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Will climate change increase ozone depletion from low-energy-electron precipitation?

We investigate the effects of a strengthened stratospheric/mesospheric residual circulation on the transport of nitric oxide (NO) produced by energetic particle precipitation. During periods of high geomagnetic activity, energetic electron precipitation (EEP) is responsible for winter time ozone loss in the polar middle atmosphere between 1 and 6 hPa. However, as climate change is expected to increase the strength of the Brewer-Dobson circulation including extratropical downwelling, the enhancements of EEP NOx concentrations are expected to be transported to lower altitudes in extratropical regions, becoming more significant in the ozone budget. Changes in the mesospheric residual circulation are also considered. We use simulations with the chemistry climate model system EMAC to compare present day effects of EEP NOx with expected effects in a climate change scenario for the year 2100. In years of strong geomagnetic activity, similar to that observed in 2003, an additional polar ozone loss of up to 0.4 μmol/mol at 5 hPa is found in the Southern Hemisphere. However, this would be approximately compensated by an ozone enhancement originating from a stronger poleward transport of ozone from lower latitudes caused by a strengthened Brewer-Dobson circulation, as well as by slower photochemical ozone loss reactions in a stratosphere cooled by risen greenhouse gas concentrations. In the Northern Hemisphere the EEP NOx effect appears to lose importance due to the different nature of the climate-change induced circulation changes.
Updated African biomass burning emission inventories in the framework of the AMMA-IDAF program, with an evaluation of combustion aerosols

African biomass burning emission inventories for gaseous and particulate species have been constructed at a resolution of 1 km by 1km with daily coverage for the 2000–2007 period. These inventories are higher than the GFED2 inventories, which are currently widely in use. Evaluation specifically focusing on combustion aerosol has been carried out with the ORISAM-TM4 global chemistry transport model which includes a detailed aerosol module. This paper compares modeled results with measurements of surface BC concentrations and scattering coefficients from the AMMA Enhanced Observations period, aerosol optical depths and single scattering albedo from AERONET sunphotometers, LIDAR vertical distributions of extinction coefficients as well as satellite data. Aerosol seasonal and interannual evolutions over the 2004–2007 period observed at regional scale and more specifically at the Djougou (Benin) and Banizoumbou (Niger) AMMA/IDAF sites are well reproduced by our global model, indicating that our biomass burning emission inventory appears reasonable.
Ozone production during the field campaign RISFEX 2003 in the sea of Japan: analysis of sensitivity and behaviour based on an improved indicator

The ratio Φ=kHC+OH[HC]/kNOx+OH[NOx] is used as an indicator for the sensitivity of ozone production (P(O3)) to HC and NOx in the field campaign RISFEX 2003 (RIShiri Fall EXperiment 2003) at Rishiri Island (45.07° N, 141.12° E, and 35 m a.s.l.) in the sea of Japan during September 2003. Four different sensitivity regimes are obtained based on the indicator. The sensitivity is found to show a distinctive pattern in each regime. In Regime I (Φ<1), P(O3) almost linearly increases with increasing HC and almost linearly decreases with increasing NOx. In Regime II (1<Φ<9 ± 5), there is a less-than-linear increase in P(O3) with HC and a less-than-linear decrease with NOx. P(O3) less-than-linearly increases with both HC and NOx in Regime III (9 ± 5<Φ<45 ± 7), and near linearly increases with NOx and is nearly constant with increasing HC in Regime IV (Φ>45 ± 7). During the campaign, 91 percent of P(O3) data appear in Regime III and IV, indicating that NOx is a limiting factor of ozone production. Hence, it may be an efficient strategy to control NOx emission for ozone abatement at the site. Comparisons between the observed P(O3) and the ones modelled have represented general agreement. However, the model tends to underestimate P(O3) in Regime II, implying that an important source of peroxy radicals is possibly missed. In Regime IV, the modelled P(O3) is systematically larger than the measured one under a low j(O1D) condition, which may be caused by the over-estimated yields of peroxy radicals from the reactions of monoterpenes with ozone. A budget analysis indicates that sensitivity of P(O3) is declining with HC and enhancing with NO when the condition shifts from Regime II to Regime IV, which is also observed through the analysis of P(O3) sensitivity using Φ. Sensitivity studies for P(O3) are conducted to determine the effect of NOx and monoterpenes on ozone production and the conclusions are very consistent with those derived from the indicator. This study demonstrates that the ratio Φ could be a useful index to ascertain the sensitivity of P(O3) to HC and NOx in the clean marine boundary layer.
Seasonal variation and spatial distribution of carbonaceous aerosols in Taiwan

