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During the fourth Fire Lab at Missoula Experiment (FLAME-4, October–November 2012) a large variety of regionally and globally significant biomass fuels was burned at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The particle emissions were characterized by an extensive suite of instrumentation that measured aerosol chemistry, size distribution, optical properties, and cloud-nucleating properties. The trace gas measurements included high-resolution mass spectrometry, one- and two-dimensional gas chromatography, and open-path Fourier transform infrared (OP-FTIR) spectroscopy. This paper summarizes the overall experimental design for FLAME-4 – including the fuel properties, the nature of the burn simulations, and the instrumentation employed – and then focuses on the OP-FTIR results. The OP-FTIR was used to measure the initial emissions of 20 trace gases: CO<sub>2</sub>, CO, CH<sub>4</sub>, C<sub>2</sub>H<sub>2</sub>, C<sub>2</sub>H<sub>4</sub>, C<sub>3</sub>H<sub>6</sub>, HCHO, HCOOH, CH<sub>3</sub>OH, CH<sub>3</sub>COOH, glycolaldehyde, furan, H<sub>2</sub>O, NO, NO<sub>2</sub>, HONO, NH<sub>3</sub>, HCN, HCl, and SO<sub>2</sub>. These species include most of the major trace gases emitted by biomass burning, and for several of these compounds, this is the first time their emissions are reported for important fuel types. The main fire types included African grasses, Asian rice straw, cooking fires (open (three-stone), rocket, and gasifier stoves), Indonesian and extratropical peat, temperate and boreal coniferous canopy fuels, US crop residue, shredded tires, and trash. Comparisons of the OP-FTIR emission factors (EFs) and emission ratios (ERs) to field measurements of biomass burning verify that the large body of FLAME-4 results can be used to enhance the understanding of global biomass burning and its representation in atmospheric chemistry models. <br><br> Crop residue fires are widespread globally and account for the most burned area in the US, but their emissions were previously poorly characterized. Extensive results are presented for burning rice and wheat straw: two major global crop residues. Burning alfalfa produced the highest average NH<sub>3</sub> EF observed in the study (6.63 ± 2.47 g kg<sup>−1</sup>), while sugar cane fires produced the highest EF for glycolaldehyde (6.92 g kg<sup>−1</sup>) and other reactive oxygenated organic gases such as HCHO, HCOOH, and CH<sub>3</sub>COOH. Due to the high sulfur and nitrogen content of tires, they produced the highest average SO<sub>2</sub> emissions (26.2 ± 2.2 g kg<sup>−1</sup>) and high NO<sub>x</sub> and HONO emissions. High variability was observed for peat fire emissions, but they were consistently characterized by large EFs for NH<sub>3</sub> (1.82 ± 0.60 g kg<sup>−1</sup>) and CH<sub>4</sub> (10.8 ± 5.6 g kg<sup>−1</sup>). The variability observed in peat fire emissions, the fact that only one peat fire had previously been subject to detailed emissions characterization, and the abundant emissions from tropical peatlands all impart high value to our detailed measurements of the emissions from burning three Indonesian peat samples. This study also provides the first EFs for HONO and NO<sub>2</sub> for Indonesian peat fires. Open cooking fire emissions of HONO and HCN are reported for the first time, and the first emissions data for HCN, NO, NO<sub>2</sub>, HONO, glycolaldehyde, furan, and SO<sub>2</sub> are reported for "rocket" stoves: a common type of improved cookstove. The HCN / CO emission ratios for cooking fires (1.72 × 10<sup>−3</sup> ± 4.08 × 10<sup>−4</sup>) and peat fires (1.45 × 10<sup>−2</sup> ± 5.47 × 10<sup>−3</sup>) are well below and above the typical values for other types of biomass burning, respectively. This would affect the use of HCN / CO observations for source apportionment in some regions. Biomass burning EFs for HCl are rare and are reported for the first time for burning African savanna grasses. High emissions of HCl were also produced by burning many crop residues and two grasses from coastal ecosystems. HCl could be the main chlorine-containing gas in very fresh smoke, but rapid partitioning to aerosol followed by slower outgassing probably occurs.
