[Herndon2005] "Characterization of urban pollutant emission fluxes and ambient concentration distributions using a mobile laboratory with rapid response instrumentation",
, vol. 130: Royal Society of Chemistry, pp. 327–339, 2005.
A large and increasing fraction of the planet’s population lives in megacities, especially in the developing world. These large metropolitan areas generally have very high levels of both gaseous and particulate air pollutants that have severe impacts on human health, ecosystem viability, and climate on local, regional, and even continental scales. Emissions fluxes and ambient pollutant concentration distributions are generally poorly characterized for large urban areas even in developed nations. Much less is known about pollutant sources and concentration patterns in the faster growing megacities of the developing world. New methods of locating and measuring pollutant emission sources and tracking subsequent atmospheric chemical transformations and distributions are required. Measurement modes utilizing an innovative van based mobile laboratory equipped with a suite of fast response instruments to characterize the complex and “nastier” chemistry of the urban boundary layer are described. Instrumentation and measurement strategies are illustrated with examples from the Mexico City and Boston metropolitan areas. It is shown that fleet average exhaust emission ratios of formaldehyde (HCHO), acetaldehyde (CH3CHO) and benzene (C6H6) are substantial in Mexico City, with gasoline powered vehicles emitting higher levels normalized by fuel consumption. NH3 exhaust emissions from newer light duty vehicles in Mexico City exceed levels from similar traffic in Boston. A mobile conditional sampling air sample collection mode designed to collect samples from intercepted emission plumes for later analysis is also described.
[FeilbergTavsNyord2011] "Chemical evaluation of odor reduction by soil injection of animal manure.",
J Environ Qual
, vol. 40, no. 5: Dep. of Biosystem Engineering, Faculty of Science and Technology, Aarhus Univ., Denmark. firstname.lastname@example.org, pp. 1674–1682, 2011.
Field application of animal manure is a major cause of odor nuisance in the local environment. Therefore, there is a need for methods for measuring the effect of technologies for reducing odor after manure application. In this work, chemical methods were used to identify key odorants from field application of pig manure based on experiments with surface application by trailing hoses and soil injection. Results from three consecutive years of field trials with full-scale equipment are reported. Methods applied were: membrane inlet mass spectrometry (MIMS), proton-transfer-reaction mass spectrometry (PTR-MS), gold-film hydrogen sulfide (H?S) detection, all performed on site, and thermal desorption gas chromatography with mass spectrometry (TD-GC/MS) based on laboratory analyses of field samples. Samples were collected from a static flux chamber often used for obtaining samples for dynamic olfactometry. While all methods were capable of detecting relevant odorants, PTR-MS gave the most comprehensive results. Based on odor threshold values, 4-methylphenol, H?S, and methanethiol are suggested as key odorants. Significant odorant reductions by soil injection were consistently observed in all trials. The flux chamber technique was demonstrated to be associated with critical errors due to compound instabilities in the chamber. This was most apparent for H?S, on a time scale of a few minutes, and on a longer time scale for methanethiol.
[Karl2008] "Chemical sensing of plant stress at the ecosystem scale",
, vol. 5, no. 3, pp. 2381–2399, 2008.
Significant ecosystem-scale emissions of methylsalicylate (MeSA), a semivolatile plant hormone thought to act as the mobile signal for systemic acquired resistance (SAR) (Park et al., 2006), were observed in an agroforest. Our measurements show that plant internal defence mechanisms can be activated in response to temperature stress and are modulated by water availability on large scales. Highest MeSA fluxes (up to 0.25 mg/m2/h) were observed after plants experienced ambient night-time temperatures of 7.5°C followed by a large daytime temperature increase (e.g. up to 22°C). Under these conditions estimated night-time leaf temperatures were as low as 4.6°C, likely inducing a response to prevent chilling injury (Ding et al., 2002). Our observations imply that plant hormones can be a significant component of ecosystem scale volatile organic compound (VOC) fluxes (e.g. as high as the total monoterpene (MT) flux) and therefore contribute to the missing VOC budget (de Carlo et al., 2004; Goldstein and Galbally, 2007). If generalized to other ecosystems and different types of stresses these findings suggest that semivolatile plant hormones have been overlooked by investigations of the impact of biogenic VOCs on aerosol formation events in forested regions (Kulmala et al., 2001; Boy et al., 2000). Our observations show that the presence of MeSA in canopy air serves as an early chemical warning signal indicating ecosystem-scale stresses before visible damage becomes apparent. As a chemical metric, ecosystem emission measurements of MeSA in ambient air could therefore support field studies investigating factors that adversely affect plant growth.
 "The Chemistry of Atmosphere-Forest Exchange (CAFE) Model ￢ﾀﾓ Part 2: Application to BEARPEX-2007 observations",
Atmospheric Chemistry and Physics
, vol. 11, pp. 1269–1294, Feb, 2011.
