H. Cachier

A global three‐dimensional model study of carbonaceous aerosols

We have developed detailed emission inventories for the amount of both black and organic carbon particles from biomass burning sources (wood fuel, charcoal burning, dung, charcoal production, agricultural, savanna and forest fires). We have also estimated an inventory for organic carbon particles from fossil fuel burning and urban activities from an existing inventory for fossil fuel sources of black carbon. We also provide an estimate for the natural source of organic matter. These emissions have been used together with our global aerosol model to study the global distribution of carbonaceous aerosols. The accuracy of the inventories and the model formulation has been tested by comparing the model simulations of carbonaceous aerosols in the atmosphere and in precipitation with observations reported in the literature. For most locations and seasons, the predicted concentrations are in reasonable agreement with the observations, although the model underpredicts black carbon concentrations in polar regions. The predicted concentrations in remote areas are extremely sensitive to both the rate of removal by wet deposition and the height of injection of the aerosols. Finally, a global map of the aerosol single scattering albedo was developed from the simulated carbonaceous particle distribution and a previously developed model for aerosol sulfates. The computed aerosol single scattering albedos compare well with observations, suggesting that most of the important aerosol species have been included in the model. For most locations and seasons, the single scattering albedo is larger than 0.85, indicating that these aerosols, in general, lead to a net cooling.

Construction of a 1° × 1° fossil fuel emission data set for carbonaceous aerosol and implementation and radiative impact in the ECHAM4 model

Global-scale emissions of carbonaceous aerosol from fossil fuel usage have been calculated with a resolution of 1° × 1°. Emission factors for black and organic carbon have been gathered from the literature and applied to domestic, transport, and industrial combustion of various fuel types. In addition, allowance has been made for the level of development when calculating emissions from a country. Emissions have been calculated for 185 countries for the domestic, industrial, and transport sectors using a fuel usage database published by the United Nations [1993]. Some inconsistencies were found for a small number of countries with regard to the distribution of fuel usage between the industrial and domestic sectors. Care has been taken to correct for this using data from the fuel use database for the period 1970–1990. Emissions based on total particulate matter (TPM) and submicron emission factors have been calculated. Global emissions for 1984 of black carbon total 6.4 TgC yr−1 and organic carbon emissions of 10.1 TgC yr−1 were found using bulk aerosol emission factors, while global black carbon emissions of 5.1 TgC yr−1 and organic carbon emissions of 7.0 TgC yr−1 were found using submicron emission factors. Use of the database is quite flexible and can be easily updated as emission factor data are updated. There is at least a factor of 2 uncertainty in the derived emissions due to the lack of exactly appropriate emission data. The emission fields have been introduced into the ECHAM4 atmospheric general circulation model and run for 5 model years. Monthly mean model results are compared to measurements in regions influenced by anthropogenic fossil fuel emissions. The resultant aerosol fields have been used to calculate the instantaneous solar radiative forcing at the top of the troposphere due to an external mixture of fossil fuel derived black carbon and organic carbon aerosol. Column burdens of 0.143 mgBC m−2 and 0.170 mgOC m−2 were calculated. Because of secondary production of organic carbon aerosol, it is recommended that the burden of organic carbon aerosol be doubled to 0.341 mgOC m−2. The resultant forcing when clouds are included is +0.173 W m−2 for black carbon and −0.024 W m−2 for organic carbon (×2) as a global annual average. The results are compared to previous works, and the differences are discussed.

Optical and thermal measurements of black carbon aerosol content in different environments: Variation of the specific attenuation cross-section, sigma (σ)

In optical analysers devoted to the analysis of atmospheric black carbon concentration, the specific attenuation cross-section, σ is the factor used to convert the attenuation of a light beam due to the absorption of aerosols deposited on a filter into their black carbon content. We have tried to gain further insight for a suitable choice of sigma value, using both optical analysis (with an aethalometer) and thermal analysis of black carbon aerosols and comparison of the two sets of results. Samples which were investigated originate from varying environments, including suburban areas, tropical areas where biomass burning was prevalent and from more remote locations. In a given type of atmospheric environment, σ values are found to be constant. However, σ displays an important variability (range: 5–20 m2 g−1) which may be related to the variability of the aerosol mix (internal or external mixture) and the aging of the atmospheric particulate phase. Our results quote unambiguously the need for a modulated calibration of optical analysers depending on the type of atmospheric environments which are studied. They suggest the need to reconsider carefully the black carbon data obtained at remote locations.

