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Emissions of biogenic volatile organic compounds (BVOCs) are a crucial component of biosphere-atmosphere interactions. In northern latitudes, climate change is amplified by feedback processes in which BVOCs have a recognized, yet poorly quantified role, mainly due to a lack of measurements and concomitant modeling gaps. Hence, current Earth system models mostly rely on temperature responses measured on vegetation from lower latitudes, rendering their predictions highly uncertain. Here, we show how tundra isoprene emissions respond vigorously to temperature increases, compared to model results. Our unique dataset of direct eddy covariance ecosystem-level isoprene measurements in two contrasting ecosystems exhibited Q 10 (the factor by which the emission rate increases with a 10 °C rise in temperature) temperature coefficients of up to 20.8, that is, 3.5 times the Q 10 of 5.9 derived from the equivalent model calculations. Crude estimates using the observed temperature responses indicate that tundra vegetation could enhance their isoprene emissions by up to 41% (87%)-that is, 46% (55%) more than estimated by models-with a 2 °C (4 °C) warming. Our results demonstrate that tundra vegetation possesses the potential to substantially boost its isoprene emissions in response to future rising temperatures, at rates that exceed the current Earth system model predictions.

The ecosystem–atmosphere flux of biogenic volatile organic compounds (BVOCs) has important impacts on tropospheric oxidative capacity and the formation of secondary organic aerosols, influencing air quality and climate. Here we present within-canopy measurements of a set of dominant BVOCs in a managed spruce- and pine-dominated boreal forest located at the ICOS (Integrated Carbon Observation System) station Norunda in Sweden, collected using proton-transfer-reaction mass spectrometry (PTR-MS) during 2014–2016 and vertical emission profiles derived from these data. Ozone concentrations were simultaneously measured in conjunction with these PTR-MS measurements. The main BVOCs investigated with the PTR-MS were isoprene, monoterpenes, methanol, acetaldehyde, and acetone. The distribution of BVOC sources and sinks in the forest canopy was explored using Lagrangian dispersion matrix methods, in particular continuous near-field theory. The forest canopy was found to contribute ca. 86 % to the total monoterpene emission in summertime, whereas the below-canopy and canopy emissions were comparable (ca. 42 % and 58 %, respectively) during the fall period. This result indicates that boreal forest litter and other below-canopy emitters are a principal source of total forest monoterpene emissions during the fall months. During night, our results for methanol, acetone, and acetaldehyde seasonally present strong sinks in the forest canopy, especially in the fall, likely due to the nighttime formation of dew on vegetation surfaces. [ABSTRACT FROM AUTHOR]

Ecosystems exchange climate-relevant trace gases with the atmosphere, including volatile organic compounds (VOCs) that are a small but highly reactive part of the carbon cycle. VOCs have important ecological functions and implications for atmospheric chemistry and climate. We measured the ecosystem-level surface–atmosphere VOC fluxes using the eddy covariance technique at a shallow subarctic lake and an adjacent graminoid-dominated fen in northern Sweden during two contrasting periods: the peak growing season (mid-July) and the senescent period post-growing season (September–October). In July, the fen was a net source of methanol, acetaldehyde, acetone, dimethyl sulfide, isoprene, and monoterpenes. All of these VOCs showed a diel cycle of emission with maxima around noon and isoprene dominated the fluxes (93±22 µ mol m -2 d -1 , mean ± SE). Isoprene emission was strongly stimulated by temperature and presented a steeper response to temperature (Q10=14.5) than that typically assumed in biogenic emission models, supporting the high temperature sensitivity of arctic vegetation. In September, net emissions of methanol and isoprene were drastically reduced, while acetaldehyde and acetone were deposited to the fen, with rates of up to -6.7±2.8 µ mol m -2 d -1 for acetaldehyde. Remarkably, the lake was a sink for acetaldehyde and acetone during both periods, with average fluxes up to -19±1.3 µ mol m -2 d -1 of acetone in July and up to -8.5±2.3 µ mol m -2 d -1 of acetaldehyde in September. The deposition of both carbonyl compounds correlated with their atmospheric mixing ratios, with deposition velocities of -0.23±0.01 and -0.68±0.03 cm s -1 for acetone and acetaldehyde, respectively. Even though these VOC fluxes represented less than 0.5 % and less than 5 % of the CO 2 and CH 4 net carbon ecosystem exchange, respectively, VOCs alter the oxidation capacity of the atmosphere. Thus, understanding the response of their emissions to climate change is important for accurate prediction of the future climatic conditions in this rapidly warming area of the planet. [ABSTRACT FROM AUTHOR]

