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 (S25â -â 50). To date, however, S25â -â 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 S25â -â 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 S25â -â 50 have smaller-scale temperature changes and lack uniform sign. These pronounced spatial differences between S25â -â 50 signal and noise patterns are accompanied by large cooling of S25â -â 50 (1 to 2[Formula: see text]C over 1986 to 2022) and low S25â -â 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.
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.
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.
Climate Change/statistics & numerical data , Climate Models , Temperature , Global Warming/prevention & control , Global Warming/statistics & numerical data , Oceans and Seas , Time Factors
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 â 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 â 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 â 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.
Atmosphere , Chlorofluorocarbons/adverse effects , Environmental Pollutants/adverse effects , Oceans and Seas , Ozone , Climate Change , Environmental Monitoring , Models, Theoretical
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.
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.
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.
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.
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.
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 â¼1 ps, consistent with a vibrational coherence and relaxation from a higher υ(N-H) vibrational level or levels on the timescale for back EPT.
Lung surfactant is a complex mixture of lipid and protein, responsible for alveolar stability, becomes dysfunctional due to alteration of its structure and function by leaked serum materials in disease. Serum proteins, cholesterol and low density lipoprotein (LDL) were studied with bovine lipid extract surfactant (BLES) using Langmuir films, and bilayer dispersions using Raman spectroscopy. While small amount of cholesterol (10 wt%) and LDL did not significantly affect the adsorption and surface tension lowering properties of BLES. However serum lipids, whole serum as well as higher amounts of cholesterol, and LDL dramatically altered the surface properties of BLES films, as well as gel-fluid structures formed in such films observed using atomic force microscopy (AFM). Raman-spectroscopic studies revealed that serum proteins, LDL and excess cholesterol had fluidizing effects on BLES bilayers dispersion, monitored from the changes in hydrocarbon vibrational modes during gel-fluid thermal phase transitions. This study clearly suggests that patho-physiological amounts of serum lipids (and not proteins) significantly alter the molecular arrangement of surfactant in films and bilayers, and can be used to model lung disease.
Pulmonary Surfactants/chemistry , Adsorption , Blood Proteins/analysis , Cholesterol/analysis , Lipid Bilayers/analysis , Lipoproteins, LDL/analysis , Membrane Fluidity , Microscopy, Atomic Force , Molecular Structure , Phase Transition , Spectrum Analysis, Raman , Surface Properties
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.
Air Movements , Climate Change , Hot Temperature , Periodicity
Hybrids of tetrathiafulvalene vinylogues (TTFVs) and planar arenes were synthesized via the click reaction to form tweezer-like and macrocyclic structures. These compounds were investigated as receptors for fullerenes (C60 and C70) by UV-vis absorption and fluorescence spectroscopy.
Fullerenes/chemistry , Macrocyclic Compounds/chemical synthesis , Macrocyclic Compounds/chemistry , Magnetic Resonance Spectroscopy , Molecular Structure , Spectrometry, Fluorescence , Spectrophotometry, Ultraviolet
A new iterative bridge formation strategy has been employed in the synthesis of a series of [n](2,11)teropyrenophanes (n = 7-9). The generation of the nonplanar teropyrene system, which is calculated to be bent through 178.7° for the smallest homologue (n = 7), is accomplished using a VID reaction of a cyclophanemonoene precursor for the first time.
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.
Altitude , Atmosphere , Temperature , Uncertainty , Atmosphere/analysis , Climate , Global Warming/history , Global Warming/statistics & numerical data , History, 20th Century , History, 21st Century , Human Activities , Models, Theoretical , Spacecraft , Time Factors
A very short synthesis (5 steps), the crystal structure and resolution of an elaborate, inherently chiral [n](1,6)pyrenophane is reported. The synthesis hinges upon two very productive events: a multicomponent reaction and an unprecedented double-McMurry/valence isomerization/dehydrogenation step. Aromatization reactions are involved in the formation of all four of the rings of the pyrene system.
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.
Side-chain functionalized poly(p-phenylene ethynylene)s (PPEs) carrying triazole linkers, amino donors/receptors, and solubilizing groups have been found to yield remarkably high efficiency of fluorescence turn-on sensing for Zn(2+) and Cd(2+) ions in THF, and for H(+) and Cd(2+) ions in water.
A concise, highly regioselective synthesis of 1,8-dibromo-4,5-dialkoxypyrenes has been developed and exploited in the synthesis of some 1,8-pyrenylene-ethynylene macrocycles. The (1)H NMR data and NICS calculations indicate that there is little or no macrocyclic ring current. Concentration-dependent UV-visible studies indicate no aggregation at low concentration, but 8b forms dimers with voids suitable for intercalation of small molecules in the solid state.
