Properties and Processing of Aviation Exhaust Aerosol at Cruise Altitude Observed from the IAGOS-CARIBIC Flying Laboratory.

The characteristics of aviation-induced aerosol, its processing, and effects on cirrus clouds and climate are still associated with large uncertainties. Properties of aviation-induced aerosol, however, are crucially needed for the assessment of aviation's climate impacts today and in the future. We identified more than 1100 aircraft plume encounters during passenger aircraft flights of the IAGOS-CARIBIC Flying Laboratory from July 2018 to March 2020. The aerosol properties inside aircraft plumes were similar, independent of the altitude (i.e., upper troposphere, tropopause region, and lowermost stratosphere). The exhaust aerosol was found to be mostly externally mixed compared to the internally mixed background aerosol, even at a plume age of 1 to 3 h. No enhancement of accumulation mode particles (diameter >250 nm) could be detected inside the aircraft plumes. Particle number emission indices (EIs) deduced from the observations in aged plumes are in the same range as values reported from engine certifications. This finding, together with the observed external mixing state inside the plumes, indicates that the aviation exhaust aerosol almost remains in its emission state during plume expansion. It also reveals that the particle number EIs used in global models are within the range of the EIs measured in aged plumes.

Single-Molecule Magnetism, Enhanced Magnetocaloric Effect, and Toroidal Magnetic Moments in a Family of Ln4 Squares.

Three cationic [Ln4 ] squares (Ln=lanthanide) were isolated as single crystals and their structures solved as [Dy4 (µ4 -OH)(HL)(H2 L)3 (H2 O)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)8 (1), [Tb4 (µ4 -OH)(HL)(H2 L)3 (MeOH)4 ]Cl2 ⋅(CH3 OH)4 ⋅(H2 O)4 (2) and [Gd4 (µ4 -OH)(HL)(H2 L)3 (H2 O)2 (MeOH)2 ]Br2 ⋅(CH3 OH)4 ⋅(H2 O)3 (3). The structures are described as hydroxo-centered squares of lanthanide ions, with each edge of the square bridged by a doubly deprotonated H2 L(2-) ligand. Alternating current magnetic susceptibility measurements show frequency-dependent out-of-phase signals with two different thermally assisted relaxation processes for 1, whereas no maxima in χM " appears above 2.0 K for complex 2. For 1, the estimated effective energy barrier for these two relaxation processes is 29 and 100 K. Detailed ab initio studies reveal that complex 1 possesses a toroidal magnetic moment. The ab initio calculated anisotropies of the metal ions in complex 1 were employed to simulate the magnetic susceptibility by using the Lines model (POLY_ANISO) and this procedure yields J1 =+0.01 and J2 =-0.01 cm(-1) for 1 as the two distinct exchange interactions between the Dy(III) ions. Similar parameters are also obtained for complex 1 (and 2) from specific heat measurements. A very weak antiferromagnetic super-exchange interaction (J1 =-0.043 cm(-1) and g=1.99) is observed between the metal centers in 3. The magnetocaloric effect (MCE) was estimated by using field-dependent magnetization and temperature-dependent heat-capacity measurements. An excellent agreement is found for the -ΔSm values extracted from these two measurements for all three complexes. As expected, 3 shows the largest -ΔSm variation (23 J Kg(-1) K(-1) ) among the three complexes. The negligible magnetic anisotropy of Gd indeed ensures near degeneracy in the (2S+1) ground state microstates, and the weak super-exchange interaction facilitates dense population of low-lying excited states, all of which are likely to contribute to the MCE, making complex 3 an attractive candidate for cryogenic refrigeration.

Global air quality and climate.

Emissions of air pollutants and their precursors determine regional air quality and can alter climate. Climate change can perturb the long-range transport, chemical processing, and local meteorology that influence air pollution. We review the implications of projected changes in methane (CH(4)), ozone precursors (O(3)), and aerosols for climate (expressed in terms of the radiative forcing metric or changes in global surface temperature) and hemispheric-to-continental scale air quality. Reducing the O(3) precursor CH(4) would slow near-term warming by decreasing both CH(4) and tropospheric O(3). Uncertainty remains as to the net climate forcing from anthropogenic nitrogen oxide (NO(x)) emissions, which increase tropospheric O(3) (warming) but also increase aerosols and decrease CH(4) (both cooling). Anthropogenic emissions of carbon monoxide (CO) and non-CH(4) volatile organic compounds (NMVOC) warm by increasing both O(3) and CH(4). Radiative impacts from secondary organic aerosols (SOA) are poorly understood. Black carbon emission controls, by reducing the absorption of sunlight in the atmosphere and on snow and ice, have the potential to slow near-term warming, but uncertainties in coincident emissions of reflective (cooling) aerosols and poorly constrained cloud indirect effects confound robust estimates of net climate impacts. Reducing sulfate and nitrate aerosols would improve air quality and lessen interference with the hydrologic cycle, but lead to warming. A holistic and balanced view is thus needed to assess how air pollution controls influence climate; a first step towards this goal involves estimating net climate impacts from individual emission sectors. Modeling and observational analyses suggest a warming climate degrades air quality (increasing surface O(3) and particulate matter) in many populated regions, including during pollution episodes. Prior Intergovernmental Panel on Climate Change (IPCC) scenarios (SRES) allowed unconstrained growth, whereas the Representative Concentration Pathway (RCP) scenarios assume uniformly an aggressive reduction, of air pollutant emissions. New estimates from the current generation of chemistry-climate models with RCP emissions thus project improved air quality over the next century relative to those using the IPCC SRES scenarios. These two sets of projections likely bracket possible futures. We find that uncertainty in emission-driven changes in air quality is generally greater than uncertainty in climate-driven changes. Confidence in air quality projections is limited by the reliability of anthropogenic emission trajectories and the uncertainties in regional climate responses, feedbacks with the terrestrial biosphere, and oxidation pathways affecting O(3) and SOA.

