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Modelling molecular iodine emissions in a coastal marine environment: the link to new particle formation

A model of iodine chemistry in the marine boundary layer (MBL) has been used to investigate the impact of daytime coastal emissions of molecular iodine (I2). The model contains a full treatment of gas-phase iodine chemistry, combined with a description of the nucleation and growth, by condensation and coagulation, of iodine oxide nano-particles. In-situ measurements of coastal emissions of I2 made by the broadband cavity ring-down spectroscopy (BBCRDS) and inductively coupled plasma-mass spectrometry (ICP/MS) techniques are presented and compared to long path differential optical absorption spectroscopy (DOAS) observations of I2 at Mace Head, Ireland. Simultaneous measurements of enhanced I2 emissions and particle bursts show that I2 is almost certainly the main precursor of new particles at this coastal location. The ratio of IO to I2 predicted by the model indicates that the iodine species observed by the DOAS are concentrated over a short distance (about 8% of the 4.2 km light path) consistent with the intertidal zone, bringing them into good agreement with the I2 measurements made by the two in-situ techniques. The model is then used to investigate the effect of iodine emission on ozone depletion, and the production of new particles and their evolution to form stable cloud condensation nuclei (CCN).
Large-scale atmospheric circulation biases and changes in global climate model simulations and their importance for climate change in Central Europe

The quality of global sea level pressure patterns has been assessed for simulations by 23 coupled climate models. Most models showed high pattern correlations. With respect to the explained spatial variance, many models showed serious large-scale deficiencies, especially at mid-latitudes. Five models performed well at all latitudes and for each month of the year. Three models had a reasonable skill. We selected the five models with the best pressure patterns for a more detailed assessment of their simulations of the climate in Central Europe. We analysed observations and simulations of monthly mean geostrophic flow indices and of monthly mean temperature and precipitation. We used three geostrophic flow indices: the west component and south component of the geostrophic wind at the surface and the geostrophic vorticity. We found that circulation biases were important, and affected precipitation in particular. Apart from these circulation biases, the models showed other biases in temperature and precipitation, which were for some models larger than the circulation induced biases. For the 21st century the five models simulated quite different changes in circulation, precipitation and temperature. Precipitation changes appear to be primarily caused by circulation changes. Since the models show widely different circulation changes, especially in late summer, precipitation changes vary widely between the models as well. Some models simulate severe drying in late summer, while one model simulates significant precipitation increases in late summer. With respect to the mean temperature the circulation changes were important, but not dominant. However, changes in the distribution of monthly mean temperatures, do show large indirect influences of circulation changes. Especially in late summer, two models simulate very strong warming of warm months, which can be attributed to severe summer drying in the simulations by these models. The models differ also significantly in the simulated warming of cold winter months. Finally, the models simulate rather different changes in North Atlantic sea surface temperature, which is likely to impact on changes in temperature and precipitation. These results imply that several important aspects of climate change in Central Europe are highly uncertain. Other aspects of the simulated climate change appear to be more robust. All models simulate significant warming all year round and an increase in precipitation in the winter half-year.
Characterization of ambient aerosols in Mexico City during the MCMA-2003 campaign with Aerosol Mass Spectrometry: results from the CENICA Supersite