Biogenic volatile organic compounds (BVOCs) play an important role in the chemistry of the troposphere, especially in the formation of tropospheric ozone (O3) and secondary organic aerosols (SOA). Ecosystems produce and emit a large number of BVOCs. It is estimated on a global scale that approximately 90% of annual BVOC emissions are from terrestrial sources. In this study, measurements of BVOCs were conducted at the Welgegund measurement station (South Africa), which is considered to be a regionally representative background site situated in savannah grasslands. Very few BVOC measurements exist for savannah grasslands and results presented in this study are the most extensive for this type of landscape. Samples were collected twice a week for 2 h during the daytime and 2 h during the night-time through two long-term sampling campaigns from February 2011 to February 2012 and from December 2013 to February 2015, respectively. Individual BVOCs were identified and quantified using a thermal desorption instrument, which was connected to a gas chromatograph and a mass selective detector. The annual median concentrations of isoprene, 2-methyl-3-butene-2-ol (MBO), monoterpene and sesquiterpene (SQT) during the first campaign were 14, 7, 120 and 8 pptv, respectively, and 14, 4, 83 and 4 pptv, respectively, during the second campaign. The sum of the concentrations of the monoterpenes were at least an order of magnitude higher than the concentrations of other BVOC species during both sampling campaigns, with -pinene being the most abundant species. The highest BVOC concentrations were observed during the wet season and elevated soil moisture was associated with increased BVOC concentrations. However, comparisons with measurements conducted at other landscapes in southern Africa and the rest of the world that have more woody vegetation indicated that BVOC concentrations were, in general, significantly lower for savannah grasslands. Furthermore, BVOC concentrations were an order of magnitude lower compared to total aromatic concentrations measured at Welgegund. An analysis of concentrations by wind direction indicated that isoprene concentrations were higher from the western sector that is considered to be a relatively clean regional background region with no large anthropogenic point sources, while wind direction did not indicate any significant differences in the concentrations of the other BVOC species. Statistical analysis indicated that soil moisture had the most significant impact on atmospheric levels of MBO, monoterpene and SQT concentrations, whereas temperature had the greatest influence on isoprene levels. The combined O3 formation potentials of all the BVOCs measured calculated with maximum incremental reactivity (MIR) coefficients during the first and second campaign were 1162 and 1022 pptv, respectively. -Pinene and limonene had the highest reaction rates with O3, whereas isoprene exhibited relatively small contributions to O3 depletion. Limonene, α-pinene and terpinolene had the largest contributions to the OH reactivity of BVOCs measured at Welgegund for all of the months during both sampling campaigns. [ABSTRACT FROM AUTHOR]

Recently, the number and amount of biogenically emitted volatile organic compounds (VOCs) has been discussed in great detail. Depending on the ecosystem, the published number varies between a dozen and several hundred compounds. We present ecosystem exchange fluxes from a mixed oak-hornbeam forest in the Po Valley, Italy. The fluxes were measured by a proton transfer reaction-timeof- flight (PTR-ToF) mass spectrometer and calculated using the eddy covariance (EC) method. Detectable fluxes were observed for up to 29 compounds, dominated by isoprene, which comprised over 60% of the total upward flux (on a molar basis). The daily average of the total VOC upward flux was 10.4 nmolm-2 s-1. Methanol had the highest concentration and accounted for the largest downward flux. Methanol seemed to be deposited to dew, as the downward flux happened in the early morning, right after the calculated surface temperature came closest to the calculated dew point temperature. We estimated that up to 30% of the upward flux of methyl vinyl ketone (MVK) and methacrolein (MACR) originated from atmospheric oxidation of isoprene. A comparison between two methods for the flux detection (manual and automated) was made. Their respective advantages and disadvantages were discussed and the differences in their results shown. Both provide comparable results. [ABSTRACT FROM AUTHOR]

Abstract: We determined the accuracy of the dynamic chamber system for measuring VOC emissions of trees and soil in the field at SMEAR II station, Hyytiälä, Southern Finland. The study was based on creating a known source of different VOCs inside the chamber and measuring the concentration dynamics in the chamber by a proton transfer reaction mass spectrometer (PTR-MS) connected to the chamber. The chamber system underestimated the artificially generated VOC emission rates at varying degree. In isoprene, monoterpene and many oxygenated VOCs the underestimation was 5–30% but in some compounds with protonated mass >100 amu the signal was almost completely lost. The underestimation mainly originated in the chamber but the length of the sample tubing also affected the observed magnitude of the standard gas emission. The systematic error was higher at high relative humidity than in drier conditions, which suggests that the thickness of the water film adsorbed on the chamber inner surfaces contributes to the VOC loss rate in the chamber. Increasing the length of the chamber closure time slightly reduced the systematic underestimation of emission in most of the studied compounds although the underestimation persisted for at least 10 min. A dynamic chamber setup enables measurement of VOC emissions with good accuracy and precision while minimising the disturbance of the chamber to the object being measured. [Copyright &y& Elsevier]