Browsing by Subject "VOLATILE ORGANIC-COMPOUNDS"

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  • Neefjes, Ivo; Laapas, Mikko; Liu, Yang; Medus, Erika; Miettunen, Elina; Ahonen, Lauri; Quelever, Lauriane; Aalto, Juho; Bäck, Jaana; Kerminen, Veli-Matti; Lampilahti, Janne; Luoma, Krista; Mäki, Mari; Mammarella, Ivan; Petäjä, Tuukka; Räty, Meri; Sarnela, Nina; Ylivinkka, Ilona; Hakala, Simo; Kulmala, Markku; Nieminen, Tuomo; Lintunen, Anna (2022)
    Boreal forests are an important source of trace gases and atmospheric aerosols, as well as a crucial carbon sink. As such, they form a strongly interconnected coupled system with the atmosphere. The SMEAR II station is located in a boreal Scots pine forest in Hyytiala, Finland, and has over 25 years of continuous measurements of atmospheric and ecosystem variables. In this study, we analyse the seasonal variations of trace gases, atmospheric aerosols, greenhouse gases, and meteorological variables, measured at the SMEAR II sta-tion during the past two and a half decades. Several ecosystem and atmospheric variables show seasonal correlations with each other, which suggests seasonal interactions within the climate system that links together ecosystem processes, greenhouse gases, trace gases and atmospheric aerosols. For instance, increased global radiation in summer increases air temperature and consequently affects the plant phenology, which promotes the ecosystem carbon exchange and biogenic volatile organic compound (biogenic VOC) release. This further affects the ambient concentrations of highly oxygenated organic molecules (HOMs) as well as the formation and growth of atmospheric organic aerosols. Organic aerosols subsequently influence aerosol optical properties and, through increased scattering, have the potential to cool the climate. We also discuss the impacts of the warm and dry summers of 2010 and 2018 on the studied variables. For these years, we find a higher-than-average ecosystem primary production especially in June, leading to an increased VOC flux from the forest. The increased VOC flux in turn leads to higher HOM and secondary aerosol concentration in the atmosphere. The latter increases light scattering by atmospheric aero-sol particles and thus leads to climate cooling. The results obtained in this study improve our understanding of how boreal forests respond to climate change.
  • Dal Maso, M.; Liao, L.; Wildt, J.; Kiendler-Scharr, A.; Kleist, E.; Tillmann, R.; Sipilä, M.; Hakala, J.; Lehtipalo, K.; Ehn, M.; Kerminen, V. -M.; Kulmala, M.; Worsnop, D.; Mentel, T. (2016)
    Aerosol formation from biogenic and anthropogenic precursor trace gases in continental background areas affects climate via altering the amount of available cloud condensation nuclei. Significant uncertainty still exists regarding the agents controlling the formation of aerosol nanoparticles. We have performed experiments in the Julich plant-atmosphere simulation chamber with instrumentation for the detection of sulfuric acid and nanoparticles, and present the first simultaneous chamber observations of nanoparticles, sulfuric acid, and realistic levels and mixtures of biogenic volatile compounds (BVOCs). We present direct laboratory observations of nanoparticle formation from sulfuric acid and realistic BVOC precursor vapour mixtures performed at atmospherically relevant concentration levels. We directly measured particle formation rates separately from particle growth rates. From this, we established that in our experiments, the formation rate was proportional to the product of sulfuric acid and biogenic VOC emission strength. The formation rates were consistent with a mechanism in which nucleating BVOC oxidation products are rapidly formed and activate with sulfuric acid. The growth rate of nanoparticles immediately after birth was best correlated with estimated products resulting from BVOC ozonolysis.