An Aerodyne Aerosol Mass Spectrometer (AMS) was deployed at the CENICA Supersite, during the Mexico City Metropolitan Area field study (MCMA-2003) from 31 March-4 May 2003 to investigate particle concentrations, sources, and processes. The AMS provides real time information on mass concentration and composition of the non-refractory species in particulate matter less than 1 µm (NR-PM1) with high time and size-resolution. In order to account for the refractory material in the aerosol, we also present estimates of Black Carbon (BC) using an aethalometer and an estimate of the aerosol soil component obtained from Proton-Induced X-ray Emission Spectrometry (PIXE) analysis of impactor substrates. Comparisons of AMS + BC + soil mass concentration with other collocated particle instruments (a LASAIR Optical Particle Counter, a PM2.5 Tapered Element Oscillating Microbalance (TEOM), and a PM2.5 DustTrak Aerosol Monitor) show that the AMS + BC + soil mass concentration is consistent with the total PM2.5 mass concentration during MCMA-2003 within the combined uncertainties. In Mexico City, the organic fraction of the estimated PM2.5 at CENICA represents, on average, 54.6% (standard deviation σ=10%) of the mass, with the rest consisting of inorganic compounds (mainly ammonium nitrate and sulfate/ammonium salts), BC, and soil. Inorganic compounds represent 27.5% of PM2.5 (σ=10%); BC mass concentration is about 11% (σ=4%); while soil represents about 6.9% (σ=4%). Size distributions are presented for the AMS species; they show an accumulation mode that contains mainly oxygenated organic and secondary inorganic compounds. The organic size distributions also contain a small organic particle mode that is likely indicative of fresh traffic emissions; small particle modes exist for the inorganic species as well. Evidence suggests that the organic and inorganic species are not always internally mixed, especially in the small modes. The aerosol seems to be neutralized most of the time; however, there were some periods when there was not enough ammonium to completely neutralize the nitrate, chloride and sulfate present. The diurnal cycle and size distributions of nitrate suggest local photochemical production. On the other hand, sulfate appears to be produced on a regional scale. There are indications of new particle formation and growth events when concentrations of SO2 were high. Although the sources of chloride are not clear, this species seems to condense as ammonium chloride early in the morning and to evaporate as the temperature increases and RH decreases. The total and speciated mass concentrations and diurnal cycles measured during MCMA-2003 are similar to measurements during a previous field campaign at a nearby location.
Constraining the total aerosol indirect effect in the LMDZ and ECHAM4 GCMs using MODIS satellite data

Aerosol indirect effects are considered to be the most uncertain yet important anthropogenic forcing of climate change. The goal of the present study is to reduce this uncertainty by constraining two different general circulation models (LMDZ and ECHAM4) with satellite data. We build a statistical relationship between cloud droplet number concentration and the optical depth of the fine aerosol mode as a measure of the aerosol indirect effect using MODerate Resolution Imaging Spectroradiometer (MODIS) satellite data, and constrain the model parameterizations to match this relationship. We include here "empirical" formulations for the cloud albedo effect as well as parameterizations of the cloud lifetime effect. When fitting the model parameterizations to the satellite data, consistently in both models, the radiative forcing by the combined aerosol indirect effect is reduced considerably, down to −0.5 and −0.3 Wm−2, for LMDZ and ECHAM4, respectively.
Global estimation of burned area using MODIS active fire observations

We present a method for estimating monthly burned area globally at 1° spatial resolution using Terra MODIS data and ancillary vegetation cover information. Using regression trees constructed for 14 different global regions, MODIS active fire observations were calibrated to burned area estimates derived from 500-m MODIS imagery based on the assumption that burned area is proportional to counts of fire pixels. Unlike earlier methods, we allow the constant of proportionality to vary as a function of tree and herbaceous vegetation cover, and the mean size of monthly cumulative fire-pixel clusters. In areas undergoing active deforestation, we implemented a subsequent correction based on tree cover information and a simple measure of fire persistence. Regions showing good agreement between predicted and observed burned area included Boreal Asia, Central Asia, Europe, and Temperate North America, where the estimates produced by the regression trees were relatively accurate and precise. Poorest agreement was found for southern-hemisphere South America, where predicted values of burned area are both inaccurate and imprecise; this is most likely a consequence of multiple factors that include extremely persistent cloud cover, and lower quality of the 500-m burned area maps used for calibration. Application of our approach to the nine remaining regions yielded comparatively accurate, but less precise, estimates of monthly burned area. We applied the regional regression trees to the entire archive of Terra MODIS fire data to produce a monthly global burned area data set spanning late 2000 through mid-2005. Annual totals derived from this approach showed good agreement with independent annual estimates available for nine Canadian provinces, the United States, and Russia. With our data set we estimate the global annual burned area for the years 2001-2004 to vary between 2.97 million and 3.74 million km2, with the maximum occurring in 2001. These coarse-resolution burned area estimates may serve as a useful interim product until long-term burned area data sets from multiple sensors and retrieval approaches become available.
Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project

