Biomass burning in the tropical savannas of Ivory Coast: An overview of the field experiment Fire of Savannas (FOS/DECAFE 91)

FOS/DECAFE 91 (Fire of Savannas/Dynamique et Chimie Atmosphérique en Forêt Equatoriale) was the first multidisciplinary experiment organized in Africa to determine gas and aerosol emissions by prescribed savanna fires. The humid savanna of Lamto in Ivory Coast was chosen for its ecological characteristics representative of savannas with a high biomass density (900 g m^–2 dry matter). Moreover the vegetation and the climate of Lamto have been studied for more than twenty years. The emission ratios (X/CO₂) of the carbon compounds (CO₂, CO, NMHC, CH₄, PAH, organic acids and aerosols), nitrogen compounds (NO_x, N₂O, NH₃ and soluble aerosols) and sulfur compounds (SO₂, COS and aerosols) were experimentally determined by ground and aircraft measurements. To perform this experiment, 4 small plots (100×100 m) and 2 large areas (10×10 km) were prepared and burnt in January 1991 during the period of maximum occurrence of fires in this type of savanna. The detailed ecological study shows that the carbon content of the vegetation is constant within 1% (42 g C for 100 g of vegetal dry matter), the nitrogen content (0.29 g N for 100 g of dry matter) may vary by 10% and the sulfur content (0.05 g S/100 d.m.) by 20%. These variations of the biomass chemical content do not constitute an important factor in the variation of the gas and particle emission levels. With the emission ratios characteristic of humid savanna and flaming conditions (CO/CO₂ of 6.1% at the ground and 8% for airborne measurements), we propose a set of new emission factors, taking into account the burning efficiency which is about 80%: 74.4% of the carbon content of the savanna biomass is released to the atmosphere in the form of CO₂, 4.6% as CO, 0.2% as CH₄, 0.5% as NMHC and 0.7% as aerosols. 17.2% of the nitrogen content of the biomass is released as NO_x, 3.5% as N₂O, 0.6% as NH₃ and 0.5% as soluble aerosols.     

Field study of the emissions of methyl chloride and other halocarbons from biomass burning in Western Africa

A field study of trace gas emissions from biomass burning in Equatorial Africa gave methyl chloride emission ratios of 4.3×10^–5±0.8×10^–5 mol CH₃Cl/mol CO₂. Based on the global emission rates for CO₂ from biomass burning we estimate a range of 226–904×10⁹ g/y as global emission rate with a best estimate of 515×10⁹ g/y. This is somewhat lower than a previous estimate which has been based on laboratory studies. Nevertheless, our emission rate estimates correspond to 10–40% of the global turnover of methyl chloride and thus support the importance of biomass burning as methyl chloride source. The emission ratios for other halocarbons (CH₂Cl₂, CHCl₃, CCl₄, CH₃CCl₃, C₂HCl₃, C₂Cl₄, F-113) are lower. In general there seems to be a substantial decrease with increasing complexity of the compounds and number of halogen atoms. For dichloromethane biomass burning still contributes significantly to the total global budget and in the Southern Hemisphere biomass burning is probably the most important source for atmospheric dichloromethane. For the global budgets of other halocarbons biomass burning is of very limited relevance.     

Kinetics of the Gas-Phase Reactions of OH Radicals, NO3 Radicals and O3 with Three C7-Carbonyls Formed From The Atmospheric Reactions of Myrcene, Ocimene and Terpinolene

Rate constants for the gas-phase reactions of OH radicals, NO₃ radicals and O₃ with the C₇-carbonyl compounds 4-methylenehex-5-enal [CH₂=CHC(=CH₂)CH₂CH₂CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH₂=CHC(CH₃)=CHCH₂CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm³ molecule^–1 s^–1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10^–10, (4.75 ± 0.35) × 10^–13 and (1.46 ± 0.12) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10^–10, (2.17 ± 0.30) × 10^–12, and (4.13 ± 0.81) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10^–10, (1.75 ± 0.27) × 10^–12, and (5.36 ± 0.28) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10^–10, (1.81 ± 0.35) × 10^–12, and (6.98 ± 0.40) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO₃ radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.     