  • Zhang, Yanjun; Peräkylä, Otso; Yan, Chao; Heikkinen, Liine; Äijälä, Mikko; Dällenbach, Kaspar; Zha, Qiaozhi; Riva, Matthieu; Garmash, Olga; Junninen, Heikki; Paatero, Pentti; Worsnop, Douglas; Ehn, Mikael (2019)
    Recent advancements in atmospheric mass spectrometry provide huge amounts of new information but at the same time present considerable challenges for the data analysts. High-resolution (HR) peak identification and separation can be effort- and time-consuming yet still tricky and inaccurate due to the complexity of overlapping peaks, especially at larger mass-to-charge ratios. This study presents a simple and novel method, mass spectral binning combined with positive matrix factorization (binPMF), to address these problems. Different from unit mass resolution (UMR) analysis or HR peak fitting, which represent the routine data analysis approaches for mass spectrometry datasets, binPMF divides the mass spectra into small bins and takes advantage of the positive matrix factorization's (PMF) strength in separating different sources or processes based on different temporal patterns. In this study, we applied the novel approach to both ambient and synthetic datasets to evaluate its performance. It not only succeeded in separating overlapping ions but was found to be sensitive to subtle variations as well. Being fast and reliable, binPMF has no requirement for a priori peak information and can save much time and effort from conventional HR peak fitting, while still utilizing nearly the full potential of HR mass spectra. In addition, we identify several future improvements and applications for binPMF and believe it will become a powerful approach in the data analysis of mass spectra.
  • Rannik, Ullar; Zhou, Luxi; Zhou, Putian; Gierens, Rosa; Mammarella, Ivan; Sogachev, Andrey; Boy, Michael (2016)
    A 1-D atmospheric boundary layer (ABL) model coupled with a detailed atmospheric chemistry and aerosol dynamical model, the model SOSAA, was used to predict the ABL and detailed aerosol population (characterized by the number size distribution) time evolution. The model was applied over a period of 10 days in May 2013 to a pine forest site in southern Finland. The period was characterized by frequent new particle formation events and simultaneous intensive aerosol transformation. The aim of the study was to analyze and quantify the role of aerosol and ABL dynamics in the vertical transport of aerosols. It was of particular interest to what extent the fluxes above the canopy deviate from the particle dry deposition on the canopy foliage due to the above-mentioned processes. The model simulations revealed that the particle concentration change due to aerosol dynamics frequently exceeded the effect of particle deposition by even an order of magnitude or more. The impact was, however, strongly dependent on particle size and time. In spite of the fact that the timescale of turbulent transfer inside the canopy is much smaller than the timescales of aerosol dynamics and dry deposition, leading us to assume well-mixed properties of air, the fluxes at the canopy top frequently deviated from deposition inside the forest. This was due to transformation of aerosol concentration throughout the ABL and resulting complicated pattern of vertical transport. Therefore we argue that the comparison of timescales of aerosol dynamics and deposition defined for the processes below the flux measurement level do not unambiguously describe the importance of aerosol dynamics for vertical transport above the canopy. We conclude that under dynamical conditions reported in the current study the micrometeorological particle flux measurements can significantly deviate from the dry deposition into the canopy. The deviation can be systematic for certain size ranges so that the time-averaged particle fluxes can be also biased with respect to deposition sink.
  • Kajos, M. K.; Rantala, P.; Hill, M.; Hellen, H.; Aalto, J.; Patokoski, J.; Taipale, R.; Hoerger, C. C.; Reimann, S.; Ruuskanen, T. M.; Rinne, J.; Petäjä, T. (2015)
    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.
  • Rantala, Pekka; Järvi, Leena; Taipale, Risto; Laurila, Terhi K.; Patokoski, Johanna; Kajos, Maija K.; Kurppa, Mona; Haapanala, Sami; Siivola, Erkki; Petäjä, Tuukka; Ruuskanen, Taina M.; Rinne, Janne (2016)
    We measured volatile organic compounds (VOCs), carbon dioxide (CO2) and carbon monoxide (CO) at an urban background site near the city centre of Helsinki, Finland, northern Europe. The VOC and CO2 measurements were obtained between January 2013 and September 2014 whereas for CO a shorter measurement campaign in April-May 2014 was conducted. Both anthropogenic and biogenic sources were identified for VOCs in the study. Strong correlations between VOC fluxes and CO fluxes and traffic rates indicated anthropogenic source of many VOCs. The VOC with the highest emission rate to the atmosphere was methanol, which originated mostly from traffic and other anthropogenic sources. The traffic was also a major source for aromatic compounds in all seasons whereas isoprene was mostly emitted from biogenic sources during summer. Some amount of traffic-related isoprene emissions were detected during other seasons but this might have also been an instrumental contamination from cycloalkane products. Generally, the observed VOC fluxes were found to be small in comparison with previous urban VOC flux studies. However, the differences were probably caused by lower anthropogenic activities as the CO2 fluxes were also relatively small at the site.
