Global Troposphere Research Articles

Variation of Modified Combustion Efficiency and Its Impact on Biomass Burning Emission Estimation in Africa

AbstractBiomass burning (BB) is one of the largest sources of trace gases and primary carbonaceous particles in the global troposphere, posing great impacts on air quality and regional climate. Accurate quantification of BB emissions is vital for assessing its environmental and climate impacts. However, there are still large uncertainties in current BB emission inventories due to poorly characterized emission rates under different combustion states. The fixed emission factor (EF) instead of varying EF associated with different combustion efficiencies may be the reason for the bias. Here, based on satellite‐retrieved carbon dioxide (CO2) and carbon monoxide (CO), the modified combustion efficiency (MCE) is derived for fire‐prone regions in Africa. The monthly and inter‐annual variability of MCE shows a good correlation with meteorological variables such as relative humidity. Therefore, variable EF was established based on its statistical relationship with MCE for different fire‐emitted species. Application of such MCE‐dependent EF in the global climate‐chemistry model can greatly improve the performance of wildfire smoke pollution during the fire season, indicated by an increase of 31% in aerosol optical depth (AOD) and a 50% reduction in normalized mean bias compared with AOD observations. The study elucidates the critical role of meteorology in BB emission estimates and highlights the importance of implementing a dynamic fire emission inventory in response to meteorological conditions.

Observations of cyanogen bromide (BrCN) in the global troposphere and their relation to polar surface O3 destruction

Abstract. Bromine activation (the production of Br in an elevated oxidation state) promotes ozone destruction and mercury removal in the global troposphere and commonly occurs in both springtime polar boundary layers, often accompanied by nearly complete ozone destruction. The chemistry and budget of active bromine compounds (e.g., Br2, BrCl, BrO, HOBr) reflect the cycling of Br and affect its environmental impact. Cyanogen bromide (BrCN) has recently been measured by iodide ion high-resolution time-of-flight mass spectrometry (I− CIMS), and trifluoro methoxide ion time-of-flight mass spectrometry (CF3O− CIMS) during the NASA Atmospheric Tomography Mission second, third, and fourth deployments (NASA ATom), and could be a previously unquantified participant in active Br chemistry. BrCN mixing ratios ranged from below the detection limit (1.5 pptv) up to as high as 36 pptv (10 s average) and enhancements were almost exclusively confined to the polar boundary layers in the Arctic winter and in both polar regions during spring and fall. The coincidence of BrCN with active Br chemistry (often observable BrO, BrCl and O3 loss) and high CHBr3/CH2Br2 ratios imply that much of the observed BrCN is from atmospheric Br chemistry rather than a biogenic source. Likely BrCN formation pathways involve the heterogeneous reactions of active Br (Br2, HOBr) with reduced nitrogen compounds, for example hydrogen cyanide (HCN/CN−), on snow, ice, or particle surfaces. Competitive reaction calculations of HOBr reactions with Cl−/Br− and HCN/CN− in solution, as well as box model calculations with bromine chemistry, confirm the viability of this formation channel and show a distinct pH dependence, with BrCN formation favored at higher pH values. Gas-phase loss processes of BrCN due to reaction with radical species are likely quite slow and photolysis is known to be relatively slow (BrCN lifetime of ∼ 4 months in midlatitude summer). These features, and the lack of BrCN enhancements above the polar boundary layer, imply that surface reactions must be the major loss processes. The fate of BrCN determines whether BrCN production fuels or terminates bromine activation. BrCN reactions with other halogens (Br−, HOCl, HOBr) may perpetuate the active Br cycle; however, preliminary laboratory experiments showed that BrCN did not react with aqueous bromide ion (< 0.1 %) to reform Br2. Liquid-phase reactions of BrCN are more likely to convert Br to bromide (Br−) or form a C–Br bonded organic species, as these are the known condensed-phase reactions of BrCN and would therefore constitute a loss of atmospheric active Br. Thus, further study of the chemistry of BrCN will be important for diagnosing polar Br cycling.

