Browsing by Subject "AMBIENT AIR"

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  • Hoerger, C. C.; Claude, A.; Plass-Duelmer, C.; Reimann, S.; Eckart, E.; Steinbrecher, R.; Aalto, J.; Arduini, J.; Bonnaire, N.; Cape, J. N.; Colomb, A.; Connolly, R.; Diskova, J.; Dumitrean, P.; Ehlers, C.; Gros, V.; Hakola, H.; Hill, M.; Hopkins, J. R.; Jaeger, J.; Junek, R.; Kajos, M. K.; Klemp, D.; Leuchner, M.; Lewis, A. C.; Locoge, N.; Maione, M.; Martin, D.; Michl, K.; Nemitz, E.; O'Doherty, S.; Ballesta, P. Perez; Ruuskanen, T. M.; Sauvage, S.; Schmidbauer, N.; Spain, T. G.; Straube, E.; Vana, M.; Vollmer, M. K.; Wegener, R.; Wenger, A. (2015)
    The performance of 18 European institutions involved in long-term non-methane hydrocarbon (NMHC) measurements in ambient air within the framework of the Global Atmosphere Watch (GAW) and the European Monitoring and Evaluation Programme (EMEP) was assessed with respect to data quality objectives (DQOs) of ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) and GAW. Compared to previous intercomparison studies the DQOs define a novel approach to assess and ensure a high quality of the measurements. Having already been adopted by GAW, the ACTRIS DQOs are demanding with deviations to a reference value of less than 5% and a repeatability of better than 2% for NMHC mole fractions above 0.1 nmol mol(-1). The participants of the intercomparison analysed two dry gas mixtures in pressurised cylinders, a 30-component NMHC mixture in nitrogen (NMHC_N-2 /at approximately 1 nmol mol(-1) and a whole air sample (NMHC_air), following a standardised operation procedure including zero-and calibration gas measurements. Furthermore, participants had to report details on their instruments and assess their measurement uncertainties. The NMHCs were analysed either by gas chromatography-flame ionisation detection (GC-FID) or by gas chromatography-mass spectrometry (GC-MS). For the NMHC_N-2 measurements, 62% of the reported values were within the 5% deviation class corresponding to the ACTRIS DQOs. For NMHC_air, generally more frequent and larger deviations to the assigned values were observed, with 50% of the reported values within the 5% deviation class. Important contributors to the poorer performance in NMHC_air compared to NMHC_N-2 were a more complex matrix and a larger span of NMHC mole fractions (0.03-2.5 nmol mol(-1)). The performance of the participating laboratories were affected by the different measurement procedures such as the usage of a two-step vs. a one-step calibration, breakthroughs of C-2-C-3 hydrocarbons in the focussing trap, blank values in zero-gas measurements (especially for those systems using a Nafion (R) Dryer), adsorptive losses of aromatic compounds, and insufficient chromatographic separation.