  • Zhou, Putian; Ganzeveld, Laurens; Taipale, Ditte; Rannik, Ullar; Rantala, Pekka; Rissanen, Matti Petteri; Chen, Dean; Boy, Michael (2017)
    A multilayer gas dry deposition model has been developed and implemented into a one-dimensional chemical transport model SOSAA (model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition, and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g. monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes, and oxidation products of mono-and sesquiterpenes) in July 2010 at the boreal forest site SMEAR II (Station for Measuring Ecosystem-Atmosphere Relations). According to the significance of modelled monthly-averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: 1. Most of emitted gases are transported out of the canopy (monoterpenes, isoprene + MBO). 2. Chemical reactions remove a significant portion of emitted gases (sesquiterpenes). 3. Bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde). 4. Gases removed by deposition inside the canopy are compensated for by the gases transported from above the canopy (acetol, pinic acid, beta-caryophyllene's oxidation product BCSOZOH). 5. The chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 0.2 h(c) (canopy height) for oxidation products and above about 0.4 h(c) for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understorey vegetation) contributed 11-61% to the overall in-canopy deposition. The emission sources peaked at about 0.8-0.9 h(c), which was higher than 0.6 h(c) where the maximum of dry deposition onto overstorey vegetation was located. This study provided a method to enable the quantification of the exchange between atmosphere and biosphere for numerous BVOCs, which could be applied in large-scale models in future. With this more explicit canopy exchange modelling system, this study analysed both the temporal and spatial variations in individual in-canopy sources and sinks, as well as their combined effects on driving BVOC exchange. In this study 12 featured BVOCs or BVOC groups were analysed. Other compounds could also be investigated similarly by being classified into these five categories.
  • Ghimire, Rajendra P.; Silfver, Tarja; Myller, Kristiina; Oksanen, Elina; Holopainen, Jarmo K.; Mikola, Juha (2022)
    The biogenic volatile organic compounds, BVOCs have a central role in ecosystem-atmosphere interactions. High-latitude ecosystems are facing increasing temperatures and insect herbivore pressure, which may affect their BVOC emission rates, but evidence and predictions of changes remain scattered. We studied the long-term effects of + 3 degrees C warming and reduced insect herbivory (achieved through insecticide sprayings) on mid- and late summer BVOC emissions from field layer vegetation, supplemented with birch saplings, and the underlying soil in Subarctic mountain birch forest in Finland in 2017-2018. Reduced insect herbivory decreased leaf damage by 58-67% and total ecosystem BVOC emissions by 44-72%. Of the BVOC groups, total sesquiterpenes had 70-80% lower emissions with reduced herbivory, and in 2017 the decrease was greater in warmed plots (89% decrease) than in ambient plots (34% decrease). While non-standardized total BVOC, monoterpene, sesquiterpene and GLV emissions showed instant positive responses to increasing chamber air temperature in midsummer samplings, the long-term warming treatment effects on standardized emissions mainly appeared as changes in the compound structure of BVOC blends and varied with compounds and sampling times. Our results suggest that the effects of climate warming on the total quantity of BVOC emissions will in Subarctic ecosystems be, over and above the instant temperature effects, mediated through changes in insect herbivore pressure rather than plant growth. If insect herbivore numbers will increase as predicted under climate warming, our results forecast herbivory-induced increases in the quantity of Subarctic BVOC emissions.
