Sensitivity of direct radiative forcing by mineral dust to particle characteristics

Airborne dust affects the Earth's energy balance — an impact that is measured in terms of the implied change in net radiation (or radiative forcing, in W m-2) at the top of the atmosphere. There remains considerable uncertainty in the magnitude and sign of direct forcing by airborne dust under current climate. Much of this uncertainty stems from simplified assumptions about mineral dust-particle size, composition and shape, which are applied in remote sensing retrievals of dust characteristics and dust-cycle models. Improved estimates of direct radiative forcing by dust will require improved characterization of the spatial variability in particle characteristics to provide reliable information dust optical properties. This includes constraints on: (1) particle-size distribution, including discrimination of particle subpopulations and quantification of the amount of dust in the sub-10 µm to <0.1 µm mass fraction; (2) particle composition, specifically the abundance of iron oxides, and whether particles consist of single or multi-mineral grains; (3) particle shape, including degree of sphericity and surface roughness, as a function of size and mineralogy; and (4) the degree to which dust particles are aggregated together. The use of techniques that measure the size, composition and shape of individual particles will provide a better basis for optical modelling.

Radiative forcing effect of ice-age dust

During glacial periods, dust deposition rates and inferred atmospheric concentrations were globally much higher than present. According to recent model results, the large enhancement of atmospheric dust content at the last glacial maximum (LGM) can be explained only if increases in the potential dust source areas are taken into account. Such increases are to be expected, due to effects of low precipitation and low atmospheric (CO2) on plant growth. Here the modelled three-dimensional dust fields from Mahowald et al. and modelled seasonally varying surface-albedo fields derived in a parallel manner, are used to quantify the mean radiative forcing due to modern (non-anthropogenic) and LGM dust. The effect of mineralogical provenance on the radiative properties of the dust is taken into account, as is the range of optical properties associated with uncertainties about the mixing state of the dust particles. The high-latitude (poleward of 45°) mean change in forcing (LGM minus modern) is estimated to be small (–0.9 to +0.2 W m–2), especially when compared to nearly –20 W m–2 due to reflection from the extended ice sheets. Although the net effect of dust over ice sheets is a positive forcing (warming), much of the simulated high-latitude dust was not over the ice sheets, but over unglaciated regions close to the expanded dust source region in central Asia. In the tropics the change in forcing is estimated to be overall negative, and of similarly large magnitude (–2.2 to –3.2 W m–2) to the radiative cooling effect of low atmospheric (CO2). Thus, the largest long-term climatic effect of the LGM dust is likely to have been a cooling of the tropics. Low tropical sea-surface temperatures, low atmospheric (CO2) and high atmospheric dust loading may be mutually reinforcing due to multiple positive feedbacks, including the negative radiative forcing effect of dust.

Power transfer in velocity-vortex acceleration

A theoretical model is presented of an electron acceleration-as-oscillator method derived from the work of Joseph Larmor unified with J. Clerk Maxwell’s theory of vorticity for the displacement of radiation into free-space at an antenna interface.

Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

Changes in global net radiative imbalance 1985-2012

Combining satellite data, atmospheric reanalyses and climate model simulations, variability in the net downward radiative flux imbalance at the top of Earth's atmosphere (N) is reconstructed and linked to recent climate change. Over the 1985-1999 period mean N (0.34 ± 0.67 Wm–2) is lower than for the 2000-2012 period (0.62 ± 0.43 Wm–2, uncertainties at 90% confidence level) despite the slower rate of surface temperature rise since 2000. While the precise magnitude of N remains uncertain, the reconstruction captures interannual variability which is dominated by the eruption of Mt. Pinatubo in 1991 and the El Niño Southern Oscillation. Monthly deseasonalized interannual variability in N generated by an ensemble of 9 climate model simulations using prescribed sea surface temperature and radiative forcings and from the satellite-based reconstruction is significantly correlated (r ∼ 0.6) over the 1985-2012 period.