  • Feijo Barreira, Luis Miguel; Duporte, Geoffroy; Rönkkö, Tuukka; Parshintsev, Jevgeni; Hartonen, Kari; Schulman, Lydia; Heikkinen, Enna; Jussila, Matti; Kulmala, Markku; Riekkola, Marja-Liisa (2018)
    Biogenic volatile organic compounds (BVOCs) emitted by terrestrial vegetation participate in a diversity of natural processes. These compounds impact both on short-range processes, such as on plant protection and communication, and on high-range processes, by e.g. participation on aerosol particle formation and growth. The biodiversity of plant species around the Earth, the vast assortment of emitted BVOCs, and their trace atmospheric concentrations contribute to the high remaining uncertainties about the effects of these compounds on atmospheric chemistry and physics, and call for the development of novel collection devices that can offer portability with improved selectivity and capacity. In this study, a novel solid-phase microextraction (SPME) Arrow sampling system was used for the static and dynamic collection of BVOCs from the boreal forest, and samples were subsequently analysed on-site by gas chromatography-mass spectrometry (GC-MS). This system offers higher sampling capacity and improved robustness than the traditional equilibrium-based SPME techniques, such as SPME fibers. Field measurements were performed in summer 2017 at the Station for Measuring Ecosystem-Atmosphere Relations (SMEAR II) in Hyytiälä, Finland. Complementary laboratory tests were also performed to compare the SPME-based techniques under controlled experimental conditions and to evaluate the effect of temperature and relative humidity on their extraction performance. The most abundant monoterpenes and aldehydes were successfully collected. A significant improvement on sampling capacity was observed with the new SPME Arrow system when compared to SPME fibers, with collected amounts being approximately 2 times higher for monoterpenes and 7-8 times higher for aldehydes. BVOC species exhibited different affinities for the type of sorbent materials used (PDMS/Carbon WR vs. PDMS/DVB). Higher extraction efficiencies were obtained with dynamic collection prior to equilibrium regime, but this benefit during the field measurements was small probably due to the natural agitation provided by the wind. An increase in temperature and relative humidity caused a decrease in the amounts of analytes extracted under controlled experimental conditions, even though the effect was more significant for PDMS/Carbon WR than for PDMS/DVB. Overall, results demonstrated the benefits and challenges of using SPME Arrow for the sampling of BVOCs in the atmosphere.
  • Crowley, John N.; Pouvesle, Nicolas; Phillips, Gavin J.; Axinte, Raoul; Fischer, Horst; Petäjä, Tuukka; Noelscher, Anke; Williams, Jonathan; Hens, Korbinian; Harder, Hartwig; Martinez-Harder, Monica; Novelli, Anna; Kubistin, Dagmar; Bohn, Birger; Lelieveld, Jos (2018)
    Unlike many oxidised atmospheric trace gases, which have numerous production pathways, peroxyacetic acid (PAA) and PAN are formed almost exclusively in gasphase reactions involving the hydroperoxy radical (HO2), the acetyl peroxy radical (CH3C(O)O-2) and NO2 and are not believed to be directly emitted in significant amounts by vegetation. As the self-reaction of HO2 is the main photochemical route to hydrogen peroxide (H2O2), simultaneous observation of PAA, PAN and H2O2 can provide insight into the HO2 budget. We present an analysis of observations taken during a summertime campaign in a boreal forest that, in addition to natural conditions, was temporarily impacted by two biomass-burning plumes. The observations were analysed using an expression based on a steady-state assumption using relative PAA-to-PAN mixing ratios to derive HO2 concentrations. The steady-state approach generated HO2 concentrations that were generally in reasonable agreement with measurements but sometimes overestimated those observed by factors of 2 or more. We also used a chemically simple, constrained box model to analyse the formation and reaction of radicals that define the observed mixing ratios of PAA and H2O2. After nudging the simulation towards observations by adding extra, photochemical sources of HO2 and CH3C(O)O-2, the box model replicated the observations of PAA, H2O2, ROOH and OH throughout the campaign, including the biomass-burning-influenced episodes during which significantly higher levels of many oxidized trace gases were observed. A dominant fraction of CH3O2 radical generation was found to arise via reactions of the CH3C(O)O-2 radical. The model indicates that organic peroxy radicals were present at night in high concentrations that sometimes exceeded those predicted for daytime, and initially divergent measured and modelled HO2 concentrations and daily concentration profiles are reconciled when organic peroxy radicals are detected (as HO2) at an efficiency of 35 %. Organic peroxy radicals are found to play an important role in the recycling of OH radicals subsequent to their loss via reactions with volatile organic compounds.
