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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.

Aims Vegetation emissions of volatile organic compounds (VOCs) are intensively studied world-wide, because oxidation products of VOCs contribute to atmospheric processes. The overall aim of this study was to identify and quantify the VOCs that originate from boreal podzolized forest soil at different depths, in addition to studying the association of VOC concentrations with VOC and CO 2 fluxes from the boreal forest floor. Methods This is the first published study that measures belowground VOC concentrations at different depths in a podzol soil combined with simultaneous flux measurements from the boreal forest floor. The VOC concentrations were determined by sampling VOCs from air inside soil layers using the gas collectors and adsorbent tubes. Forest floor VOC fluxes were determined using a dynamic enclosure technique. All the VOC samples were analysed using a thermal desorption-gas chromatograph-mass spectrometer. Results More than 50 VOCs, dominated by monoterpenes and sesquiterpenes, were detected in the air space in the soil during two measurement campaigns. The O-horizon was a significant monoterpene source, because it contained fresh isoprenoid-rich litter. Belowground monoterpene concentrations were largely decoupled from forest floor monoterpene fluxes; thus, it seems that production processes and storages of VOCs partly differ from those VOCs that are simultaneously released from the forest floor. Both fluxes and concentrations of the monoterpenes and sesquiterpenes correlated with the CO 2 fluxes in autumn, indicating that VOC release was driven by microbial activity. Conclusions This is the first study where below-ground VOC concentrations were quantified in situ, and for this reason, this study provides valuable insights to the VOC sources present in soils.

ABSTRACT Effect of three wood-decaying fungi on decomposition of spruce wood was studied in solid-state cultivation conditions for a period of three months. Two white rot species (Trichaptum abietinum and Phlebia radiata) were challenged by a brown rot species (Fomitopsis pinicola) in varying combinations. Wood decomposition patterns as determined by mass loss, carbon to nitrogen ratio, accumulation of dissolved sugars and release of volatile organic compounds (VOCs) were observed to depend on both fungal combinations and growth time. Similar dependence of fungal species combination, either white or brown rot dominated, was observed for secreted enzyme activities on spruce wood. Fenton chemistry suggesting reduction of Fe3+ to Fe2+ was detected in the presence of F. pinicola, even in co-cultures, together with substantial degradation of wood carbohydrates and accumulation of oxalic acid. Significant correlation was perceived with two enzyme activity patterns (oxidoreductases produced by white rot fungi; hydrolytic enzymes produced by the brown rot fungus) and wood degradation efficiency. Moreover, emission of four signature VOCs clearly grouped the fungal combinations. Our results indicate that fungal decay type, either brown or white rot, determines the loss of wood mass and decomposition of polysaccharides as well as the pattern of VOCs released upon fungal growth on spruce wood. Fungal decay type, either brown rot or white rot, determines not only the degree of degradation of wood carbohydrates but also the pattern of VOCs released by fungal decay action.

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 µm mesh size) or the ingrowth of roots and fungi (1 µm 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 µg m−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 α-pinene, camphene, β-pinene, and Δ3-carene fluxes.

In this study, a thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) method following sorbent tube sampling was developed for the determination of monoterpenes (MTs), sesquiterpenes (SQTs) and diterpenes (DTs) in gas-phase samples. The analytical figures of merit were determined, and the method performance was tested by conducting experiments related to, for example, sampling recovery, storage stability and ozone reactivity. The limit-of-quantification values were 13–518 pg (0.5–9.3 pptv), intermediate precision was in the range of 3 %–10 % and the expanded measurement uncertainty was in the range of 16 %–55 % for terpenes. The sampling recoveries of terpenes were approximately within 100±20 % with different inlet lines (15 m long Teflon and 1 m long heated stainless steel) and branch enclosure cuvette (6 L Teflon bag) tested. Ozone is an important factor causing losses of the studied compounds during sampling. Therefore, losses of terpenes upon ozone exposure were studied and the reaction rate coefficients were estimated. The ozone reaction rate coefficient (kO3) of ent-kaurene was experimentally estimated to be 2 orders of magnitude greater than the respective literature kO3 value, demonstrating the potential underestimation of DT contribution to atmospheric reactivity. The preliminary comparison between offline- and online-mode TD–GC–MS sampling and analysis revealed that diterpenes and oxygenated sesquiterpenes are lost in excessive amounts in online-mode sampling, hindering the online-mode applicability for the quantitative analysis of these compounds. A few applications to real samples were tested to identify DTs potentially emitted by boreal forest tree species. In dynamic headspace samples of pine needles and spruce twigs heated to 60 ∘C, five DTs and 13 DTs could be detected in emissions, respectively. The semi-quantitatively estimated emission rates of DTs were roughly 1 to 3 orders of magnitude lower than those of MTs and SQTs. Similarly, in spruce branch enclosure emissions from a living tree, six DTs were detected once the enclosure was heated to ca. 60 ∘C. In summary, the developed analytical procedure was demonstrated to be applicable for the analysis of MTs, SQTs and DTs. In addition, DTs could be detected in needles, twigs and branch enclosure emissions; however, high temperatures were required to promote the emissions and for obtaining detectable concentrations.

