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

Trends and seasonal variability in ammonia across major biomes in western and central Africa inferred from long-term series of ground-based and satellite measurements

Ammonia (NH3) is the most abundant alkaline component in the atmosphere. Changes in NH3 concentrations have important implications for atmospheric chemistry, air quality, and ecosystem integrity. We present a long-term ammonia (NH3) assessment in the western and central African regions within the framework of the International Network to study Deposition and Atmospheric chemistry in Africa (INDAAF) programme. We analyse seasonal variations and trends in NH3 concentrations and total column densities along an African ecosystem transect spanning dry savannas in Banizoumbou, Niger, and Katibougou, Mali; wet savannas in Djougou, Benin, and Lamto, Côte d'Ivoire; and forests in Bomassa, Republic of the Congo, and Zoétélé, Cameroon. We use a 21-year record of observations (1998–2018) from INDAAF passive samplers and an 11-year record of observations (2008–2018) of atmospheric vertical column densities from the Infrared Atmospheric Sounding Interferometer (IASI) to evaluate NH3 ground-based concentrations and total column densities, respectively. Climatic data (air temperature, rainfall amount, and leaf area index), as well as ammonia emission data of biomass combustion from the fourth version of the Global Fire Emissions Database (GFED4) and anthropogenic sources from the Community Emissions Data System (CEDS), were compared with total NH3 concentrations and total columns over the same periods. Annual mean ground-based NH3 concentrations are around 5.7–5.8 ppb in dry savannas, 3.5–4.7 ppb in wet savannas, and 3.4–5.6 ppb in forests. Annual IASI NH3 total column densities are 10.0–10.7 × 1015 molec. cm−2 in dry savanna, 16.0–20.9 × 1015 molec. cm−2 in wet savanna, and 12.4–13.8 × 1015 molec. cm−2 in forest stations. Non-parametric statistical Mann–Kendall trend tests applied to annual data show that ground-based NH3 concentrations increase at Bomassa (+2.56 % yr−1) but decrease at Zoétélé (−2.95 % yr−1) over the 21-year period. The 11-year period of IASI NH3 total column density measurements show yearly increasing trends at Katibougou (+3.46 % yr−1), Djougou (+2.24 % yr−1), and Zoétélé (+3.42 % yr−1). From the outcome of our investigation, we conclude that air temperature, leaf area index, and rainfall combined with biomass burning, agricultural, and residential activities are the key drivers of atmospheric NH3 in the INDAAF stations. The results also show that the drivers of trends are (1) agriculture in the dry savanna of Katibougou; (2) air temperature and agriculture in the wet savanna of Djougou and Lamto; and (3) leaf area index, air temperature, residential, and agriculture in the forest of Bomassa.</p

Personal exposure to PM_2.5 emitted from typical anthropogenic sources in southern West Africa: chemical characteristics and associated health risks

Urbanization is an issue that is strongly emerging in southern West Africa (sWA). There is a lack of full understanding on chemical compositions and personal exposure levels to fine particulate matter (hereafter defined as PE PM2.5) and its health risks related to various anthropogenic sources in this region. In this study, PE PM2.5 was studied in dry (January) and wet (July) seasons of 2016 for the first time to characterize the contributions of a domestic fire site (DF) to the exposure of women and a waste burning site (WB) to that of students in Abidjan, Côte d'Ivoire, and a motorcycle traffic site (MT) to that of drivers in Cotonou, Benin. The average PE PM2.5 mass concentrations were 331.7±190.7, 356.9±71.9 and 242.8±67.6&thinsp;µg&thinsp;m−3 at DF, WB and MT sites for women, students and drivers, which were 2.4, 10.3 and 6.4 times the ambient PM2.5 concentrations, respectively. Elevated PE PM2.5 levels in the dry season were found at DF (358.8±100.5&thinsp;µg&thinsp;m−3), WB (494.3±15.8&thinsp;µg&thinsp;m−3) and MT (335.1±72.1&thinsp;µg&thinsp;m−3) sites, on average 15&thinsp;% higher than that at DF and 55&thinsp;% higher at both WB and MT sites in the wet season. The seasonal variations were attributed to emission sources, meteorological factors and personal activities. In addition, the results show that geological material (35.8&thinsp;%, 46.0&thinsp;% and 42.4&thinsp;%) and organic matter (34.1&thinsp;%, 23.3&thinsp;% and 24.9&thinsp;%) were the major components of PE PM2.5 at DF, WB and MT sites. It is worth noting that the contribution of heavy metals was higher at WB (1.0&thinsp;%) than at DF (0.7&thinsp;%) and MT (0.4&thinsp;%) sites, strongly influenced by waste burning emission. This results in the highest non-cancer risks of heavy metals to students, 5.1 and 4.8 times the values for women and drivers, respectively. By conducting organic speciation, fingerprints were used to access the exposure and identify the source contributions from typical local anthropogenic sources. The women's exposure concentration to particulate polycyclic aromatic hydrocarbons (PAHs) at DF (77.4±47.9&thinsp;ng&thinsp;m−3) was 1.6 and 2.1 times, respectively, that of students at WB (49.9±30.7&thinsp;ng&thinsp;m−3) and of drivers at MT (37.0±7.4&thinsp;ng&thinsp;m−3). This can be associated with the higher contributions from solid fuels' burning and meat grilling activities to women, resulting in a level 5 times in exceedance of the cancer risk safety threshold (1×10-6). Phthalate esters (PAEs), commonly used as plasticizers in products, were in high levels in the student exposure PM2.5 samples (1380.4±335.2&thinsp;ng&thinsp;m−3), owing to obvious waste burning activities nearby. The drivers' exposures to fossil fuel combustion markers of hopanes in PE PM2.5 at MT (50.9±7.9&thinsp;ng&thinsp;m−3) was 3.0–3.3 times those for women at DF (17.1±6.4&thinsp;ng&thinsp;m−3) and students at WB (15.6±6.1&thinsp;ng&thinsp;m−3). Overall, the current study shows that wood combustion, waste burning, fugitive dust and motor vehicle emissions were the dominant sources of PE PM2.5 and mainly contributed to its toxicities. The exposure to the heavy metals Pb and Mn caused high non-cancer risks to students at WB, while the severe cancer risk of PAHs was found for women at DF via inhalation. The result of this study provides original data, initial perspective of PM2.5 personal exposure and health risk assessment in the developing areas. The information encourages the governments to improve the air quality and living standards of residents in this region.</p

