Cooperative LBA Airborne Regional Experiment Research Articles

Impact of Manaus City on the Amazon Green Ocean atmosphere: ozone production, precursor sensitivity and aerosol load

Abstract. As a contribution to the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001) field campaign in the heart of the Amazon Basin, we analyzed the temporal and spatial dynamics of the urban plume of Manaus City during the wet-to-dry season transition period in July 2001. During the flights, we performed vertical stacks of crosswind transects in the urban outflow downwind of Manaus City, measuring a comprehensive set of trace constituents including O3, NO, NO2, CO, VOC, CO2, and H2O. Aerosol loads were characterized by concentrations of total aerosol number (CN) and cloud condensation nuclei (CCN), and by light scattering properties. Measurements over pristine rainforest areas during the campaign showed low levels of pollution from biomass burning or industrial emissions, representative of wet season background conditions. The urban plume of Manaus City was found to be joined by plumes from power plants south of the city, all showing evidence of very strong photochemical ozone formation. One episode is discussed in detail, where a threefold increase in ozone mixing ratios within the atmospheric boundary layer occurred within a 100 km travel distance downwind of Manaus. Observation-based estimates of the ozone production rates in the plume reached 15 ppb h−1. Within the plume core, aerosol concentrations were strongly enhanced, with ΔCN/ΔCO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. ΔCN/ΔCO ratios tended to decrease with increasing transport time, indicative of a significant reduction in particle number by coagulation, and without substantial new particle nucleation occurring within the time/space observed. While in the background atmosphere a large fraction of the total particle number served as CCN (about 60–80% at 0.6% supersaturation), the CCN/CN ratios within the plume indicated that only a small fraction (16±12%) of the plume particles were CCN. The fresh plume aerosols showed relatively weak light scattering efficiency. The CO-normalized CCN concentrations and light scattering coefficients increased with plume age in most cases, suggesting particle growth by condensation of soluble organic or inorganic species. We used a Single Column Chemistry and Transport Model (SCM) to infer the urban pollution emission fluxes of Manaus City, implying observed mixing ratios of CO, NOx and VOC. The model can reproduce the temporal/spatial distribution of ozone enhancements in the Manaus plume, both with and without accounting for the distinct (high NOx) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NOx. The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the background rainforest atmosphere, and therefore NOx control is assumed to be the most effective ozone abatement strategy. Both observations and models show that the agglomeration of NOx emission sources, like power plants, in a well-arranged area can decrease the ozone production efficiency in the near field of the urban populated cores. But on the other hand remote areas downwind of the city then bear the brunt, being exposed to increased ozone production and N-deposition. The simulated maximum stomatal ozone uptake fluxes were 4 nmol m−2 s−1 close to Manaus, and decreased only to about 2 nmol m−2 s−1 within a travel distance >1500 km downwind from Manaus, clearly exceeding the critical threshold level for broadleaf trees. Likewise, the simulated N deposition close to Manaus was ~70 kg N ha−1 a−1 decreasing only to about 30 kg N ha−1 a−1 after three days of simulation.

Isoprene and monoterpene fluxes from Central Amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget

Abstract. We estimated the isoprene and monoterpene source strengths of a pristine tropical forest north of Manaus in the central Amazon Basin using three different micrometeorological flux measurement approaches. During the early dry season campaign of the Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001), a tower-based surface layer gradient (SLG) technique was applied simultaneously with a relaxed eddy accumulation (REA) system. Airborne measurements of vertical profiles within and above the convective boundary layer (CBL) were used to estimate fluxes on a landscape scale by application of the mixed layer gradient (MLG) technique. The mean daytime fluxes of organic carbon measured by REA were 2.1 mg C m−2 h−1 for isoprene, 0.20 mg C m−2 h−1 for α-pinene, and 0.39 mg C m−2 h−1 for the sum of monoterpenes. These values are in reasonable agreement with fluxes determined with the SLG approach, which exhibited a higher scatter, as expected for the complex terrain investigated. The observed VOC fluxes are in good agreement with simulations using a single-column chemistry and climate model (SCM). In contrast, the model-derived mixing ratios of VOCs were by far higher than observed, indicating that chemical processes may not be adequately represented in the model. The observed vertical gradients of isoprene and its primary degradation products methyl vinyl ketone (MVK) and methacrolein (MACR) suggest that the oxidation capacity in the tropical CBL is much higher than previously assumed. A simple chemical kinetics model was used to infer OH radical concentrations from the vertical gradients of (MVK+MACR)/isoprene. The estimated range of OH concentrations during the daytime was 3–8×106 molecules cm−3, i.e., an order of magnitude higher than is estimated for the tropical CBL by current state-of-the-art atmospheric chemistry and transport models. The remarkably high OH concentrations were also supported by results of a simple budget analysis, based on the flux-to-lifetime relationship of isoprene within the CBL. Furthermore, VOC fluxes determined with the airborne MLG approach were only in reasonable agreement with those of the tower-based REA and SLG approaches after correction for chemical decay by OH radicals, applying a best estimate OH concentration of 5.5×106 molecules cm−3. The SCM model calculations support relatively high OH concentration estimates after specifically being constrained by the mixing ratios of chemical constituents observed during the campaign. The relevance of the VOC fluxes for the local carbon budget of the tropical rainforest site during the measurements campaign was assessed by comparison with the concurrent CO2 fluxes, estimated by three different methods (eddy correlation, Lagrangian dispersion, and mass budget approach). Depending on the CO2 flux estimate, 1–6% or more of the carbon gained by net ecosystem productivity appeared to be re-emitted through VOC emissions.

