Index Geophysics

Items

• Analysis of CCN activity of Arctic aerosol and Canadian biomass burning during summer 2008

  The NASA DC-8 aircraft characterized the aerosol properties, chemical composition, and cloud condensation nuclei (CCN) concentrations of the summertime Arctic during the 2008 NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. Air masses characteristic of fresh and aged biomass burning, boreal forest, Arctic background, and anthropogenic industrial pollution were sampled. Observations were spatially extensive (50–85° N and 40–130° W) and exhibit significant variability in aerosol and CCN concentrations. The chemical composition was dominated by highly oxidized organics (66–94% by volume), with a water-soluble mass fraction of more than 50%. The aerosol hygroscopicity parameter, κ, ranged between κ = 0.08–0.32 for all air mass types. Industrial pollution had the lowest κ of 0.08 ± 0.01, while the Arctic background had the highest and most variable κ of 0.32 ± 0.21, resulting from a lower and more variable organic fraction. Both fresh and aged (long-range transported) biomass burning air masses exhibited remarkably similar κ (0.18 ± 0.13), consistent with observed rapid chemical and physical aging of smoke emissions in the atmosphere, even in the vicinity of fresh fires. The organic hygroscopicity (κ_org) was parameterized by the volume fraction of water-soluble organic matter (ε_WSOM), with a κ = 0.12, such that κ_org = 0.12ε_WSOM. Assuming bulk (size-independent) composition and including the κ_org parameterization enabled CCN predictions to within 30% accuracy for nearly all environments sampled. The only exception was for industrial pollution from Canadian oil sands exploration, where an external mixture and size-dependent composition was required. Aerosol mixing state assumptions (internal vs. external) in all other environments did not significantly affect CCN predictions; however, the external mixing assumption provided the best results, even though the available observations could not determine the true degree of external mixing and therefore may not always be representative of the environments sampled. No correlation was observed between κ_org and O : C. A novel correction of the CCN instrument supersaturation for water vapor depletion, resulting from high concentrations of CCN, was also employed. This correction was especially important for fresh biomass burning plumes where concentrations exceeded 1.5×10⁴ cm^−3 and introduced supersaturation depletions of ≥25%. Not accounting for supersaturation depletion in these high concentration environments would therefore bias CCN closure up to 25% and inferred κ by up to 50%.

• Sensitivity of cloud condensation nuclei to regional changes in dimethyl-sulphide emissions

  The atmospheric oxidation of dimethyl-sulphide (DMS) derived from marine phytoplankton is a significant source of marine sulphate aerosol. DMS has been proposed to regulate climate via changes in cloud properties, though recent studies have shown that present-day global cloud condensation nuclei (CCN) concentrations have only a weak dependence on the total emission flux of DMS. Here, we use a global aerosol microphysics model to examine how efficiently CCN are produced when DMS emissions are changed in different marine regions. We find that global CCN production per unit mass of sulphur emitted varies by more than a factor of 20 depending on where the change in oceanic DMS emission flux is applied. The variation in CCN production efficiency depends upon where CCN production processes (DMS oxidation, SO₂ oxidation, nucleation and growth) are most efficient and removal processes (deposition) least efficient. The analysis shows that the production of aerosol sulphate through aqueous-phase oxidation of SO₂ limits the amount of H₂SO₄ available for nucleation and condensational growth and therefore suppresses CCN formation, leading to the weak response of CCN to changes in DMS emission. Our results show that past and future changes in the spatial distribution of DMS emissions (through changes in the phytoplankton population or wind speed patterns) could exert a stronger control on climate than net increases in biological productivity.

• Carbon dioxide and climate impulse response functions for the computation of greenhouse gas metrics: a multi-model analysis

  The responses of carbon dioxide (CO₂) and other climate variables to an emission pulse of CO₂ into the atmosphere are often used to compute the Global Warming Potential (GWP) and Global Temperature change Potential (GTP), to characterize the response timescales of Earth System models, and to build reduced-form models. In this carbon cycle-climate model intercomparison project, which spans the full model hierarchy, we quantify responses to emission pulses of different magnitudes injected under different conditions. The CO₂ response shows the known rapid decline in the first few decades followed by a millennium-scale tail. For a 100 Gt-C emission pulse added to a constant CO₂ concentration of 389 ppm, 25 ± 9% is still found in the atmosphere after 1000 yr; the ocean has absorbed 59 ± 12% and the land the remainder (16 ± 14%). The response in global mean surface air temperature is an increase by 0.20 ± 0.12 °C within the first twenty years; thereafter and until year 1000, temperature decreases only slightly, whereas ocean heat content and sea level continue to rise. Our best estimate for the Absolute Global Warming Potential, given by the time-integrated response in CO₂ at year 100 multiplied by its radiative efficiency, is 92.5 × 10^−15 yr W m⁻² per kg-CO₂. This value very likely (5 to 95% confidence) lies within the range of (68 to 117) × 10^−15 yr W m⁻² per kg-CO₂. Estimates for time-integrated response in CO₂ published in the IPCC First, Second, and Fourth Assessment and our multi-model best estimate all agree within 15% during the first 100 yr. The integrated CO₂ response, normalized by the pulse size, is lower for pre-industrial conditions, compared to present day, and lower for smaller pulses than larger pulses. In contrast, the response in temperature, sea level and ocean heat content is less sensitive to these choices. Although, choices in pulse size, background concentration, and model lead to uncertainties, the most important and subjective choice to determine AGWP of CO₂ and GWP is the time horizon.