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Particles containing soot, or black carbon, are generally considered to contribute to global warming. However, large uncertainties remain in the net climate forcing resulting from anthropogenic emissions of black carbon (BC), to a large extent due to the fact that BC is co-emitted with gases and primary particles, both organic and inorganic, and subject to atmospheric ageing processes. In this study, diesel exhaust particles and particles from a flame soot generator spiked with light aromatic secondary organic aerosol (SOA) precursors were processed by UV radiation in a 6 m<sup>3</sup> Teflon chamber in the presence of NO<sub>x</sub>. The time-dependent changes of the soot nanoparticle properties were characterised using a Cloud Condensation Nuclei Counter, an Aerosol Particle Mass Analyzer and a Soot Particle Aerosol Mass Spectrometer. The results show that freshly emitted soot particles do not activate into cloud droplets at supersaturations ≤2%, i.e. the BC core coated with primary organic aerosol (POA) from the exhaust is limited in hygroscopicity. Before the onset of UV radiation it is unlikely that any substantial SOA formation is taking place. An immediate change in cloud-activation properties occurs at the onset of UV exposure. This change in hygroscopicity is likely attributed to SOA formed from intermediate volatility organic compounds (IVOCs) in the diesel engine exhaust. The change of cloud condensation nuclei (CCN) properties at the onset of UV radiation implies that the lifetime of soot particles in the atmosphere is affected by the access to sunlight, which differs between latitudes. The ageing of soot particles progressively enhances their ability to act as cloud condensation nuclei, due to changes in: (I) organic fraction of the particle, (II) chemical properties of this fraction (e.g. primary or secondary organic aerosol), (III) particle size, and (IV) particle morphology. Applying κ-Köhler theory, using a κ<sub>SOA</sub> value of 0.13 (derived from independent input parameters describing the organic material), showed good agreement with cloud droplet activation measurements for particles with a SOA mass fraction ≥0.12 (slightly aged particles). The activation properties are enhanced with only a slight increase in organic material coating the soot particles (SOA mass fraction < 0.12), however not as much as predicted by Köhler theory. The discrepancy between theory and experiments during the early stages of ageing might be due to solubility limitations, unevenly distributed organic material or hindering particle morphology. <br><br> The change in properties of soot nanoparticles upon photochemical processing clearly increases their hygroscopicity, which affects their behaviour both in the atmosphere and in the human respiratory system.
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This study is the first in a series of papers that aim to develop high-resolution emission databases for different anthropogenic sources in China. Here we focus on on-road transportation. Because of the increasing impact of on-road transportation on regional air quality, developing an accurate and high-resolution vehicle emission inventory is important for both the research community and air quality management. This work proposes a new inventory methodology to improve the spatial and temporal accuracy and resolution of vehicle emissions in China. We calculate, for the first time, the monthly vehicle emissions for 2008 in 2364 counties (an administrative unit one level lower than city) by developing a set of approaches to estimate vehicle stock and monthly emission factors at county-level, and technology distribution at provincial level. We then introduce allocation weights for the vehicle kilometers traveled to assign the county-level emissions onto 0.05° × 0.05° grids based on the China Digital Road-network Map (CDRM). The new methodology overcomes the common shortcomings of previous inventory methods, including neglecting the geographical differences between key parameters and using surrogates that are weakly related to vehicle activities to allocate vehicle emissions. The new method has great advantages over previous methods in depicting the spatial distribution characteristics of vehicle activities and emissions. This work provides a better understanding of the spatial representation of vehicle emissions in China and can benefit both air quality modeling and management with improved spatial accuracy.