Infrared absorption spectra, radiative efficiencies, and global warming potentials of newly-detected halogenated compounds: CFC-113a, CFC-112 and HCFC-133a

CFC-113a (CF3CCl3), CFC-112 (CFCl2CFCl2) and HCFC-133a (CF3CH2Cl) are three newly detected molecules in the atmosphere that are almost certainly emitted as a result of human activity. It is important to characterise the possible contribution of these gases to radiative forcing of climate change and also to provide information on the CO2-equivalence of their emissions. We report new laboratory measurements of absorption cross-sections of these three compounds at a resolution of 0.01 cm−1 for two temperatures 250 K and 295 K in the spectral range of 600–1730 cm−1. These spectra are then used to calculate the radiative efficiencies and global warming potentials (GWP). The radiative efficiencies are found to be between 0.15 and 0.3 W∙m−2∙ppbv−1. The GWP for a 100 year time horizon, relative to carbon dioxide, ranges from 340 for the relatively short-lived HCFC-133a to 3840 for the longer-lived CFC-112. At current (2012) concentrations, these gases make a trivial contribution to total radiative forcing; however, the concentrations of CFC-113a and HCFC-133a are continuing to increase. The 2012 CO2-equivalent emissions, using the GWP (100), are estimated to be about 4% of the current global CO2-equivalent emissions of HFC-134a

Global radiative and climate effect of the water vapour continuum at visible and near-infrared wavelengths

Recent laboratory measurements show that absorption by the water vapour continuum in near-infrared windows may be about an order of magnitude higher than assumed in many radiation codes. The radiative impact of the continuum at visible and near-infrared wavelengths is examined for the present day and for a possible future warmer climate (with a global-mean total column water increase of 33%). The calculations use a continuum model frequently used in climate models (‘CKD’) and a continuum model where absorption is enhanced at wavelengths greater than 1 µm based on recent measurements (‘CAVIAR’). The continuum predominantly changes the partitioning between solar radiation absorbed by the surface and the atmosphere; changes in top-of-atmosphere net irradiances are smaller. The global-mean clear-sky atmospheric absorption is enhanced by 1.5 W m−2 (about 2%) and 2.8 W m−2 (about 3.5%) for CKD and CAVIAR respectively, relative to a hypothetical no-continuum case, with all-sky enhancements about 80% of these values. The continuum is, in relative terms, more important for radiation budget changes between the present day and a possible future climate. Relative to the no-continuum case, the increase in global-mean clear-sky absorption is 8% higher using CKD and almost 20% higher using CAVIAR; all-sky enhancements are about half these values. The effect of the continuum is estimated for the solar component of the water vapour feedback, the reduction in downward surface irradiance and precipitation change in a warmer world. For CKD and CAVIAR respectively, and relative to the no-continuum case, the solar component of the water vapour feedback is enhanced by about 4 and 9%, the change in clear-sky downward surface irradiance is 7 and 18% more negative, and the global-mean precipitation response decreases by 1 and 4%. There is a continued need for improved continuum measurements, especially at atmospheric temperatures and at wavelengths below 2 µm.

Vertical structure of stratospheric water vapour trends derived from merged satellite data

Stratospheric water vapour is a powerful greenhouse gas. The longest available record from balloon observations over Boulder, Colorado, USA shows increases in stratospheric water vapour concentrations that cannot be fully explained by observed changes in the main drivers, tropical tropopause temperatures and methane. Satellite observations could help resolve the issue, but constructing a reliable long-term data record from individual short satellite records is challenging. Here we present an approach to merge satellite data sets with the help of a chemistry–climate model nudged to observed meteorology. We use the models’ water vapour as a transfer function between data sets that overcomes issues arising from instrument drift and short overlap periods. In the lower stratosphere, our water vapour record extends back to 1988 and water vapour concentrations largely follow tropical tropopause temperatures. Lower and mid-stratospheric long-term trends are negative, and the trends from Boulder are shown not to be globally representative. In the upper stratosphere, our record extends back to 1986 and shows positive long-term trends. The altitudinal differences in the trends are explained by methane oxidation together with a strengthened lower-stratospheric and a weakened upper stratospheric circulation inferred by this analysis. Our results call into question previous estimates of surface radiative forcing based on presumed global long-term increases in water vapour concentrations in the lower stratosphere.