  • Sporre, Moa K.; Blichner, Sara M.; Karset, Inger H. H.; Makkonen, Risto; Berntsen, Terje K. (2019)
    Both higher temperatures and increased CO2 concentrations are (separately) expected to increase the emissions of biogenic volatile organic compounds (BVOCs). This has been proposed to initiate negative climate feedback mechanisms through increased formation of secondary organic aerosol (SOA). More SOA can make the clouds more reflective, which can provide a cooling. Furthermore, the increase in SOA formation has also been proposed to lead to increased aerosol scattering, resulting in an increase in diffuse radiation. This could boost gross primary production (GPP) and further increase BVOC emissions. In this study, we have used the Norwegian Earth System Model (NorESM) to investigate both these feedback mechanisms. Three sets of experiments were set up to quantify the feedback with respect to (1) doubling the CO2, (2) increasing temperatures corresponding to a doubling of CO2 and (3) the combined effect of both doubling CO2 and a warmer climate. For each of these experiments, we ran two simulations, with identical setups, except for the BVOC emissions. One simulation was run with interactive BVOC emissions, allowing the BVOC emissions to respond to changes in CO2 and/or climate. In the other simulation, the BVOC emissions were fixed at present-day conditions, essentially turning the feedback off. The comparison of these two simulations enables us to investigate each step along the feedback as well as estimate their overall relevance for the future climate. We find that the BVOC feedback can have a significant impact on the climate. The annual global BVOC emissions are up to 63 % higher when the feedback is turned on compared to when the feedback is turned off, with the largest response when both CO2 and climate are changed. The higher BVOC levels lead to the formation of more SOA mass (max 53 %) and result in more particles through increased new particle formation as well as larger particles through increased condensation. The corresponding changes in the cloud properties lead to a -0.43 W m(-2) stronger net cloud forcing. This effect becomes about 50 % stronger when the model is run with reduced anthropogenic aerosol emissions, indicating that the feedback will become even more important as we decrease aerosol and precursor emissions. We do not find a boost in GPP due to increased aerosol scattering on a global scale. Instead, the fate of the GPP seems to be controlled by the BVOC effects on the clouds. However, the higher aerosol scattering associated with the higher BVOC emissions is found to also contribute with a potentially important enhanced negative direct forcing (-0.06 W m(-2)). The global total aerosol forcing associated with the feedback is -0.49 W m(-2), indicating that it has the potential to offset about 13 % of the forcing associated with a doubling of CO2.
  • Smolander, S.; He, Q.; Mogensen, D.; Zhou, L.; Back, J.; Ruuskanen, T.; Noe, S.; Guenther, A.; Aaltonen, Hermanni; Kulmala, M.; Boy, M. (2014)
    Biogenic volatile organic compounds (BVOCs) are essential in atmospheric chemistry because of their chemical reactions that produce and destroy tropospheric ozone, their effects on aerosol formation and growth, and their potential influence on global warming. As one of the important BVOC groups, monoterpenes have been a focus of scientific attention in atmospheric research. Detailed regional measurements and model estimates are needed to study emission potential and the monoterpene budget on a global scale. Since the use of empirical measurements for upscaling is limited by many physical and biological factors, such as genetic variation, temperature and light, water availability, seasonal changes, and environmental stresses, comprehensive inventories over larger areas are difficult to obtain. We applied the boundary-layer–chemistry-transport model SOSA (model to Simulate the concentrations of Organic vapours and Sulphuric Acid) to investigate Scots pine (Pinus sylvestris) monoterpene emissions in a boreal coniferous forest at the SMEAR (Station for Measuring forest Ecosystem–Atmosphere Relations) II site, southern Finland. SOSA was applied to simulate monoterpene emissions with three different emission modules: the semiempirical G95, MEGAN (Model of Emissions of Gases and Aerosols from Nature) 2.04 with improved descriptions of temperature and light responses and including also carbonyl emissions, and a process-based model SIM–BIM (Seasonal Isoprenoid synthase Model – Biochemical Isoprenoid biosynthesis Model). For the first time, the emission models included seasonal and diurnal variations in both quantity and chemical species of emitted monoterpenes, based on parameterizations obtained from field measurements. Results indicate that modelling and observations agreed reasonably well and that the model can be used for investigating regional air chemistry questions related to monoterpenes. The predominant modelled monoterpene concentrations, α-pinene and Δ3-carene, are consistent with observations.