  • Hellen, Heidi; Praplan, Arnaud P.; Tykkä, Toni; Ylivinkka, Ilona; Vakkari, Ville; Bäck, Jaana; Petäjä, Tuukka; Kulmala, Markku; Hakola, Hannele (2018)
    The concentrations of terpenoids (isoprene; monoterpenes, MTs; and sesquiterpenes, SQTs) and oxygenated volatile organic compounds (OVOCs; i.e. aldehydes, alcohols, acetates and volatile organic acids, VOAs) were investigated during 2 years at a boreal forest site in Hyytiala, Finland, using in situ gas chromatograph mass spectrometers (GC-MSs). Seasonal and diurnal variations of terpenoid and OVOC concentrations as well as their relationship with meteorological factors were studied. Of the VOCs examined, C-2-C-7 unbranched VOAs showed the highest concentrations, mainly due to their low reactivity. Of the terpenoids, MTs showed the highest concentrations at the site, but seven different highly reactive SQTs were also detected. The monthly and daily mean concentrations of most terpenoids, aldehydes and VOAs were highly dependent on the temperature. The highest exponential correlation with temperature was found for a SQT (beta-caryophyllene) in summer. The diurnal variations in the concentrations could be explained by sources, sinks and vertical mixing. The diurnal variations in MT concentrations were strongly affected by vertical mixing. Based on the temperature correlations and mixing layer height (MLH), simple proxies were developed for estimating the MT and SQT concentrations. To estimate the importance of different compound groups and compounds in local atmospheric chemistry, reactivity with main oxidants (hydroxyl radical, OH; nitrate radical, NO3; and ozone, O-3) and production rates of oxidation products (OxPRs) were calculated. The MTs dominated OH and NO3 radical chemistry, but the SQTs greatly impacted O-3 chemistry, even though the concentrations of SQT were 30 times lower than the MT concentrations. SQTs were also the most important for the production of oxidation products. Since the SQTs show high secondary organic aerosol (SOA) yields, the results clearly indicate the importance of SQTs for local SOA production.
  • Praplan, Arnaud P.; Tykka, Toni; Chen, Dean; Boy, Michael; Taipale, Ditte; Vakkari, Ville; Zhou, Putian; Petaja, Tuukka; Hellen, Heidi (2019)
    Total hydroxyl radical (OH) reactivity measurements were conducted at the second Station for Measuring Ecosystem-Atmosphere Relations (SMEAR II), a boreal forest site located in Hyytiala, Finland, from April to July 2016. The measured values were compared with OH reactivity calculated from a combination of data from the routine trace gas measurements (station mast) as well as online and offline analysis with a gas chromatographer coupled to a mass spectrometer (GC-MS) and offline liquid chromatography. Up to 104 compounds, mostly volatile organic compounds (VOCs) and oxidized VOCs, but also inorganic compounds, were included in the analysis, even though the data availability for each compound varied with time. The monthly averaged experimental total OH reactivity was found to be higher in April and May (ca. 20 s(-1)) than in June and July (7.6 and 15.4 s(-1), respectively). The measured values varied much more in spring with high reactivity peaks in late afternoon, with values higher than in the summer, in particular when the soil was thawing. Total OH reactivity values generally followed the pattern of mixing ratios due to change of the boundary layer height. The missing reactivity fraction (defined as the difference between measured and calculated OH reactivity) was found to be high. Several reasons that can explain the missing reactivity are discussed in detail such as (1) missing measurements due to technical issues, (2) not measuring oxidation compounds of detected biogenic VOCs, and (3) missing important reactive compounds or classes of compounds with the available measurements. In order to test the second hypothesis, a one-dimensional chemical transport model (SOSAA) has been used to estimate the amount of unmeasured oxidation products and their expected contribution to the reactivity for three different short periods in April, May, and July. However, only a small fraction (<4.5 %) of the missing reactivity can be explained by modelled secondary compounds (mostly oxidized VOCs). These findings indicate that compounds measured but not included in the model as well as unmeasured primary emissions contribute the missing reactivity. In the future, non-hydrocarbon compounds from sources other than vegetation (e.g. soil) should be included in OH reactivity studies.