Production of N2O,CH4, and CO2 from soils in the tropical savanna during the dry season

Emissions of N₂O, CH₄, and CO₂ from soils at two sites in the tropical savanna of central Venezuela were determined during the dry season in February 1987. Measured arithmetic mean fluxes of N₂O, CH₄, and CO₂ from undisturbed soil plots to the atmosphere were 2.5×10⁹, 4.3×10¹⁰, and 3.0×10¹³ molecules cm^-2 s^-1, respectively. These fluxes were not significantly affected by burning the grass layer. Emissions of N₂O increased fourfold after simulated rainfall, suggesting that production of N₂O in savanna soils during the rainy season may be an important source for atmospheric N₂O. The CH₄ flux measurements indicate that these savanna soils were not a sink, but a small source, for atmospheric methane. Fluxes of CO₂ from savanna soils increased ninefold two hours after simulated rainfall, and remained three times higher than normal after 16 hours. More research is needed to clarify the significance of savannas in the global cycles of N₂O, CH₄, CO₂, and other trace gases, especially during the rainy season.     

A determination of the CH4, NO x and CO2 emissions from the Prudhoe Bay,Alaska oil development

In this paper we quantify the CH₄, CO₂ and NO _x emissions during routine operations at a major oil and gas production facility, Prudhoe Bay, Alaska, using the concentrations of combustion by products measured at the NOAA-CMDL observatory at Barrow, Alaska and fuel consumption data from Prudhoe Bay. During the 1989 and 1990 measurement campaigns, 10 periods (called events) were unambiguously identified where surface winds carry the Prudhoe Bay emissions to Barrow (approximately 300 km). The events ranged in duration from 8–48 h and bring ambient air masses containing substantially elevated concentrations of CH₄, CO₂ and NO _y to Barrow. Using the slope of the observed CH₄ vs CO₂ concentrations during the events and the CO₂ emissions based on reported fuel consumption data, we calculate annual CH₄ emissions of (24+/–8)×10³ metric tons from the facility. In a similar manner, the annual NO _x emissions are calculated to be (12+/–4)×10³ metric tons, which is in agreement with an independently determined value. The calculated CH₄ emissions represent the amount released during routine operations including leakage. However this quantity would not include CH₄ released during non-routine operations, such as from venting or gas flaring.     

Measurements of trace gases emitted by Australian savanna fires during the 1990 dry season

During 18–23 July 1990, 31 smoke samples were collected from an aircraft flying at low altitudes through the plumes of tropical savanna fires in the Northern Territory, Australia. The excess (above background) mixing ratios of 17 different trace gases including CO₂, CO, CH₄, several non-methane hydrocarbons (NMHC), CH₃CHO, NO _x (– NO + NO₂), NH₃, N₂O, HCN and total unspeciated NMHC and sulphur were measured. Emissionratios relative to excess CO₂ and CO, and emissionfactors relative to the fuel carbon, nitrogen or sulphur content are determined for each measured species. The emission ratios and factors determined here for carbon-based gases, NO _x , and N₂O are in good agreement with those reported from other biomass burning studies. The ammonia data represent the first such measurements from savanna fires, and indicate that NH₃ emissions are more than half the strength of NO _x emissions. The emissions of NO _x , NH₃, N₂O and HCN together represent only 27% of the volatilised fuel N, and are primarily NO _x (16%) and NH₃ (9%). Similarly, only 56% of the volatilised fuel S is accounted for by our measurements of total unspeciated sulphur.     

Field studies of methane emission from termite nests into the atmosphere and measurements of methane uptake by tropical soils

The flux of CH₄ and CO₂ from termite nests into the atmosphere has been measured in a broad-leafed-type savannah in South Africa. Measurements were carried out on nests of species of six genera, i.e., Hodotermes, Macrotermes, Odontotermes, Trinervitermes, Cubitermes, and Amitermes. The flux rates of CH₄ relative to the flux rate of CO₂ in terms of carbon obtained for the individual species showed ratios of 2.9×10^-3, 7.0×10^-4, 6.7×10^-5, 8.7×10^-3, 2.0×10^-3 and 4.2×10^-3, respectively. Using data published on the assimulation efficiencies of termites, the flux of carbon as CH₄ accounts for 6.0×10^-5 to 2.6×10^-3 of the carbon ingested which results in a global CH₄ emission by termites of 2 to 5×10¹² g/yr. Methane is decomposed in the soil with average decomposition rates of 52 g/m²/h. The annual CH₄ consumption in the tropics and subtropics is estimated to be 21×10¹² g which exceeds the CH₄ emission rate by termites.     

