Long-term flux measurements of volatile organic compounds (VOC) over boreal forests are rare, although the forests are known to emit considerable amounts of VOCs into the atmosphere. Thus, we ...measured fluxes of several VOCs and oxygenated VOCs over a Scots-pine-dominated boreal forest semi-continuously between May 2010 and December 2013. The VOC profiles were obtained with a proton transfer reaction mass spectrometry, and the fluxes were calculated using vertical concentration profiles and the surface layer profile method connected to the Monin-Obukhov similarity theory. In total fluxes that differed significantly from zero on a monthly basis were observed for 13 out of 27 measured masses. Monoterpenes had the highest net emission in all seasons and statistically significant positive fluxes were detected from March until October. Other important compounds emitted were methanol, ethanol+formic acid, acetone and isoprene+methylbutenol. Oxygenated VOCs showed also deposition fluxes that were statistically different from zero. Isoprene+methylbutenol and monoterpene fluxes followed well the traditional isoprene algorithm and the hybrid algorithm, respectively. Emission potentials of monoterpenes were largest in late spring and autumn which was possibly driven by growth processes and decaying of soil litter, respectively. Conversely, largest emission potentials of isoprene+methylbutenol were found in July. Thus, we concluded that most of the emissions of m/z 69 at the site consisted of isoprene that originated from broadleaved trees. Methanol had deposition fluxes especially before sunrise. This can be connected to water films on surfaces. Based on this assumption, we were able to build an empirical algorithm for bi-directional methanol exchange that described both emission term and deposition term. Methanol emissions were highest in May and June and deposition level increased towards autumn, probably as a result of increasing relative humidity levels leading to predominance of deposition.
Boreal forests emit large amounts of volatile organic compounds (VOCs) which react with the hydroxyl radical (OH) to influence regional ozone levels and form secondary organic aerosol. Using OH ...reactivity measurements within a boreal forest in Finland, we investigated the budget of reactive VOCs. OH reactivity was measured using the comparative reactivity method, whereas 30 individual VOCs were measured using proton transfer reaction mass spectrometry, thermal-desorption gas chromatography mass spectrometry, and liquid chromatography mass spectrometry, in August 2008. The measured OH reactivity ranged from below detection limit (3.5 s−1), to ∼60 s−1 in a single pollution event. The average OH reactivity was ∼9 s−1 and no diel variation was observed in the profiles. The measured OH sinks (∼30 species) accounted for only 50% of the total measured OH reactivity, implying unknown reactive VOCs within the forest. The five highest measured OH sinks were: monoterpenes (1 s−1), CO (0.7 s−1), isoprene (0.5 s−1), propanal and acetone (0.3 s−1), and methane (0.3 s−1). We suggest that models be constrained by direct OH reactivity measurements to accurately assess the impact of boreal forest emissions on regional atmospheric chemistry and climate.
This study scrutinizes a decade-long series of ozone deposition measurements in a boreal forest in search for the signature and relevance of the different deposition processes. The canopy-level ozone ...flux measurements were analysed for deposition characteristics and partitioning into stomatal and non-stomatal fractions, with the main focus on growing season day-time data. Ten years of measurements enabled the analysis of ozone deposition variation at different time-scales, including daily to inter-annual variation as well as the dependence on environmental variables and concentration of biogenic volatile organic compounds (BVOC-s). Stomatal deposition was estimated by using multi-layer canopy dispersion and optimal stomatal control modelling from simultaneous carbon dioxide and water vapour flux measurements, non-stomatal was inferred as residual. Also, utilising the big-leaf assumption stomatal conductance was inferred from water vapour fluxes for dry canopy conditions. The total ozone deposition was highest during the peak growing season (4 mm s−1) and lowest during winter dormancy (1 mm s−1). During the course of the growing season the fraction of the non-stomatal deposition of ozone was determined to vary from 26 to 44% during day time, increasing from the start of the season until the end of the growing season. By using multi-variate analysis it was determined that day-time total ozone deposition was mainly driven by photosynthetic capacity of the canopy, vapour pressure deficit (VPD), photosynthetically active radiation and monoterpene concentration. The multi-variate linear model explained the high portion of ozone deposition variance on daily average level (R2 = 0.79). The explanatory power of the multi-variate model for ozone non-stomatal deposition was much lower (R2 = 0.38). The set of common environmental variables and terpene concentrations used in multivariate analysis were able to predict the observed average seasonal variation in total and non-stomatal deposition but failed to explain the inter-annual differences, suggesting that some still unknown mechanisms might be involved in determining the inter-annual variability. Model calculation was performed to evaluate the potential sink strength of the chemical reactions of ozone with sesquiterpenes in the canopy air space, which revealed that sesquiterpenes in typical amounts at the site were unlikely to cause significant ozone loss in canopy air space. The results clearly showed the importance of several non-stomatal removal mechanisms. Unknown chemical compounds or processes correlating with monoterpene concentrations, including potentially reactions at the surfaces, contribute to non-stomatal sink term.
