Long-term high frequency measurements of ethane, benzene and methyl chloride at Ragged Point, Barbados: Identification of long-range transport events

Abstract Here we present high frequency long-term observations of ethane, benzene and methyl chloride from the AGAGE Ragged Point, Barbados, monitoring station made using a custom built GC-MS system. Our analysis focuses on the first three years of data (2005–2007) and on the interpretation of periodic episodes of high concentrations of these compounds. We focus specifically on an exemplar episode during September 2007 to assess if these measurements are impacted by long-range transport of biomass burning and biogenic emissions. We use the Lagrangian Particle Dispersion model, NAME, run forwards and backwards in time to identify transport of air masses from the North East of Brazil during these events. To assess whether biomass burning was the cause we used hot spots detected using the MODIS instrument to act as point sources for simulating the release of biomass burning plumes. Excellent agreement for the arrival time of the simulated biomass burning plumes and the observations of enhancements in the trace gases indicates that biomass burning strongly influenced these measurements. These modelling data were then used to determine the emissions required to match the observations and compared with bottom up estimates based on burnt area and literature emission factors. Good agreement was found between the two techniques highlight the important role of biomass burning. The modelling constrained by in situ observations suggests that the emission factors were representative of their known upper limits, with the in situ data suggesting slightly greater emissions of ethane than the literature emission factors account for. Further analysis was performed concluding only a small role for biogenic emissions of methyl chloride from South America impacting measurements at Ragged Point. These results highlight the importance of long-term high frequency measurements of NMHC and ODS and highlight how these data can be used to determine sources of emissions 1000’s km away.ATA would like to thank the GWR and the Met Office for the PhD funding that was useful in the initiation of this research and the Herchel Smith foundation for a Postdoctoral fellowship, and NCAS for funding. The operation of the AGAGE station at Ragged Point is supported by the National Aeronautic and Space Administration (NASA, USA) (grants NNX07AE89G and NNX11AF17G to MIT) and the National Oceanic and Atmospheric Administration (NOAA, USA) (contract RA133R09CN0062).This is the final version of the article. It first appeared from BioOne via http://dx.doi.org/10.12952/journal.elementa.00006

Molecular composition of organic aerosols in central Amazonia: An ultra-high-resolution mass spectrometry study

The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM$_{2.5}$ aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen-and/or sulfur-containing organic species contributed up to 60% of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen-and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic-biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.Research at the University of Cambridge was supported by European Research Council grant no. 279405. The authors would like to thank Jason Surratt (University of North Carolina) for providing a synthesised IEPOX-OS standard. O3, CO, NOy , RH and rain data were obtained from the Atmospheric Radiation Measurement (ARM) Climate Research Facility, a U.S. Department of Energy (grant DE-SC0011122) Office of Science user facility sponsored by the Office of Biological and Environmental Research. We acknowledge the support from the Central Office of the Large Scale Biosphere Atmosphere Experiment in Amazonia (LBA), the Instituto Nacional de Pesquisas da Amazonia (INPA), and the Universidade do Estado do Amazonia (UEA). The work was conducted under 001030/2012-4 of the Brazilian National Council for Scientific and Technological Development (CNPq)

Molecular composition of organic aerosols in central Amazonia: An ultra-high-resolution mass spectrometry study

The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM$_{2.5}$ aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen-and/or sulfur-containing organic species contributed up to 60% of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen-and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic-biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.Research at the University of Cambridge was supported by European Research Council grant no. 279405. The authors would like to thank Jason Surratt (University of North Carolina) for providing a synthesised IEPOX-OS standard. O3, CO, NOy , RH and rain data were obtained from the Atmospheric Radiation Measurement (ARM) Climate Research Facility, a U.S. Department of Energy (grant DE-SC0011122) Office of Science user facility sponsored by the Office of Biological and Environmental Research. We acknowledge the support from the Central Office of the Large Scale Biosphere Atmosphere Experiment in Amazonia (LBA), the Instituto Nacional de Pesquisas da Amazonia (INPA), and the Universidade do Estado do Amazonia (UEA). The work was conducted under 001030/2012-4 of the Brazilian National Council for Scientific and Technological Development (CNPq)