Nitrogen compound emission from biomass burning in tropical African savanna FOS/DECAFE 1991 experiment (Lamto,Ivory Coast)

Gaseous nitrogen compounds (NO _x , NO _y , NH₃, N₂O) were measured at ground level in smoke plumes of prescribed savanna fires in Lamto, in the southern Ivory Coast, during the FOS/DECAFE experiment in January 1991. During the flaming phase, the linear regression between [NO _x ] and [CO₂] (differences in concentration between smoke plumes and atmosheric background) results volumic emission ratio [NO _x ]/[CO₂]=1.37×10^–3 with only slight differences between heading and backing fires. Nearly 90% of the nitrogen oxides are emitted as NO. Average emission ratios of other compounds are: 1.91, 0.047, and 0.145×10^–3 for NO _y , NH₃ and N₂O, respectively. The emission ratios obtained during this field experiment are compred with corresponding values measured during former experiments with the same plant species in combustion chambers. An accurate determination of both the biomass actually burned and of the plant nitrogen content, allows an assessment of emission fluxes of N-compounds from Guinean savanna burns. Preliminary results dealing with the influence of fire on biogenic emissions from soils are also reported.     

Carbonyl sulfide emissions from biomass burning in the tropics

Carbonyl sulfide emissions from biomass burning have been studied during field experiments conducted both in an African savanna area (Ivory Coast) and rice fields, central highland pine forest and savanna areas in Viet-Nam. During these experiments CO₂, CO and C₂H₂ or CH₄ have also been also monitored. COS values range from 0.6 ppbv outside the fires to 73 ppbv in the plumes. Significant correlations have been observed between concentrations of COS and CO (R ²=0.92,n=25) and COS and C₂H₂ (R ²=0.79,n=26) indicating a COS production during the smoldering combustion. COS/CO₂ emission factors (COS/CO₂) during field experiments ranged from 1.2 to 61×10^–6 (11.4×10^–6 mean value). COS emission by biomass burning was estimated to be up to 0.05 Tg S/yr in tropics and up to 0.07 Tg S/yr on a global basis, contributing thus about 10% to the global COS flux. Based on the S/C ratio measured in the dry plant biomass and the COS/CO₂ emission factor, COS can account for only about 7% of the sulfur emitted in the atmosphere by biomass burning.     

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

GREENHOUSE GASES FROM DEFORESTATION IN BRAZILIAN AMAZONIA: NET COMMITTED EMISSIONS

Deforestation in Brazilian Amazonia is a significant source of greenhouse gases today and, with almost 90% of the originally forested area still uncleared, is a very large potential source of future emissions. The 1990 rate of loss of forest (13.8 × 10³ km²/year) and cerrado savanna (approximately 5 × 10³ km²/year) was responsible for releasing approximately 261 × 10⁶ metric tons of carbon (10⁶ t C) in the form of CO2, or 274–285 × 10⁶ t of CO2-equivalent C considering IPCC 1994 global warming potentials for trace gases over a 100-year horizon. These calculations consider conversion to a landscape of agriculture, productive pasture, degraded pasture, secondary forest, and regenerated forest in the proportions corresponding to the equilibrium condition implied by current land-use patterns. Emissions are expressed as net committed emissions, or the gases released over a period of years as the carbon stock in each hectare deforested approaches a new equilibrium in the landscape that replaces the original forest. For low and high trace gas scenarios, respectively, 1990 clearing produced net committed emissions (in 10⁶ t of gas) of 957–958 for CO2, 1.10–1.42 for CH₄, 28–35 for CO, 0.06–0.16 for N₂O, 0.74–0.74 for NO_x and 0.58–1.16 for non-methane hydrocarbons.     

Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early Earth

One-dimensional radiative-convective and photochemical models are used to examine the effects of enhanced CO₂ concentrations on the surface temperature of the early Earth and the composition of the prebiotic atmosphere. Carbon dioxide concentrations of the order of 100–1000 times the present level are required to compensate for an expected solar luminosity decrease of 25–30%, if CO₂ and H₂O were the only greenhouse gases present. The primitive stratosphere was cold and dry, with a maximum H₂O volume mixing ratio of 10^–6. The atmospheric oxidation state was controlled by the balance between volcanic emission of reduced gases, photo-stimulated oxidation of dissolved Fe⁺² in the oceans, escape of hydrogen to space, and rainout of H₂O₂ and H₂CO. At high CO₂ levels, production of hydrogen owing to rainout of H₂O₂ would have kept the H₂ mixing ratio above 2×10^–4 and the ground-level O₂ mixing ratio below 10^–11, even if no other sources of hydrogen were present. Increased solar UV fluxes could have led to small changes in the ground-level mixing ratios of both O₂ and H₂.     