Full latitudinal marine atmospheric measurements of iodine monoxide

Abstract. Iodine compounds destroy ozone (O3) in the global troposphere and form new aerosols, thereby affecting the global radiative balance. However, few reports have described the latitudinal distribution of atmospheric iodine compounds. This work reports iodine monoxide (IO) measurements taken over unprecedented sampling areas from the Arctic to the Southern Hemisphere and spanning sea surface temperatures (SSTs) of approximately 0 to 31.5 ∘C. The highest IO concentrations were observed over the Western Pacific warm pool (WPWP), where O3 minima were also measured. There, a negative correlation was found between O3 and IO mixing ratios at extremely low O3 concentrations. This correlation is not explained readily by the O3-dependent oceanic fluxes of photolabile inorganic iodine compounds, which is the dominant source in recent global-scale chemistry transport models representing iodine chemistry. Actually, the correlation rather implies that O3-independent pathways can be similarly important in the WPWP. The O3-independent fluxes result in a 15 % greater O3 loss than that estimated for O3-dependent processes alone. The daily O3 loss rate related to iodine over the WPWP is as high as approximately 2 ppbv (parts per billion by volume) despite low O3 concentrations of approximately 10 ppbv, with the loss being up to 100 % greater than that without iodine. This finding suggests that warming SST driven by climate change might affect the marine atmospheric chemical balance through iodine–ozone chemistry.

Impact of biomass burning and stratospheric intrusions in the remote South Pacific Ocean troposphere

Abstract. The ozone mixing ratio spatiotemporal variability in the pristine South Pacific Ocean is studied, for the first time, using 21-year-long ozone (O3) records from the entire southern tropical and subtropical Pacific between 1994 and 2014. The analysis considered regional O3 vertical observations from ozonesondes, surface carbon monoxide (CO) observations from flasks, and three-dimensional chemistry-transport model simulations of the global troposphere. Two 21-year-long numerical simulations, with and without biomass burning emissions, were performed to disentangle the importance of biomass burning relative to stratospheric intrusions for ambient ozone levels in the region. Tagged tracers of O3 from the stratosphere and CO from various biomass burning regions have been used to track the impact of these different regions on the southern tropical Pacific O3 and CO levels. Patterns have been analyzed based on atmospheric dynamics variability. Considering the interannual variability in the observations, the model can capture the observed ozone gradients in the troposphere with a positive bias of 7.5 % in the upper troposphere/lower stratosphere (UTLS) as well as near the surface. Remarkably, even the most pristine region of the global ocean is affected by distant biomass burning emissions by convective outflow through the mid and high troposphere and subsequent subsidence over the pristine oceanic region. Therefore, the biomass burning contribution to tropospheric CO levels maximizes in the UTLS. The Southeast Asian open fires have been identified as the major contributing source to CO from biomass burning in the tropical South Pacific, contributing on average for the study period about 8.5 and 13 ppbv of CO at Rapa Nui and Samoa, respectively, at an altitude of around 12 km during the burning season in the spring of the Southern Hemisphere. South America is the second-most important biomass burning source region that influences the study area. Its impact maximizes in the lower troposphere (6.5 ppbv for Rapa Nui and 3.8 ppbv for Samoa). All biomass burning sources contribute about 15–23 ppbv of CO at Rapa Nui and Samoa and account for about 25 % of the total CO in the entire troposphere of the tropical and subtropical South Pacific. This impact is also seen on tropospheric O3, to which biomass burning O3 precursor emissions contribute only a few ppbv during the burning period, while the stratosphere–troposphere exchange is the most important source of O3 for the mid troposphere of the South Pacific Ocean, contributing about 15–20 ppbv in the subtropics.

Assessment of Empirical Troposphere Model GPT3 Based on NGL's Global Troposphere Products.

