• Energy Research

Plantations of hybrid poplar are used in temperate regions to produce woody biomass for forestry‐related industries and are likely to become more prevalent if they are used as a source of cellulose for second‐generation biofuels. Species in the genus Populus are known to emit great quantities of the volatile organic compounds (VOCs) isoprene and methanol, and lesser quantities of terpene VOCs, giving poplar plantations the potential to significantly influence regional atmospheric chemistry. The goals of this study were to quantify the differences in isoprene, methanol, and monoterpene emissions from 30 hybrid poplar genotypes, determine how well VOC emissions could be explained by growth, photosynthesis, and stomatal conductance, determine whether the parental crosses that created a genotype could be used to predict its emissions, and determine whether VOC emissions from different genotypes exhibit different responses to elevated CO2. We found that 40–50% of the variation in isoprene emissions across genotypes could be explained by a combination of instantaneous photosynthesis rate and seasonal aboveground growth and 30–35% of methanol emissions could be explained by stomatal conductance. We observed a threefold range in isoprene emissions across all 30 genotypes. Both genotype and parental cross were significant predictors of isoprene and monoterpene emissions. Genotypes from P. tricocarpa × P. deltoides (T × D) crosses generally had higher isoprene emissions and lower monoterpene emissions than those from P. deltoides × P. nigra (D × N) crosses. While isoprene and monoterpene emissions generally decreased under elevated CO2 and methanol emissions generally increased, the responses varied among genotypes. Our findings suggest that genotypes with greater productivity tend to have higher isoprene emissions. Additionally, the genotypes with the lowest isoprene emissions under current CO2 are not necessarily the ones with the lowest emissions under elevated CO2.

Abstract. Vegetation commonly managed by prescribed burning was collected from five southeastern and southwestern US military bases and burned under controlled conditions at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The smoke emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP-FTIR) spectrometer for measurement of gas-phase species. The OP-FTIR detected and quantified 19 gas-phase species in these fires: CO2, CO, CH4, C2H2, C2H4, C3H6, HCHO, HCOOH, CH3OH, CH3COOH, furan, H2O, NO, NO2, HONO, NH3, HCN, HCl, and SO2. Emission factors for these species are presented for each vegetation type burned. Gas-phase nitrous acid (HONO), an important OH precursor, was detected in the smoke from all fires. The HONO emission factors ranged from 0.15 to 0.60 g kg−1 and were higher for the southeastern fuels. The fire-integrated molar emission ratios of HONO (relative to NOx) ranged from approximately 0.03 to 0.20, with higher values also observed for the southeastern fuels. The majority of non-methane organic compound (NMOC) emissions detected by OP-FTIR were oxygenated volatile organic compounds (OVOCs) with the total identified OVOC emissions constituting 61±12% of the total measured NMOC on a molar basis. These OVOC may undergo photolysis or further oxidation contributing to ozone formation. Elevated amounts of gas-phase HCl and SO2 were also detected during flaming combustion, with the amounts varying greatly depending on location and vegetation type. The fuels with the highest HCl emission factors were all located in the coastal regions, although HCl was also observed from fuels farther inland. Emission factors for HCl were generally higher for the southwestern fuels, particularly those found in the chaparral biome in the coastal regions of California.

The Marcellus Shale is a rapidly developing unconventional natural gas resource found in part of the Appalachian region. Air quality and climate concerns have been raised regarding development of unconventional natural gas resources. Two ground-based mobile measurement campaigns were conducted to assess the impact of Marcellus Shale natural gas development on local scale atmospheric background concentrations of air pollution and climate relevant pollutants in Pennsylvania. The first campaign took place in Northeastern and Southwestern PA in the summer of 2012. Compounds monitored included methane (CH4), ethane, carbon monoxide (CO), nitrogen dioxide, and Proton Transfer Reaction Mass Spectrometer (PTR-MS) measured volatile organic compounds (VOC) including oxygenated and aromatic VOC. The second campaign took place in Northeastern PA in the summer of 2015. The mobile monitoring data were analyzed using interval percentile smoothing to remove bias from local unmixed emissions to isolate local-scale background concentrations. Comparisons were made to other ambient monitoring in the Marcellus region including a NOAA SENEX flight in 2013. Local background CH4 mole fractions were 140 ppbv greater in Southwestern PA compared to Northeastern PA in 2012 and background CH4 increased 100 ppbv from 2012 to 2015. CH4 local background mole fractions were not found to have a detectable relationship between well density or production rates in either region. In Northeastern PA, CO was observed to decrease 75 ppbv over the three year period. Toluene to benzene ratios in both study regions were found to be most similar to aged rural air masses indicating that the emission of aromatic VOC from Marcellus Shale activity may not be significantly impacting local background concentrations. In addition to understanding local background concentrations the ground-based mobile measurements were useful for investigating the composition of natural gas emissions in the region.