  • Iyer, Siddharth; Reiman, Heidi; Moller, Kristian H.; Rissanen, Matti P.; Kjaergaard, Henrik G.; Kurten, Theo (2018)
    The oxidation of biogenically emitted volatile organic compounds (BVOC) plays an important role in the formation of secondary organic aerosols (SOA) in the atmosphere. Peroxy radicals (RO2) are central intermediates in the BVOC oxidation process. Under clean (low-NOx) conditions, the main bimolecular sink reactions for RO2 are with the hydroperoxy radical (HO2) and with other RO2 radicals. Especially for small RO2, the RO2 + HO2 reaction mainly leads to closed-shell hydroperoxide products. However, there exist other known RO2 + HO2 and RO2 + RO2 reaction channels that can recycle radicals and oxidants in the atmosphere, potentially leading to lower-volatility products and enhancing SOA formation. In this work, we present a thermodynamic overview of two such reactions: (a) RO2 + HO2 -> RO + OH + O-2 and (b) R'O-2 + RO2 -> R'O + RO + O-2 for selected monoterpene + oxidant derived peroxy radicals. The monoterpenes considered are alpha-pinene, beta-pinene, limonene, trans-beta-ocimene, and Delta(3)-carene. The oxidants considered are the hydroxyl radical (OH), the nitrate radical (NO3), and ozone (O-3). The reaction Gibbs energies were calculated at the DLPNO-CCSD(T)/def2-QZVPP//omega B97X-D/aug-cc-pVTZ level of theory. All reactions studied here were found to be exergonic in terms of Gibbs energy. On the basis of a comparison with previous mechanistic studies, we predict that reaction a and reaction b are likely to be most important for first-generation peroxy radicals from O-3 oxidation (especially for beta-pinene), while being less so for most first-generation peroxy radicals from OH and NO3 oxidation. This is because both reactions are comparatively more exergonic for the O-3 oxidized systems than their OH and NO3 oxidized counterparts. Our results indicate that bimolecular reactions of certain complex RO, may contribute to an increase in radical and oxidant recycling under high HO2 conditions in the atmosphere, which can potentially enhance SOA formation.
  • Kurten, Theo; Rissanen, Matti P.; Mackeprang, Kasper; Thornton, Joel A.; Hyttinen, Noora; Jorgensen, Solvejg; Ehn, Mikael; Kjaergaard, Henrik G. (2015)
    Autoxidation by: sequential peroxy radical hydrogen shifts (H-shifts) and O-2 additions has recently emerged as a promising mechanism for the rapid formation of highly oxidized, low-Volatility organic Compounds in the. atmosphere: A kg prerequisite for auto)ddation is that the H-shifts of the initial peroxy radicals formed by, e.g., OH or O-3 oxidation are fast enough to compete with bimolecular sink reactions. In most atmospheric conditions, these restrict the lifetime Of peroxy.radicals to be on the order of seconds. We have systematically investigated all potentially important (nonmethyl, sterically unhindered) H-shifts of all four peroxy radicals formed in the ozonolysis of alpha-pinene using density functional (omega B97XD) and coupled cluster [CCSD(T)-F12] theory. In contrast to the related but chemically simpler tyclohexene ozonolysis system, none of the calculated li-shifts have rate constants above 1 s(-1) at 298 K, and most are below 0.01 s(-1). The law rate constants are connected to the presence of the' strained tyclobutyi sing in the alpha-pinene-derived peroxy radicals, which hinders H-shifts both from and across the ring. For autoxidation to yield the experimentally observed highly oxidized products in the alpha-pinene ozonolysis system, additional ring-opening reaction mechanisms breaking the cyclobutyl ring are therefore needed. We further investigate possible uni- and bimolecular pathways for,opening the cydobutyl ring in, the alpha-pinene ozonolysis system.
