Photochemistry and transport of tropospheric ozone and its precursors in urban and remote environments

Tropospheric ozone (O3) adversely affects human health, reduces crop yields, and contributes to climate forcing. To limit these effects, the processes controlling O3 abundance as well as that of its precursor molecules must be fully characterized. Here, I examine three facets of O3 production, both in heavily polluted and remote environments. First, using in situ observations from the DISCOVER-AQ field campaign in the Baltimore/Washington region, I evaluate the emissions of the O3 precursors CO and NOx (NOx = NO + NO2) in the National Emissions Inventory (NEI). I find that CO/NOx emissions ratios derived from observations are 21% higher than those predicted by the NEI. Comparisons to output from the CMAQ model suggest that CO in the NEI is accurate within 15 ± 11%, while NOx emissions are overestimated by 51-70%, likely due to errors in mobile sources. These results imply that ambient ozone concentrations will respond more efficiently to NOx controls than current models suggest. I then investigate the source of high O3 and low H2O structures in the Tropical Western Pacific (TWP). A combination of in situ observations, satellite data, and models show that the high O3 results from photochemical production in biomass burning plumes from fires in tropical Southeast Asia and Central Africa; the low relative humidity results from large-scale descent in the tropics. Because these structures have frequently been attributed to mid-latitude pollution, biomass burning in the tropics likely contributes more to the radiative forcing of climate than previously believed. Finally, I evaluate the processes controlling formaldehyde (HCHO) in the TWP. Convective transport of near surface HCHO leads to a 33% increase in upper tropospheric HCHO mixing ratios; convection also likely increases upper tropospheric CH3OOH to ~230 pptv, enough to maintain background HCHO at ~75 pptv. The long-range transport of polluted air, with NO four times the convectively controlled background, intensifies the conversion of HO2 to OH, increasing OH by a factor of 1.4. Comparisons between the global chemistry model CAM-Chem and observations show that consistent underestimates of HCHO by CAM-Chem throughout the troposphere result from underestimates in both NO and acetaldehyde.

Global interactions between fire and vegetation, human activities and climate

Doutoramento em Engenharia Florestal - Instituto Superior de Agronomia - UL

A review of measurement-based assessments of the aerosol direct radiative effect and forcing

Aerosols affect the Earth's energy budget directly by scattering and absorbing radiation and indirectly by acting as cloud condensation nuclei and, thereby, affecting cloud properties. However, large uncertainties exist in current estimates of aerosol forcing because of incomplete knowledge concerning the distribution and the physical and chemical properties of aerosols as well as aerosol-cloud interactions. In recent years, a great deal of effort has gone into improving measurements and datasets. It is thus feasible to shift the estimates of aerosol forcing from largely model-based to increasingly measurement-based. Our goal is to assess current observational capabilities and identify uncertainties in the aerosol direct forcing through comparisons of different methods with independent sources of uncertainties. Here we assess the aerosol optical depth (τ), direct radiative effect (DRE) by natural and anthropogenic aerosols, and direct climate forcing (DCF) by anthropogenic aerosols, focusing on satellite and ground-based measurements supplemented by global chemical transport model (CTM) simulations. The multi-spectral MODIS measures global distributions of aerosol optical depth (τ) on a daily scale, with a high accuracy of ±0.03±0.05τ over ocean. The annual average τ is about 0.14 over global ocean, of which about 21%±7% is contributed by human activities, as estimated by MODIS fine-mode fraction. The multi-angle MISR derives an annual average AOD of 0.23 over global land with an uncertainty of ~20% or ±0.05. These high-accuracy aerosol products and broadband flux measurements from CERES make it feasible to obtain observational constraints for the aerosol direct effect, especially over global the ocean. A number of measurement-based approaches estimate the clear-sky DRE (on solar radiation) at the top-of-atmosphere (TOA) to be about -5.5±0.2 Wm-2 (median ± standard error from various methods) over the global ocean. Accounting for thin cirrus contamination of the satellite derived aerosol field will reduce the TOA DRE to -5.0 Wm-2. Because of a lack of measurements of aerosol absorption and difficulty in characterizing land surface reflection, estimates of DRE over land and at the ocean surface are currently realized through a combination of satellite retrievals, surface measurements, and model simulations, and are less constrained. Over the oceans the surface DRE is estimated to be -8.8±0.7 Wm-2. Over land, an integration of satellite retrievals and model simulations derives a DRE of -4.9±0.7 Wm-2 and -11.8±1.9 Wm-2 at the TOA and surface, respectively. CTM simulations derive a wide range of DRE estimates that on average are smaller than the measurement-based DRE by about 30-40%, even after accounting for thin cirrus and cloud contamination. A number of issues remain. Current estimates of the aerosol direct effect over land are poorly constrained. Uncertainties of DRE estimates are also larger on regional scales than on a global scale and large discrepancies exist between different approaches. The characterization of aerosol absorption and vertical distribution remains challenging. The aerosol direct effect in the thermal infrared range and in cloudy conditions remains relatively unexplored and quite uncertain, because of a lack of global systematic aerosol vertical profile measurements. A coordinated research strategy needs to be developed for integration and assimilation of satellite measurements into models to constrain model simulations. Enhanced measurement capabilities in the next few years and high-level scientific cooperation will further advance our knowledge.

