Emissions Relationships in Western Forest Fire Plumes: I. Reducing the Effect of Mixing Errors on Emission Factors

Studies of emission factors from biomass burning using aircraft data complement the results of lab studies and extend them to conditions of immense hot conflagrations. We illustrate and discuss emission relationships for 422 individual samples from many forest-fire plumes in the Western US. The samples are from two NASA investigations: ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) and SEAC4RS (Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys). This work provides sample-by-sample enhancement ratios (EnRs) for 23 gases and particulate properties. Many EnRs provide candidates for emission ratios (ERs, corresponding to the EnR at the source) when the origin and degree of transformation is understood and appropriate. From these, emission factors (EFs) can be estimated when the fuel dry mass consumed is known or can be estimated using the carbon mass budget approach. This analysis requires understanding the interplay of mixing of the plume with surrounding air. Some initial examples emphasize that measured C(tot) = CO2 + CO in a fire plume does not necessarily describe the emissions of the total carbon liberated in the flames, C(burn). Rather, it represents C(tot) = C(burn) + C(bkgd), which includes possibly varying background concentrations for entrained air. Consequently, we present a simple theoretical description for plume entrainment for multiple tracers from flame to hundreds of kilometers downwind and illustrate some intrinsic linear behaviors. The analysis suggests a Mixed Effects Regression Emission Technique (MERET), which can eliminate occasional strong biases associated with the commonly used normalized excess mixing ratio (NEMR) method. MERET splits C(tot) to reveal C(burn) by exploiting the fact that C(burn) and all tracers respond linearly to dilution, while each tracer has consistent EnR behavior (slope of tracer concentration with respect to C(burn)). The two effects are separable. Two or three or preferably more emission indicators are required as a minimum; here we used ten. Limited variations in the EnRs for each tracer can be incorporated and the variations and co-variations analyzed. The percentage CO yield (or the modified combustion efficiency) plays some role. Other co-relationships involving nitrogen and organic classes are more prominent; these have strong relationships to the C(burn) to O3 emission relationship. In summary, MERET allows fine spatial resolution (EnRs for individual observations) and comparison of similar plumes distant in time and space. Alkene ratios provide us with an approximate photochemical timescale. This allows discrimination and definition, by fire situation, of ERs, allowing us to estimate emission factors

Techniques for Estimating Emissions Factors from Forest Burning: ARCTAS and SEAC4RS Airborne Measurements Indicate which Fires Produce Ozone

Previous studies of emission factors from biomass burning are prone to large errors since they ignore the interplay of mixing and varying pre-fire background CO2 levels. Such complications severely affected our studies of 446 forest fire plume samples measured in the Western US by the science teams of NASA's SEAC4RS and ARCTAS airborne missions. Consequently we propose a Mixed Effects Regression Emission Technique (MERET) to check techniques like the Normalized Emission Ratio Method (NERM), where use of sequential observations cannot disentangle emissions and mixing. We also evaluate a simpler "consensus" technique. All techniques relate emissions to fuel burned using C(burn) = delta C(tot) added to the fire plume, where C(tot) approximately equals (CO2 = CO). Mixed-effects regression can estimate pre-fire background values of C(tot) (indexed by observation j) simultaneously with emissions factors indexed by individual species i, delta, epsilon lambda tau alpha-x(sub I)/C(sub burn))I,j. MERET and "consensus" require more than emissions indicators. Our studies excluded samples where exogenous CO or CH4 might have been fed into a fire plume, mimicking emission. We sought to let the data on 13 gases and particulate properties suggest clusters of variables and plume types, using non-negative matrix factorization (NMF). While samples were mixtures, the NMF unmixing suggested purer burn types. Particulate properties (b scant, b abs, SSA, AAE) and gas-phase emissions were interrelated. Finally, we sought a simple categorization useful for modeling ozone production in plumes. Two kinds of fires produced high ozone: those with large fuel nitrogen as evidenced by remnant CH3CN in the plumes, and also those from very intense large burns. Fire types with optimal ratios of delta-NOy/delta- HCHO associate with the highest additional ozone per unit Cburn, Perhaps these plumes exhibit limited NOx binding to reactive organics. Perhaps these plumes exhibit limited NOx binding to reactive organic