• Observation-based assessment of stratospheric fractional release, lifetimes, and ozone depletion potentials of ten important source gases

  Estimates of the recovery time of stratospheric ozone heavily rely on the exact knowledge of the processes that lead to the decomposition of the relevant halogenated source gases. Crucial parameters in this context are fractional release factors (FRFs) as well as stratospheric lifetimes and ozone depletion potentials (ODPs). We here present data from the analysis of air samples collected between 2009 and 2011 on board research aircraft flying in the mid- and high-latitude stratosphere and infer the above-mentioned parameters for ten major source gases: CFCl₃ (CFC-11), CF₂Cl₂ (CFC-12), CF₂ClCFCl₂ (CFC-113), CCl₄ (carbon tetrachloride), CH₃CCl₃ (methyl chloroform), CHF₂Cl (HCFC-22), CH₃CFCl₂ (HCFC-141b), CH₃CF₂Cl (HCFC-142b), CF₂ClBr (H-1211), and CF₃Br (H-1301). The inferred correlations of their FRFs with mean ages of air reveal less decomposition as compared to previous studies for most compounds. When using the calculated set of FRFs to infer equivalent stratospheric chlorine, we find a reduction of more than 20% as compared to the values inferred in the most recent Scientific Assessment of Ozone Depletion by the World Meteorological Organisation (WMO, 2011). We also note that FRFs and their correlations with mean age are not generally time-independent as often assumed. The stratospheric lifetimes were calculated relative to that of CFC-11. Within our uncertainties the ratios between stratospheric lifetimes inferred here agree with the values in recent WMO reports except for CFC-11, CFC-12 and CH₃CCl₃. Finally, we calculate lower ODPs than recommended by WMO for six out of ten compounds, with changes most pronounced for the three HCFCs. Collectively these newly calculated values may have important implications for the severity and recovery time of stratospheric ozone loss.

• Formation of anthropogenic secondary organic aerosol (SOA) and its influence on biogenic SOA properties

  Secondary organic aerosol (SOA) formation from mixed anthropogenic and biogenic precursors has been studied exposing reaction mixtures to natural sunlight in the SAPHIR chamber in Jülich, Germany. In this study aromatic compounds served as examples of anthropogenic volatile organic compound (VOC) and a mixture of &alpha;-pinene and limonene as an example for biogenic VOC. Several experiments with exclusively aromatic precursors were performed to establish a relationship between yield and organic aerosol mass loading for the atmospheric relevant range of aerosol loads of 0.01 to 10 μg m⁻³. The yields (0.5 to 9%) were comparable to previous data and further used for the detailed evaluation of the mixed biogenic and anthropogenic experiments. For the mixed experiments a number of different oxidation schemes were addressed. The reactivity, the sequence of addition, and the amount of the precursors influenced the SOA properties. Monoterpene oxidation products, including carboxylic acids and dimer esters were identified in the aged aerosol at levels comparable to ambient air. OH radicals were measured by Laser Induced Fluorescence, which allowed for establishing relations of aerosol properties and composition to the experimental OH dose. Furthermore, the OH measurements in combination with the derived yields for aromatic SOA enabled application of a simplified model to calculate the chemical turnover of the aromatic precursor and corresponding anthropogenic contribution to the mixed aerosol. The estimated anthropogenic contributions were ranging from small (&approx;8%) up to significant fraction (>50%) providing a suitable range to study the effect of aerosol composition on the aerosol volatility (volume fraction remaining (VFR) at 343 K: 0.86–0.94). The aromatic aerosol had higher oxygen to carbon ratio O/C and was less volatile than the biogenic fraction. However, in order to produce significant amount of aromatic SOA the reaction mixtures needed a higher OH dose that also increased O/C and provided a less volatile aerosol. The SOA yields, O/C, and <i>f</i>₄₄ (the mass fraction of CO₂⁺ ions in the mass spectra which can be considered as a measure of carboxylic groups) in the mixed photo-chemical experiments could be described as linear combinations of the corresponding properties of the pure systems. For VFR there was in addition an enhancement effect, making the mixed aerosol significantly less volatile than what could be predicted from the pure systems. A strong positive correlation was found between changes in volatility and O/C with the exception during dark hours where the SOA volatility decreased while O/C did not change significantly. Thus, this change in volatility under dark conditions as well as the anthropogenic enhancement is due to chemical or morphological changes not affecting O/C.