On the tropospheric response to anomalous stratospheric wave drag and radiative heating

Observational and numerical evidence suggest that variability in the extratropical stratospheric circulation has a demonstrable impact on tropospheric variability on intraseasonal time scales. In this study, it is demonstrated that the amplitude of the observed tropospheric response to vacillations in the stratospheric flow is quantitatively similar to the zonal-mean balanced response to the anomalous wave forcing at stratospheric levels. It is further demonstrated that the persistence of the tropospheric response is consistent with the impact of anomalous diabatic heating in the polar stratosphere as stratospheric temperatures relax to climatology. The results contradict previous studies that suggest that variations in stratospheric wave drag are too weak to account for the attendant changes in the tropospheric flow. However, the results also reveal that stratospheric processes alone cannot account for the observed meridional redistribution of momentum within the troposphere.

The effect of non-uniform radiative damping on the zonal-mean dynamics of the extratropical middle atmosphere

The effect of spatial and temporal variations in the radiative damping rate on the response to an imposed forcing or diabatic heating is examined in a zonal-mean model of the middle atmosphere. Attention is restricted to the extratropics, where a linear approach is viable. It is found that regions with weak radiative damping rates are more sensitive in terms of temperature to the remote influence of the diabatic circulation. The delay in the response in such regions can mean that ‘downward’ control is not achieved on seasonal time-scales. A seasonal variation in the radiative damping rate modulates the evolution of the response and leaves a transient-like signature in the annual mean temperature field. Several idealized examples are considered, motivated by topical questions. It is found that wave drag outside the polar vortex can significantly affect the temperatures in its interior, so that high-latitude, high-altitude gravity-wave drag is not the only mechanism for warming the southern hemisphere polar vortex. Diabatic mass transport through the 100 hPa surface is found to lag the seasonal evolution of the wave drag that drives the transport, and thus cannot be considered to be in the downward control regime. On the other hand, the seasonal variation of the radiative damping rate is found to make only a weak contribution to the annual mean temperature increase that has been observed above the ozone hole. Copyright © 2002 Royal Meteorological Society.

An “A-train” strategy for quantifying direct climate forcing by anthropogenic aerosols

This document outlines a practical strategy for achieving an observationally based quantification of direct climate forcing by anthropogenic aerosols. The strategy involves a four-step program for shifting the current assumption-laden estimates to an increasingly empirical basis using satellite observations coordinated with suborbital remote and in situ measurements and with chemical transport models. Conceptually, the problem is framed as a need for complete global mapping of four parameters: clear-sky aerosol optical depth δ, radiative efficiency per unit optical depth E, fine-mode fraction of optical depth ff, and the anthropogenic fraction of the fine mode faf. The first three parameters can be retrieved from satellites, but correlative, suborbital measurements are required for quantifying the aerosol properties that control E, for validating the retrieval of ff, and for partitioning fine-mode δ between natural and anthropogenic components. The satellite focus is on the “A-Train,” a constellation of six spacecraft that will fly in formation from about 2005 to 2008. Key satellite instruments for this report are the Moderate Resolution Imaging Spectroradiometer (MODIS) and Clouds and the Earth's Radiant Energy System (CERES) radiometers on Aqua, the Ozone Monitoring Instrument (OMI) radiometer on Aura, the Polarization and Directionality of Earth's Reflectances (POLDER) polarimeter on the Polarization and Anistropy of Reflectances for Atmospheric Sciences Coupled with Observations from a Lidar (PARASOL), and the Cloud and Aerosol Lider with Orthogonal Polarization (CALIOP) lidar on the Cloud–Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO). This strategy is offered as an initial framework—subject to improvement over time—for scientists around the world to participate in the A-Train opportunity. It is a specific implementation of the Progressive Aerosol Retrieval and Assimilation Global Observing Network (PARAGON) program, presented earlier in this journal, which identified the integration of diverse data as the central challenge to progress in quantifying global-scale aerosol effects. By designing a strategy around this need for integration, we develop recommendations for both satellite data interpretation and correlative suborbital activities that represent, in many respects, departures from current practice