Rainwater Chemistry and Wet Deposition over the Wet Savanna Ecosystem of Lamto (Côte d'Ivoire)

From the IGAC-DEBITS Africa network (IDAF), data sets on precipitation chemistry collected from the ‘wet savanna ecosystem’ site of Lamto (Côte d'Ivoire), are analyzed (1995–2002). Inorganic (Ca^{2 +}, Mg^{2 +}, Na⁺, K⁺, NH₄ ⁺, Cl^?, SO₄ ^{2 ?}, NO₃ ^?) and organic (HCOO^?, CH₃COO^?) ions content were determined using Ion Chromatography. The analyzed 631 rainfall events represent 8420.9 mm of rainfall from a 9631.1 mm total. The precipitation chemistry at Lamto is influenced by four main sources: natural biogenic emissions from savanna soils (NO _x and NH₃), biomass burning (savanna and domestic fires), terrigeneous particles emissions from dry savanna soils, and marine compounds embedded in the summer monsoon. The inter-annual variability of the weighted volume mean concentration of chemical species linked with wet deposition fluctuates by ～ 20% over the period. Ammonium concentration is found to be the highest (17.6 μ eq.l^{? 1}) from all IDAF sites belonging to the West Africa ecosystems. Ammonia sources are from domestic animals, fertilizers and biomass burning. In spite of the high potential acidity of 30.5 μ eq.l^{? 1} from NO₃ ^?, SO₄ ^{2 ?}, HCOO^? and CH₃COO^?, a relatively weak acidity is measured: 6.9 μ eq.l^{? 1}. The 40% acid neutralization is explained by the acid gas – alkaline soil particles interaction. The remaining neutralization is from inclusion of gaseous ammonia. When results from Lamto, are compared with those from Banizoumbou (dry savanna) and Zoetele (equatorial forest), a regional view for wet tropospheric chemistry processes is obtained. The high concentration of the particulate phase in precipitation emphasizes the importance of multiphases processes between gases and particles in the atmospheric chemistry of the West Africa ecosystems. For example, the nss Ca^{2 +} precipitation content, main indicator of terrigeneous particles, goes from 30.8 μ eq.l^{? 1} in dry savanna to 9.2 μ eq.l^{? 1} at Lamto and 8.9 μ eq.l^{? 1} in the Cameroon forest. A similar gradient is obtained for rainfall mineral particles precipitation content with contribution of 80% in dry savanna, 40% in wet savanna, and 20% in the equatorial forest.     

FTIR studies of reactions between the nitrate radical and haloethenes

Products and mechanisms for the gas-phase reactions of NO₃ radicals with CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂,cis-CHCl=CHCl andtrans-CHCl=CHCl in air have been studied. The experiments were carried out at 295±2 K and 740±5 Torr in a 480-L Teflon-coated reaction chamber and at 295±2 K and 760±5 Torr in a 250-L stainless steel reactor. NO₃ was generated by the thermal dissociation of N₂O₅. Experiments with¹⁵NO₃ and CD₂CDCl have also been performed. The initially formed nitrate peroxynitrates decay into carbonyl compounds, nitrates, HCl and ClNO₂. In adidtion, there are indications of nitrooxy acid chlorides being produced. The reactions with CH₂=CCl₂ and CHCl=CCl₂ are more complex due to release of chlorine atoms which eventually lead to formation of chloroacid chlorides.A general reaction mechanism is proposed and the observed concentration-time profiles of reactants and products are simulated for each compound. The rate constants for the initial step of NO₃ addition to the chloroethenes are determined as: (2.6±0.5, 9.4±0.9, 2.0±0.4 and 1.4±0.4) × 10^–16 cm³ molecule^–1 s^–1 for CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂ andcis-CHCl=CHCl, respectively.     