Size-segregated aerosol samples were collected during the QUEST field campaign at Hyytiälä, a boreal forest site in Southern Finland, during spring 2003. Aerosol samples were selectively collected during both particle formation events and periods in which no particle formation occurred. A comprehensive characterisation of the aerosol chemical properties (water-soluble inorganic and organic fraction) and an analysis of the relevant meteorological parameters revealed how aerosol chemistry and meteorology combine to determine a favorable "environment" for new particle formation. The results indicated that all events, typically favored during northerly air mass advection, were background aerosols (total mass concentrations range between 1.97 and 4.31 µg m-3), with an increasingly pronounced marine character as the northerly air flow arrived progressively from the west and, in contrast, with a moderate SO2-pollution influence as the air arrived from more easterly directions. Conversely, the non-event aerosol, transported from the south, exhibited the chemical features of European continental sites, with a marked increase in the concentrations of all major anthropogenic aerosol constituents. The higher non-event mass concentration (total mass concentrations range between 6.88 and 16.30 µg m-3) and, thus, a larger surface area, tended to suppress new particle formation, more efficiently depleting potential gaseous precursors for nucleation. The analysis of water-soluble organic compounds showed that clean nucleation episodes were dominated by aliphatic biogenic species, while non-events were characterised by a large abundance of anthropogenic oxygenated species. Interestingly, a significant content of α-pinene photo-oxidation products was observed in the events aerosol, accounting for, on average, 72% of their WSOC; while only moderate amounts of these species were found in the non-event aerosol. If the organic vapors condensing onto accumulation mode particles are responsible also for the growth of newly formed thermodynamically stable clusters, our finding allows one to postulate that, at the site, α-pinene photo-oxidation products (and probably also photo-oxidation products from other terpenes) are the most likely species to contribute to the growth of nanometer-sized particles.
A new inorganic atmospheric aerosol phase equilibrium model (UHAERO)

A variety of thermodynamic models have been developed to predict inorganic gas-aerosol equilibrium. To achieve computational efficiency a number of the models rely on a priori specification of the phases present in certain relative humidity regimes. Presented here is a new computational model, named UHAERO, that is both efficient and rigorously computes phase behavior without any a priori specification. The computational implementation is based on minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. The mathematical details of the solution are given elsewhere. The model computes deliquescence behavior without any a priori specification of the relative humidities of deliquescence. Also included in the model is a formulation based on classical theory of nucleation kinetics that predicts crystallization behavior. Detailed phase diagrams of the sulfate/nitrate/ammonium/water system are presented as a function of relative humidity at 298.15 K over the complete space of composition.
Atmospheric number size distributions of soot particles and estimation of emission factors

Number fractions of externally mixed particles of four different sizes (30, 50, 80, and 150 nm in diameter) were measured using a Volatility Tandem DMA. The system was operated in a street canyon (Eisenbahnstrasse, EI) and at an urban background site (Institute for Tropospheric Research, IfT), both in the city of Leipzig, Germany as well as at a rural site (Melpitz (ME), a village near Leipzig). Intensive campaigns of 3–5 weeks each took place in summer 2003 as well as in winter 2003/04. The data set thus obtained provides mean number fractions of externally mixed soot particles of atmospheric aerosols in differently polluted areas and different seasons (e.g. at 80 nm on working days, 60% (EI), 22% (IfT), and 6% (ME) in summer and 26% (IfT), and 13% (ME) in winter). Furthermore, a new method is used to calculate the size distribution of these externally mixed soot particles from parallel number size distribution measurements. A decrease of the externally mixed soot fraction with decreasing urbanity and a diurnal variation linked to the daily traffic changes demonstrate, that the traffic emissions have a significant impact on the soot fraction in urban areas. This influence becomes less in rural areas, due to atmospheric mixing and transformation processes. For estimating the source strength of soot particles emitted by vehicles (veh), soot particle emission factors were calculated using the Operational Street Pollution Model (OSPM). The emission factor for an average vehicle was found to be (1.5±0.4)·1014 #(km·veh). The separation of the emission factor into passenger cars ((5.8±2)·1013} #(km·veh)) and trucks ((2.5±0.9)·1015 #(km·veh)) yielded in a 40-times higher emission factor for trucks compared to passenger cars.
Tropopause referenced ozone climatology and inter-annual variability (1994–2003) from the MOZAIC programme