Tropospheric delay is one of the major error sources in GNSS (Global Navigation Satellite Systems) positioning. Over the years, many approaches have been devised which aim at accurately modeling tropospheric delays, so-called troposphere models. Using the troposphere data of over 16,000 global stations in the last 10 years, as calculated by the Nevada Geodetic Laboratory (NGL), this paper evaluates the performance of the empirical troposphere model GPT3, which is the latest version of the GPT (Global Pressure and Temperature) series model. Owing to the large station number, long time-span and diverse station distribution, the spatiotemporal properties of the empirical model were analyzed using the average deviation (BIAS) and root mean square (RMS) error as indicators. The experimental results demonstrate that: (1) the troposphere products of NGL have the same accuracy as the IGS (International GNSS Service) products and can be used as a reference for evaluating general troposphere models. (2) The global average BIAS of the ZTD (zenith total delay) estimated by GPT3 is −0.99 cm and the global average RMS is 4.41 cm. The accuracy of the model is strongly correlated with latitude and ellipsoidal height, showing obviously seasonal variations. (3) The global average RMS of the north gradient and east gradient estimated by GPT3 is 0.77 mm and 0.73 mm, respectively, which are strongly correlated with each other, with values increasing from the equator to lower latitudes and decreasing from lower to higher latitudes.

Research on Accelerating Single-Frequency Precise Point Positioning Convergence with Atmospheric Constraint

An increasing number of researchers have conducted in-depth research on the advantages of low-cost single-frequency (SF) receivers, which can effectively use ionospheric information when compared to dual-frequency ionospheric-free combination. However, SF observations are bound to increase the unknown parameters and prolong the convergence time. It is desirable if the convergence time can be reduced by external information constraints, for example atmospheric constraints, which include ionosphere- or troposphere constraints. In this study, ionospheric delay constraints, tropospheric delay constraints, and their dual constraints were considered. Additionally, a total of 18,720 test experiments were performed. First, the nearest-neighbor extrapolation (NENE), bilinear- (BILI), bicubic- (BICU), and Junkins weighted-interpolation (JUNK) method of Global Ionospheric Map (GIM) grid products were analyzed. The statistically verified BILI in the percentage of convergence time, average convergence time, and computation time consumption of them shows a good advantage. Next, the influences of global troposphere- and ionosphere-constrained on the convergence time of SF Precise Point Positioning (PPP) were analyzed. It is verified that the ionosphere-constrained (TIC2) has significant influence on the convergence time in the horizontal and vertical components, while the troposphere-constrained (TIC1) has better effect on the convergence time in the vertical components within some thresholds. Of course, the dual constraint (TIC3) has the shortest average convergence time, which is at least 46.5% shorter in static mode and 5.4% in kinematic mode than standard SF PPP (TIC0).

The effects of lateral boundary conditions resolution for heat island studies in tropical urban of Kuala Lumpur

Lateral boundary condition (LBC) is one of the key features included in the Weather Research and Forecasting (WRF) simulation model. Nowadays, numerous LBCs were developed with various spatial (grid) and temporal resolutions for a wide range of applications. Choosing the most suitable LBCs to ensure appropriate representation of climates should be properly conducted. Thus, this paper analysed the effects of the LBC resolutions on the regional climate downscaling for heat island studies. The comparisons were made on the performance of respective LBCs to regenerate the near-surface temperature distributions within the Kuala Lumpur city. NCEP GDAS/FNL 0.25 Degree Global Tropospheric Analyses dataset with higher spatial and temporal resolution was found to perform better than the other LBC during intermonsoon season. However, both datasets were determined to give reliable representations of urban climate condition within the city as both datasets depicted close results in determining the impact of urbanization on the thermal environment.

The distribution of sea-salt aerosol in the global troposphere

Abstract. We present the first data on the concentration of sea-salt aerosol throughout most of the depth of the troposphere and over a wide range of latitudes, which were obtained during the Atmospheric Tomography (ATom) mission. Sea-salt concentrations in the upper troposphere are very small, usually less than 10 ng per standard m3 (about 10 parts per trillion by mass) and often less than 1 ng m−3. This puts stringent limits on the contribution of sea-salt aerosol to halogen and nitric acid chemistry in the upper troposphere. Within broad regions the concentration of sea-salt aerosol is roughly proportional to water vapor, supporting a dominant role for wet scavenging in removing sea-salt aerosol from the atmosphere. Concentrations of sea-salt aerosol in the winter upper troposphere are not as low as in the summer and the tropics. This is mostly a consequence of less wet scavenging in the drier, colder winter atmosphere. There is also a source of sea-salt aerosol over pack ice that is distinct from that over open water. With a well-studied and widely distributed source, sea-salt aerosol provides an excellent test of wet scavenging and vertical transport of aerosols in chemical transport models.