Global-mean temperature change from shipping toward 2050: improved representation of the indirect aerosol effect in simple climate models.

We utilize a range of emission scenarios for shipping to determine the induced global-mean radiative forcing and temperature change. Ship emission scenarios consistent with the new regulations on nitrogen oxides (NO(x)) and sulfur dioxide (SO(2)) from the International Maritime Organization and two of the Representative Concentration Pathways are used as input to a simple climate model (SCM). Based on a complex aerosol-climate model we develop and test new parametrizations of the indirect aerosol effect (IAE) in the SCM that account for nonlinearities in radiative forcing of ship-induced IAE. We find that shipping causes a net global cooling impact throughout the period 1900-2050 across all parametrizations and scenarios. However, calculated total net global-mean temperature change in 2050 ranges from -0.03[-0.07,-0.002]°C to -0.3[-0.6,-0.2]°C in the A1B scenario. This wide range across parametrizations emphasizes the importance of properly representing the IAE in SCMs and to reflect the uncertainties from complex global models. Furthermore, our calculations show that the future ship-induced temperature response is likely a continued cooling if SO(2) and NO(x) emissions continue to increase due to a strong increase in activity, despite current emission regulations. However, such cooling does not negate the need for continued efforts to reduce CO(2) emissions, since residual warming from CO(2) is long-lived.

Climate impact of biofuels in shipping: global model studies of the aerosol indirect effect.

Aerosol emissions from international shipping are recognized to have a large impact on the Earth's radiation budget, directly by scattering and absorbing solar radiation and indirectly by altering cloud properties. New regulations have recently been approved by the International Maritime Organization (IMO) aiming at progressive reductions of the maximum sulfur content allowed in marine fuels from current 4.5% by mass down to 0.5% in 2020, with more restrictive limits already applied in some coastal regions. In this context, we use a global bottom-up algorithm to calculate geographically resolved emission inventories of gaseous (NO(x), CO, SO(2)) and aerosol (black carbon, organic matter, sulfate) species for different kinds of low-sulfur fuels in shipping. We apply these inventories to study the resulting changes in radiative forcing, attributed to particles from shipping, with the global aerosol-climate model EMAC-MADE. The emission factors for the different fuels are based on measurements at a test bed of a large diesel engine. We consider both fossil fuel (marine gas oil) and biofuels (palm and soy bean oil) as a substitute for heavy fuel oil in the current (2006) fleet and compare their climate impact to that resulting from heavy fuel oil use. Our simulations suggest that ship-induced surface level concentrations of sulfate aerosol are strongly reduced, up to about 40-60% in the high-traffic regions. This clearly has positive consequences for pollution reduction in the vicinity of major harbors. Additionally, such reductions in the aerosol loading lead to a decrease of a factor of 3-4 in the indirect global aerosol effect induced by emissions from international shipping.

The effect of future ambient air pollution on human premature mortality to 2100 using output from the ACCMIP model ensemble.

Ambient air pollution from ground-level ozone and fine particulate matter (PM2.5) is associated with premature mortality. Future concentrations of these air pollutants will be driven by natural and anthropogenic emissions and by climate change. Using anthropogenic and biomass burning emissions projected in the four Representative Concentration Pathway scenarios (RCPs), the ACCMIP ensemble of chemistry-climate models simulated future concentrations of ozone and PM2.5 at selected decades between 2000 and 2100. We use output from the ACCMIP ensemble, together with projections of future population and baseline mortality rates, to quantify the human premature mortality impacts of future ambient air pollution. Future air pollution-related premature mortality in 2030, 2050 and 2100 is estimated for each scenario and for each model using a health impact function based on changes in concentrations of ozone and PM2.5 relative to 2000 and projected future population and baseline mortality rates. Additionally, the global mortality burden of ozone and PM2.5 in 2000 and each future period is estimated relative to 1850 concentrations, using present-day and future population and baseline mortality rates. The change in future ozone concentrations relative to 2000 is associated with excess global premature mortality in some scenarios/periods, particularly in RCP8.5 in 2100 (316 thousand deaths/year), likely driven by the large increase in methane emissions and by the net effect of climate change projected in this scenario, but it leads to considerable avoided premature mortality for the three other RCPs. However, the global mortality burden of ozone markedly increases from 382,000 (121,000 to 728,000) deaths/year in 2000 to between 1.09 and 2.36 million deaths/year in 2100, across RCPs, mostly due to the effect of increases in population and baseline mortality rates. PM2.5 concentrations decrease relative to 2000 in all scenarios, due to projected reductions in emissions, and are associated with avoided premature mortality, particularly in 2100: between -2.39 and -1.31 million deaths/year for the four RCPs. The global mortality burden of PM2.5 is estimated to decrease from 1.70 (1.30 to 2.10) million deaths/year in 2000 to between 0.95 and 1.55 million deaths/year in 2100 for the four RCPs, due to the combined effect of decreases in PM2.5 concentrations and changes in population and baseline mortality rates. Trends in future air pollution-related mortality vary regionally across scenarios, reflecting assumptions for economic growth and air pollution control specific to each RCP and region. Mortality estimates differ among chemistry-climate models due to differences in simulated pollutant concentrations, which is the greatest contributor to overall mortality uncertainty for most cases assessed here, supporting the use of model ensembles to characterize uncertainty. Increases in exposed population and baseline mortality rates of respiratory diseases magnify the impact on premature mortality of changes in future air pollutant concentrations and explain why the future global mortality burden of air pollution can exceed the current burden, even where air pollutant concentrations decrease.