Aerosol emissions by tropical forest and savanna biomass burning: Characteristic trace elements and fluxes

Aerosol particles were collected during the dry season in the amazonian forest and in African and Brazilian savannas. Sampling was performed inside the plumes of vegetation fires and in the local background atmosphere. Samples were analysed for their elemental composition by Particle Induced X-Ray Emission (PIXE). Enrichment factors relative to the local background were calculated. Savanna fire aerosols are characterised by enrichments in elements like K, P, Cl, Zn, and Br, whereas forest fire emissions are enriched in Si and Ca. The unexpected low potassium enrichment factor for the forest fires could be due to the prevailing smoldering conditions, whereas the high values of potassium enrichment factor during savanna fires could be associated with the predominant flaming conditions. This result indicates that potassium may be considered a good tracer of the flaming phase of fires only. Emission factors of P, S, Cl, K, Ca, Mn, Zn, Br and total particulate matter were calculated for African savanna fires. Our estimates of the annual potassium and zinc emissions by tropical savanna fires indicate that the contribution of this source should be taken into account to understand the biogeochemical cycle of these elements.

Modeling of carbonaceous particles emitted by boreal and temperate wildfires at northern latitudes

For the first time, a spatial and monthly inventory has been constructed for carbonaceous particles emitted by boreal and temperate wildfires in forests, shrublands, and grasslands, with burned area data statistics, fuel load maps, fire characteristics, and particle emission factors. The time period considered is 1960–1997, and an important year-to-year variability was observed. On average, boreal and temperate vegetation fires represent 4% of global biomass burning, but during extreme years, their contribution may reach 12%, producing 9% and 20% of black carbon (BC) and particulate organic matter (POM), respectively, emitted by worldwide fires. The North American component of the boreal forest fires (Canada and Alaska) represents 4 to 122 Gg C yr-1 of BC and 0.07 to 2.4 Tg yr-1 of POM emitted, whereas the Eurasiatic component (Russia and northern Mongolia) may vary in the 16 to 474 Gg C yr-1 range for BC and between 0.3 and 9.4 Tg yr-1 for POM, with however great uncertainty. Temperate forests in conterminous United States and Europe have a much lower contribution with an average of 11 Gg C yr-1 of BC and 0.2 Tg yr-1 of POM. Grassland fires in Mongolia represent significant BC and POM sources which may reach 62 Gg C and 0.4 Tg, respectively. Finally, an annual average of BC emissions for shrubland fires in both the Mediterranean region and California is 20 Gg C yr-1, with average POM emissions of 0.1 Tg yr-1. These source maps obtained with a high spatial resolution (lox lo) can now be added to previous ones developed for other global carbonaceous aerosol sources (fossil fuel combustion, tropical biomass burning, agricultural and domestic fires) in order to provide global maps of particulate carbon emissions. Taking into account particle injection height in relation with each type of fire, our source map is a useful tool for studying the atmospheric transport and the impact of carbonaceous aerosols in three-dimensional transport and climate models.

Particulate content of savanna fire emissions

As part of the FOS-DECAFE experiment at Lamto (Ivory Coast) in January 1991, various aerosol samples were collected at ground level near prescribed fires or under local background conditions, to characterize the emissions of particulate matter from the burning of savanna vegetation. This paper deals with total aerosol (TPM) and carbon measurements. Detailed trace element and polycyclic hydrocarbon data are discussed in other papers presented in this issue.Near the fire plumes, the aerosols from biomass burning are primarily of a carbonaceous nature (C%∼70% of the aerosol mass) and consist predominantly of submicron particles (more than 90% in mass.) They are characterized by their organic nature (black to total carbon ratio Cb/Ct in the range 3–20%) and their high potassium content (K/Cb∼0.6). These aerosols undergo aging during their first minutes in the atmosphere causing slight alterations in their size distribution and chemical composition. However, they remain enriched in potassium (K/Cb=0.21) and pyrene, a polycyclic aromatic hydrocarbon, such that both of these species may be used as tracers of savanna burning aerosols. We show that during this period of the year, the background atmosphere experiences severe pollution from both terrigenous sources and regional biomass burning (44% of the aerosol). Daynight variations of the background carbon concentrations suggest that fire ignition and spreading occur primarily during the day. Simultaneous TPM and CO2 real-time measurements point to a temporal and spatial heterogeneity of the burning so that the ratio of the above background concentrations (ΔTPM/ΔCO2) varies from 2 to 400 g/kg C. Smoldering processes are intense sources of particles but particulate emissions may also be important during the rapidly spreading heading fires in connection with the generation of heavy brown smoke. We propose emission factor values (EF) for aerosols from the savanna biomass burning aerosols: EF (TPM)=11.4±4.6 and 69±25 g/kg Cdry plant and EF(Ct)=7.4±3.4 and 56±16 g C/kg Cdry plant for flaming and smoldering processes respectively. In these estimates, the range of uncertainty is mostly due to the intra-fire variability. These values are significantly lower than those reported in the literature for the combustion of other types of vegetation. But due to the large amounts of vegetation biomass being burnt in African savannas, the annual flux of particulate carbon into the atmosphere is estimated to be of the order of 8 Tg C, which rivals particulate carbon emissions from anthropogenic activities in temperate regions.