Impact of the modal aerosol scheme GLOMAP-mode on aerosol forcing in the Hadley Centre Global Environmental Model

The Hadley Centre Global Environmental Model (HadGEM) includes two aerosol schemes: the Coupled Large-scale Aerosol Simulator for Studies in Climate (CLASSIC), and the new Global Model of Aerosol Processes (GLOMAP-mode). GLOMAP-mode is a modal aerosol microphysics scheme that simulates not only aerosol mass but also aerosol number, represents internally-mixed particles, and includes aerosol microphysical processes such as nucleation. In this study, both schemes provide hindcast simulations of natural and anthropogenic aerosol species for the period 2000–2006. HadGEM simulations of the aerosol optical depth using GLOMAP-mode compare better than CLASSIC against a data-assimilated aerosol re-analysis and aerosol ground-based observations. Because of differences in wet deposition rates, GLOMAP-mode sulphate aerosol residence time is two days longer than CLASSIC sulphate aerosols, whereas black carbon residence time is much shorter. As a result, CLASSIC underestimates aerosol optical depths in continental regions of the Northern Hemisphere and likely overestimates absorption in remote regions. Aerosol direct and first indirect radiative forcings are computed from simulations of aerosols with emissions for the year 1850 and 2000. In 1850, GLOMAP-mode predicts lower aerosol optical depths and higher cloud droplet number concentrations than CLASSIC. Consequently, simulated clouds are much less susceptible to natural and anthropogenic aerosol changes when the microphysical scheme is used. In particular, the response of cloud condensation nuclei to an increase in dimethyl sulphide emissions becomes a factor of four smaller. The combined effect of different 1850 baselines, residence times, and abilities to affect cloud droplet number, leads to substantial differences in the aerosol forcings simulated by the two schemes. GLOMAP-mode finds a presentday direct aerosol forcing of −0.49Wm−2 on a global average, 72% stronger than the corresponding forcing from CLASSIC. This difference is compensated by changes in first indirect aerosol forcing: the forcing of −1.17Wm−2 obtained with GLOMAP-mode is 20% weaker than with CLASSIC. Results suggest that mass-based schemes such as CLASSIC lack the necessary sophistication to provide realistic input to aerosol-cloud interaction schemes. Furthermore, the importance of the 1850 baseline highlights how model skill in predicting present-day aerosol does not guarantee reliable forcing estimates. Those findings suggest that the more complex representation of aerosol processes in microphysical schemes improves the fidelity of simulated aerosol forcings.

Estimates of global multicomponent aerosol optical depth and direct radiative perturbation in the Laboratoire de Météorologie Dynamique general circulation model