  • Mäki, Mari; Heinonsalo, Jussi; Hellen, Heidi; Back, Jaana (2017)
    Boreal forest floor emits biogenic volatile organic compounds (BVOCs) from the understorey vegetation and the heterogeneous soil matrix, where the interactions of soil organisms and soil chemistry are complex. Earlier studies have focused on determining the net exchange of VOCs from the forest floor. This study goes one step further, with the aim of separately determining whether the photosynthesized carbon allocation to soil affects the isoprenoid production by different soil organisms, i.e., decomposers, mycorrhizal fungi, and roots. In each treatment, photosynthesized carbon allocation through roots for decomposers and mycorrhizal fungi was controlled by either preventing root ingrowth (50 mu m mesh size) or the ingrowth of roots and fungi (1 mu m mesh) into the soil volume, which is called the trenching approach. Isoprenoid fluxes were measured using dynamic (steady-state flow-through) chambers from the different treatments. This study aimed to analyze how important the understorey vegetation is as a VOC sink. Finally, a statistical model was constructed based on prevailing temperature, seasonality, trenching treatments, understory vegetation cover, above canopy photosynthetically active radiation (PAR), soil water content, and soil temperature to estimate isoprenoid fluxes. The final model included parameters with a statistically significant effect on the isoprenoid fluxes. The results show that the boreal forest floor emits monoterpenes, sesquiterpenes, and isoprene. Monoterpenes were the most common group of emitted isoprenoids, and the average flux from the non-trenched forest floor was 23 mu gm(-2) h(-1). The results also show that different biological factors, including litterfall, carbon availability, biological activity in the soil, and physico-chemical processes, such as volatilization and absorption to the surfaces, are important at various times of the year. This study also discovered that understorey vegetation is a strong sink of monoterpenes. The statistical model, based on prevailing temperature, seasonality, vegetation effect, and the interaction of these parameters, explained 43% of the monoterpene fluxes, and 34-46% of individual alpha pinene, camphene, beta-pinene, and Delta(3)-carene fluxes.
  • Eriksson, A. C.; Wittbom, C.; Roldin, P.; Sporre, M.; Str M, E.; Nilsson, P.; Martinsson, J.; Rissler, J.; Nordin, E. Z.; Svenningsson, B.; Pagels, J.; Swietlicki, E. (2017)
    Fresh and aged diesel soot particles have different impacts on climate and human health. While fresh diesel soot particles are highly aspherical and non-hygroscopic, aged particles are spherical and hygroscopic. Aging and its effect on water uptake also controls the dispersion of diesel soot in the atmosphere. Understanding the timescales on which diesel soot ages in the atmosphere is thus important, yet knowledge thereof is lacking. We show that under cold, dark and humid conditions the atmospheric transformation from fresh to aged soot occurs on a timescale of less than five hours. Under dry conditions in the laboratory, diesel soot transformation is much less efficient. While photochemistry drives soot aging, our data show it is not always a limiting factor. Field observations together with aerosol process model simulations show that the rapid ambient diesel soot aging in urban plumes is caused by coupled ammonium nitrate formation and water uptake.
  • Liebmann, Jonathan; Karu, Einar; Sobanski, Nicolas; Schuladen, Jan; Ehn, Mikael; Schallhart, Simon; Quelever, Lauriane; Hellen, Heidi; Hakola, Hannele; Hoffmann, Thorsten; Williams, Jonathan; Fischer, Horst; Lelieveld, Jos; Crowley, John N. (2018)
    We present the first direct measurements of NO3 reactivity (or inverse lifetime, s(-1))in the Finnish boreal forest. The data were obtained during the IBAIRN campaign (Influence of Biosphere-Atmosphere Interactions on the Reactive Nitrogen budget) which took place in Hyytiala, Finland during the summer/autumn transition in September 2016. The NO3 reactivity was generally very high with a maximum value of 0.94 s(-1) and displayed a strong diel variation with a campaign-averaged nighttime mean value of 0.11 s(-1) compared to a daytime value of 0.04 s(-1). The highest nighttime NO3 reactivity was accompanied by major depletion of canopy level ozone and was associated with strong temperature inversions and high levels of monoterpenes. The daytime reactivity was sufficiently large that reactions of NO3 with organic trace gases could compete with photolysis and reaction with NO. There was no significant reduction in the measured NO3 reactivity between the beginning and end of the campaign, indicating that any seasonal reduction in canopy emissions of reactive biogenic trace gases was offset by emissions from the forest floor. Observations of biogenic hydrocarbons (BVOCs) suggested a dominant role for monoterpenes in determining the NO3 reactivity. Reactivity not accounted for by in situ measurement of NO and BVOCs was variable across the diel cycle with, on average, approximate to 30% "missing" during nighttime and approximate to 60% missing during the day. Measurement of the NO3 reactivity at various heights (8.5 to 25 m) both above and below the canopy, revealed a strong nighttime, vertical gradient with maximum values closest to the ground. The gradient disappeared during the daytime due to efficient vertical mixing.