Particle and VOC emission factor measurements for anthropogenic sources in West Africa

A number of campaigns have been carried out to establish the emission factors of pollutants from fuel combustion in West Africa, as part of work package 2 ("Air Pollution and Health") of the DACCIWA (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa) FP7 program. Emission sources considered here include wood (hevea and iroko) and charcoal burning, charcoal making, open trash burning, and vehicle emissions, including trucks, cars, buses and two-wheeled vehicles. Emission factors of total particulate matter (TPM), elemental carbon (EC), primary organic carbon (OC) and volatile organic compounds (VOCs) have been established. In addition, emission factor measurements were performed in combustion chambers in order to reproduce field burning conditions for a tropical hardwood (hevea), and obtain particulate emission factors by size (PM0.25, PM1, PM2.5 and PM10). Particle samples were collected on quartz fiber filters and analyzed using gravimetric method for TPM and thermal methods for EC and OC. The emission factors of 58 VOC species were determined using offline sampling on a sorbent tube. Emission factor results for two species of tropical hardwood burning of EC, OC and TPM are 0.98 ± 0.46 g kg-1 of fuel burned (g kg-1), 11.05 ± 4.55 and 41.12 ± 24.62 g kg-1, respectively. For traffic sources, the highest emission factors among particulate species are found for the two-wheeled vehicles with two-stroke engines (2.74 g kg-1 fuel for EC, 65.11 g kg-1 fuel for OC and 496 g kg-1 fuel for TPM). The largest VOC emissions are observed for two-stroke two-wheeled vehicles, which are up to 3 times higher than emissions from light-duty and heavy-duty vehicles. Isoprene and monoterpenes, which are usually associated with biogenic emissions, are present in almost all anthropogenic sources investigated during this work and could be as significant as aromatic emissions in wood burning (1 g kg-1 fuel). EC is primarily emitted in the ultrafine fraction, with 77 % of the total mass being emitted as particles smaller than 0.25 μm. The particles and VOC emission factors obtained in this study are generally higher than those in the literature whose values are discussed in this paper. This study underlines the important role of in situ measurements in deriving realistic and representative emission factors

Ab Initio Screening Approach for the Discovery of Lignin Polymer Breaking Pathways

The directed depolymerization of lignin biopolymers is of utmost relevance for the valorization or commercialization of biomass fuels. We present a computational and theoretical screening approach to identify potential cleavage pathways and resulting fragments that are formed during depolymerization of lignin oligomers containing two to six monomers. We have developed a chemical discovery technique to identify the chemically relevant putative fragments in eight known polymeric linkage types of lignin. Obtaining these structures is a crucial precursor to the development of any further kinetic modeling. We have developed this approach by adapting steered molecular dynamics calculations under constant force and varying the points of applied force in the molecule to diversify the screening approach. Key observations include relationships between abundance and breaking frequency, the relative diversity of potential pathways for a given linkage, and the observation that readily cleaved bonds can destabilize adjacent bonds, causing subsequent automatic cleavage.Massachusetts Institute of Technology (Research Support Corporation, Reed Grant)United States. Dept. of Energy. Computational Science Graduate Fellowship Program (DOE-CSGF)Burroughs Wellcome Fund (Career Award at the Scientific Interface