The global cycle of multicomponent aerosols including sulfate, black carbon (BC),organic matter (OM), mineral dust, and sea salt is simulated in the Laboratoire de Me´te´orologie Dynamique general circulation model (LMDZT GCM). The seasonal open biomass burning emissions for simulation years 2000–2001 are scaled from climatological emissions in proportion to satellite detected fire counts. The emissions of dust and sea salt are parameterized online in the model. The comparison of model-predicted monthly mean aerosol optical depth (AOD) at 500 nm with Aerosol Robotic Network (AERONET) shows good agreement with a correlation coefficient of 0.57(N = 1324) and 76% of data points falling within a factor of 2 deviation. The correlation coefficient for daily mean values drops to 0.49 (N = 23,680). The absorption AOD (ta at 670 nm) estimated in the model is poorly correlated with measurements (r = 0.27, N = 349). It is biased low by 24% as compared to AERONET. The model reproduces the prominent features in the monthly mean AOD retrievals from Moderate Resolution Imaging Spectroradiometer (MODIS). The agreement between the model and MODIS is better over source and outflow regions (i.e., within a factor of 2).There is an underestimation of the model by up to a factor of 3 to 5 over some remote oceans. The largest contribution to global annual average AOD (0.12 at 550 nm) is from sulfate (0.043 or 35%), followed by sea salt (0.027 or 23%), dust (0.026 or 22%),OM (0.021 or 17%), and BC (0.004 or 3%). The atmospheric aerosol absorption is predominantly contributed by BC and is about 3% of the total AOD. The globally and annually averaged shortwave (SW) direct aerosol radiative perturbation (DARP) in clear-sky conditions is �2.17 Wm�2 and is about a factor of 2 larger than in all-sky conditions (�1.04 Wm�2). The net DARP (SW + LW) by all aerosols is �1.46 and �0.59 Wm�2 in clear- and all-sky conditions, respectively. Use of realistic, less absorbing in SW, optical properties for dust results in negative forcing over the dust-dominated regions.

Direct and ozone-mediated forcing of the Southern Annular Mode by greenhouse gases

We assess the roles of long-lived greenhouse gases and ozone depletion in driving meridional surface pressure gradients in the southern extratropics; these gradients are a defining feature of the Southern Annular Mode. Stratospheric ozone depletion is thought to have caused a strengthening of this mode during summer, with increasing long-lived greenhouse gases playing a secondary role. Using a coupled atmosphere-ocean chemistry-climate model, we show that there is cancelation between the direct, radiative effect of increasing greenhouse gases by the also substantial indirect—chemical and dynamical—feedbacks that greenhouse gases have via their impact on ozone. This sensitivity of the mode to greenhouse gas-induced ozone changes suggests that a consistent implementation of ozone changes due to long-lived greenhouse gases in climate models benefits the simulation of this important aspect of Southern Hemisphere climate.

Southern Hemisphere jet latitude biases in CMIP5 models linked to shortwave cloud forcing

Substantial biases in shortwave cloud forcing (SWCF) of up to ±30 W m−2are found in the midlatitudes of the Southern Hemisphere in the historical simulations of 34 CMIP5 coupled general circulation models. The SWCF biases are shown to induce surface temperature anomalies localized in the midlatitudes, and are significantly correlated with the mean latitude of the eddy-driven jet, with a negative SWCF bias corresponding to an equatorward jet latitude bias. Aquaplanet model experiments are performed to demonstrate that the jet latitude biases are primarily induced by the midlatitude SWCF anomalies, such that the jet moves toward (away from) regions of enhanced (reduced) temperature gradients. The results underline the necessity of accurately representing cloud radiative forcings in state-of-the-art coupled models.

Volcanic forcing for climate modeling: a new microphysics-based data set covering years 1600–present

As the understanding and representation of the impacts of volcanic eruptions on climate have improved in the last decades, uncertainties in the stratospheric aerosol forcing from large eruptions are now linked not only to visible optical depth estimates on a global scale but also to details on the size, latitude and altitude distributions of the stratospheric aerosols. Based on our understanding of these uncertainties, we propose a new model-based approach to generating a volcanic forcing for general circulation model (GCM) and chemistry–climate model (CCM) simulations. This new volcanic forcing, covering the 1600–present period, uses an aerosol microphysical model to provide a realistic, physically consistent treatment of the stratospheric sulfate aerosols. Twenty-six eruptions were modeled individually using the latest available ice cores aerosol mass estimates and historical data on the latitude and date of eruptions. The evolution of aerosol spatial and size distribution after the sulfur dioxide discharge are hence characterized for each volcanic eruption. Large variations are seen in hemispheric partitioning and size distributions in relation to location/date of eruptions and injected SO2 masses. Results for recent eruptions show reasonable agreement with observations. By providing these new estimates of spatial distributions of shortwave and long-wave radiative perturbations, this volcanic forcing may help to better constrain the climate model responses to volcanic eruptions in the 1600–present period. The final data set consists of 3-D values (with constant longitude) of spectrally resolved extinction coefficients, single scattering albedos and asymmetry factors calculated for different wavelength bands upon request. Surface area densities for heterogeneous chemistry are also provided.