Emissions Relationships Among Western Forest Fire Plumes: I. Emission Factors Free from Mixing Errors

Previous studies of emission factors from biomass burning are prone to largeerrors since they ignore the interplay of mixing and varying pre-fire backgroundCO2 levels. Such complications severely affected our studies of 446 forest fireplume samples measured in the Western US by the science teams of NASAsSEAC4RS and ARCTAS airborne missions. Consequently we propose a MixedEffects Regression Emission Technique (MERET) to check techniques like theNormalized Emission Ratio Method (NERM), where use of sequentialobservations cannot disentangle emissions and mixing. We also evaluate asimpler consensus technique. All techniques relate emissions to fuel burnedusing C burn = Ctot added to the fire plume, where Ctot (CO2 + CO). Mixed-effectsregression can estimate pre-fire background values of Ctot (indexed byobservation j) simultaneously with emissions factors indexed by individual species i, -xi (Cburn )i,j., MERET and consensus require more than twoemissions indicators. Our studies excluded samples where exogenous CO orCH4 might have been fed into a fire plume, mimicking emission.We sought to let the data on 13 gases and particulate properties suggest clustersof variables and plume types, using non-negative matrix factorization (NMF).While samples were mixtures, the NMF unmixing suggested purer burn types.Particulate properties (bscat, babs, SSA, AE) and gas-phase emissions were interrelated.Finally, we sought a simple categorization useful for modeling ozone productionin plumes. Two kinds of fires produced high ozone: those with large fuel nitrogenas evidenced by remnant CH3CN in the plumes, and also those from veryintense large burns. Fire types with optimal ratios of delta-NOydelta-HCHO associate with the highest additional ozone per unit Cburn, Perhaps theseplumes exhibit limited NOx binding to reactive organics. Perhaps these plumesexhibit limited NOx binding to reactive organics

Vertical Resolved Dust Mass Concentration and Backscatter Coefficient Retrieval of Asian Dust Plume Using Quartz Raman Channel in Lidar Measurements

In this work, we present a method for estimating vertical resolved mass concentration of dust immersed in Asian dust plume using Raman scattering of quartz (silicon dioxide, silica). During the Asian dust period of March 15, 16, and 21 in 2010, Raman lidar measurements detected the presence of quartz, and successfully showed the vertical profiles of the quartz backscatter coefficient. Since the Raman backscatter coefficient was connected with the Raman backscatter differential cross section and the number density of quartz molecules, the mass concentration of quartz in the atmosphere can be estimated from the quartz backscatter coefficient. The weight percentage from 40 to 70 % for quartz in the Asian dust was estimated from references. The vertical resolved mass concentration of dust was estimated by quartz mass concentration and weight percentage. We also present a retrieval method to obtain dust backscatter coefficient from the mixed Asian dust and pollutant layer. OPAC (Optical Properties of Aerosol and Clouds) simulations were conducted to calculate dust backscatter coefficient. The retrieved dust mass concentration was used as an input parameter for the OPAC calculations. These approaches in the study will be useful for characterizing the quartz dominated in the atmospheric aerosols and estimating vertical resolved mass concentration of dust. It will be especially applicable for optically distinguishing the dust and non-dust aerosols in studies on the mixing state of Asian dust plume. Additionally, the presented method combined with satellite observations is enable qualitative and quantitative monitoring for Asian dust

Ground-based aerosol characterization during the South American Biomass Burning Analysis (SAMBBA) field experiment