To investigate the physico-chemical properties of aerosols in Taiwan, an observation network was initiated in 2003. In this work, the measurements of the mass concentration and carbonaceous composition of PM10 and PM2.5 are presented. Analysis on the data collected in the first 5-years, from 2003 to 2007, showed that there was a very strong contrast in the aerosol concentration and composition between the rural and the urban/suburban stations. The five-year means of EC at the respective stations ranged from 0.9±0.04 to 4.2±0.1 μgC m−3. In rural areas, EC accounted for 2–3% of PM10 and 3–5% of PM2.5 mass loadings, comparing to 4–6% of PM10 and 4–8% of PM2.5 in the urban areas. It was found that the spatial distribution of EC was consistent with CO and NOx across the network stations, suggesting that the levels of EC over Taiwan were dominated by local sources. The measured OC was split into POC and SOC counterparts following the EC tracer method. Five-year means of POC ranged from 1.8±0.1 to 9.7±0.2 μgC m−3 among the stations. It was estimated that the POM contributed 5–17% of PM10 and 7–18% of PM2.5 in Taiwan. On the other hand, the five-year means of SOC ranged from 1.5±0.1 to 3.8±.3 μgC m−3. The mass fractions of SOM were estimated to be 9–19% in PM10 and 14–22% in PM2.5. The results showed that the SOC did not exhibit significant urban-rural contrast as did the POC and EC. A significant cross-station correlation between SOC and total oxidant was observed, which means the spatial distribution of SOC in Taiwan was dominated by the oxidant mixing ratio. Besides, correlation was also found between SOC and particulate nitrate, implying that the precursors of SOA were mainly from local anthropogenic sources. In addition to the spatial distribution, the carbonaceous aerosols also exhibited distinct seasonality. In northern Taiwan, the concentrations of all the three carbonaceous components (EC, POC, and SOC) reached their respective minima in the fall season. POC and EC increased drastically in winter and peaked in spring, whereas the SOC was characterized by a bimodal pattern with the maximal concentration in winter and a second mode in summertime. In southern Taiwan, minimal levels of POC and EC occurred consistently in summer and the maxima were observed in winter, whereas the SOC peaked in summer and declined in wintertime. The discrepancies in the seasonality of carbonaceous aerosols between northern and southern Taiwan were most likely caused by the seasonal meteorological settings that dominated the dispersion of air pollutants. Moreover, it was inferred that the Asian pollution outbreaks could have shifted the seasonal maxima of air pollutants from winter to spring in the northern Taiwan, and that the increases in biogenic SOA precursors and the enhancement in SOA yield were responsible for the elevated SOC concentrations in summer.
Aircraft observations of enhancement and depletion of black carbon mass in the springtime Arctic

