scholarly journals Tethered balloon measurements of biogenic volatile organic compounds at a Boreal forest site

2003 ◽  
Vol 3 (5) ◽  
pp. 5357-5397
Author(s):  
C. Spirig ◽  
A. Guenther ◽  
J. P. Greenberg ◽  
P. Calanca ◽  
V. Tarvainen

Abstract. Measurements of biogenic volatile organic compounds (VOCs) were performed at Hyytiälä, a Boreal forest site in Southern Finland as part of the project OSOA (origin and formation of secondary organic aerosol) in August 2001. At this site, frequent formation of new particles has been observed and the role of biogenic VOCs in this process is still unclear. Tethered balloons served as platforms to collect VOC samples within the planetary boundary layer at heights up to 1.2 km above ground during daytime. Mean mixed layer concentrations of total monoterpenes varied between 10 and 170 pptv, with α-pinene, limonene and Δ3-carene as major compounds, isoprene was detected at levels of 2–35 pptv. A mixed layer gradient technique and a budget approach are applied to derive surface fluxes representative for areas of tens to hundreds of square kilometres. Effects of spatial heterogeneity in surface emissions are examined with a footprint analysis. Depending on the source area considered, mean afternoon emissions of the sum of terpenes range between 180 and 300 μg m−2 h−1 for the period of 2 to 12 August 2001. Surface fluxes close to Hyytiälä were higher than the regional average, and agree well with mean emissions predicted by a biogenic VOC emission model. Total rates of monoterpene oxidation were calculated with a photochemical model. The rates did not correlate with the occurrence of new particle formation, but the ozone pathway was of more importance on days with particle formation. Condensable vapour production from the oxidation of monoterpenes throughout the mixed layer can only account for a fraction of the increase in aerosol mass observed at the surface.

2004 ◽  
Vol 4 (1) ◽  
pp. 215-229 ◽  
Author(s):  
C. Spirig ◽  
A. Guenther ◽  
J. P. Greenberg ◽  
P. Calanca ◽  
V. Tarvainen

Abstract. Measurements of biogenic volatile organic compounds (VOCs) were performed at Hyytiälä, a Boreal forest site in Southern Finland as part of the OSOA (origin and formation of secondary organic aerosol) project in August 2001. At this site, frequent formation of new particles has been observed and the role of biogenic VOCs in this process is still unclear. Tethered balloons served as platforms to collect VOC samples within the planetary boundary layer at heights up to 1.2 km above ground during daytime. Mean mixed layer concentrations of total monoterpenes varied between 10 and 170 pptv, with a-pinene, limonene and D3-carene as major compounds, isoprene was detected at levels of 2-35 pptv. A mixed layer gradient technique and a budget approach are applied to derive surface fluxes representative for areas of tens to hundreds of square kilometres. Effects of spatial heterogeneity in surface emissions are examined with a footprint analysis. Depending on the source area considered, mean afternoon emissions of the sum of terpenes range between 180 and 300 mg m-2 h-1 for the period of 2-12 August 2001. Surface fluxes close to Hyytiälä were higher than the regional average, and agree well with mean emissions predicted by a biogenic VOC emission model. Total rates of monoterpene oxidation were calculated with a photochemical model. The rates did not correlate with the occurrence of new particle formation, but the ozone pathway was of more importance on days with particle formation. Condensable vapour production from the oxidation of monoterpenes throughout the mixed layer can only account for a fraction of the increase in aerosol mass observed at the surface.


2015 ◽  
Vol 15 (7) ◽  
pp. 3909-3932 ◽  
Author(s):  
D. Mogensen ◽  
R. Gierens ◽  
J. N. Crowley ◽  
P. Keronen ◽  
S. Smolander ◽  
...  