100 Years of Earth System Model Development

AbstractToday’s global Earth system models began as simple regional models of tropospheric weather systems. Over the past century, the physical realism of the models has steadily increased, while the scope of the models has broadened to include the global troposphere and stratosphere, the ocean, the vegetated land surface, and terrestrial ice sheets. This chapter gives an approximately chronological account of the many and profound conceptual and technological advances that made today’s models possible. For brevity, we omit any discussion of the roles of chemistry and biogeochemistry, and terrestrial ice sheets.

Has global warming already arrived?

The enhancement of the atmospheric greenhouse effect due to the increase in the atmospheric greenhouse gases is often considered as responsible for global warming (known as greenhouse hypothesis of global warming). In this context, the temperature field of global troposphere and lower stratosphere over the period 12/1978–07/2018 is explored using the recent Version 6 of the UAH MSU/AMSU global satellite temperature dataset. Our analysis did not show a consistent warming with gradual increase from low to high latitudes in both hemispheres, as it should be from the global warming theory. In addition, in the lower stratosphere the temperature cooling over both poles is lower than that over tropics and extratropics. To study further the thermal field variability we investigated the long-range correlations throughout the global lower troposphere-lower stratosphere region. The results show that the temperature field displays power-law behaviour that becomes stronger by going from the lower troposphere to the tropopause.This power-law behaviour suggests that the fluctuations in global tropospheric temperature at short intervals are positively correlated with those at longer intervals in a power-law manner. The latter, however, does not apply to global temperature in the lower stratosphere. This suggests that the investigated intrinsic properties of the lower stratospheric temperature are not related to those of the troposphere, as is expected by the global warming theory.

Changes in Global Tropospheric OH Expected as a Result of Climate Change Over the Last Several Decades

AbstractThe oxidizing capacity of the troposphere is controlled primarily by the abundance of hydroxyl radical (OH). The global mean concentration of tropospheric OH, [OH]TROP (the burden of OH in the global troposphere appropriate for calculating the lifetime of methane) inferred from measurements of methyl chloroform has remained relatively constant during the past several decades despite rising levels of methane that should have led to a decline. Here we examine other factors that may have affected [OH]TROP such as the changing values of stratospheric ozone, rising tropospheric H2O, varying burden of NOx (=NO+NO2), rising temperatures, and widening of the climatological tropics due to expansion of the Hadley cell. Our analysis suggests the positive trends in [OH]TROP due to H2O, NOx, and overhead O3, and tropical expansion are large enough (Δ [OH]TROP = +0.95 ± 0.18%/decade) to counter almost all of the expected decrease in [OH]TROP due to rising methane (Δ [OH]TROP = −1.01 ± 0.05%/decade) over the period 1980 to 2015, while variations in temperature contribute almost no trend (Δ [OH]TROP = −0.02 ± 0.02%/decade) in [OH]TROP. The approximated impact of Hadley cell expansion on [OH]TROP is also a small but not insignificant factor partially responsible for the steadiness of tropospheric oxidizing capacity over the past several decades, which free‐running models likely do not capture.