Climatic effects of newly-formed atmospheric secondary aerosol particles are to a large extent determined by their condensational growth rates. However, all the vapours condensing on atmospheric ...nanoparticles and growing them to climatically relevant sizes are not identified yet and the effects of particle phase processes on particle growth rates are poorly known. Besides sulfuric acid, organic compounds are known to contribute significantly to atmospheric nanoparticle growth. In this study a particle growth model MABNAG (Model for Acid-Base chemistry in NAnoparticle Growth) was developed to study the effect of salt formation on nanoparticle growth, which has been proposed as a potential mechanism lowering the equilibrium vapour pressures of organic compounds through dissociation in the particle phase and thus preventing their evaporation. MABNAG is a model for monodisperse aqueous particles and it couples dynamics of condensation to particle phase chemistry. Non-zero equilibrium vapour pressures, with both size and composition dependence, are considered for condensation. The model was applied for atmospherically relevant systems with sulfuric acid, one organic acid, ammonia, one amine and water in the gas phase allowed to condense on 3–20 nm particles. The effect of dissociation of the organic acid was found to be small under ambient conditions typical for a boreal forest site, but considerable for base-rich environments (gas phase concentrations of about 1010 cm−3 for the sum of the bases). The contribution of the bases to particle mass decreased as particle size increased, except at very high gas phase concentrations of the bases. The relative importance of amine versus ammonia did not change significantly as a function of particle size. While our results give a reasonable first estimate on the maximum contribution of salt formation to nanoparticle growth, further studies on, e.g. the thermodynamic properties of the atmospheric organics, concentrations of low-volatility organics and amines, along with studies investigating the applicability of thermodynamics for the smallest nanoparticles are needed to truly understand the acid-base chemistry of atmospheric nanoparticles.
In this study a long-term volatile organic compound (VOCs) concentration data set, measured at the SMEAR II (Station for Measuring Ecosystem–Atmosphere Relations) boreal forest site in Hyytiälä, ...Finland during the years 2006–2011, was analyzed in order to identify source areas and profiles of the observed VOCs. VOC mixing ratios were measured using proton transfer reaction mass spectrometry. Four-day HYSPLIT 4 (Hybrid Single Particle Lagrangian Integrated Trajectory) backward trajectories and the Unmix 6.0 receptor model were used for source area and source composition analysis. Two major forest fire events in Russia took place during the measurement period. The effect of these fires was clearly visible in the trajectory analysis, lending confidence to the method employed with this data set. Elevated volume mixing ratios (VMRs) of non-biogenic VOCs related to forest fires, e.g. acetonitrile and aromatic VOCs, were observed. Ten major source areas for long-lived VOCs (methanol, acetonitrile, acetaldehyde, acetone, benzene, and toluene) observed at the SMEAR II site were identified. The main source areas for all the targeted VOCs were western Russia, northern Poland, Kaliningrad, and the Baltic countries. Industrial areas in northern continental Europe were also found to be source areas for certain VOCs. Both trajectory and receptor analysis showed that air masses from northern Fennoscandia were less polluted with respect to both the VOCs studied and other trace gases (CO, SO2 and NOx), compared to areas of eastern and western continental Europe, western Russia, and southern Fennoscandia.