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We evaluate the isotopic composition of water vapor and precipitation simulated by the LMDZ (Laboratoire de Météorologie Dynamique-Zoom) GCM (General Circulation Model) over Siberia using several data sets: TES (Tropospheric Emission Spectrometer) and GOSAT (Greenhouse gases Observing SATellite) satellite observations of tropospheric water vapor, GNIP (Global Network for Isotopes in Precipitation) and SNIP (Siberian Network for Isotopes in Precipitation) precipitation networks, and daily, in situ measurements of water vapor and precipitation at the Kourovka site in Western Siberia. LMDZ captures the spatial, seasonal and daily variations reasonably well, but it underestimates humidity (<i>q</i>) in summer and overestimates δ<i>D</i> in the vapor and precipitation in all seasons. The performance of LMDZ is put in the context of other isotopic models from the SWING2 (Stable Water Intercomparison Group phase 2) models. There is significant spread among models in the simulation of δ<i>D</i>, and of the δ<i>D</i>-<i>q</i> relationship. This confirms that δ<i>D</i> brings additional information compared to <i>q</i> only. We specifically investigate the added value of water isotopic measurements to interpret the warm and dry bias featured by most GCMs over mid and high latitude continents in summer. The analysis of the slopes in δ<i>D</i>-<i>q</i> diagrams and of processes controlling δ<i>D</i> and <i>q</i> variations suggests that the cause of the dry bias could be either a problem in the large-scale advection transporting too much dry and warm air from the south, or too strong boundary-layer mixing. However, δ<i>D</i>-<i>q</i> diagrams using the available data do not tell the full story. Additional measurements would be needed, or a more sophisticated theoretical framework would need to be developed.
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Tropical trees are known to be large emitters of biogenic volatile organic compounds (BVOC), accounting for up to 75% of the global isoprene budget. Once in the atmosphere, these compounds influence multiple processes associated with air quality and climate. However, uncertainty in biogenic emissions is two-fold, (1) the environmental controls over isoprene emissions from tropical forests remain highly uncertain; and (2) our ability to accurately represent these environmental controls within models is lacking. This study evaluated the biophysical parameters that drive the global Model of Emissions of Gases and Aerosols from Nature (MEGAN) embedded in a biogeochemistry land surface model, the Community Land Model (CLM), with a focus on isoprene emissions from an Amazonian forest. Upon evaluating the sensitivity of 19 parameters in CLM that currently influence isoprene emissions by using a Monte Carlo analysis, up to 61% of the uncertainty in mean isoprene emissions was caused by the uncertainty in the parameters related to leaf temperature. The eight parameters associated with photosynthetic active radiation (PAR) contributed in total to only 15% of the uncertainty in mean isoprene emissions. Leaf temperature was strongly correlated with isoprene emission activity (<i>R</i><sup>2</sup> = 0.89). However, when compared to field measurements in the Central Amazon, CLM failed to capture the upper 10–14 °C of leaf temperatures throughout the year (i.e., failed to represent ~32 to 46 °C), and the spread observed in field measurements was not representative in CLM. This is an important parameter to accurately simulate due to the non-linear response of emissions to temperature. MEGAN-CLM 4.0 overestimated isoprene emissions by 60% for a Central Amazon forest (5.7 mg m<sup>−2</sup> h<sup>−1</sup> vs. 3.6 mg m<sup>−2</sup> h<sup>−1</sup>), but due to reductions in leaf area index (LAI) by 28% in MEGAN-CLM 4.5 isoprene emissions were within 7% of observed data (3.8 mg m<sup>−2</sup> h<sup>−1</sup>). When a slight adjustment to leaf temperature was made to match observations, isoprene emissions increased 24%, up to 4.8 mg m<sup>−2</sup> h<sup>−1</sup>. Air temperatures are very likely to increase in tropical regions as a result of human induced climate change. Reducing the uncertainty of leaf temperature in BVOC algorithms, as well as improving the accuracy of replicating leaf temperature output in land surface models is warranted in order to improve estimations of tropical BVOC emissions.