In the northern hemisphere, boreal forests are a major source of biogenic volatile organic compounds (BVOCs), which drive atmospheric processes and lead to cloud formation and changes in the Earth's radiation budget. Although forest vegetation is known to be a significant source of BVOCs, the role of soil and the forest floor, and especially interannual variations in fluxes, remains largely unknown due to a lack of long-term measurements. Our aim was to determine the interannual, seasonal and diurnal dynamics of boreal forest floor volatile organic compound (VOC) fluxes and to estimate how much they contribute to ecosystem VOC fluxes. We present here an 8-year data set of forest floor VOC fluxes, measured with three automated chambers connected to the quadrupole proton transfer reaction mass spectrometer (quadrupole PTR-MS). The exceptionally long data set shows that forest floor fluxes were dominated by monoterpenes and methanol, with relatively comparable emission rates between the years. Weekly mean monoterpene fluxes from the forest floor were highest in spring and in autumn (maximum 59 and 86 μg m h , respectively), whereas the oxygenated VOC fluxes such as methanol had highest weekly mean fluxes in spring and summer (maximum 24 and 79 μg m h , respectively). Although the chamber locations differed from each other in emission rates, the inter-annual dynamics were very similar and systematic. Accounting for this chamber location dependent variability, temperature and relative humidity, a mixed effects linear model was able to explain 79-88% of monoterpene, methanol, acetone, and acetaldehyde fluxes from the boreal forest floor. The boreal forest floor was a significant contributor in the forest stand fluxes, but its importance varies between seasons, being most important in autumn. The forest floor emitted 2-93% of monoterpene fluxes in spring and autumn and 1-72% of methanol fluxes in spring and early summer. The forest floor covered only a few percent of the forest stand fluxes in summer.

Biogenic volatile organic compounds (BVOCs; e.g. terpenes) are highly reactive compounds typically present at sub-parts-per-billion mole fractions in the air. Due to this, their measurements are challenging and they may suffer losses during sampling, storage and analyses. Even though online measurements of BVOCs are becoming more common, the use of sorbent tubes is expected to continue because they offer greater spatial coverage compared to online measurements, and no infrastructure (e.g. electricity, housing/shelter with stable temperature and humidity, sampling lines) is required for sampling. In this study, the performance of an offline technique for the measurement of BVOCs based on sorbent tube sampling was evaluated. Tested compounds included eight monoterpenes, five sesquiterpenes and five oxygenated BVOCs, which are generally either directly emitted (1,8-cineol, linalool, bornyl acetate) or oxidation products (nopinone and 4-acetyl-1-methylcyclohexene). Two sorbent materials (Tenax TA and Carbopack B) and four tube materials (stainless steel (SS), SilcoNert 1000, glass and glass-coated SS) were used. The laboratory evaluations determined the storage stability, breakthrough volumes, suitable tube materials, recovery from ozone scrubbers and particulate filters, and sampling efficiency. In addition, an intercomparison between two laboratories was conducted. No multibed configurations were tested. Of the sorbent materials Tenax TA showed acceptable results for these BVOCs, while with Carbopack B losses and increases in some compounds were detected. Studied compounds were found to be stable in Tenax TA tubes for at least 1 month at −20 and at +20 ∘C. Breakthrough tests indicated that α- and β-pinene have clearly lower breakthrough volumes in the Tenax TA tubes used (4–7 and 8–26 L, respectively) than other terpenes (> 160 L). SS, SilcoNert 1000 and glass were all shown to be suitable tube materials. Results from Tenax TA sorbent tube sampling agreed with online sampling for most compounds. Heated SS tubes, sodium thiosulfate filters and KI/Cu traps were found to be suitable ozone scrubbers for the studied BVOCs. Tested particle filters had a greater impact on limonene (relative difference < +7 %) than on α- and β-pinene (relative difference ±2 %). The laboratory intercomparison of α- and β-pinene measurements showed that in general, measured values by the two laboratories were in good agreement with Tenax TA.

Many cities attempt to mitigate poor air quality by increasing tree canopy cover. Trees can indeed capture pollutants and reduce their dispersion, but they can also negatively impact urban air quality. For example, trees emit biogenic volatile organic compounds (BVOCs) that participate in both ozone (O3) and secondary organic aerosol (SOA) formation, yet these emissions have been little studied in urban contexts. We sampled BVOCs from the leaves of mature urban trees using lightweight enclosures and adsorbent tubes in two cities: Montreal, Canada and Helsinki, Finland. In both cities, we targeted five common broadleaved species in parks and streets, comparing their standardised BVOC emission potentials to nonurban BVOC emission potential estimates from emission databases. We also calculated the potential O3 and SOA formation by the study species at the leaf scale and upscaled to the neighbourhood. We found that the measured BVOC emission potentials generally deviated little from the emission database estimates, supporting the use of database estimates for urban trees. However, tree-to-tree variation in the BVOC emission potentials was large, with slight differences between park and street trees. Compared to park trees, street tree emissions were higher in Montreal (specifically isoprene and sesquiterpenoids) and lower in Helsinki (specifically green leaf volatiles). Finally, we found that O3 formation from our study species' BVOC emissions was dominated by isoprene, while SOA formation was also affected by lower monoterpenoid and sesquiterpenoid emissions. These findings highlight the importance of species selection and management strategies that protect trees from BVOC-inducing stresses.

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.