Radiative decay of the X(3872) as a mixed molecule-charmonium state in QCD sum rules

We use QCD sum rules (QCDSR) to calculate the width of the radiative decay of the meson X(3872), assumed to be a mixture between charmonium and exotic molecular [c (q) over bar][q (c) over bar] states with J(PC) = 1(++). We find that in a small range for the values of the mixing angle, 5 degrees <= theta <= 13 degrees, we get the branching ratio Gamma(X -> J/psi gamma)/Gamma(X -> J/psi pi(+)pi(-)) = 0.19 +/- 0.13, which is in agreement, with the experimental value. This result is compatible with the analysis of the mass and decay width of the mode J/psi(n pi) performed in the same approach.

New Measurement of the pi(0) Radiative Decay Width

High precision measurements of the differential cross sections for pi(0) photoproduction at forward angles for two nuclei, (12)C and (208)Pb, have been performed for incident photon energies of 4.9-5.5 GeV to extract the pi(0) -> gamma gamma decay width. The experiment was done at Jefferson Lab using the Hall B photon tagger and a high-resolution multichannel calorimeter. The pi(0) -> gamma gamma decay width was extracted by fitting the measured cross sections using recently updated theoretical models for the process. The resulting value for the decay width is Gamma(pi(0) -> gamma gamma) = 7.82 +/- 0.14(stat) +/- 0.17(syst) eV. With the 2.8% total uncertainty, this result is a factor of 2.5 more precise than the current Particle Data Group average of this fundamental quantity, and it is consistent with current theoretical predictions.

Natural and human forcing in recent geomorphic change; case studies in the Rio de la Plata basin

An analysis of geomorphic system`s response to change in human and natural drivers in some areas within the Rio de la Plata basin is presented The aim is to determine whether an acceleration of geomorphic processes has taken place in recent years and, if so, to what extent it is due to natural (climate) or human (land-use) drivers Study areas of different size, socio-economic and geomorphic conditions have been selected: the Rio de la Plata estuary and three sub-basins within its watershed Sediment cores were extracted and dated ((210)Pb) to determine sedimentation rates since the end of the 19th century. Rates were compared with time series on rainfall as well as human drivers such as population, GDP, livestock load, crop area, energy consumption or cement consumption, all of them related to human capacity to disturb land surface Data on river discharge were also gathered Results obtained indicate that sedimentation rates during the last century have remained essentially constant in a remote Andean basin, whereas they show important increases in the other two, particularly one located by the Sao Paulo metropolitan area Rates in the estuary are somewhere in between It appears that there is an intensification of denudation/sedimentation processes within the basin. Rainfall remained stable or varied very slightly during the period analysed and does not seem to explain increases of sedimentation rates observed. Human drivers, particularly those more directly related to capacity to disturb land surface (GDP, energy or cement consumption) show variations that suggest human forcing is a more likely explanation for the observed change in geomorphic processes It appears that a marked increase in denudation, of a ""technological"" nature, is taking place in this basin and leading to an acceleration of sediment supply This is coherent with similar increases observed in other regions (C) 2010 Elsevier B V All rights reserved

Radiative Relaxation Quantum Yields for Synthetic Eumelanin

We report absolute values for the radiative relaxation quantum yield of synthetic eumelanin as a function of excitation energy. These values were determined by correcting for pump beam attenuation and emission reabsorption in both eumelanin samples and fluorescein standards over a large range of concentrations. Our results confirm that eumelanins are capable of dissipating >99.9% of absorbed UV and visible radiation through nonradiative means. Furthermore, we have found that the radiative quantum yield of synthetic eumelanin is excitation energy dependent. This observation is supported by corrected emission spectra, which also show a clear dependence of both peak position and peak width on excitation energy. Our findings indicate that photoluminescence emission in eumelanins is derived from ensembles of small chemically distinct oligomeric units that can be selectively pumped. This hypothesis lends support to the theory that the basic structural unit of eumelanin is oligomeric rather than heteropolymeric.