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Increases in free-tropospheric (FT) ozone based on ozonesonde records from the early 1990s through 2008 over two subtropical stations, Irene (near Pretoria, South Africa) and Réunion (21° S, 55° E; ~2800 km NE of Irene in the Indian Ocean), have been reported. Over Irene a large increase in the urban-influenced boundary layer (BL, 1.5–4 km) was also observed during the 18-year period, equivalent to 30% decade<sup>−1</sup>. Here we show that the Irene BL trend is at least partly due to a gradual change in the sonde launch times from early morning to the midday period. The FT ozone profiles over Irene in 1990–2007 are re-examined, filling in a 1995–1999 gap with ozone profiles taken during the Measurements of Ozone by Airbus In-service Aircraft (MOZAIC) project over nearby Johannesburg. A multivariate regression model that accounts for the annual ozone cycle, El Niño–Southern Oscillation (ENSO) and possible tropopause changes was applied to monthly averaged Irene data from 4 to 11 km and to 1992–2011 Réunion sonde data from 4 to 15 km. Statistically significant trends appear predominantly in the middle and upper troposphere (UT; 4–11 km over Irene, 4–15 km over Réunion) in winter (June–August), with increases ~1 ppbv yr<sup>−1</sup> over Irene and ~2 ppbv yr<sup>−1</sup> over Réunion. These changes are equivalent to ~25 and 35–45% decade<sup>−1</sup>, respectively. Both stations also display smaller positive trends in summer, with a 45% decade<sup>−1</sup> ozone increase near the tropopause over Réunion in December. To explain the ozone increases, we investigated a time series of dynamical markers, e.g., potential vorticity (PV) at 330–350 K. PV affects UT ozone over Irene in November–December but displays little relationship with ozone over Réunion. A more likely reason for wintertime FT ozone increases over Irene and Réunion appears to be long-range transport of growing pollution in the Southern Hemisphere. The ozone increases are consistent with trajectory origins of air parcels sampled by the sondes and with recent NO<sub>x</sub> emissions trends estimated for Africa, South America and Madagascar. For Réunion trajectories also point to sources from the eastern Indian Ocean and Asia.
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We investigate factors that drive the variability in total column CO<sub>2</sub> at the Total Carbon Column Observing Network sites in the Southern Hemisphere using fluxes tagged by process and by source region from the CarbonTracker analysed product as well as the Simple Biosphere model. We show that the terrestrial biosphere is the largest driver of variability in the Southern Hemisphere column CO<sub>2</sub>. However, it does not dominate in the same fashion as in the Northern Hemisphere. Local- and hemispheric-scale biomass burning can also play an important role, particularly at the tropical site, Darwin. The magnitude of seasonal variability in the column-average dry-air mole fraction of CO<sub>2</sub>, X<sub>CO<sub>2</sub></sub>, is also much smaller in the Southern Hemisphere and comparable in magnitude to the annual increase. Comparison of measurements to the model simulations highlights that there is some discrepancy between the two time series, especially in the early part of the Darwin data record. We show that this mismatch is most likely due to erroneously estimated local fluxes in the Australian tropical region, which are associated with enhanced photosynthesis caused by early rainfall during the tropical monsoon season.