Modeling exceptional high concentrations of carbonaceous aerosols observed at Pic du Midi in spring–summer 2003: Comparison with Sonnblick and Puy de Dôme

International audienceCarbonaceous aerosols have been sampled weekly in 2002 and 2003 at Pic du Midi (PdMO), an isolated high-altitude Pyrenean station. High concentrations of both black carbon (BC) and total organic carbon (OC) have been observed during the exceptional prolonged warm dry spell over western Europe in spring–summer 2003, culminating during the first 2 weeks in August. The aerosol ORISAM-TM4 global model, together with new updated European emission inventories, appears apt to closely simulate at this PdMO site the BC and OC aerosol components during the whole 2002–2003 period, including the August 2003 heat wave. Further, ORISAM-TM4 provides unique detailed information on both primary and secondary OC fractions together with differentiated aerosol secondary anthropogenic (SOAA) vs. biogenic OC (SOAB) contributions, not accessible to measurements. Such comparisons have been extended to two other high-altitude European sites of the CARBOSOL programme, Sonnblick (Austrian Alps) and Puy de Dôme (central France). At these two sites, the agreement between simulations and measured values is clearly not so close as at PdMO, with systematic more elevated measured values of both BC and OC, presumably due to local and regional sources

Carbonaceous Aerosols at the high altitude site Pic du Midi (Pyrénées, France).

(14-16 septembre 2004

Precipitation chemistry and wet deposition in a remote wet savanna site in West Africa : Djougou (Benin)

In the framework of the IDAF (IGAC/DEBITS/AFrica) international program, this study aims to study the chemical composition of precipitation and associated wet deposition at the rural site of Djougou in Benin, representative of a West and Central African wet savanna. Five hundred and thirty rainfall samples were collected at Djougou, Benin, from July 2005 to December 2009 to provide a unique database. The chemical composition of precipitation was analyzed for inorganic (Ca2+, Mg2+, Na+, NH4+, K+, NO3-, Cl-, SO) and organic (HCOO-, CH3COO-, C2H5COO-, C2O42-) ions, using ion chromatography. The 530 collected rain events represent a total of 5706.1 mm of rainfall compared to the measured pluviometry 6138.9 mm, indicating that the collection efficiency is about 93%. The order of total annual loading rates for soluble cations is NH4+ > Ca2+ > Mg2+ > K+. For soluble anions the order of loading is carbonates > HCOO- > NO3- > CH3COO- > SO42- > Cl- > C2O42- > C2H5COO-. In the wet savanna of Djougou, 86% of the measured pH values range between 4.7 and 5.7 with a median pH of 5.19, corresponding to a VWM (Volume Weighed Mean) H+ concentration of 6.46 mu eq . L-1. This acidity results from a mixture of mineral and organic acids. The annual sea salt contribution was computed for K+, Mg2+, Ca2+ and SO42- and represents 4.2% of K+, 41% of Mg2+, 1.3% of Ca2+, and 7.4% of SO42-. These results show that K+, Ca2+, SO42-, and Mg2+ were mainly of non-marine origin. The marine contribution is estimated at 9%. The results of the chemical composition of rainwater of Djougou indicates that, except for the carbonates, ammonium has the highest VWM concentration (143 mu eq.L-1) and nitrate concentration is 8.2 mu eq.L-1. The distribution of monthly VWM concentration for all ions is computed and shows the highest values during the dry season, comparing to the wet season. Identified nitrogenous compound sources (NOx and NH3) are domestic animals, natural emissions from savanna soils, biomass burning and biofuel combustions. The second highest contribution is the calcium ion (133 mu eq.L-1), characteristic of dust aerosols from terrigenous sources, Calcium contributes up to 46% of the precipitation chemistry in Djougou. Finally, these results are compared to those obtained for other selected African sites representative of other main natural ecosystems: dry savanna and forest. The study of the African ecosystem transect indicates a pH gradient with more acidic pH in the forested ecosystem. Nitrogenous contribution to the chemical composition of rain in Lamto, wet savanna, (24%) is equivalent to the one estimated in Djougou (24%). The last contribution concerns organic acidity, which represents 7% of total ionic content of precipitation at Djougou. The relative particulate contribution PC and the relative gaseous contribution GC are calculated using the mean chemical composition measured in Djougou for the studied period. The comparison with other African sites gives 40% and 43% PC in wet savannas of Lamto (Cote d'Ivoire) and Djougou (Benin) respectively, 20% PC in the equatorial forest of Zoetele (Cameroon) and 80% PC in dry savanna of Banizoumbou (Niger). The results shown here indicate the existence of a North-South gradients of organic, marine, terrigenous and nitrogenous contributions along the transect in West and Central Africa