Eddy covariance fluxes of formic acid, HCOOH, were measured over a boreal forest canopy in spring/summer 2014. The HCOOH fluxes were bidirectional but mostly upward during daytime, in contrast to studies elsewhere that reported mostly downward fluxes. Downward flux episodes were explained well by modeled dry deposition rates. The sum of net observed flux and modeled dry deposition yields an upward “gross flux” of HCOOH, which could not be quantitatively explained by literature estimates of direct vegetative/soil emissions nor by efficient chemical production from other volatile organic compounds, suggesting missing or greatly underestimated HCOOH sources in the boreal ecosystem. We implemented a vegetative HCOOH source into the GEOS‐Chem chemical transport model to match our derived gross flux and evaluated the updated model against airborne and spaceborne observations. Model biases in the boundary layer were substantially reduced based on this revised treatment, but biases in the free troposphere remain unexplained.

Abstract. A multi-layer ozone (O 3 ) dry deposition model has been implemented into SOSAA (a model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to improve the representation of O 3 concentration and flux within and above the forest canopy in the planetary boundary layer. We aim to predict the O 3 uptake by a boreal forest canopy under varying environmental conditions and analyse the influence of different factors on total O 3 uptake by the canopy as well as the vertical distribution of deposition sinks inside the canopy. The newly implemented dry deposition model was validated by an extensive comparison of simulated and observed O 3 turbulent fluxes and concentration profiles within and above the boreal forest canopy at SMEAR II (Station to Measure Ecosystem-Atmosphere Relations II) in Hyytiälä, Finland, in August 2010.In this model, the fraction of wet surface on vegetation leaves was parametrised according to the ambient relative humidity (RH). Model results showed that when RH was larger than 70 % the O 3 uptake onto wet skin contributed ∼ 51 % to the total deposition during nighttime and ∼ 19 % during daytime. The overall contribution of soil uptake was estimated about 36 %. The contribution of sub-canopy deposition below 4.2 m was modelled to be ∼ 38 % of the total O 3 deposition during daytime, which was similar to the contribution reported in previous studies. The chemical contribution to O 3 removal was evaluated directly in the model simulations. According to the simulated averaged diurnal cycle the net chemical production of O 3 compensated up to ∼ 4 % of dry deposition loss from about 06:00 to 15:00 LT. During nighttime, the net chemical loss of O 3 further enhanced removal by dry deposition by a maximum ∼ 9 %. Thus the results indicated an overall relatively small contribution of airborne chemical processes to O 3 removal at this site.

No abstract

Abstract. 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 nmol m −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. 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:

No abstract

Abstract. 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 (<4.5 %) of the missing reactivity can be explained by modelled secondary compounds (mostly oxidized VOCs). These findings indicate that compounds measured but not included in the model as well as unmeasured primary emissions contribute the missing reactivity. In the future, non-hydrocarbon compounds from sources other than vegetation (e.g. soil) should be included in OH reactivity studies.

&lt;p&gt;&lt;strong&gt;Abstract.&lt;/strong&gt; 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 Hyyti&amp;#228;l&amp;#228;, 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&amp;#8201;s&lt;sup&gt;&amp;#8722;1&lt;/sup&gt;) and decreased in July (8.8&amp;#8201;s&lt;sup&gt;&amp;#8722;1&lt;/sup&gt;) 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 (&lt;&amp;#8201;9&amp;#8201;%) of the missing reactivity can be explained by modelled secondary compounds (mostly oxidised VOCs). These findings indicate that compounds measured but not included in the model as well as unmeasured primary emissions contribute the missing reactivity. In the future, non-hydrocarbon compounds from other sources than trees (e.g. soil) should be included in OH reactivity studies.&lt;/p&gt;