This paper investigates the physical and chemical characteristics of aerosols at ground level at a site heavily impacted by biomass burning. The site is located near Porto Velho, Rondônia, in the southwestern part of the Brazilian Amazon rainforest, and was selected for the deployment of a large suite of instruments, among them an Aerosol Chemical Speciation Monitor. Our measurements were made during the South American Biomass Burning Analysis (SAMBBA) field experiment, which consisted of a combination of aircraft and ground-based measurements over Brazil, aimed to investigate the impacts of biomass burning emissions on climate, air quality, and numerical weather prediction over South America. The campaign took place during the dry season and the transition to the wet season in September/October 2012. During most of the campaign, the site was impacted by regional biomass burning pollution (average CO mixing ratio of 0.6 ppm), occasionally superimposed by intense (up to 2 ppm of CO), freshly emitted biomass burning plumes. Aerosol number concentrations ranged from ∼ 1000 cm−3 to peaks of up to 35 000 cm−3 (during biomass burning (BB) events, corresponding to an average submicron mass mean concentrations of 13.7 µg m−3 and peak concentrations close to 100 µg m−3 . Organic aerosol strongly dominated the submicron non-refractory composition, with an average concentration of 11.4 µg m−3 . The inorganic species, NH4, SO4, NO3, and Cl, were observed, on average, at concentrations of 0.44, 0.34, 0.19, and 0.01 µg m−3 , respectively. Equivalent black carbon (BCe) ranged from 0.2 to 5.5 µg m−3 , with an average concentration of 1.3 µg m−3 . During BB peaks, organics accounted for over 90 % of total mass (submicron non-refractory plus BCe), among the highest values described in the literature. We examined the ageing of biomass burning organic aerosol (BBOA) using the changes in the H : C and O : C ratios, and found that throughout most of the aerosol processing (O : C ∼= 0.25 to O : C ∼= 0.6), no remarkable change is observed in the H : C ratio (∼ 1.35). Such a result contrasts strongly with previous observations of chemical ageing of both urban and Amazonian biogenic aerosols. At higher levels of processing (O : C > 0.6), the H : C ratio changes with a H : C/O : C slope of −0.5, possibly due to the development of a combination of BB (H : C/O : C slope = 0) and biogenic (H : C/O : C slope = −1) organic aerosol (OA). An analysis of the 1OA/1CO mass ratios yields very little enhancement in the OA loading with atmospheric processing, consistent with previous observations. These results indicate that negligible secondary organic aerosol (SOA) formation occurs throughout the observed BB plume Published by Copernicus Publications on behalf of the European Geosciences Union. 12070 J. Brito et al.: Ground-based aerosol characterization during SAMBBA processing, or that SOA formation is almost entirely balanced by OA volatilization. Positive matrix factorization (PMF) of the organic aerosol spectra resulted in three factors: fresh BBOA, aged BBOA, and low-volatility oxygenated organic aerosol (LV-OOA). Analysis of the diurnal patterns and correlation with external markers indicates that during the first part of the campaign, OA concentrations are impacted by local fire plumes with some chemical processing occurring in the near-surface layer. During the second part of the campaign, long-range transport of BB plumes above the surface layer, as well as potential SOAs formed aloft, dominates OA concentrations at our ground-based sampling site. This manuscript describes the first ground-based deployment of the aerosol mass spectrometry at a site heavily impacted by biomass burning in the Amazon region, allowing a deeper understanding of aerosol life cycle in this important ecosystem.This work was supported by the Foundation for Research Support of the State of São Paulo (FAPESP, projects 2012/14437-9 and 2013/05014-0), CNPq project 475735- 2012-9, INCT Amazonia, and Natural Environment Research Council (NERC) project NE/J010073/1. We thank A. Ribeiro, A. L. Loureiro, F. Morais, F. Jorge, and S. Morais for technical and logistics support. We thank the National Institute of Meteorology for providing valuable meteorological data. We gratefully acknowledge S. Hacon, J. Silva, and W. Bastos for support in the successful operation of the sampling site

Seasonal variation of carbon monoxide in northern Japan: Fourier transform IR measurements and source-labeled model calculations