  • Berndt, Torsten; Herrmann, Hartmut; Kurten, Theo (2017)
    Criegee intermediates (CIs), mainly formed from gas-phase ozonolysis of alkenes, are considered as atmospheric oxidants besides OH and NO3 radicals as well as ozone. Direct CI measurement techniques are inevitably needed for reliable assessment of CIs' role in atmospheric processes. We found that CIs from ozonolysis reactions can be directly probed by means of chemical ionization mass spectrometry with a detection limit of about 10(4)-10(5) molecules cm(-3). Results from quantum chemical calculations support the experimental findings. The simplest CI, CH2OO, is detectable as an adduct with protonated ethers, preferably with protonated tetrahydrofuran. Kinetic measurements yielded k(CH2OO + SO2) = (3.3 +/- 0.9) X 10(-11) and k(CH2OO + acetic acid) = (1.25 +/- 0.30) x 10(-10) cm(3) molecule(-1) s(-1) at 295 +/- 2 K, in very good agreement with recent measurements using diiodomethane photolysis for CH2OO generation. CIs from the ozonolysis of cydohexene, acting as surrogate for cyclic terpenes, are followed as protonated species (CI)H+ using protonated amines as reagent ions. Kinetic investigations indicate a different reactivity of cydohexene-derived CIs compared with that of simple CIs, such as CH2OO. It is supposed that the aldehyde group significantly influences the CI reactivity of the cydohexene-derived CIs. The direct CI detection method presented here should allow study of the formation and reactivity of a wide range of different CIs formed from atmospheric ozonolysis reactions.
  • Schurgers, G.; Hickler, T.; Miller, P. A.; Arneth, A. (2009)
  • Mäkitie, Antti A.; Almangush, Alhadi; Youssef, Omar; Metsälä, Markus; Silen, Suvi; Nixon, Iain J.; Haigentz, Missak; Rodrigo, Juan P.; Saba, Nabil F.; Vander Poorten, Vincent; Ferlito, Alfio (2020)
    Head and neck cancer (HNC) comprises a heterogeneous group of upper aerodigestive tract malignant neoplasms, the most frequent of which is squamous cell carcinoma. HNC forms the eighth most common cancer type and the incidence is increasing. However, survival has improved only moderately during the past decades. Currently, early diagnosis remains the mainstay for improving treatment outcomes in this patient population. Unfortunately, screening methods to allow early detection of HNC are not yet established. Therefore, many cases are still diagnosed at advanced stage, compromising outcomes. Exhaled breath analysis (EBA) is a diagnostic tool that has been recently introduced for many cancers. Breath analysis is non-invasive, cost-effective, time-saving, and can potentially be applied for cancer screening. Here, we provide a summary of the accumulated evidence on the feasibility of EBA in the diagnosis of HNC.
  • Kulmala, Markku; Lappalainen, Hanna K.; Back, Jaana; Laaksonen, An; Nikinmaa, Eero; Riekkola, Marja-Liisa; Vesala, Timo; Viisanen, Yrjo; Aalto, Tuula; Boy, Michael; Dal Maso, Miikka; Ehn, Mikael; Hakola, Hannele; Hari, Pertti; Hartonen, Kari; Hameri, Kaarle; Holtta, Teemu; Junninen, Heikki; Jarvi, Leena; Kurten, Theo; Lauri, Antti; Laurila, Tuomas; Lehtipalo, Katrianne; Lihavainen, Heikki; Lintunen, Anna; Mammarella, Ivan; Manninen, Hanna E.; Petaja, Tuukka; Pihlatie, Mari; Pumpanen, Jukka; Rinne, Janne; Romakkaniemi, Sami; Ruuskanen, Taina; Sipila, Mikko; Sorvari, Sanna; Vehkamaki, Hanna; Virtanen, Annele; Worsnop, Douglas R.; Kerminen, Veli-Matti (2014)