Degradation of plant material by animals is an important transformation pathway in the nitrogen (N) cycle. During the involved processes, volatile reduced alkaline nitrogen compounds, mainly ammonia ...(NH3) and aliphatic amines such as trimethylamine (TMA), are formed. Today, animal husbandry is estimated to constitute a main source of aliphatic amines in the atmosphere with TMA being the main emitted compound. Here, we show how the interaction between faeces and urine in animal production systems provides the primary source for agricultural TMA emissions. Excreted urine contains large quantities of urea and TMA-N-oxide, which are transformed into NH3 and TMA, respectively, via enzymatic processes provided by microbes present in faeces. TMA emissions from areas polluted with urine–faeces mixtures are on average of the order of 10 to 50 nmol m−2s−1. Released amines promote secondary aerosol particle formation in the agricultural emission plume. The atmospheric lifetime of TMA, which was estimated to be of the order of 30 to 1000 s, is determined by the condensation onto aerosol particles.
In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the exchange at the surface. Thus one assumes the chemical degradation to be much ...slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.
Eddy covariance (EC) is the preferable technique for flux measurements since it is the only direct flux determination method. It requires a continuum of high time resolution measurements (e.g. 5-20 ...Hz). For volatile organic compounds (VOC) soft ionization via proton transfer reaction has proven to be a quantitative method for real time mass spectrometry; here we use a proton transfer reaction time of flight mass spectrometer (PTR-TOF) for 10 Hz EC measurements of full mass spectra up to
315. The mass resolution of the PTR-TOF enabled the identification of chemical formulas and separation of oxygenated and hydrocarbon species exhibiting the same nominal mass. We determined 481 ion mass peaks from ambient air concentration above a managed, temperate mountain grassland in Neustift, Stubai Valley, Austria. During harvesting we found significant fluxes of 18 compounds distributed over 43 ions, including protonated parent compounds, as well as their isotopes and fragments and VOC-H
- water clusters. The dominant BVOC fluxes were methanol, acetaldehyde, ethanol, hexenal and other C
leaf wound compounds, acetone, acetic acid, monoterpenes and sequiterpenes. The smallest reliable fluxes we determined were less than 0.1 nmol m
s
, as in the case of sesquiterpene emissions from freshly cut grass. Terpenoids, including mono- and sesquiterpenes, were also deposited to the grassland before and after the harvesting. During cutting, total VOC emission fluxes up to 200 nmolC m
s
were measured. Methanol emissions accounted for half of the emissions of oxygenated VOCs and a third of the carbon of all measured VOC emissions during harvesting.
Proton transfer reaction mass spectrometry (PTR-MS) and gas chromatography mass spectrometry GC-MS) are commonly used methods for automated in situ measurements of various volatile organic compounds ...(VOCs) in the atmosphere. In order to investigate the reliability of such measurements, we operated four automated analyzers using their normal field measurement protocol side by side at a boreal forest site. We measured methanol, acetaldehyde, acetone, benzene and toluene by two PTR-MS and two GC-MS instruments. The measurements were conducted in southern Finland between 13 April and 14 May 2012. This paper presents correlations and biases between the concentrations measured using the four instruments. A very good correlation was found for benzene and acetone measurements between all instruments (the mean R value was 0.88 for both compounds), while for acetaldehyde and toluene the correlation was weaker (with a mean R value of 0.50 and 0.62, respectively). For some compounds, notably for methanol, there were considerable systematic differences in the mixing ratios measured by the different instruments, despite the very good correlation between the instruments (mean R = 0.90). The systematic difference manifests as a difference in the linear regression slope between measurements conducted between instruments, rather than as an offset. This mismatch indicates that the systematic uncertainty in the sensitivity of a given instrument can lead to an uncertainty of 50–100 % in the methanol emissions measured by commonly used methods.
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