Tropospheric carbon monoxide (CO) was measured throughout 2001 using groundbased Fourier transform IR (FTIR) spectrometers at Moshiri 44.4N and Rikubetsu 43.5N) observatories in northern Japan, which are separated by 150 km. Seasonal and day-to-day variations of CO are studied using these data, and contributions from various CO sources are evaluated using three-dimensional global chemistry transport model (GEOS-CHEM) calculations. Seasonal maximum and minimum FTIR-derived tropospheric CO amounts occurred in April and September, respectively. The ratio of partial column amounts between the 0–4 and 0–12 km altitude ranges is found to be slightly greater in early spring. The GEOS-CHEM model calculations generally reproduce these observed features. Source-labeled CO model calculations suggest that the observed seasonal variation is caused by seasonal contributions from various sources, in addition to a seasonal change in chemical CO loss by OH. Changes in meteorological fields largely control the relative importance of various source contributions. The contributions from fossil fuel (FF) combustion in Asia and photochemical CO production have the greatest yearly averaged contribution at 1 km among the CO sources (31% each). The Asian FF contribution increases from winter to summer, because weak southwesterly wind in summer brings more Asian pollutants to the observation sites. The seasonal variation from photochemical CO production is small (±17% at 1 km), likely because of concurrent increases (decreases) of photochemical production and loss rates in summer (winter), with the largest contribution between August and December. The contribution from intercontinental transport of European FF combustion CO is found to be comparable to that of Asian FF sources in winter. Northwesterly wind around the Siberian high in this season brings pollutants from Europe directly to Japan, in addition to southward transport of accumulated pollution from higher latitudes. The influences are generally greater at lower altitudes, resulting in a vertical gradient in the CO profile during winter. The model underestimates total CO by 12–14% between March and June. Satellite-derived fire-count data and the relationship between FTIR-derived HCN and CO amounts are generally consistent with biomass burning influences, which could have been underestimated by the model calculations

Atmospheric mixing ratios of methyl ethyl ketone (2-butanone) in tropical, boreal, temperate and marine environments

Methyl ethyl ketone (MEK) enters the atmosphere following direct emission from vegetation and anthropogenic activities, as well as being produced by the gas-phase oxidation of volatile organic compounds (VOCs) such as n-butane. This study presents the first overview of ambient MEK measurements at six different locations, characteristic of forested, urban and marine environments. In order to understand better the occurrence and behaviour of MEK in the atmosphere, we analyse diel cycles of MEK mixing ratios, vertical profiles, ecosystem flux data, and HYSPLIT back trajectories, and compare with co-measured VOCs. MEK measurements were primarily conducted with proton-transfer-reaction mass spectrometer (PTR-MS) instruments. Results from the sites under biogenic influence demonstrate that vegetation is an important source of MEK. The diel cycle of MEK follows that of ambient temperature and the forest structure plays an important role in air mixing. At such sites, a high correlation of MEK with acetone was observed (e.g. r2 = 0.96 for the SMEAR Estonia site in a remote hemiboreal forest in Tartumaa, Estonia, and r2 = 0.89 at the ATTO pristine tropical rainforest site in central Amazonia). Under polluted conditions, we observed strongly enhanced MEK mixing ratios. Overall, the MEK mixing ratios and flux data presented here indicate that both biogenic and anthropogenic sources contribute to its occurrence in the global atmosphere

Biomass burning emission inventory with daily resolution: Application to aircraft observations of Asian outflow

Asian outflo

An airborne regional carbon balance for central amazonia

We obtained regional estimates of surface CO2 exchange rates using atmospheric boundary layer budgeting techniques above tropical forest near Manaus, Brazil. Comparisons were made with simultaneous measurements from two eddy covariance towers below. Although there was good agreement for daytime measurements, large differences emerged for integrating periods dominated by the night-time fluxes. These results suggest that a systematic underestimation of night time respiratory effluxes may be responsible for the high Amazonian carbon sink suggested by several previous eddy covariance studies. Large CO2 fluxes from riverine sources or high respiratory losses from recently disturbed forests do not need to be invoked in order to balance the carbon budget of the Amazon. Our results do not, however, discount some contribution of these processes to the overall Amazon carbon budget

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

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).\ud \ud 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 3–8×10^6 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 5.5×10^6 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.\ud \ud 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