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An increase in atmospheric aerosol loading could alter the microphysics, dynamics, and radiative characteristics of deep convective clouds. Earlier modeling studies have shown that the effects of increased aerosols on the amount of precipitation from deep convective clouds are model-dependent. This study aims to understand the effects of increased aerosol loading on a deep convective cloud throughout its lifetime with the use of the Weather Research and Forecasting (WRF) model as a cloud-resolving model (CRM). It simulates an idealized supercell thunderstorm with 8 different aerosol loadings, for three different cloud microphysics schemes. Variation in aerosol concentration is mimicked by varying either cloud droplet number concentration or the number of activated cloud condensation nuclei. We show that the sensitivity to aerosol loading is dependent on the choice of microphysics scheme. For the schemes that are sensitive to aerosols loading, the production of graupel via riming of snow is the key factor determining the precipitation response. The formulation of snow riming depends on the microphysics scheme and is usually a function of two competing effects, the size effect and the number effect. In many simulations, a decrease in riming is seen with increased aerosol loading, due to the decreased droplet size that lowers the riming efficiency drastically. This decrease in droplet size also results in a delay in the onset of precipitation, as well as so-called warm rain suppression. Although these characteristics of convective invigoration (Rosenfeld et al., 2008) are seen in the first few hours of the simulations, variation in the accumulated precipitation mainly stems from graupel production rather than convective invigoration. These results emphasize the importance of accurate representations of graupel formation in microphysics schemes.
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We report on one year of high-precision direct hourly radon observations at King Sejong Station (King George Island) beginning in February 2013. Findings are compared with historic and ongoing radon measurements from other Antarctic sites. Monthly median concentrations reduced from 72 mBq m<sup>−3</sup> in late-summer to 44 mBq m<sup>−3</sup> in late winter and early spring. Monthly 10th percentiles, ranging from 29 to 49 mBq m<sup>−3</sup>, were typical of oceanic baseline values. Diurnal cycles were rarely evident and local influences were minor, consistent with regional radon flux estimates one tenth of the global average for ice-free land. The predominant fetch region for terrestrially influenced air masses was South America (47–53° S), with minor influences also attributed to aged Australian air masses and local sources. Plume dilution factors of 2.8–4.0 were estimated for the most terrestrially influenced (South American) air masses, and a seasonal cycle in terrestrial influence on tropospheric air descending at the pole was identified and characterised.
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Lightning is one of the major natural sources of NO<sub>x</sub> in the atmosphere. A suite of time slice experiments using a stratosphere-resolving configuration of the Unified Model (UM), containing the United Kingdom Chemistry and Aerosols sub-model (UKCA), has been performed to investigate the impact of climate change on emissions of NO<sub>x</sub> from lightning (LNO<sub>x</sub>) and to highlight its critical impacts on photochemical ozone production and the oxidising capacity of the troposphere. Two Representative Concentration Pathway (RCP) scenarios (RCP4.5 and RCP8.5) are explored. LNO<sub>x</sub> is simulated to increase in a year-2100 climate by 33% (RCP4.5) and 78% (RCP8.5), primarily as a result of increases in the depth of convection. The total tropospheric chemical odd oxygen production (<i>P</i>(O<sub>x</sub>)) increases linearly with increases in total LNO<sub>x</sub> and consequently, tropospheric ozone burdens of 29 ± 4 Tg(O<sub>3</sub>) (RCP4.5) and 46 ± 4 Tg(O<sub>3</sub>) (RCP8.5) are calculated here. By prescribing a uniform surface boundary concentration for methane in these simulations, methane-driven feedbacks are essentially neglected. A simple estimate of the contribution of the feedback reduces the increase in ozone burden to 24 and 33 Tg(O<sub>3</sub>), respectively. We thus show that, through changes in LNO<sub>x</sub>, the effects of climate change counteract the simulated mitigation of the ozone burden, which results from reductions in ozone precursor emissions as part of air quality controls projected in the RCP scenarios. Without the driver of increased LNO<sub>x</sub>, our simulations suggest that the net effect of climate change would be to lower free tropospheric ozone. <br><br> In addition, we identify large climate-change-induced enhancements in the concentration of the hydroxyl radical (OH) in the tropical upper troposphere (UT), particularly over the Maritime Continent, primarily as a consequence of greater LNO<sub>x</sub>. The OH enhancement in the tropics increases oxidation of both methane (with feedbacks onto chemistry and climate) and very short-lived substances (VSLS) (with implications for stratospheric ozone depletion). We emphasise that it is important to improve our understanding of LNO<sub>x</sub> in order to gain confidence in model projections of composition change under future climate.