Light absorption properties of laboratory-generated tar ball particles

Abstract. Tar balls (TBs) are a specific particle type that is abundant in the global troposphere, in particular in biomass smoke plumes. These particles belong to the family of atmospheric brown carbon (BrC), which can absorb light in the visible range of the solar spectrum. Albeit TBs are typically present as individual particles in biomass smoke plumes, their absorption properties have been only indirectly inferred from field observations or calculations based on their electron energy-loss spectra. This is because in biomass smoke TBs coexist with various other particle types (e.g., organic particles with inorganic inclusions and soot, the latter emitted mainly during flaming conditions) from which they cannot be physically separated; thus, a direct experimental determination of their absorption properties is not feasible. Very recently we have demonstrated that TBs can be generated in the laboratory from droplets of wood tar that resemble atmospheric TBs in all of their observed properties. As a follow-up study, we have installed on-line instruments to our laboratory set-up, which generate pure TB particles to measure the absorption and scattering, as well as the size distribution of the particles. In addition, samples were collected for transmission electron microscopy (TEM) and total carbon (TC) analysis. The effects of experimental parameters were also studied. The mass absorption coefficients of the laboratory-generated TBs were found to be in the range of 0.8–3.0 m2 g−1 at 550 nm, with absorption Ångström exponents (AAE) between 2.7 and 3.4 (average 2.9) in the wavelength range 467–652 nm. The refractive index of TBs as derived from Mie calculations was about 1.84 − 0.21i at 550 nm. In the brown carbon continuum, these values fall closer to those of soot than to other light-absorbing species such as humic-like substances (HULIS). Considering the abundance of TBs in biomass smoke and the global magnitude of biomass burning emissions, these findings may have substantial influence on the understanding of global radiative energy fluxes.

Arctic and Antarctic cells in the troposphere

The three-cell model, including the Hadley, Ferrel, and Polar cells in each of two hemispheres, has been accepted for a long time and the strongest Hadley cell has been used to study the climate change in recent years. However, two questions, why the upper level flow of Ferrel cell does not match observations and how many cells exist in the two polar regions, still exist. Using three different reanalysis datasets for the last 30 years, this paper showed that there might be an additional cell in each of two polar regions. The analyses of meridional-vertical section streamline (MSS), meridional-mass stream function (MSF), and climatic vertical velocity provide some evidences to support the existence of the new Arctic and Antarctic cells located in the troposphere. Thus, an eight-cell model in the global troposphere is proposed in this study. The maximum intensity of the Hadley cell in the boreal winter indicated by MSF in the Northern Hemisphere (NH) is stronger than that of the Ferrel cell for about 4.8 times, so the upper level northeasterly wind of Ferrel cell is too weak to be detected when compared with the stronger southwesterly wind of the Hadley cell.

Indirect Evidence for the Presence of Secondary Phosphorus in Continental Fine Aerosol

The role of the atmosphere in the biogeochemical cycle of phosphorus (P) is generally associated with the emission of soil dust, sea-salt particles, bioaerosols and industrial aerosols. Quite independently, a reduced gaseous phosphorus compound (phosphine, PH3) was measured over various sources such as marshes and sewage plants and also in the global troposphere. Given that phosphine is a reactive gas that rapidly yields low-volatility phosphoric acid in the atmosphere, secondary aerosol formation can be an important sink that has never been considered in the global phosphorus cycle. In our study we present mass size-distribution measurements of phosphorus in aerosol samples collected at two locations in Hungary. The bimodal size distribution of phosphorus indicated two distinct formation mechanisms in the fine (d < 1 µm) and coarse modes (d > 1 µm). As expected, the mass concentration of phosphorus was dominated by the coarse particles; the contribution of fine mode phosphorus to the total was in the range of 11–61% (median 19%). The contribution of biomass burning and to a lesser extent bioaerosols to the fine mode phosphorus was inferred from measured ambient potassium (K) concentrations and P/K ratios reported for biomass smoke. It was found that biomass burning accounted for only a small fraction of fine mode phosphorus, the rest of which likely formed as secondary aerosol component from gaseous phosphine. Secondary aerosol phosphorus can be even more important in providing this essential nutrient for remote ecosystems because it is associated with fine aerosol particles which have longer residence time and thus are more prone to long-range atmospheric transport than coarse primary particles.