Physical properties of the sub-micrometer aerosol over the Amazon rain forest during the wet-to-dry season transition - comparison of modeled and measured CCN concentrations

Abstract. Sub-micrometer atmospheric aerosol particles were studied in the Amazon region, 125 km northeast of Manaus, Brazil (-1°55.2'S, 59°28.1'W). The measurements were performed during the wet-to-dry transition period, 4-28 July 2001 as part of the LBA (Large-Scale Biosphere Atmosphere Experiment in Amazonia) CLAIRE-2001 (Cooperative LBA Airborne Regional Experiment) experiment. The number size distribution was measured with two parallel differential mobility analyzers, the hygroscopic growth at 90% RH with a Hygroscopic Tandem Mobility Analyzer (H-TDMA) and the concentrations of cloud condensation nuclei (CCN) with a cloud condensation nuclei counter. A model was developed that uses the H-TDMA data to predict the number of soluble molecules or ions in the individual particles and the corresponding minimum particle diameter for activation into a cloud droplet at a certain supersaturation. Integrating the number size distribution above this diameter, CCN concentrations were predicted with a time resolution of 10 min and compared to the measured concentrations. During the study period, three different air masses were identified and compared: clean background, air influenced by aged biomass burning, and moderately polluted air from recent local biomass burning. For the clean period 2001, similar number size distributions and hygroscopic behavior were observed as during the wet season at the same site in 1998, with mostly internally mixed particles of low diameter growth factor (~1.3 taken from dry to 90% RH). During the periods influenced by biomass burning the hygroscopic growth changed slightly, but the largest difference was seen in the number size distribution. The CCN model was found to be successful in predicting the measured CCN concentrations, typically within 25%. A sensitivity study showed relatively small dependence on the assumption of which model salt that was used to predict CCN concentrations from H-TDMA data. One strength of using H-TDMA data to predict CCN concentrations is that the model can also take into account soluble organic compounds, insofar as they go into solution at 90% RH. Another advantage is the higher time resolution compared to using size-resolved chemical composition data.

Composition and diurnal variability of the natural Amazonian aerosol

As part of the Large‐Scale Biosphere‐Atmosphere Experiment in Amazonia (LBA)‐Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign, separate day and nighttime aerosol samples were collected in July 2001 at a ground‐based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural “background” aerosol. A combination of analytical techniques was used to characterize the elemental and ionic composition of the aerosol. Major particle types larger than ∼0.5 μm were identified by electron and light microscopy. Both the coarse and fine aerosol were found to consist primarily of organic matter (∼70 and 80% by mass, respectively), with the coarse fraction containing small amounts of soil dust and sea‐salt particles and the fine fraction containing some non‐sea‐salt sulfate. Coarse particulate mass concentrations (CPM ≈ PM10− PM2) were found to be highest at night (average = 3.9 ± 1.4 μg m−3, mean night‐to‐day ratio = 1.9 ± 0.4), while fine particulate mass concentrations (FPM ≈ PM2) increased during the daytime (average = 2.6 ± 0.8 μg m−3, mean night‐to‐day ratio = 0.7 ± 0.1). The nocturnal increase in CPM coincided with an increase in primary biological particles in this size range (predominantly yeasts and other fungal spores), resulting from the trapping of surface‐derived forest aerosol under a shallow nocturnal boundary layer and a lake‐land breeze effect at the site, although active nocturnal sporulation may have also contributed. Associated with this, we observed elevated nighttime concentrations of biogenic elements and ions (P, S, K, Cu, Zn, NH4+) in the CPM fraction. For the FPM fraction a persistently higher daytime concentration of organic carbon was found, which indicates that photochemical production of secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Dust and sea‐salt‐associated elements/ions in the CPM fraction, and non‐sea‐salt sulfate in the FPM fraction, showed higher daytime concentrations, most likely due to enhanced convective downward mixing of long‐range transported aerosol.