The impact of social and relational contexts on innovation transfer in foreign subsidiaries

It is widely acknowledged that innovation is one of the pillars of multinational enterprises (MNEs) and that technological knowledge from different host locations is a key factor to the MNEs’ competitive advantages development. Concerning these assumptions, in this paper we aim to understand how the social and the relational contexts affect the conventional and reverse transfer of innovation from MNEs’ subsidiaries hosted in emerging markets. We analyzed the social context through the institutional profile (CIP) level and the relational context through trust and integration levels utilizing a survey sent to 172 foreign subsidiaries located in Brazil, as well as secondary data. Through an ordinary least squares regression (OLS) analysis we found that the relational context affects the conventional and reverse innovation transfer in subsidiaries hosted in emerging markets. We however did not find support for the social context effect.

The dependence of radiative forcing and feedback on evolving patterns of surface temperature change in climate models

Experiments with CO2 instantaneously quadrupled and then held constant are used to show that the relationship between the global-mean net heat input to the climate system and the global-mean surface-air-temperature change is nonlinear in Coupled Model Intercomparison Project phase 5 (CMIP5) Atmosphere-Ocean General Circulation Models (AOGCMs). The nonlinearity is shown to arise from a change in strength of climate feedbacks driven by an evolving pattern of surface warming. In 23 out of the 27 AOGCMs examined the climate feedback parameter becomes significantly (95% confidence) less negative – i.e. the effective climate sensitivity increases – as time passes. Cloud feedback parameters show the largest changes. In the AOGCM-mean approximately 60% of the change in feedback parameter comes from the topics (30N-30S). An important region involved is the tropical Pacific where the surface warming intensifies in the east after a few decades. The dependence of climate feedbacks on an evolving pattern of surface warming is confirmed using the HadGEM2 and HadCM3 atmosphere GCMs (AGCMs). With monthly evolving sea-surface-temperatures and sea-ice prescribed from its AOGCM counterpart each AGCM reproduces the time-varying feedbacks, but when a fixed pattern of warming is prescribed the radiative response is linear with global temperature change or nearly so. We also demonstrate that the regression and fixed-SST methods for evaluating effective radiative forcing are in principle different, because rapid SST adjustment when CO2 is changed can produce a pattern of surface temperature change with zero global mean but non-zero change in net radiation at the top of the atmosphere (~ -0.5 Wm-2 in HadCM3).

Regional and monthly and clear-sky aerosol direct radiative effect (and forcing) derived from the GlobAEROSOL-AATSR satellite aerosol product

Using the GlobAEROSOL-AATSR dataset, estimates of the instantaneous, clear-sky, direct aerosol radiative effect and radiative forcing have been produced for the year 2006. Aerosol Robotic Network sun-photometer measurements have been used to characterise the random and systematic error in the GlobAEROSOL product for 22 regions covering the globe. Representative aerosol properties for each region were derived from the results of a wide range of literature sources and, along with the de-biased GlobAEROSOL AODs, were used to drive an offline version of the Met Office unified model radiation scheme. In addition to the mean AOD, best-estimate run of the radiation scheme, a range of additional calculations were done to propagate uncertainty estimates in the AOD, optical properties, surface albedo and errors due to the temporal and spatial averaging of the AOD fields. This analysis produced monthly, regional estimates of the clear-sky aerosol radiative effect and its uncertainty, which were combined to produce annual, global mean values of (−6.7±3.9)Wm−2 at the top of atmosphere (TOA) and (−12±6)Wm−2 at the surface. These results were then used to give estimates of regional, clear-sky aerosol direct radiative forcing, using modelled pre-industrial AOD fields for the year 1750 calculated for the AEROCOM PRE experiment. However, as it was not possible to quantify the uncertainty in the pre-industrial aerosol loading, these figures can only be taken as indicative and their uncertainties as lower bounds on the likely errors. Although the uncertainty on aerosol radiative effect presented here is considerably larger than most previous estimates, the explicit inclusion of the major sources of error in the calculations suggest that they are closer to the true constraint on this figure from similar methodologies, and point to the need for more, improved estimates of both global aerosol loading and aerosol optical properties.