Conversion of Iodide to Hypoiodous Acid and Iodine in Aqueous Microdroplets Exposed to Ozone

Halides are incorporated into aerosol sea spray, where they start the catalytic destruction of ozone (O3) over the oceans and affect the global troposphere. Two intriguing environmental problems undergoing continuous research are (1) to understand how reactive gas phase molecular halogens are directly produced from inorganic halides exposed to O3 and (2) to constrain the environmental factors that control this interfacial process. This paper presents a laboratory study of the reaction of O3 at variable iodide (I(-)) concentration (0.010-100 μM) for solutions aerosolized at 25 °C, which reveal remarkable differences in the reaction intermediates and products expected in sea spray for low tropospheric [O3]. The ultrafast oxidation of I(-) by O3 at the air-water interface of microdroplets is evidenced by the appearance of hypoiodous acid (HIO), iodite (IO2(-)), iodate (IO3(-)), triiodide (I3(-)), and molecular iodine (I2). Mass spectrometry measurements reveal an enhancement (up to 28%) in the dissolution of gaseous O3 at the gas-liquid interface when increasing the concentration of NaI or NaBr from 0.010 to 100 μM. The production of iodine species such as HIO and I2 from NaI aerosolized solutions exposed to 50 ppbv O3 can occur at the air-water interface of sea spray, followed by their transfer to the gas-phase, where they contribute to the loss of tropospheric ozone.

In-cloud oxalate formation in the global troposphere: a 3-D modeling study

Abstract. Organic acids attract increasing attention as contributors to atmospheric acidity, secondary organic aerosol mass and aerosol hygroscopicity. Oxalic acid is globally the most abundant dicarboxylic acid, formed via chemical oxidation of gas-phase precursors in the aqueous phase of aerosols and droplets. Its lifecycle and atmospheric global distribution remain highly uncertain and are the focus of this study. The first global spatial and temporal distribution of oxalate, simulated using a state-of-the-art aqueous-phase chemical scheme embedded within the global 3-dimensional chemistry/transport model TM4-ECPL, is here presented. The model accounts for comprehensive gas-phase chemistry and its coupling with major aerosol constituents (including secondary organic aerosol). Model results are consistent with ambient observations of oxalate at rural and remote locations (slope = 1.16 ± 0.14, r2 = 0.36, N = 114) and suggest that aqueous-phase chemistry contributes significantly to the global atmospheric burden of secondary organic aerosol. In TM4-ECPL most oxalate is formed in-cloud and less than 5 % is produced in aerosol water. About 62 % of the oxalate is removed via wet deposition, 30 % by in-cloud reaction with hydroxyl radical, 4 % by in-cloud reaction with nitrate radical and 4 % by dry deposition. The in-cloud global oxalate net chemical production is calculated to be about 21–37 Tg yr−1 with almost 79 % originating from biogenic hydrocarbons, mainly isoprene. This condensed phase net source of oxalate in conjunction with a global mean turnover time against deposition of about 5 days, maintain oxalate's global tropospheric burden of 0.2–0.3 Tg, i.e. 0.05–0.1 Tg-C that is about 5–9 % of model-calculated water soluble organic carbon burden.

Emission factors for open and domestic biomass burning for use in atmospheric models

Abstract. Biomass burning (BB) is the second largest source of trace gases and the largest source of primary fine carbonaceous particles in the global troposphere. Many recent BB studies have provided new emission factor (EF) measurements. This is especially true for non-methane organic compounds (NMOC), which influence secondary organic aerosol (SOA) and ozone formation. New EF should improve regional to global BB emissions estimates and therefore, the input for atmospheric models. In this work we present an up-to-date, comprehensive tabulation of EF for known pyrogenic species based on measurements made in smoke that has cooled to ambient temperature, but not yet undergone significant photochemical processing. All EFs are converted to one standard form (g compound emitted per kg dry biomass burned) using the carbon mass balance method and they are categorized into 14 fuel or vegetation types. Biomass burning terminology is defined to promote consistency. We compile a large number of measurements of biomass consumption per unit area for important fire types and summarize several recent estimates of global biomass consumption by the major types of biomass burning. Post emission processes are discussed to provide a context for the emission factor concept within overall atmospheric chemistry and also highlight the potential for rapid changes relative to the scale of some models or remote sensing products. Recent work shows that individual biomass fires emit significantly more gas-phase NMOC than previously thought and that including additional NMOC can improve photochemical model performance. A detailed global estimate suggests that BB emits at least 400 Tg yr−1 of gas-phase NMOC, which is almost 3 times larger than most previous estimates. Selected recent results (e.g. measurements of HONO and the BB tracers HCN and CH3CN) are highlighted and key areas requiring future research are briefly discussed.