Understanding the processes controlling black carbon (BC) in the Arctic is crucial for evaluating the impact of anthropogenic and natural sources of BC on Arctic climate. Vertical profiles of BC mass loadings were observed from the surface to near 7-km altitude in April 2008 using a Single-Particle Soot Photometer (SP2) during flights on the NOAA WP-3D research aircraft from Fairbanks, Alaska. These measurements were conducted during the NOAA-sponsored Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) project. In the free troposphere, the Arctic air mass was influenced by long-range transport from biomass-burning and anthropogenic source regions at lower latitudes especially during the latter part of the campaign. Average BC mass mixing ratios peaked at about 150 ng BC (kg dry air )−1 near 5.5 km altitude in the aged Arctic air mass and 250 ng kg−1 at 4.5 km in biomass-burning influenced air. BC mass loadings were enhanced by up to a factor of 5 in biomass-burning influenced air compared to the aged Arctic air mass. At the bottom of some of the profiles, positive vertical gradients in BC were observed over the sea-ice. The vertical profiles generally occurred in the vicinity of open leads in the sea-ice. In the aged Arctic air mass, BC mass loadings more than doubled with increasing altitude within the ABL and across the boundary layer transition while carbon monoxide (CO) remained constant. This is evidence for depletion of BC mass in the ABL. BC mass loadings were positively correlated with O3 in ozone depletion events (ODEs) for all the observations in the ABL. Since bromine catalytically destroys ozone in the ABL after being released as molecular bromine in regions of new sea-ice formation at the surface, the BC–O3 correlation suggests that BC particles were removed by a surface process such as dry deposition. We develop a box model to estimate the dry deposition flux of BC mass to the snow constrained by the vertical profiles of BC mass in the ABL. Open leads in the sea-ice may increase vertical mixing and entrainment of pollution from the free troposphere possibly enhancing the deposition of BC aerosol to the snow.
Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: comparison of measurements with the box model MECCA

As a major source region of the hydroxyl radical OH, the Tropics largely control the oxidation capacity of the atmosphere on a global scale. However, emissions of hydrocarbons from the tropical rainforest that react rapidly with OH can potentially deplete the amount of OH and thereby reduce the oxidation capacity. The airborne GABRIEL field campaign in equatorial South America (Suriname) in October 2005 investigated the influence of the tropical rainforest on the HOx budget (HOx = OH + HO2). The first observations of OH and HO2 over a tropical rainforest are compared to steady state concentrations calculated with the atmospheric chemistry box model MECCA. The important precursors and sinks for HOx chemistry, measured during the campaign, are used as constraining parameters for the simulation of OH and HO2. Significant underestimations of HOx are found by the model over land during the afternoon, with mean ratios of observation to model of 12.2 ± 3.5 and 4.1 ± 1.4 for OH and HO2, respectively. The discrepancy between measurements and simulation results is correlated to the abundance of isoprene. While for low isoprene mixing ratios (above ocean or at altitudes >3 km), observation and simulation agree fairly well, for mixing ratios >200 pptV (<3 km over the rainforest) the model tends to underestimate the HOx observations as a function of isoprene. Box model simulations have been performed with the condensed chemical mechanism of MECCA and with the detailed isoprene reaction scheme of MCM, resulting in similar results for HOx concentrations. Simulations with constrained HO2 concentrations show that the conversion from HO2 to OH in the model is too low. However, by neglecting the isoprene chemistry in the model, observations and simulations agree much better. An OH source similar to the strength of the OH sink via isoprene chemistry is needed in the model to resolve the discrepancy. A possible explanation is that the oxidation of isoprene by OH not only dominates the removal of OH but also produces it in a similar amount. Several additional reactions which directly produce OH have been implemented into the box model, suggesting that upper limits in producing OH are still not able to reproduce the observations (improvement by factors of ≈2.4 and ≈2 for OH and HO2, respectively). We determine that OH has to be recycled to 94% instead of the simulated 38% to match the observations, which is most likely to happen in the isoprene degradation process, otherwise additional sources are required.
Sub-10 nm particle growth by vapor condensation – effects of vapor molecule size and particle thermal speed