Organic compounds present in the natural Amazonian aerosol: Characterization by gas chromatography–mass spectrometry

As part of the Large‐Scale Biosphere‐Atmosphere Experiment in Amazonia (LBA)‐Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign in July 2001, separate day and nighttime aerosol samples were collected at a ground‐based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural “background” aerosol. We used a high‐volume sampler to separate the aerosol into fine (aerodynamic diameter, AD < 2.5 μm) and coarse (AD > 2.5 μm) size fractions and quantified a range of organic compounds in methanolic extracts of the samples by a gas chromatographic‐mass spectrometric technique. The carbon fraction of the compounds could account for an average of 7% of the organic carbon (OC) in both the fine and coarse aerosol fractions. We observed the highest concentrations of sugars, sugar alcohols, and fatty acids in the coarse aerosol samples, which suggests that these compounds are associated with primary biological aerosol particles (PBAP) observed in the forest atmosphere. Of these, trehalose, mannitol, arabitol, and the fatty acids were found to be more prevalent at night, coinciding with a nocturnal increase in PBAP in the 2–10 μm size range (predominantly yeasts and other small fungal spores). In contrast, glucose, fructose, and sucrose showed persistently higher daytime concentrations, coinciding with a daytime increase in large fungal spores, fern spores, pollen grains, and, to a lesser extent, plant fragments (generally >20 μm in diameter), probably driven by lowered relative humidity and enhanced wind speeds/convective activity during the day. For the fine aerosol samples a series of dicarboxylic and hydroxyacids were detected with persistently higher daytime concentrations, suggesting that photochemical production of a secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Anhydrosugars (levoglucosan, mannosan, galactosan), which are specific tracers for biomass burning, were detected only at low levels in the fine aerosol samples. On the basis of the levoglucosan‐to‐OC emission ratio measured for biomass burning aerosol, we estimate that an average of ∼16% of the OC in the fine aerosol was due to biomass burning during CLAIRE 2001, indicating that the major fraction was associated with biogenic particles.

Evolution of aerosol properties over the rain forest in Surinam, South America, observed from aircraft during the LBA‐CLAIRE 98 experiment

As part of the Large‐Scale Biosphere‐Atmosphere Experiment in Amazonia (LBA)‐Cooperative LBA Airborne Regional Experiment, airborne measurements of aerosol properties over the northeast Amazonian rain forest at an altitude range between 0.2 and 12.6 km were performed in March 1998. The particle number densities in the free troposphere, normalized to standard temperature and pressure, exceed number densities observed in boundary layer by a factor of 2–15. Typical number densities in the boundary layer were around 500 cm−3. The large difference in particle number density between the boundary layer and the free troposphere agrees with previous observations of the in situ new particle production in the free troposphere. Analysis of the air mass history showed that even after more than a week of transport in the middle free troposphere, the newly formed ultrafine particles were more than one third of the total aerosol number concentration. Aerosol size distributions between 0.006 and 3 μm, divided into six vertical layers, show a C‐shaped vertical structure with high concentrations of accumulation mode aerosols in the mixing layer and in the free troposphere above 10 km. The lower concentrations were observed in the free troposphere between 4 and 8 km. Enrichment in accumulation mode aerosol at altitudes above 10 km was attributed to outflow from deep convective clouds.