• Comparison of different real time VOC measurement techniques in a ponderosa pine forest

  Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (<i>Pinus Ponderosa</i>) during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser-Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and likely points to an offset in calibration, rather than a difference in the ability to measure the sum of terpenes. The contribution of isoprene relative to MBO inferred from PTR-MS and PTR-TOF-MS was smaller than 12% while GC-MS data suggested an average of 21% of isoprene relative to MBO. This comparison demonstrates that the current capability of VOC measurements to account for OH reactivity associated with the measured VOCs is within 20%.

• Quantifying the uncertainty in simulating global tropospheric composition due to the variability in global emission estimates of Biogenic Volatile Organic Compounds

  The emission of organic compounds from biogenic processes acts as an important source of trace gases in remote regions away from urban conurbations, and is likely to become more important in future decades due to the further mitigation of anthropogenic emissions that affect air quality and climate forcing. In this study we examine the contribution of biogenic volatile organic compounds (BVOCs) towards global tropospheric composition using the global 3-D chemistry transport model TM5 and the recently developed modified CB05 chemical mechanism. By comparing regional BVOC emission estimates we show that biogenic processes act as dominant sources for many regions and exhibit a large variability in the annually and seasonally integrated emission fluxes. By performing sensitivity studies we find that the contribution of BVOC species containing between 1 to 3 carbon atoms has an impact on the resident mixing ratios of tropospheric O₃ and CO, accounting for ~2.5% and ~10.8% of the simulated global distribution, respectively. This is approximately a third of the cumulative effect introduced by isoprene and the monoterpenes. By examining an ensemble of 3-D global chemistry transport simulations which adopt different global BVOC emission inventories we determine the associated uncertainty introduced towards simulating the composition of the troposphere for the year 2000. By comparing the model ensemble values against a composite of atmospheric measurements we show that the effects on tropospheric O₃ are limited to the lower troposphere (with an uncertainty between −2% to 10%), whereas that for tropospheric CO extends up to the upper troposphere (with an uncertainty of between 10 to 45%). Comparing the mixing ratios for low molecular weight alkenes in TM5 against surface measurements taken in Europe implies that the cumulative emission estimates are too low, regardless of the chosen BVOC inventory. This variability in the global distribution of CO due to BVOC emissions introduces an associated uncertainty in the tropospheric CO burden of 11.4%, which impacts strongly on the oxidative capacity of the troposphere, introducing an uncertainty in the atmospheric lifetime of the greenhouse gas CH₄ of ~3.3%. This study thus identifies the necessity of placing further constraints on non-CH₄ global biogenic emission estimates in large-scale global atmospheric chemistry models.

• Observationally-constrained estimates of global fine-mode AOD

  Small aerosols are mostly anthropogenic, and the fine-mode aerosol optical depth (fAOD) can be used to infer anthropogenic aerosol amounts. We estimate AOD and fAOD globally on a monthly time scale from 2001 to 2010 by integrating monthly satellite-based (MODIS and MISR) and ground-based (AERONET) observations. For fAOD, three integration methods are developed to utilize global coverage by satellite data and maximize the influence of AERONET data. We evaluate each method by applying the method without a few randomly-chosen AERONET data and comparing its output with the few AERONET data. The best method of the three is based on integrating the Ångström exponent (AE) data from MODIS, MISR and AERONET, and its output is closer to AERONET fAOD accuracy than MODIS or MISR fAOD over both ocean and land. <br><br> Using our integrated data, we find that the global 2001–2010 average of 500 nm AOD and fAOD is 0.17 and 0.089, respectively. Eastern China as a region shows the largest decadal-mean fAOD. The linear trend of global AOD or global fAOD from 2001 to 2010 is found to be slightly negative. This decreasing trend is particularly pronounced over the West (Western Europe and US/Canada combined) where AOD and fAOD reductions are about −20%. By contrast, fAOD in India and eastern China combined increased slightly. These results reflect the overall anthropogenic aerosol emission reduction in the West, and stagnating conditions in Asia. Moreover, our results in the West are consistent with the so-called surface brightening phenomenon in the recent decades.

