereas the linear fluorophore gave very limited sensing functions. The different fluorescent sensing behaviours highlight the important role of oligomer fluorophore in the development of effective saccharide sensors.

Synthesis of Oligo(1,8-pyrenylene)s: A Series of Functional Molecular Liquids.

A monomer-through-pentamer series of oligo(1,8-pyrenylene)s was synthesized using a two-step iterative synthetic strategy. The trimer, tetramer, and pentamer are mixtures of atropisomers that interconvert slowly at room temperature (as shown by variable-temperature NMR analysis). They are liquids well below room temperature, as indicated by POM, DSC and SWAXS analysis. These oligomers are highly fluorescent both in the liquid state and in dilute solution (λF,max = 444-457 nm, φF = 0.80) and an investigation of their photophysical properties demonstrated that delocalization plays a larger role in their excited states than it does in related pyrene-based oligomers.

Highly pi-extended TTF analogues with a conjugated macrocyclic enyne core.

The synthesis of a class of highly pi-extended tetrathiafulvalene derivatives (1a and 1b) was explored using Sonogashira macrocyclization as a key step. The solid-state structure of 1b was characterized by X-ray single crystallography, showing a substantially bent, S-shaped molecular backbone and an ordered packing geometry in a pi-alkyl-alkyl-pi stacking fashion. Electronic and redox properties of 1b were investigated by UV-vis absorption, fluorescence spectroscopy, and cyclic voltammetry.

H-shaped OPE/OPV oligomers: a new member of 2D-conjugated fluorophore cores.

A new class of two-dimensional (2D), pi-conjugated, skewed H-shaped co-oligomers of phenylene vinylene and phenylene ethynylene (11a- d, termed H-mers) were synthesized using Sonogashira coupling and Wittig-Horner reactions as the key steps. Electronic and spectroscopic properties of the H-mers were investigated by UV-vis absorption, fluorescence spectroscopic techniques, and ab initio calculations (HF/3-21G). Two amino-containing functional H-mers (11b and 11d) were found to exhibit appealing fluorescence sensitivity to selected Brønsted acids and transition-metal ions.

Pyrenoimidazolyl-Benzaldehyde Fluorophores: Synthesis, Properties, and Sensing Function for Fluoride Anions.

Two structural isomers of (9H-pyreno[4,5-d]imidazol-10-yl)-benzaldehyde, with para and meta substitution patterns, were synthesized by condensation of 4,5-pyrenedione with terephthalaldehyde and isophthalaldehyde, respectively. These new pyrenoimidazole derivatives were characterized by single-crystal X-ray crystallography, UV-vis absorption spectroscopy, fluorescence spectroscopy, and cyclic voltammetry to elucidate their structural, solid-state packing, and electronic properties. Interactions of these compounds with fluoride anions in polar organic solvents (acetone and dimethyl sulfoxide) were investigated by NMR, UV-vis, and fluorescence techniques in conjunction with density functional theory calculations. UV-vis analysis showed that the binding of the two pyrenoimidazolyl benzaldehydes with fluoride anions resulted in significant colorimetric responses, while fluorescence studies showed that the para-pyrenoimidazolyl benzaldehyde behaved as an intramolecular charge transfer fluorescent probe, exhibiting ratiometric sensing performance to efficiently detect and quantify fluoride anions at the sub-millimolar level.

Rigid medium stabilization of metal-to-ligand charge transfer excited states.

The salts [Ru(bpy)3](PF6)2, cis-[Ru(bpy)2(py)2](PF6)2, trans-[Ru(bpy)2(4-Etpy)2](PF6)2, [Ru(tpy)2](PF6)2, and [Re(bpy)(CO)3(4-Etpy)](PF6) (bpy=2,2'-bipyridine, py=pyridine, 4-Etpy=4-ethylpyridine, and tpy=2,2':6',2-terpyridine) have been incorporated into poly(methyl methacrylate) (PMMA) films and their photophysical properties examined by both steady-state and time-resolved absorption and emission measurements. Excited-state lifetimes for the metal salts incorporated in PMMA are longer and emission energies enhanced due to a rigid medium effect when compared to fluid CH3CN solution. In PMMA part of the fluid medium reorganization energy, lambdaoo, contributes to the energy gap with lambdaoo approximately 700 cm-1 for [Ru(bpy)3](PF6)2 from emission measurements. Enhanced lifetimes can be explained by the energy gap law and the influence of the excited-to-ground state energy gap, Eo, on nonradiative decay. From the results of emission spectral fitting on [Ru(bpy)3](PF6)2* in PMMA, Eo is temperature dependent above 200 K with partial differentialEo/ partial differentialT=2.8 cm-1/deg. cis-[Ru(bpy)2(py)2](PF6)2 and trans-[Ru(bpy)2(4-Etpy)2](PF6)2 are nonemissive in CH3CN and undergo photochemical ligand loss. Both emit in PMMA and are stable toward ligand loss even for extended photolysis periods. The lifetime of cis-[Ru(bpy)2(py)2](PF6)2* in PMMA is temperature dependent, consistent with a contribution to excited-state decay from thermal population and decay through a low-lying dd state or states. At temperatures above 190 K, coinciding with the onset of the temperature dependence of Eo for [Ru(bpy)3](PF6)2*, lifetimes become significantly nonexponential. The nonexponential behavior is attributed to dynamic coupling between MLCT and dd states, with the lifetime of the latter greatly enhanced in PMMA with tau approximately 3 ns. On the basis of these data and data in 4:1 (v/v) EtOH/MeOH, the energy gap between the MLCT and dd states is decreased by approximately 700 cm-1 in PMMA with the dd state at higher energy by DeltaH0 approximately 1000 cm-1. The "rigid medium stabilization effect" for cis-[Ru(bpy)2(py)2](PF6)2* in PMMA is attributed to inhibition of metal-ligand bond breaking and a photochemical cage effect.

The art of interviewing your next CEO.

If conducted properly, an interview is a highly effective tool for evaluating managers at any level of an organization. Broad, general questions, gently put, elicit sincere behavior from others, allowing them the freedom to respond as they wish. Their responses tell us what they typically focus on. Moreover, the interviewee is inclined to find us "safe" to talk to. This reduces their fear or discomfort, which should be any interviewer's goal. Probing often elicits the most spontaneous, hence truest, behavior revealing who this person is and how he or she will respond in a particular position or situation. Good probes, which should be used frequently in any conversation, also convey the message that we care about the interviewee and his or her views. Interviewing means focusing on others. It should be an integral part of the board's repertoire of skills. It is also an integral part of being a good manager. Few people are emotionally capable of implementing the principles described here. It is incumbent on the board, therefore, to select those members who can conduct in-depth interviews for a new CEO.

Periodic variability in the large-scale Southern Hemisphere atmospheric circulation.

Periodic behavior in the climate system has important implications not only for weather prediction but also for understanding and interpreting the physical processes that drive climate variability. Here we demonstrate that the large-scale Southern Hemisphere atmospheric circulation exhibits marked periodicity on time scales of approximately 20 to 30 days. The periodicity is tied to the Southern Hemisphere baroclinic annular mode and emerges in hemispheric-scale averages of the eddy fluxes of heat, the eddy kinetic energy, and precipitation. Observational and theoretical analyses suggest that the oscillation results from feedbacks between the extratropical baroclinicity, the wave fluxes of heat, and radiative damping. The oscillation plays a potentially profound role in driving large-scale climate variability throughout much of the mid-latitude Southern Hemisphere.