The MOZAIC programme collects ozone and water vapour data using automatic equipment installed on board five long-range Airbus A340 aircraft flying regularly all over the world since August 1994. Those measurements made between September 1994 and August 1996 allowed the first accurate ozone climatology at 9–12 km altitude to be generated. The seasonal variability of the tropopause height has always provided a problem when constructing climatologies in this region. To remove any signal from the seasonal and synoptic scale variability in tropopause height we have chosen in this further study of these and subsequent data to reference our climatology to the altitude of the tropopause. We define the tropopause as a mixing zone 30 hPa thick across the 2 pvu potential vorticity surface. A new ozone climatology is now available for levels characteristic of the upper troposphere (UT) and the lower stratosphere (LS) regardless of the seasonal variations of the tropopause over the period 1994–2003. Moreover, this new presentation has allowed an estimation of the monthly mean climatological ozone concentration at the tropopause showing a sine seasonal variation with a maximum in May (120 ppbv) and a minimum in November (65 ppbv). Besides, we present a first assessment of the inter-annual variability of ozone in this particular critical region. The overall increase in the UTLS is about 1%/yr for the 9 years sampled. However, enhanced concentrations about 10–15 % higher than the other years were recorded in 1998 and 1999 in both the UT and the LS. This so-called "1998–1999 anomaly" may be attributed to a combination of different processes involving large scale modes of atmospheric variability, circulation features and local or global pollution, but the most dominant one seems to involve the variability of the North Atlantic Oscillation (NAO) as we find a strong positive correlation (above 0.60) between ozone recorded in the upper troposphere and the NAO index. A strong anti-correlation is also found between ozone and the extremes of the Northern Annular Mode (NAM) index, attributing the lower stratospheric variability to dynamical anomalies. Finally this analysis highlights the coupling between the troposphere, at least the upper one, and the stratosphere, at least the lower one.
Mid-latitude tropospheric ozone columns from the MOZAIC program: climatology and interannual variability

Several thousands of ozone vertical profiles collected in the course of the MOZAIC programme (Measurements of Ozone, Water Vapour, Carbon Monoxide and Nitrogen Oxides by In-Service Airbus Aircraft) from August 1994 to February 2002 are investigated to bring out climatological and interannual variability aspects. The study is centred on the most frequently visited MOZAIC airports, i.e. Frankfurt (Germany), Paris (France), New York (USA) and the cluster of Tokyo, Nagoya and Osaka (Japan). The analysis focuses on the vertical integration of ozone from the ground to the dynamical tropopause and the vertical integration of stratospheric-origin ozone throughout the troposphere. The characteristics of the MOZAIC profiles: frequency of flights, accuracy, precision, and depth of the troposphere observed, are presented. The climatological analysis shows that the Tropospheric Ozone Column (TOC) seasonal cycle ranges from a wintertime minimum at all four stations to a spring-summer maximum in Frankfurt, Paris, and New York. Over Japan, the maximum occurs in spring presumably because of the earlier springtime sun. The incursion of monsoon air masses into the boundary layer and into the mid troposphere then steeply diminishes the summertime value. Boundary layer contributions to the TOC are 10% higher in New York than in Frankfurt and Paris during spring and summer, and are 10% higher in Japan than in New York, Frankfurt and Paris during autumn and early spring. Local and remote anthropogenic emissions, and biomass burning over upstream regions of Asia may be responsible for the larger low- and mid-tropospheric contributions to the tropospheric ozone column over Japan throughout the year except during the summer-monsoon season. A simple Lagrangian analysis has shown that a minimum of 10% of the TOC is of stratospheric-origin throughout the year. Investigation of the short-term trends of the TOC over the period 1995–2001 shows a linear increase 0.7%/year in Frankfurt, 0.8%/year in Japan, 1.1%/year in New York and 1.6%/year in Paris for the reduced 1995–1999 period. Dominant ingredients of these positive short-term trends are the continuous increase of wintertime tropospheric ozone columns from 1996 to 1999 and the positive contributions of the mid troposphere whatever the season.