Abstract
Abstract. We present the first eddy covariance flux measurements of volatile organic compounds (VOCs) using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) above a ponderosa pine forest in Colorado, USA. The high mass resolution of the PTR-TOF-MS enabled the identification of chemical sum formulas. During a 30 day measurement period in August and September 2010, 649 different ion mass peaks were detected in the ambient air mass spectrum (including primary ions and mass calibration compounds). Eddy covariance with the vertical wind speed was calculated for all ion mass peaks. On a typical day, 17 ion mass peaks, including protonated parent compounds, their fragments and isotopes as well as VOC-H+-water clusters, showed a significant flux with daytime average emissions above a reliable flux threshold of 0.1 mg compound m−2 h−1. These ion mass peaks could be assigned to seven compound classes. The main flux contributions during daytime (10:00–18:00 LT) are attributed to the sum of 2-methyl-3-buten-2-ol (MBO) and isoprene (50%), methanol (12%), the sum of acetic acid and glycolaldehyde (10%) and the sum of monoterpenes (10%). The total MBO + isoprene flux was composed of 10% isoprene and 90% MBO. There was good agreement between the light- and temperature dependency of the sum of MBO and isoprene observed for this work and those of earlier studies. The above canopy flux measurements of the sum of MBO and isoprene and the sum of monoterpenes were compared to emissions calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN 2.1). The best agreement between MEGAN 2.1 and measurements was reached using emission factors determined from site-specific leaf cuvette measurements. While the modeled and measured MBO + isoprene fluxes agree well, the emissions of the sum of monoterpenes is underestimated by MEGAN 2.1. This is expected as some factors impacting monoterpene emissions, such as physical damage of needles and branches due to storms, are not included in MEGAN 2.1. After a severe hailstorm event, 22 ion mass peaks (attributed to six compound classes plus some unknown compounds) showed an elevated flux for the two following days. The sum of monoterpene emissions was 4–23 times higher compared to emissions prior to the hailstorm while MBO emissions remained unchanged. The monoterpene emission (in mg compound m−2) during this measurement period is underestimated by 40% if the effect of this disturbance source is not considered.
Highlights
A great variety of volatile organic compounds (VOCs) is continuously emitted into the atmosphere by pyrogenic, anthropogenic and biogenic sources
biogenic VOCs (BVOCs) emissions from the biosphere have been measured using proton-transfer-reaction mass spectrometer (PTR-MS) instruments, which allow monitoring a selected set of ion mass peaks that are related to different compounds based on disjunct eddy covariance flux measurements (e.g., Karl et al, 2002)
In this paper we present above canopy flux measurements of light- and temperature-driven emissions of BVOCs from a ponderosa pine forest during 30 days in August/September 2010
Summary
A great variety of volatile organic compounds (VOCs) is continuously emitted into the atmosphere by pyrogenic, anthropogenic and biogenic sources. Total biogenic VOC sources are considered to be approximately ten times larger than the sum of anthropogenic emissions (Muller, 1992; Olivier et al, 1999; Guenther, 2002; Lamarque et al, 2010). BVOC emissions from the biosphere have been measured using proton-transfer-reaction mass spectrometer (PTR-MS) instruments, which allow monitoring a selected set of ion mass peaks that are related to different compounds based on disjunct eddy covariance flux measurements (e.g., Karl et al, 2002). The high mass resolution of the time-of-flight mass spectrometer allows for separation of isobaric compounds This instrument has been tested for flux measurements above grassland (Müller et al, 2010; Ruuskanen et al, 2011; Bamberger et al, 2011) and above a citrus plantation (Park et al, 2013).
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