Spatial distributions of particle number concentrations in the global troposphere: Simulations, observations, and implications for nucleation mechanisms

Particle number concentration in the troposphere is an important parameter controlling the climate and health impacts of atmospheric aerosols. We show that nucleation rates and total particle number concentrations in the troposphere, predicted by different nucleation schemes, differ significantly. Our extensive comparisons of simulated results with land‐, ship‐, and aircraft‐based measurements indicate that, among six widely used nucleation schemes involving sulfuric acid, only the ion‐mediated nucleation (IMN) scheme can reasonably account for both absolute values (within a factor of ∼2) and spatial distributions of particle number concentrations in the whole troposphere. Binary homogeneous nucleation (BHN) schemes significantly underpredict particle number concentration in the lower troposphere (below ∼500 mbar), especially in the boundary layer over major continents (by a factor of up to ∼10). BHN is also insignificant in the upper troposphere based on a recent kinetically self‐consistent nucleation model constrained by multiple independent laboratory data. Previous conclusions about the importance of BHN in the upper troposphere should be revisited. Empirical activation and kinetic nucleation formulas significantly overpredict the particle number concentrations over tropical and subtropical oceans (by a factor of up to ∼10 in the boundary layer), and the overpredictions extend from ocean surface to around ∼400 mbar. This study represents the first comprehensive comparison of global particle number simulations with relevant measurements that have a 3‐D global spatial coverage. Our results suggest that ion‐mediated H2SO4‐H2O nucleation appears to dominate over neutral H2SO4‐H2O nucleation, not only in the lower troposphere but also in the middle and upper troposphere.

On the altitude dependence of the temperature scaling behaviour at the global troposphere

Detrended fluctuation analysis is applied to the mean monthly temperature values, over different heights of the global troposphere, during 1980–2004, to search for self-similarity properties. The results show that the tropospheric temperature anomalies obey persistent long-range power-law correlations for time-scales longer than about four months and shorter than about six years. This suggests that the temperature fluctuations over small time periods (i.e. a few months) are related to those over longer time periods (i.e. a few years). In addition, the long-range power-law persistence in the global tropospheric temperature fluctuations becomes stronger as the altitude increases.

Differences between trends in atmospheric CO2 and the reported trends in anthropogenic CO2 emissions

Averaged annual accumulation of CO2 in the atmosphere, dCa/dt, has been slowing from peak growth in 2002/2003 associated with anomalous climate-induced emissions at high northern latitudes. This slowing is widespread but determined with greatest certainty in the largest well-mixed portion of the global troposphere (30◦S–90◦S). We rely on atmospheric mixing for global integration and selection of atmospheric data for spatial representativeness. Prior to 2002/2003, after empirical adjustment for perturbations associated with ENSO and volcanic activity (EV), dCa/dt increases are well represented by linear regression, using direct monitoring records from 1990 or 1965, also from preindustrial times using archived air. In contrast,modelled atmospheric trends due to reported emissions dCE/dt (assuming historically consistent oceanic and terrestrial uptake mechanisms), agree with dCa/dt or dCa/dt-EV up until 1990, are near-stable through the 1990s and increase by 29% between 2000 and 2008. Using atmospheric constraints based on trends in both dCa/dt-EV and interhemispheric gradient, the differences between trends in dCE/dt and atmospheric CO2 growth are most simply explained as an artefact of underestimating 1994–2003 emissions by around 6%. This is achieved with a near constant post-1965 airborne fraction; otherwise unusually complicated sink changes are required for the period.