  • Praplan, Arnaud P.; Tykka, Toni; Schallhart, Simon; Tarvainen, Virpi; Back, Jaana; Hellen, Heidi (2020)
    In forested area, a large fraction of total hydroxyl radical (OH) reactivity remains unaccounted for. Very few studies have looked at the variations in total OH reactivity from biogenic emissions. In the present study, we investigate the total OH reactivity from three common boreal tree species (Scots pine, Norway spruce, and downy birch) by comparing it with the calculated reactivity from the chemically identified emissions. Total OH reactivity was measured using the comparative reactivity method (CRM), and the chemical composition of the emissions was quantified with two gas chromatographs coupled with mass spectrometers (GC-MSs). Dynamic branch enclosures were used, and emissions from one branch of a tree at the time were measured by periodically rotating between them. Results show that birch had the highest values of total OH reactivity of the emissions (TOHRE), while pine had the lowest. The main drivers for the known reactivity of pine and spruce were monoterpenes and sesquiterpenes. Birch emissions were dominated by sesquiterpenes, but monoterpenes and green leaf volatiles (GLVs) were present as well. However, calculated reactivity values remained low, leading to the highest missing fraction of reactivity (> 96 %), while pine and spruce had similar missing reactivity fractions between 56% and 82% (higher in the spring and decreasing as the summer proceeded). The high average values were driven by low-reactivity periods, and the fraction of missing reactivity got smaller for pine and spruce when the TOHRE values increased. Important exceptions were identified for periods when the emission profiles changed from terpenes to GLVs, a family of compounds containing a backbone of six carbon atoms with various functionalities (e.g. alcohols, aldehydes, esters) that indicate that the plant is suffering from stress. Then, very high TOHRE values were measured, and the missing fraction remained high. This study found a different trend in the missing OHRE fraction of the Norway spruce from spring to autumn compared to one previous study (Nolscher et al., 2013), which indicates that additional studies are required to fully understand the complexity of biogenic reactive emissions. Future studies of boreal trees in situ should be conducted to confirm the findings presented.
  • Hellen, Heidi; Praplan, Arnaud P.; Tykka, Toni; Helin, Aku; Schallhart, Simon; Schiestl-Aalto, Piia P.; Back, Jaana; Hakola, Hannele (2021)
    Biogenic volatile organic compounds (BVOCs) emitted by the forests are known to have strong impacts in the atmosphere. However, lots of missing reactivity is found, especially in the forest air. Therefore better characterization of sources and identification/quantification of unknown reactive compounds is needed. While isoprene and monoterpene (MT) emissions of boreal needle trees have been studied quite intensively, there is much less knowledge on the emissions of boreal deciduous trees and emissions of larger terpenes and oxygenated volatile organic compounds (OVOCs). Here we quantified the downy birch (Betula pubescens) leaf emissions of terpenes, oxygenated terpenes and green leaf volatiles (GLVs) at the SMEAR II boreal forest site using in situ gas chromatographs with mass spectrometers. Sesquiterpenes (SQTs) and oxygenated sesquiterpenes (OSQTs) were the main emitted compounds. Mean emission rates of SQTs and OSQTs were significantly higher in the early growing season (510 and 650 ng g(dw)(-1) h(-1), respectively) compared to in the main (40 and 130 ng g(dw)(-1) h(-1), respectively) and late (14 and 46 ng g(dw)(-1) h(-1), respectively) periods, indicating that early leaf growth is a strong source of these compounds. The emissions had a very clear diurnal variation with afternoon maxima being on average 4 to 8 times higher than seasonal means for SQTs and OSQTs, respectively. fi Caryophyllene and fi-farnesene were the main SQTs emitted. The main emitted OSQTs were tentatively identified as 14-hydroxy-beta-caryophyllene acetate (M = 262 g mol(-1)) and 6-hydroxy-beta-caryophyllene (M D 220 g mol(-1)). Over the whole growing season, the total MT emissions were only 24% and 17% of the total SQT and OSQT emissions, respectively. A stressed tree growing in a pot was also studied, and high emissions of ff -farnesene and an unidentified SQT were detected together with high emissions of GLVs. Due to the relatively low volatility and the high reactivity of SQTs and OSQTs, downy birch emissions are expected to have strong impacts on atmospheric chemistry, especially on secondary organic aerosol (SOA) production.