Technical Note: Quantitative long-term measurements of VOC concentrations by PTR-MS ? measurement, calibration, and volume mixing ratio calculation methods

International audienceProton transfer reaction mass spectrometry (PTR-MS) is a technique for online measurements of atmospheric concentrations, or volume mixing ratios, of volatile organic compounds (VOCs). The aim of this paper is to give a detailed description of our measurement, calibration, and volume mixing ratio calculation methods, which have been designed for long-term stand-alone field measurements by PTR-MS. We also show how the information obtained from a calibration can be used to determine the instrument specific relative transmission curve, which enables quantitative mixing ratio calculation for VOCs which are not present in a calibration gas standard. To illustrate the functionality of our measurement, calibration, and calculation methods, we present a one-month period of ambient mixing ratio data measured in a boreal forest ecosystem at the SMEAR II station in southern Finland. During the measurement period 27 March?26 April 2007, the hourly averages of mixing ratios were 0.1?0.5 ppbv for formaldehyde, 0.2?3.0 ppbv for methanol, 0.04?0.39 ppbv for benzene, and 0.03?1.25 ppbv for monoterpenes

Hydrocarbon fluxes above a Scots pine forest canopy: Measurements and modeling

International audienceWe measured the fluxes of several hydrocarbon species above a Scots pine (Pinus sylvestris) stand using disjunct eddy covariance technique with proton transfer reaction ? mass spectrometry. The measurements were conducted during four days in July at SMEAR II research station in Hyytiälä, Finland. Compounds which showed significant emission fluxes were methanol, acetaldehyde, acetone, and monoterpenes. A stochastic Lagrangian transport model with simple chemical degradation was applied to assess the sensitivity of the above canopy fluxes to chemistry. According to the model, the chemical degradation had a minor effect on the fluxes measured in this study but has a major effect on the vertical flux profiles of more reactive compounds, such as sesquiterpenes. The monoterpene fluxes followed the traditional exponential temperature dependent emission algorithm but were considerably higher than the fluxes measured before at the same site. The normalized emission potential (30°C) was 2.5 ?g gdw?1 h?1 obtained using the temperature dependence coefficient of 0.09°C?1

Continuous flux measurements of VOCs using PTR-MS — reliability and feasibility of disjunct-eddy-covariance, surface-layer-gradient, and surface-layer-profile methods

Peer reviewe

Future biogeochemical forcing in Eastern Siberia: cooling or warming?

Over-proportional warming in the northern high latitudes, and large carbon stocks in boreal and (sub)arctic ecosystems have raised concerns as to whether substantial positive climate feedbacks from biogeochemical process responses should be expected. Such feedbacks occur if increasing temperatures lead to e.g., a net release of CO2 or CH4. However, temperature-enhanced emissions of biogenic volatile organic compounds (BVOC) have been shown to contribute to a cooling feedback via growth of secondary organic aerosol (SOA), and related aerosol forcings. Combining measurements in Eastern Siberia with model-based estimates of vegetation and permafrost dynamics, BVOC emissions and aerosol growth, we show here that the additional climate forcing from changes in ecosystem CO2 balance and BVOC-SOA interactions nearly cancel on a regional scale. The interactions between emissions and vegetation dynamics that underlie individual forcing estimates are complex and highlight the importance of addressing ecosystem-climate feedbacks in consistent, process-based model frameworks that account for a multitude of system processes

Winter to spring transition and diurnal variation of VOCs in Finland at an urban background site and a rural site

Peer reviewe

Future vegetation–climate interactions in Eastern Siberia: an assessment of the competing effects of CO2 and secondary organic aerosols

Disproportional warming in the northern high latitudes, and large carbon stocks in boreal and (sub)arctic ecosystems have raised concerns as to whether substantial positive climate feedbacks from biogeochemical process responses should be expected. Such feedbacks occur if increasing temperatures lead to e.g. a net release of CO2 or CH4. However, temperature-enhanced emissions of biogenic volatile organic compounds (BVOC) have been shown to contribute to the growth of secondary organic aerosol (SOA) which is known to have a negative radiative climate effect. Combining measurements in Eastern Siberia with model-based estimates of vegetation and permafrost dynamics, BVOC emissions and aerosol growth, we assess here possible future changes in ecosystem CO2 balance and BVOC-SOA interactions, and discuss these changes in terms of possible climate effects. On global level, both are very small but when concentrating on Siberia and the northern hemisphere the negative forcing from changed aerosol direct and indirect effects become notable – even though the associated temperature response would not necessarily follow a similar spatial pattern. While our analysis does not include other important processes that are of relevance for the climate system, the CO2 and BVOC-SOA interplay used serves as an example of the complexity of the interactions between emissions and vegetation dynamics that underlie individual terrestrial feedbacks and highlights the importance of addressing ecosystem-climate feedbacks in consistent, process-based model frameworks

Trimethylamine emissions in animal husbandry

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(-2) s(-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.Peer reviewe

Terpenoid emissions from fully grown east Siberian Larix cajanderi trees

Peer reviewe

Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.Research at the University of Cambridge was supported by a Marie Curie Intra-European fellowship (project no. 254319) and the ERC grant no. 279405. We thank the SAPHIR and TNA2012 team in Jülich for supporting our measurements and the support by EUROCHAMP2 contract no. 228335. The field-work was funded by ERC grant 227463 and the Academy of Finland Centre of Excellence (grants 1118615 and 272041) and by the Office of Science (BER), US Department of Energy via Biogenic Aerosols - Effects on Clouds and Climate (BAECC). European Union’s Horizon 2020 research and innovation programme under grant agreement no. 654109 and previously from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement no. 262254. We thank the Met Office for use of the NAME model. S.C. thanks the UK Natural Environment Research Council for her studentship