Abstract. Using the 1-D atmospheric chemistry transport model SOSAA, we have investigated the atmospheric reactivity of a boreal forest ecosystem during the HUMPPA-COPEC-10 campaign (summer 2010, at SMEAR~II in southern Finland). For the very first time, we present vertically resolved model simulations of the NO3 and O3 reactivity (R) together with the modelled and measured reactivity of OH. We find that OH is the most reactive oxidant (R ∼ 3 s-1) followed by NO3 (R ∼ 0.07 s-1) and O3 (R ∼ 2 × 10-5s-1). The missing OH reactivity was found to be large in accordance with measurements (∼ 65%) as would be expected from the chemical subset described in the model. The accounted OH radical sinks were inorganic compounds (∼ 41%, mainly due to reaction with CO), emitted monoterpenes (∼ 14%) and oxidised biogenic volatile organic compounds (∼ 44%). The missing reactivity is expected to be due to unknown biogenic volatile organic compounds and their photoproducts, indicating that the true main sink of OH is not expected to be inorganic compounds. The NO3 radical was found to react mainly with primary emitted monoterpenes (∼ 60%) and inorganic compounds (∼ 37%, including NO2). NO2 is, however, only a temporary sink of NO3 under the conditions of the campaign (with typical temperatures of 20–25 °C) and does not affect the NO3 concentration. We discuss the difference between instantaneous and steady-state reactivity and present the first boreal forest steady-state lifetime of NO3 (113 s). O3 almost exclusively reacts with inorganic compounds (∼ 91%, mainly NO, but also NO2 during night) and less with primary emitted sesquiterpenes (∼ 6%) and monoterpenes (∼ 3%). When considering the concentration of the oxidants investigated, we find that OH is the oxidant that is capable of removing organic compounds at a faster rate during daytime, whereas NO3 can remove organic molecules at a faster rate during night-time. O3 competes with OH and NO3 during a short period of time in the early morning (around 5 a.m. local time) and in the evening (around 7–8 p.m.). As part of this study, we developed a simple empirical parameterisation for conversion of measured spectral irradiance into actinic flux. Further, the meteorological conditions were evaluated using radiosonde observations and ground-based measurements. The overall vertical structure of the boundary layer is discussed, together with validation of the surface energy balance and turbulent fluxes. The sensible heat and momentum fluxes above the canopy were on average overestimated, while the latent heat flux was underestimated.


2019 ◽  
Vol 19 (15) ◽  
pp. 10391-10403 ◽  
Author(s):  
Jonathan Liebmann ◽  
Nicolas Sobanski ◽  
Jan Schuladen ◽  
Einar Karu ◽  
Heidi Hellén ◽  
...  

Abstract. The formation of alkyl nitrates in various oxidation processes taking place throughout the diel cycle can represent an important sink of reactive nitrogen and mechanism for chain termination in atmospheric photo-oxidation cycles. The low-volatility alkyl nitrates (ANs) formed from biogenic volatile organic compounds (BVOCs), especially terpenoids, enhance rates of production and growth of secondary organic aerosol. Measurements of the NO3 reactivity and the mixing ratio of total alkyl nitrates (ΣANs) in the Finnish boreal forest enabled assessment of the relative importance of NO3-, O3- and OH-initiated formation of alkyl nitrates from BVOCs in this environment. The high reactivity of the forest air towards NO3 resulted in reactions of the nitrate radical, with terpenes contributing substantially to formation of ANs not only during the night but also during daytime. Overall, night-time reactions of NO3 accounted for 49 % of the local production rate of ANs, with contributions of 21 %, 18 % and 12 % for NO3, OH and O3 during the day. The lifetimes of the gas-phase ANs formed in this environment were on the order of 2 h due to efficient uptake to aerosol (and dry deposition), resulting in the transfer of reactive nitrogen from anthropogenic sources to the forest ecosystem.


2013 ◽  
Vol 13 (4) ◽  
pp. 1689-1712 ◽  
Author(s):  
D. C. Oderbolz ◽  
S. Aksoyoglu ◽  
J. Keller ◽  
I. Barmpadimos ◽  
R. Steinbrecher ◽  
...  