Trace elements in tropical African savanna biomass burning aerosols

As a part of the FOS/DECAFE experiment, aerosol particles emitted during prescribed savanna fires were collected in January 1991 at Lamto (Ivory Coast), either close to the emission or in ambient air. Analytical transmission electron microscopy pointed out the presence of sub-micrometer soots, salt condensates, vegetation relicts and soil derived particles. The samples were also analyzed for their total particulate matter (TPM) content and elemental composition by PIXE or XRF. At the emission, high concentrations of soil derived elements (Fe and Al) pointed out an intense remobilization process during the fires. Biomass burning emissions contributed to more than 90% of the measured concentrations, of P, Cl, S, K, Cu and Zn, which were found primarily in the fine fraction with the exception of P. Near the emission, K was mainly present as KCl, evolving to K2SO4 in the ambient samples. Trace elements emission factors were obtained for the first time for the African savanna burning and their annual emissions were estimated: our median K emission factor (0.78 g/kg of C) is higher than estimates for other ecosystems (0.2–0.58 g/kg of C); Zn emissions (0.008 Tg/year) account for 4 to 11% of the global anthropogenic emissions.

Determination of black carbon by chemical oxidation and thermal treatment in recent marine and lake sediments and Cretaceous-Tertiary clays

Abstract Several sample treatments and analytical methods for the measurement of black carbon in a wide variety of sediments were considered in which the removal of organic carbon is a critical step in the procedure. A comparison between chemical oxidation and thermal treatment was conducted and the latter was shown to be inappropriate due to the polymerisation of organic matter. Using acid dichromate oxidation, reactive kerogen was separated from black carbon in a variety of lake and marine, and recent and ancient sediments with relatively small and quantifiable losses (1–6%) of black carbon under carefully controlled reaction conditions.

Black carbon formation by savanna fires: Measurements and implications for the global carbon cycle

During a field study in southern Africa (Southern African Fire-Atmosphere Research Initiative (SAFARI-92)), black carbon formation was quantified in the residues of savanna fires. The volatilization ratios of C, H, N, and S were determined by measuring their contents in the fuel and residue loads on six experimental sites. The volatilization of sulfur (86±8%) was significantly higher than previously reported. Volatilization of H, N, and S was significantly correlated with that of carbon, enabling us to estimate their volatilization during savanna fires by extrapolation from those of carbon. By partitioning the residues in various fractions (unburned, partially burned, and ash), a strong correlation between the H/C ratio in the residue and the fonnation of black carbon was obtained. The ratio of carbon contained in ash to carbon contained in the unburned and partially burned fraction is introduced as an indicator of the degree of charring. As nitrogen was enriched in the residue, especially in the ash fraction of > 0.63 mm, this indicator may be useful for an assessment of nutrient cycling. We show that the formation of black carbon is dependent on the volatilization of carbon as well as the degree of charring. The ratio of black carbon produced to the carbon exposed to the fire in this field study (0.6-1.5%) was somewhat lower than in experimental fires under laboratory conditions (1.0-1.8%) which may be due to less complete combustion. The average ratio of black carbon in the residue to carbon emitted as CO 2 ranged from 0.7 to 2.0%. Using these ratios together with various estimates of carbon exposed or emitted by savanna fires, the worldwide black carbon fonnation was estimated to be 10-26 Tg C yr -1 with more than 90% of the black carbon remaining on the ground. The formation of this black carbon is a net sink of biospheric carbon and thus of atmospheric CO 2 as well as a source of O 2 .

Source terms and source strengths of the carbonaceous aerosol in the tropics

Atmospheric aerosol samples were collected in the Ivory Coast, primarily at Lamto (6°N, 5°W) between 1979 and 1981. The samples were analysed for total particulate carbon concentration and isotopic composition (13C/12C) by mass spectrometry. Observed concentrations were found high compared to values reported for temperate regions. Fine particulate carbon in the submicrometersize range accounted for 50 to 80% of the reported concentrations. At Lamto, both particulate carbon concentrations and isotopic ratios exhibit a large temporal variability which is shown to reflect the diversity of sources and their seasonal evolution. Natural emissions from the equatorial forest during the wet season, and biomass burning during the dry season, appear to be the major sources. The latter, though active during only a third of the year, is, on an annual basis, the most important source. Based on the data obtained at Lamto, an attempt has been made to estimate the flux of fine particulate carbon emitted from the tropical regions into the global troposphere. This flux, which is of the order of 20×1012 g C/yr, appears to be equivalent to the flux of fine particulate carbon emitted from industrial sources. These results suggest that the tropospheric burden of fine particulate carbon in lowlatitude regions is dominated by the long-range transport of carbonaceous aerosols originating from the Tropics.