Methane emissions from a landfill measured by eddy correlation using a fast response diode laser sensor

We describe a fast response methane sensor based on the absorption of radiation generated with a near-infrared InGaAsP diode laser. The sensor uses an open path absorption region 0.5 m long; multiple pass optics provide an optical path of 50 m. High frequency wavelength modulation methods give stable signals with detection sensitivity (S/N=1, 1 Hz bandwidth) for methane of 65 ppb at atmospheric pressure and room temperature. Improvements in the optical stability are expected to lower the current detection limit. We used the new sensor to measure, by eddy correlation, the CH₄ flux from a clay-capped sanitary landfill. Simultaneously we measured the flux of CO₂ and H₂O. From seven half-hourly periods of data collected after a rainstorm on November 23, 1991, the average flux of CH₄ was 17 mmol m^–2 hr^–1 (6400 mg CH₄ m^–2 d^–1) with a coefficient of variation of 25%. This measurement may underrepresent the flux by 15% due to roll-off of the sensor response at high frequency. The landfill was also a source of CO₂ with an average flux of 8.1 mmol m^–2 hr^–1 (8550 mg CO₂ m^–2 d^–1) and a coefficient of variation of 26%. A spectral analysis of the data collected from the CH₄, CO₂, and H₂O sensors showed a strong similarity in the turbulent transfer mechanisms.     

A Long Term Study on Chemical Composition of Rainwater at Dayalbagh, a Suburban Site of Semiarid Region

Rainwater samples were collected for the monsoon period of 1988 and 1991–1996 at Dayalbagh (Agra), a suburban site situated in semiaridregion. The mean pH was 7.01 ±1.03 well above 5.6, which is the reference pH. Concentration of Ca²⁺ was observed to be highest followed by Mg²⁺, NH₄ ⁺,SO₄ ^2–, Cl^–,NO₃ ^–, Na⁺, F^– and K⁺. The ratios of SO₄ ^2– + NO₃ ^– andCa²⁺ + Mg²⁺ (TA/TC) have been considered as indicatorfor acidity. In the Agra region ratio of TA/TC is quite below 1.0 indicating alkaline nature of rainwater. The lowest value of 0.24 was observed in 1991 likely due to the lowest rain depth of the decade. The highest value of 0.54 was observed in 1996, a year with a large rain depth and increase in line (vehicular traffic) and area sources (population growth). Good correlation between Ca²⁺ and NO₃ ^–,Ca²⁺ and SO₄ ^2– andSO₄ ^2– and NO₃ ^–,indicates that wind carried dust and soil play a significant role in neutralization of precipitation acidity.     

A Local-Scale Study of the Trace Gas Emissions from Vegetation Burning around the Village of Dalun, Ghana, with Respect to Seasonal Vegetation Changes and Burning Practices

The annual trace gas emissions from a West African rural region were calculated using direct observations of gas emissions and burning practices, and the findings compared to the guidelines published by the IPCC. This local-scale study was conducted around the village of Dalun in the Northern Region of Ghana, near the regional capital of Tamale. Two types of fires were found in the region – agricultural fires andwildfires. Agricultural fires are intentionally set in order to remove shrub and crop residues; wildfires are mostly ignited by herders to remove inedible grasses and to promote the growth of fresh grass. An agricultural fire is ignited with a fire front moving against the wind (backfire), whereas a wildfire moves with the wind (headfire). Gas emissions (CO₂, CO and NO) weremeasured by burning eight experimental plots, simulating both headfires and backfires. A common method of evaluating burning conditions is to calculate modified combustion efficiency (MCE), which expresses the percentage of the trace gases released as CO₂. Modified combustion efficiency was95% in the wildfires burned as headfires, but only 90% in the backfires.The burned area in the study region was determined by classifying a SPOT HRV satellite image taken about two months into the dry season. Fires were classified as either old burned areas or new burned areas as determined by the gradient in moisture content in the vegetation from the onset of the dry season. Classified burned areas were subsequently divided into two classes depending on whether the location was in the cultivated area or in the rangeland area, this sub-classification thus indicating whether the fire had been burned as a backfire or headfire. Findings showed that the burned area was 48% of the total region, and that the ratio of lowland wildfiresto agricultural fires was 3:1. The net trace gas release from the classified vegetation burnings were extrapolated to 26–46×10⁸ gCO₂, 78–302×10⁶ g CO,17–156×10⁵ g CH₄,16–168×10⁵ g NMHC and 11–72×10³ NO_x. Calculation of the emissionsusing proposed IPCC default values on burned area and average biomass resulted in a net emission 5 to 10 times higher than the measured emission values. It was found that the main reason for this discrepancy was not the emission factorsused by the IPCC, but an exaggerated fuel load estimate.     