Biomass burning (BB) is a large source of reactive compounds in the atmosphere. While the daytime photochemistry of BB emissions has been studied in some detail, there has been little focus on nighttime reactions despite the potential for substantial oxidative and heterogeneous chemistry. Here, we present the first analysis of nighttime aircraft intercepts of agricultural BB plumes using observations from the NOAA WP-3D aircraft during the 2013 Southeast Nexus (SENEX) campaign. We use these observations in conjunction with detailed chemical box modeling to investigate the formation and fate of oxidants (NO3, N2O5, O3, and OH) and BB volatile organic compounds (BBVOCs), using emissions representative of agricultural burns (rice straw) and western wildfires (ponderosa pine). Field observations suggest NO3 production was approximately 1 ppbv hr-1, while NO3 and N2O5 were at or below 3 pptv, indicating rapid NO3/N2O5 reactivity. Model analysis shows that >99% of NO3/N2O5 loss is due to BBVOC + NO3 reactions rather than aerosol uptake of N2O5. Nighttime BBVOC oxidation for rice straw and ponderosa pine fires is dominated by NO3 (72, 53%, respectively) but O3 oxidation is significant (25, 43%), leading to roughly 55% overnight depletion of the most reactive BBVOCs and NO2.

Catechol (1,2-benzenediol) is emitted from biomass burning and produced from a reaction of phenol with OH radicals. It has been suggested as an important secondary organic aerosol (SOA) precursor, but the mechanisms of gas-phase oxidation and SOA formation have not been investigated in detail. In this study, catechol was reacted with OH and NO3 radicals in the presence of NOx in an environmental chamber to simulate daytime and nighttime chemistry. These reactions produced SOA with exceptionally high mass yields of 1.34 ± 0.20 and 1.50 ± 0.20, respectively, reflecting the low volatility and high density of reaction products. The dominant SOA product, 4-nitrocatechol, for which an authentic standard is available, was identified through thermal desorption particle beam mass spectrometry and Fourier transform infrared spectroscopy and was quantified in filter samples by liquid chromatography using UV detection. Molar yields of 4-nitrocatechol were 0.30 ± 0.03 and 0.91 ± 0.06 for reactions with OH and NO3 radicals, and thermal desorption measurements of volatility indicate that it is semivolatile at typical atmospheric aerosol loadings, consistent with field studies that have observed it in aerosol particles. Formation of 4-nitrocatechol is initiated by abstraction of a phenolic H atom by an OH or NO3 radical to form a β-hydroxyphenoxy/o-semiquinone radical, which then reacts with NO2 to form the final product.

Biomass burning is the largest combustion-related source of volatile organic compounds (VOCs) to the atmosphere. We describe the development of a state-of-the-science model to simulate the photochemical formation of secondary organic aerosol (SOA) from biomass-burning emissions observed in dry (RH <20%) environmental chamber experiments. The modeling is supported by (i) new oxidation chamber measurements, (ii) detailed concurrent measurements of SOA precursors in biomass-burning emissions, and (iii) development of SOA parameters for heterocyclic and oxygenated aromatic compounds based on historical chamber experiments. We find that oxygenated aromatic compounds, including phenols and methoxyphenols, account for slightly less than 60% of the SOA formed and help our model explain the variability in the organic aerosol mass (R2 = 0.68) and O/C (R2 = 0.69) enhancement ratios observed across 11 chamber experiments. Despite abundant emissions, heterocyclic compounds that included furans contribute to ∼20% of the total SOA. The use of pyrolysis-temperature-based or averaged emission profiles to represent SOA precursors, rather than those specific to each fire, provide similar results to within 20%. Our findings demonstrate the necessity of accounting for oxygenated aromatics from biomass-burning emissions and their SOA formation in chemical mechanisms.