Aerosol direct radiative effect of smoke over clouds over the southeast Atlantic Ocean from 2006 to 2009

The aerosol direct radiative effect (DRE) of African smoke was analyzed in cloud scenes over the southeast Atlantic Ocean, using Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) satellite observations and Hadley Centre Global Environmental Model version 2 (HadGEM2) climate model simulations. The observed mean DRE was about 30–35 W m−2 in August and September 2006–2009. In some years, short episodes of high-aerosol DRE can be observed, due to high-aerosol loadings, while in other years the loadings are lower but more prolonged. Climate models that use evenly distributed monthly averaged emission fields will not reproduce these high-aerosol loadings. Furthermore, the simulated monthly mean aerosol DRE in HadGEM2 is only about 6 W m−2 in August. The difference with SCIAMACHY mean observations can be partly explained by an underestimation of the aerosol absorption Ångström exponent in the ultraviolet. However, the subsequent increase of aerosol DRE simulation by about 20% is not enough to explain the observed discrepancy between simulations and observations.

On the cause of a magnetospheric flux transfer event

We present a detailed investigation of a magnetospheric flux transfer event (FTE) seen by the Active Magnetospheric Tracer Explorer (AMPTE) UKS and IRM satellites around 1046 UT on October 28, 1984. This event has been discussed many times previously in the literature and has been cited as support for a variety of theories of FTE formation. We make use of a model developed to reproduce ion precipitations seen in the cusp ionosphere. The analysis confirms that the FTE is well explained as a brief excursion into an open low-latitude boundary layer (LLBL), as predicted by two theories of magnetospheric FTEs: namely, that they are bulges in the open LLBL due to reconnection rate enhancements or that they are indentations of the magnetopause by magnetosheath pressure increases (but in the presence of ongoing steady reconnection). The indentation of the inner edge of the open LLBL that these two models seek to explain is found to be shallow for this event. The ion model reproduces the continuous evolution of the ion distribution function between the sheath-like population at the event center and the surrounding magnetospheric populations; it also provides an explanation of the high-pressure core of the event as comprising field lines that were reconnected considerably earlier than those that are draped over it to give the event boundary layer. The magnetopause transition parameter is used to isolate a field rotation on the boundaries of the core, which is subjected to the tangential stress balance test. The test identifies this to be a convecting structure, which is neither a rotational discontinuity (RD) nor a contact discontinuity, but could possibly be a slow shock. In addition, evidence for ion reflection off a weak RD on the magnetospheric side of this structure is found. The event structure is consistent in many ways with features predicted for the open LLBL by analytic MHD theories and by MHD and hybrid simulations. The de Hoffman-Teller velocity of the structure is significantly different from that of the magnetosheath flow, indicating that it is not an indentation caused by a high-pressure pulse in the sheath but is consistent with the motion of newly opened field lines (different from the sheath flow because of the magnetic tension force) deduced from the best fit to the ion data. However, we cannot here rule out the possibility that the sheath flow pattern has changed in the long interval between the two satellites observing the FTE and subsequently emerging into the magnetosheath; thus this test is not conclusive in this particular case. Analysis of the fitted elapsed time since reconnection shows that the core of the event was reconnected in one pulse and the event boundary layer was reconnected in a subsequent pulse. Between these two pulses is a period of very low (but nonzero) reconnection rate, which lasts about 14 mins. Thus the analysis supports, but does not definitively verify, the concept that the FTE is a partial passage into an open LLBL caused by a traveling bulge in that layer produced by a pulse in reconnection rate.