Influence of Transport over a Mountain Ridge on the Chemical Composition of Marine Aerosols during the ACE-2 Hillcloud Experiment

Aerosol chemical composition and trace gas measurements were made at twolocations on the northeastern peninsula of Tenerife during the ACE-2HILLCLOUD experiment, between 28 June and 23 July 1997. Measurementswere made of coarse (#gt;2.5 m aerodynamic diameter) and fine (#lt; 2.5m) aerosol Cl^–, NO₃ ^–,SO₄ ^2–, non-sea saltSO₄ ^2– (NSSS),CH₃SO₃ ^– (MSA) andNH₄ ⁺, and gas phase dimethylsulphide (DMS), HCl,HNO₃, SO₂, CH₃COOH, HCOOH andNH₃. Size distributions were measured using a cascadeimpactor. Results show that in marine air masses NSSS and MSA wereformed via DMS oxidation, with additional NSSS present in air massescontaining a continental component. Using a Eulerian box model approachfor aerosols transported between upwind and downwind sites, a mean NSSSproduction rate of 4.36 × 10^–4 gm^–3 s^–1 was calculated for daytimeclear sky periods (highest insolation), with values for cloudy periodsduring daytime and nighttime of 3.55 × 10^–4 and2.40 × 10^–4 g m^–3s^–1, respectively. The corresponding rates for MSA were6.23 × 10^–6, 8.49 × 10^–6and 6.95 × 10^–6 g m^–3s^–1, respectively. Molar concentration ratios forMSA/NSSS were 8.7% (1.8–18.2%) and 1.9%(1.3–3.5%) in clean and polluted air masses, respectively.Reactions occurring within clouds appeared to have a greater influenceon rates of MSA production, than of NSSS, while conversely daytime gasphase reactions were more important for NSSS. For MSA, nighttimein-cloud oxidation rates exceeded rates of daytime gas phase productionvia OH oxidation of DMS. NSSS, MSA and ammonium had trimodal sizedistributions, with modes at 0.3, 4.0 and >10.0 m (NSSS andNH₄ ⁺), and 0.3, 1.5 and 4.0 m (MSA). Nosignificant production of other aerosol species was observed, with theexception of ammonium, which was formed at variable rates dependent onneutralisation of the aerosol with ammonia released from spatiallynon-uniform surface sources. Seasalt components were mainly present incoarse particles, although sub-micrometre chloride was also measured.Losses by deposition exceeded calculated expectations for all species,and were highest for the seasalt fraction and nitrate.     

Domestic Combustion of Biomass Fuels in Developing Countries: A Major Source of Atmospheric Pollutants

Biomass burning has important impacts on atmospheric chemistry and climate. Fires in tropical forests and savannas release large quantities of trace gases and particulate matter. Combustion of biofuels for cooking and heating constitutes a less spectacular but similarly widespread biomass burning activity. To provide the groundwork for a quantification of this source, we determined in rural Zimbabwe the emissions of CO₂, CO, and NO from more than 100 domestic fires fueled by wood, agricultural residues, and dung. The results indicate that, compared to open savanna fires, emissions from domestic fires are shifted towards products of incomplete combustion. A tentative global analysis shows that the source strength of domestic biomass burning is on the order of 1500 Tg CO₂–C yr^–1, 140 Tg CO–C yr^–1, and 2.5 Tg NO–N yr^–1. This represents contributions of about 7 to 20% to the global budget of these gases.     

The role of clouds in tropospheric photochemistry

We show that photochemical processes in the lower half of the troposphere are strongly affected by the presence of liquid water clouds. Especially CH₂O, an important intermediate of CH₄ (and of other hydrocarbon) oxidation, is subject to enhanced breakdown in the aqueous phase. This reduces the formation of HO _x -radicals via photodissociation of CH₂O in the gas phase. In the droplets, the hydrated form of CH₂O, its oxidation product HCO₂ ^–, and H₂O₂ recycle O₂ ^– radicals which, in turn, react with ozone. We show that the latter reaction is a significant sink for O₃. Further O₃ concentrations are reduced as a result of decreased formation of O₃ during periods with clouds. Additionally, NO _x , which acts as a catalyst in the photochemical formation of O₃, is depleted by clouds during the night via scavenging of N₂O₅. This significantly reduces NO _x -concentrations during subsequent daylight hours, so that less NO _x is available for O₃ production. Clouds thus directly reduce the concentrations of O₃, CH₂O, NO _x , and HO _x . Indirectly, this also affects the budgets of other trace gases, such as H₂O₂, CO, and H₂.