Atlantic multidecadal variability and the U.K. acsis program

Abstract Atlantic multidecadal variability (AMV) is the term used to describe the pattern of variability in North Atlantic sea surface temperatures (SSTs) that is characterized by decades of basinwide warm or cool anomalies, relative to the global mean. AMV has been associated with numerous climate impacts in many regions of the world including decadal variations in temperature and rainfall patterns, hurricane activity, and sea level changes. Given its importance, understanding the physical processes that drive AMV and the extent to which its evolution is predictable is a key challenge in climate science. A leading hypothesis is that natural variations in ocean circulation control changes in ocean heat content and consequently AMV phases. However, this view has been challenged recently by claims that changing natural and anthropogenic radiative forcings are critical drivers of AMV. Others have argued that changes in ocean circulation are not required. Here, we review the leading hypotheses and mechanisms for AMV and discuss the key debates. In particular, we highlight the need for a holistic understanding of AMV. This perspective is a key motivation for a major new U.K. research program: the North Atlantic Climate System Integrated Study (ACSIS), which brings together seven of the United Kingdom’s leading environmental research institutes to enable a broad spectrum approach to the challenges of AMV. ACSIS will deliver the first fully integrated assessment of recent decadal changes in the North Atlantic, will investigate the attribution of these changes to their proximal and ultimate causes, and will assess the potential to predict future changes.</jats:p

Tropospheric jet response to Antarctic ozone depletion: An update with Chemistry-Climate Model Initiative (CCMI) models

The Southern Hemisphere (SH) zonal-mean circulation change in response to Antarctic ozone depletion is re-visited by examining a set of the latest model simulations archived for the Chemistry-Climate Model Initiative (CCMI) project. All models reasonably well reproduce Antarctic ozone depletion in the late 20th century. The related SH-summer circulation changes, such as a poleward intensification of westerly jet and a poleward expansion of the Hadley cell, are also well captured. All experiments exhibit quantitatively the same multi-model mean trend, irrespective of whether the ocean is coupled or prescribed. Results are also quantitatively similar to those derived from the Coupled Model Intercomparison Project phase 5 (CMIP5) high-top model simulations in which the stratospheric ozone is mostly prescribed with monthly- and zonally-averaged values. These results suggest that the ozone-hole-induced SH-summer circulation changes are robust across the models irrespective of the specific chemistry-atmosphere-ocean coupling

On the Changing Role of the Stratosphere on the Tropospheric Ozone Budget: 1979–2010

We study the evolution of tropospheric ozone over the period 1979-2010 using a chemistry-climate model employing a stratosphere-troposphere chemistry scheme. By running with specified dynamics, the key feedback of composition on meteorology is suppressed, isolating the chemical response. By using historical forcings and emissions, interactions between processes are realistically represented. We use the model to assess how the ozone responds over time and to investigate model responses and trends. We find that the CFC-driven decrease in stratospheric ozone plays a significant role in the tropospheric ozone burden. Over the period 1979-1994, the decline in transport of ozone from the stratosphere, partially offsets an emissions-driven increase in tropospheric ozone production. From 1994-2010, despite a levelling off in emissions increased stratosphere-to-troposphere transport of ozone drives a small increase in the tropospheric ozone burden. These results have implications for the impact of future stratospheric ozone recovery on air quality and radiative forcing.European Community’s Seventh Framework Programme 10 (FP7/2007-2013) under grant agreement no. 603557 (StratoClim)

Evaluation of biospheric components in earth system models using modern and palaeo-observations: The state-of-the-art

PublishedJournal ArticleEarth system models (ESMs) are increasing in complexity by incorporating more processes than their predecessors, making them potentially important tools for studying the evolution of climate and associated biogeochemical cycles. However, their coupled behaviour has only recently been examined in any detail, and has yielded a very wide range of outcomes. For example, coupled climate-carbon cycle models that represent land-use change simulate total land carbon stores at 2100 that vary by as much as 600 Pg C, given the same emissions scenario. This large uncertainty is associated with differences in how key processes are simulated in different models, and illustrates the necessity of determining which models are most realistic using rigorous methods of model evaluation. Here we assess the state-of-the-art in evaluation of ESMs, with a particular emphasis on the simulation of the carbon cycle and associated biospheric processes. We examine some of the new advances and remaining uncertainties relating to (i) modern and palaeodata and (ii) metrics for evaluation. We note that the practice of averaging results from many models is unreliable and no substitute for proper evaluation of individual models. We discuss a range of strategies, such as the inclusion of pre-calibration, combined process-and system-level evaluation, and the use of emergent constraints, that can contribute to the development of more robust evaluation schemes. An increasingly data-rich environment offers more opportunities for model evaluation, but also presents a challenge. Improved knowledge of data uncertainties is still necessary to move the field of ESM evaluation away from a "beauty contest" towards the development of useful constraints on model outcomes. © 2013 Author(s).This paper emerged from the GREENCYCLESII mini-conference “Evaluation of Earth system models using modern and palaeo-observations” held at Clare College, Cambridge, UK, in September 2012. We would like to thank the Marie Curie FP7 Research and Training Network GREENCYCLESII for providing funding which made this meeting possible. Research leading to these results has received funding from the European Community’s Seventh Framework Programme (FP7 2007–2013) under grant agreement no. 238366. The work of C. D. Jones was supported by the Joint DECC/Defra Met Office Hadley Centre Climate Programme (GA01101). N. R. Edwards acknowledges support from FP7 grant no. 265170 (ERMITAGE). N. Vázquez Riveiros acknowledges support from the AXA Research Fund and the Newton Trust

