ALBERT

Description: We have studied biogenic volatile organic compound (BVOC) emissions and their ambient concentrations at a sub-Arctic wetland (Lompolojänkkä, Finland), which is an open, nutrient-rich sedge fen and a part of the Pallas-Sodankylä Global Atmosphere Watch (GAW) station. Measurements were conducted during the growing season in 2018 using an in situ thermal-desorption–gas-chromatograph–mass-spectrometer (TD-GC-MS). Earlier studies have shown that isoprene is emitted from boreal wetlands, and it also turned out to be the most abundant compound in the current study. Monoterpene (MT) emissions were generally less than 10 % of the isoprene emissions (mean isoprene emission over the growing season, 44 µg m−2 h−1), but sesquiterpene (SQT) emissions were higher than MT emissions all the time. The main MTs emitted were α-pinene, 1,8-cineol, myrcene, limonene and 3Δ-carene. Of SQTs cadinene, β-cadinene and α-farnesene had the major contribution. During early growing season the SQT∕MT emission rate ratio was ∼10, but it became smaller as summer proceeded, being only ∼3 in July. Isoprene, MT and SQT emissions were exponentially dependent on temperature (correlation coefficients (R2) 0.75, 0.66 and 0.52, respectively). Isoprene emission rates were also found to be exponentially correlated with the gross primary production of CO2 (R2=0.85 in July). Even with the higher emissions from the wetland, ambient air concentrations of isoprene were on average 〉 100, 〉 10 and 〉 6 times lower than MT concentrations in May, June and July, respectively. This indicates that wetland was not the only source affecting atmospheric concentrations at the site, but surrounding coniferous forests, which are high MT emitters, contribute as well. Daily mean MT concentrations had high negative exponential correlation (R2=0.96) with daily mean ozone concentrations indicating that vegetation emissions can be a significant chemical sink of ozone in this sub-Arctic area.

Description: 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 (Nölscher 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.

Description: 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 Hyytiälä, 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, C2–C7 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 (β-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, O3) and production rates of oxidation products (OxPRs) were calculated. The MTs dominated OH and NO3 radical chemistry, but the SQTs greatly impacted O3 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.

Description: 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 Hyytiälä, 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 (

Description: 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 Hyytiälä, 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 gas chromatography coupled to mass spectrometry (GC-MS) and offline liquid chromatography. Up to 104 compounds, mostly Volatile Organic Compounds (VOCs) and oxidised VOCs, but also inorganic compounds, were included in the analysis, even though the data availability for each compound varied with time. The averaged experimental total OH reactivity increased from April to June (from 5.3 to 11.3 s−1) and decreased in July (8.8 s−1) due to different environmental conditions during the measurement days. In general, the total OH reactivity increased in late-afternoon and is high at night. It decreases in the morning and is low during the day, following the pattern of mixing ratios due to change of the boundary layer height. The missing reactivity fraction (defined as the different 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, (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 (

Description: Concentrations of terpenoids (isoprene, monoterpenes, sesquiterpenes) and oxygenated volatile organic compounds (OVOCs, i.e. aldehydes, alcohols, acetates and volatile organic acids) were investigated during two years at a boreal forest site in Hyytiälä, Finland, using in situ gas chromatograph-mass spectrometers (GC-MS). Seasonal and diurnal variations of terpenoid and OVOC concentrations as well as their relationship with meteorological factors were studied. Of the studied VOCs, C2-C7 unbranched volatile organic acids (VOAs) were found to have the highest concentrations mainly due to their low reactivity. Of the terpenoids, monoterpenes (MTs) had highest concentrations at the site, but also 7 different highly reactive sesquiterpenes (SQTs) were detected. Monthly and daily mean concentrations of most terpenoids, aldehydes and VOAs were found to be highly dependent on the temperature. Highest exponential correlation with temperature was found for a SQT (β-caryophyllene) in summer. The diurnal variations of the concentrations could be explained by sources, sinks and vertical mixing. Especially the diurnal variations of MT concentrations were strongly affected by vertical mixing. Based on the temperature correlations and mixing layer height simple proxies were developed for estimating MT and SQT concentrations. To estimate the importance of different compound groups and compounds for the local atmospheric chemistry, reactivity with main oxidants (OH, NO3 and O3) and production rates of oxidation products (OxPR) were calculated. MTs dominated OH and NO3 radical chemistry, but SQTs had a major impact on ozone chemistry, even though concentrations of SQT were 30 times lower than MT concentrations. SQTs were the most important also for the production of oxidation products. Since SQTs have high secondary organic aerosol (SOA) yields, results clearly indicate the importance of SQTs for local SOA production.