• Tropospheric ozone changes, radiative forcing and attribution to emissions in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

  Ozone (O₃) from 17 atmospheric chemistry models taking part in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) has been used to calculate tropospheric ozone radiative forcings (RFs). All models applied a common set of anthropogenic emissions, which are better constrained for the present-day than the past. Future anthropogenic emissions follow the four Representative Concentration Pathway (RCP) scenarios, which define a relatively narrow range of possible air pollution emissions. We calculate a value for the pre-industrial (1750) to present-day (2010) tropospheric ozone RF of 410 mW m⁻². The model range of pre-industrial to present-day changes in O₃ produces a spread (±1 standard deviation) in RFs of ±17%. Three different radiation schemes were used – we find differences in RFs between schemes (for the same ozone fields) of ±10%. Applying two different tropopause definitions gives differences in RFs of ±3%. Given additional (unquantified) uncertainties associated with emissions, climate-chemistry interactions and land-use change, we estimate an overall uncertainty of ±30% for the tropospheric ozone RF. Experiments carried out by a subset of six models attribute tropospheric ozone RF to increased emissions of methane (44±12%), nitrogen oxides (31 ± 9%), carbon monoxide (15 ± 3%) and non-methane volatile organic compounds (9 ± 2%); earlier studies attributed more of the tropospheric ozone RF to methane and less to nitrogen oxides. Normalising RFs to changes in tropospheric column ozone, we find a global mean normalised RF of 42 mW m⁻² DU⁻¹, a value similar to previous work. Using normalised RFs and future tropospheric column ozone projections we calculate future tropospheric ozone RFs (mW m⁻²; relative to 1750) for the four future scenarios (RCP2.6, RCP4.5, RCP6.0 and RCP8.5) of 350, 420, 370 and 460 (in 2030), and 200, 300, 280 and 600 (in 2100). Models show some coherent responses of ozone to climate change: decreases in the tropical lower troposphere, associated with increases in water vapour; and increases in the sub-tropical to mid-latitude upper troposphere, associated with increases in lightning and stratosphere-to-troposphere transport. Climate change has relatively small impacts on global mean tropospheric ozone RF.

• The diurnal variability of atmospheric nitrogen oxides (NO and NO2) above the Antarctic Plateau driven by atmospheric stability and snow emissions

  Atmospheric nitrogen oxides (NO and NO₂) were observed at Dome C, East Antarctica (75.1&deg; S, 123.3&deg; E, 3233 m), for a total of 50 days, from 10 December 2009 to 28 January 2010. Average (±1σ) mixing ratios at 1.0 m of NO and NO₂, the latter measured for the first time on the East Antarctic Plateau, were 111 (±89) and 98 (±89) pptv, respectively. Atmospheric mixing ratios are on average comparable to those observed previously at South Pole, but in contrast show strong diurnal variability: a minimum around local noon and a maximum in the early evening coincide with the development and collapse of a convective boundary layer. The asymmetric diurnal cycle of NO_x concentrations and likely any other chemical tracer with a photolytic surface source is driven by the turbulent diffusivity and height of the atmospheric boundary layer, with the former controlling the magnitude of the vertical flux and the latter the size of the volume into which snow emissions are transported. In particular, the average (±1σ) NO_x emission flux from 22 December 2009 to 28 January 2010, estimated from atmospheric concentration gradients, was 8.2 (±7.4) &times; 10¹² molecule m^&minus;2 s^&minus;1 belongs to the largest values measured so far in the polar regions and explains the 3-fold increase in mixing ratios in the early evening when the boundary layer becomes very shallow. Dome C is likely not representative for the entire East Antarctic Plateau but illustrates the need of an accurate description of the boundary layer above snow in atmospheric chemistry models. A simple nitrate photolysis model matches the observed median diurnal NO_x flux during the day but has significant low bias during the night. The difference is significant taking into account the total random error in flux observations and model uncertainties due to the variability of NO₃^&minus; concentrations in snow and potential contributions from NO₂^&minus; photolysis. This highlights uncertainties in the parameterization of the photolytic NO_x source in natural snowpacks, such as the poorly constrained quantum yield of nitrate photolysis. A steady-state analysis of the NO₂ : NO ratios indicates that peroxy (HO₂ + RO₂) or other radical concentrations in the boundary layer of Dome C are either higher than measured elsewhere in the polar regions or other processes leading to enhanced NO₂ have to be invoked. These results confirm the existence of a strongly oxidising canopy enveloping the East Antarctic Plateau in summer.