Review of the global models used within phase 1 of the Chemistry–Climate Model Initiative (CCMI)

We present an overview of state-of-the-art chemistry–climate and chemistry transport models that are used within phase 1 of the Chemistry–Climate Model Initiative (CCMI-1). The CCMI aims to conduct a detailed evaluation of participating models using process-oriented diagnostics derived from observations in order to gain confidence in the models' projections of the stratospheric ozone layer, tropospheric composition, air quality, where applicable global climate change, and the interactions between them. Interpretation of these diagnostics requires detailed knowledge of the radiative, chemical, dynamical, and physical processes incorporated in the models. Also an understanding of the degree to which CCMI-1 recommendations for simulations have been followed is necessary to understand model responses to anthropogenic and natural forcing and also to explain inter-model differences. This becomes even more important given the ongoing development and the ever-growing complexity of these models. This paper also provides an overview of the available CCMI-1 simulations with the aim of informing CCMI data users

Detection and identification of Criegee intermediates from the ozonolysis of biogenic and anthropogenic VOCs: comparison between experimental measurements and theoretical calculations

Ozonolysis of alkenes is a key reaction in the atmosphere, playing an important role in determining the oxidising capacity of the atmosphere and acting as a source of compounds that can contribute to local photochemical “smog”. The reaction products of the initial step of alkene-ozonolysis are Criegee intermediates (CIs), which have for many decades eluded direct experimental detection because of their very short lifetime. We use an innovative experimental technique, stabilisation of CIs with spin traps and analysis with proton transfer reaction mass spectrometry, to measure the gas phase concentration of a series of CIs formed from ozonolysis of a range of both biogenic and anthropogenic alkenes in flow tube experiments. Density functional theory (DFT) calculations were used to assess the stability of the CI-spin trap adducts and showed that the reaction of the investigated CIs with the spin trap occurs very rapidly except for the large β-pinene CI. Our measurement method was used successfully to measure all the expected CIs, emphasising that this new technique is applicable to a wide range of CIs with different molecular structures previously unidentified experimentally. In addition, for the first time it was possible to study CIs simultaneously in an even more complex reaction system consisting of more than one olefinic precursor. Comparison between our new experimental measurements, calculations of stability of the CI-spin trap adducts and results from numerical modelling, using the master chemical mechanism (MCM), showed that our new method can be used for quantification of CIs produced in situ in laboratory experiments.This work was funded by the European Research Council (ERC starting grant 279405) and NERC (NE/K008218/1). ATA thanks NERC for funding through NCAS

Description and Evaluation of the specified-dynamics experiment in the Chemistry-Climate Model Initiative

We provide an overview of the REF-C1SD specified-dynamics experiment that was conducted as part of phase 1 of the Chemistry-Climate Model Initiative (CCMI). The REF-C1SD experiment, which consisted of mainly nudged general circulation models (GCMs) constrained with (re)analysis fields, was designed to examine the influence of the large-scale circulation on past trends in atmospheric composition. The REF-C1SD simulations were produced across various model frameworks and are evaluated in terms of how well they represent different measures of the dynamical and transport circulations. In the troposphere there are large (∼40 %) differences in the climatological mean distributions, seasonal cycle amplitude, and trends of the meridional and vertical winds. In the stratosphere there are similarly large (∼50 %) differences in the magnitude, trends and seasonal cycle amplitude of the transformed Eulerian mean circulation and among various chemical and idealized tracers. At the same time, interannual variations in nearly all quantities are very well represented, compared to the underlying reanalyses. We show that the differences in magnitude, trends and seasonal cycle are not related to the use of different reanalysis products; rather, we show they are associated with how the simulations were implemented, by which we refer both to how the large-scale flow was prescribed and to biases in the underlying free-running models. In most cases these differences are shown to be as large or even larger than the differences exhibited by free-running simulations produced using the exact same models, which are also shown to be more dynamically consistent. Overall, our results suggest that care must be taken when using specified-dynamics simulations to examine the influence of large-scale dynamics on composition