Submicrometer aerosol particle size distribution and hygroscopic growth measured in the Amazon rain forest during the wet season

The number‐size distribution and hygroscopic growth of submicrometer aerosol particles were measured in central Amazonia during the first Cooperative LBA Airborne Regional Experiment (CLAIRE) wet season experiment in March–April 1998. This was the first time ever that these types of measurements were performed in the Amazon rain forest. A Differential Mobility Particle Sizer (DMPS) was used to measure aerosol number‐size distribution with diameters in the range 3–850 nm. The observed total number concentrations were frequently between 300 and 600 cm−3 with a mean value around 450 cm−3. Two aerosol particle modes (Aitken and accumulation mode) were always present. The average particle concentrations for those two modes were 239 and 177 cm−3, with geometric diameters of 68 and 151 nm, respectively. An ultrafine mode had a number concentration and a mean diameter of 92 cm−3 and 24 nm, respectively, and only occurred at 18% of the time, causing the size distribution to be trimodal instead of bimodal. The hygroscopic growth of aerosol particles was measured in situ with a Hygroscopic Tandem Differential Mobility Analyzer (H‐TDMA) at six dry particle diameters between 35 and 265 nm. In contrast to the bimodal hygroscopic behavior found in polluted continental environments, the hygroscopic properties of aerosol particles in the Amazon rain forest is essentially unimodal with average diameter growth factors of 1.16–1.32 from dry to 90% relative humidity (RH). Aerosol soluble volume fractions were, in general, between 0.14 and 0.27, estimated by assuming that only ammonium hydrogen sulphate interacted with water vapour.

Saharan dust in Brazil and Suriname during the Large‐Scale Biosphere‐Atmosphere Experiment in Amazonia (LBA) ‐ Cooperative LBA Regional Experiment (CLAIRE) in March 1998

Advection of Saharan dust was observed via chemical and optical measurements during March 1998 in Brazil and Suriname during the Large‐Scale Biosphere‐Atmosphere Experiment in Amazonia (LBA)‐Cooperative LBA Airborne Regional Experiment (CLAIRE)‐98 experiment. In Brazil the dust outbreak produced an increase of a factor of 3 in the daily mean mass concentration (up to 26±7 μg m−3) of particles smaller than 10 μm equivalent aerodynamic diameter (EAD), and in the daily mean aerosol particle scattering coefficient σs (up to 26±8 Mm−1 STP, ambient humidity). Background levels of aerosol scattering (ambient) were σs ∼ 10 Mm−1. The effect of dust advection was evident for all major crustal elements (Al, Si, Ca, Ti, Mn, and Fe), as well as the sea‐salt elements (Na, Cl, and S), as the dust layer was transported at low altitude (below 800 hPa). Coarse P and organic carbon (OC) concentrations were not influenced by the occurrence of dust, and were mainly emitted by the rain forest. The dry scattering mass efficiency of dust (particles smaller than 10 μm EAD) was estimated to be between 0.65 (±0.06) and 0.89 (±0.08) m2 g−1. Airborne profiles of aerosol scattering showed two distinct types of vertical structure in the dust layer over Suriname, either vertically uniform (15, 26 March), or plume‐like (25 March). Dust layers extended generally up to 700 hPa, while scattering layers occasionally encountered at higher altitudes resulted from smoke emitted by biomass burning in Venezuela and Colombia. Observations in South America were supported by measurements in Israel and Tenerife (Canary Islands), where the dust outbreaks were also detected.

Atmospheric volatile organic compounds (VOC) at a remote tropical forest site in central Amazonia

According to recent assessments, tropical woodlands contribute about half of all global natural non-methane volatile organic compound (VOC) emissions. Large uncertainties exist especially about fluxes of compounds other than isoprene and monoterpenes. During the Large-Scale Biosphere/Atmosphere Experiment in Amazonia – Cooperative LBA Airborne Regional Experiment 1998 (LBA-CLAIRE-98) campaign, we measured the atmospheric mixing ratios of different species of VOC at a ground station at Balbina, Amazonia. The station was located 100 km north of Manaus, SE of the Balbina reservoir, with 200–1000 km of pristine forest in the prevailing wind directions. Sampling methods included DNPH-coated cartridges for carbonyls and cartridges filled with graphitic carbons of different surface characteristics for other VOCs. The most prominent VOC species present in air were formaldehyde and isoprene, each up to several ppb. Concentrations of methylvinyl ketone as well as methacroleine, both oxidation products of isoprene, were relatively low, indicating a very low oxidation capacity in the lower atmospheric boundary layer, which is in agreement with a daily ozone maximum of <20 ppb. Total monoterpene concentration was below 1 ppb. We detected only very low amounts of VOC species, such as benzene, deriving exclusively from anthropogenic sources.