Link: http://nature.berkeley.edu/ahg/pubs/Wolf et al acp-11-1269-2011.pdf
<p>In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE) model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. Here, we apply CAFE to noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007). In this work we evaluate the CAFE modeling approach, demonstrate the significance of in-canopy chemistry for forest-atmosphere exchange and identify key shortcomings in the current understanding of intra-canopy processes. CAFE generally reproduces BEARPEX-2007 observations but requires an enhanced radical recycling mechanism to overcome a factor of 6 underestimate of hydroxyl (OH) concentrations observed during a warm ( 29 °C) period. Modeled fluxes of acyl peroxy nitrates (APN) are quite sensitive to gradients in chemical production and loss, demonstrating that chemistry may perturb forest-atmosphere exchange even when the chemical timescale is long relative to the canopy mixing timescale. The model underestimates peroxy acetyl nitrate (PAN) fluxes by 50% and the exchange velocity by nearly a factor of three under warmer conditions, suggesting that near-surface APN sinks are underestimated relative to the sources. Nitric acid typically dominates gross dry N deposition at this site, though other reactive nitrogen (NOy) species can comprise up to 28% of the N deposition budget under cooler conditions. Upward NO2 fluxes cause the net above-canopy NOy flux to be 30% lower than the gross depositional flux. CAFE under-predicts ozone fluxes and exchange velocities by 20%. Large uncertainty in the parameterization of cuticular and ground deposition precludes conclusive attribution of non-stomatal fluxes to chemistry or surface uptake. Model-measurement comparisons of vertical concentration gradients for several emitted species suggests that the lower canopy airspace may be only weakly coupled with the upper canopy. Future efforts to model forest-atmosphere exchange will require a more mechanistic understanding of non-stomatal deposition and a more thorough characterization of in-canopy mixing processes.</p>
 "Chemistry-turbulence interactions and mesoscale variability influence the cleansing efficiency of the atmosphere",
Geophysical Research Letters
, vol. 42, pp. 10894–10903, Dec, 2015.
<p>The hydroxyl radical (OH) is the most important oxidant in the atmosphere and the primary sink for isoprene, the dominant volatile organic compound emitted by vegetation. Recent research on the atmospheric oxidation capacity in isoprene-dominated environments has suggested missing radical sources leading to significant overestimation of the lifetime of isoprene. Here we report, for the first time, a comprehensive experimental budget of isoprene in the planetary boundary layer based on airborne flux measurements along with in situ OH observations in the Southeast and Central U.S. Our findings show that surface heterogeneity of isoprene emissions lead to a physical separation of isoprene and OH resulting in an effective slowdown in the chemistry. Depending on surface heterogeneity, the intensity of segregation (Is) could locally slow down isoprene chemistry up to 30%. The effect of segregated reactants in the planetary boundary layer on average has an influence on modeled OH radicals that is comparable to that of recently proposed radical recycling mechanisms.</p>
[Lee2005] "A comparison of new measurements of total monoterpene flux with improved measurements of speciated monoterpene flux",
Atmospheric Chemistry and Physics
, vol. 5, no. 2: Copernicus GmbH, pp. 505–513, 2005.
[Davison2009] "Concentrations and fluxes of biogenic volatile organic compounds above a Mediterranean macchia ecosystem in western Italy",
, vol. 6: EGU, pp. 1655–1670, 2009.
Emission rates and concentrations of biogenic volatile organic compounds (BVOCs) were measured at a Mediterranean coastal site at Castelporziano, approximately 25 km south-west of Rome, between 7 May and 3 June 2007, as part of the ACCENT-VOCBAS field campaign on biosphere–atmosphere interactions. Concentrations and emission rates were measured using the disjunct eddy covariance (DEC) method utilizing three different proton transfer reaction mass spectrometers (PTR-MS) so allowing a comparison between the instruments. The high resolution data from the PTR-MS instruments considerably enhances the original BEMA measurements of the mid 1990s. Depending on the measurement period, the volume mixing ratios were in the range 1.6–3.5 ppbv for methanol, 0.44–1.3 ppbv for acetaldehyde, 0.96–2.1 ppbv for acetone, 0.10–0.14 ppbv for isoprene, and 0.13–0.30 ppbv for monoterpenes. A diurnal cycle in mixing ratios was apparent with daytime maxima for methanol, acetaldehyde, acetone, and isoprene. The fluxes ranged from 370–440 μg m−2 h−1 for methanol, 180–360 μg m−2 h−1 for acetaldehyde, 180–450 μg m−2 h−1 for acetone, 71–290 μg m−2 h−1 for isoprene, and 240–860 μg m−2 h−1 for monoterpenes. From the measured flux data (7 May–3 June) an average basal emission rate for the Macchia vegetation was calculated of 430 μg m−2 h−1 for isoprene and 1100 μg m−2 h−1 for monoterpenes.
[Davison2008] "Cut-induced VOC emissions from agricultural grasslands.",
Plant Biol (Stuttg)
, vol. 10, no. 1: Department of Environmental Sciences, Lancaster University, Lancaster LA1 4YQ, UK. email@example.com, pp. 76–85, Jan, 2008.
The introduction of proton transfer reaction mass spectrometry (PTR-MS) for fast response measurements of volatile organic compounds (VOC) has enabled the use of eddy covariance methods to investigate VOC fluxes on the ecosystem scale. In this study PTR-MS flux measurements of VOC were performed over agricultural grassland during and after a cut event. Selected masses detected by the PTR-MS showed fluxes of methanol, acetaldehyde, and acetone. They were highest directly after cutting and during the hay drying phase. Simultaneously, significant fluxes of protonated ion masses 73, 81, and 83 were observed. Due to the limited identification of compounds with the PTR-MS technique, GC-MS and GC-FID-PTR-MS techniques were additionally applied. In this way, ion mass 73 could be identified as 2-butanone, mass 81 mainly as (Z)-3-hexenal, and mass 83 mainly as the sum of (Z)-3-hexenol and hexenyl acetates. Hexenal, hexenols, and the hexenyl acetates are mostly related to plant wounding during cutting. It was found that legume plants and forbs emit a higher number of different VOC species than graminoids.