Abstract. Biogenic volatile organic compounds (BVOC) emitted from vegetation are important for the formation of secondary pollutants such as ozone and secondary organic aerosols (SOA) in the atmosphere. Therefore, BVOC emission are an important input for air quality models. To model these emissions with high spatial resolution, the accuracy of the underlying vegetation inventory is crucial. We present a BVOC emission model that accommodates different vegetation inventories and uses satellite-based measurements of greenness instead of pre-defined vegetation periods. This approach to seasonality implicitly treats effects caused by water or nutrient availability, altitude and latitude on a plant stand. Additionally, we test the influence of proposed seasonal variability in enzyme activity on BVOC emissions. In its present setup, the emission model calculates hourly emissions of isoprene, monoterpenes, sesquiterpenes and the oxygenated volatile organic compounds (OVOC) methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetone and acetic acid. In this study, emissions based on three different vegetation inventories are compared with each other and diurnal and seasonal variations in Europe are investigated for the year 2006. Two of these vegetation inventories require information on tree-cover as an input. We compare three different land-cover inventories (USGS GLCC, GLC2000 and Globcover 2.2) with respect to tree-cover. The often-used USGS GLCC land-cover inventory leads to a severe reduction of BVOC emissions due to a potential miss-attribution of broad-leaved trees and reduced tree-cover compared to the two other land-cover inventories. To account for uncertainties in the land-cover classification, we introduce land-cover correction factors for each relevant land-use category to adjust the tree-cover. The results are very sensitive to these factors within the plausible range. For June 2006, total monthly BVOC emissions decreased up to −27% with minimal and increased up to +71% with maximal factors, while in January 2006, the changes in monthly BVOC emissions were −54 and +56% with minimal and maximal factors, respectively. The new seasonality approach leads to a reduction in the annual emissions compared with non-adjusted data. The strongest reduction occurs in OVOC (up to −32%), the weakest in isoprene (as little as −19%). If also enzyme seasonality is taken into account, however, isoprene reacts with the steepest decrease of annual emissions, which are reduced by −44% to −49%, annual emissions of monoterpenes reduce between −30 and −35%. The sensitivity of the model to changes in temperature depends on the climatic zone but not on the vegetation inventory. The sensitivity is higher for temperature increases of 3 K (+31% to +64%) than decreases by the same amount (−20 to −35%). The climatic zones "Cold except summer" and "arid" are most sensitive to temperature changes in January for isoprene and monoterpenes, respectively, while in June, "polar" is most sensitive to temperature for both isoprene and monoterpenes. Our model predicts the oxygenated volatile organic compounds to be the most abundant fraction of the annual European emissions (3571–5328 Gg yr−1), followed by monoterpenes (2964–4124 Gg yr−1), isoprene (1450–2650 Gg yr−1) and sesquiterpenes (150–257 Gg yr−1). We find regions with high isoprene emissions (most notably the Iberian Peninsula), but overall, oxygenated VOC dominate with 43–45% (depending on the vegetation inventory) contribution to the total annual BVOC emissions in Europe. Isoprene contributes between 18–21%, monoterpenes 33–36% and sesquiterpenes contribute 1–2%. We compare the concentrations of biogenic species simulated by an air quality model with measurements of isoprene and monoterpenes in Hohenpeissenberg (Germany) for both summer and winter. The agreement between observed and modelled concentrations is better in summer than in winter. This can partly be explained with the difficulty to model weather conditions in winter accurately, but also with the increased anthropogenic influence on the concentrations of BVOC compounds in winter. Our results suggest that land-cover inventories used to derive tree-cover must be chosen with care. Also, uncertainties in the classification of land-cover pixels must be taken into account and remain high. This problem must be addressed together with the remote sensing community. Our new approach using a greenness index for addressing seasonality of vegetation can be implemented easily in existing models. The importance of OVOC for air quality should be more deeply addressed by future studies, especially in smog chambers. Also, the fate of BVOC from the dominant region of the Iberian Peninsula should be studied more in detail.


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