The growth of freshly formed nanoparticles has been investigated. A new analytical expression based on a recently developed exact solution for the condensational growth rate has been derived. Based on the new growth rate, a new approximate but accurate analytical expression for growth time has been derived. The expression includes transition regime effects on growth, molecule size effects on the collision cross section and particle thermal speed effects on the relative collisional speeds – the last two of which are typically neglected, but may have significant effects when dealing with the growth of freshly nucleated particles. To demonstrate the use of the derived expressions, the contribution of sulphuric acid and organic compounds on sub 3 nm and sub 10 nm particle growth rates has been studied. For sulphuric acid also the effect of hydration as function of relative humidity has been taken into account. According to the new expression the sulphuric acid concentration needed for 1 nm/h growth in sub 3 nm range is ca. 1.5×107 cm−3, which is a factor of 1.5 smaller than values typically used in aerosol physics based on standard model in kinetic regime.
Nitrogen oxides and PAN in plumes from boreal fires during ARCTAS-B and their impact on ozone: an integrated analysis of aircraft and satellite observations

We determine enhancement ratios for NOx, PAN, and other NOy species from boreal biomass burning using aircraft data obtained during the ARCTAS-B campaign and examine the impact of these emissions on tropospheric ozone in the Arctic. We find an initial emission factor for NOx of 1.06 g NO per kg dry matter (DM) burned, much lower than previous observations of boreal plumes, and also one third the value recommended for extratropical fires. Our analysis provides the first observational confirmation of rapid PAN formation in a boreal smoke plume, with 40% of the initial NOx emissions being converted to PAN in the first few hours after emission. We find little clear evidence for ozone formation in the boreal smoke plumes during ARCTAS-B in either aircraft or satellite observations, or in model simulations. Only a third of the smoke plumes observed by the NASA DC8 showed a correlation between ozone and CO, and ozone was depleted in the plumes as often as it was enhanced. Special observations from the Tropospheric Emission Spectrometer (TES) also show little evidence for enhanced ozone in boreal smoke plumes between 15 June and 15 July 2008. Of the 22 plumes observed by TES, only 4 showed ozone increasing within the smoke plumes, and even in those cases it was unclear that the increase was caused by fire emissions. Using the GEOS-Chem atmospheric chemistry model, we show that boreal fires during ARCTAS-B had little impact on the median ozone profile measured over Canada, and had little impact on ozone within the smoke plumes observed by TES.
Thermodynamics of climate change: generalized sensitivities

Using a recent theoretical approach, we study how global warming impacts the thermodynamics of the climate system by performing experiments with a simplified yet Earth-like climate model. The intensity of the Lorenz energy cycle, the Carnot efficiency, the material entropy production, and the degree of irreversibility of the system change monotonically with the CO2 concentration. Moreover, these quantities feature an approximately linear behaviour with respect to the logarithm of the CO2 concentration in a relatively wide range. These generalized sensitivities suggest that the climate becomes less efficient, more irreversible, and features higher entropy production as it becomes warmer, with changes in the latent heat fluxes playing a predominant role. These results may be of help for explaining recent findings obtained with state of the art climate models regarding how increases in CO2 concentration impact the vertical stratification of the tropical and extratropical atmosphere and the position of the storm tracks.
A model study on the influence of overshooting convection on TTL water vapour

Overshooting deep convection that penetrates into the Tropical Tropopause Layer (TTL) is thought to have an important role in regulating the water vapour content of this region. Yet, the net effect of such convection and the dominant mechanisms remain unclear. This study uses two idealised three-dimensional cloud-resolving model simulations to examine the influence of overshooting convection on water vapour when it penetrates into two different TTL environments, one supersaturated and the other subsaturated with respect to ice. These simulations show that the overshooting convection plays a direct role in driving the ambient environment towards ice saturation through either net moistening (subsaturated TTL) or net dehydration (supersaturated TTL). Moreover, in these cases the extent of dehydration in supersaturated conditions is greater than the moistening in subsaturated conditions. With the aid of modelled passive tracers, the relative roles of transport, mixing and ice microphysics are assessed; ultimately, ice sublimation and scavenging processes play the most important role in defining the different TTL relative humidity tendencies. In addition, significant moistening in both cases is modelled well into the subsaturated tropical lower stratosphere (up to 450 K), even though the overshooting turrets only reach approximately 420 K. It is shown that this moistening is the result of jumping cirrus, which is induced by the localised upward transport and mixing of TTL air following the collapse of the overshooting turret.