Abstract. Atmospheric measurements of hydroxyl radicals (OH) are challenging due to a high reactivity and consequently low concentration. The importance of OH as an atmospheric oxidant has motivated a sustained effort leading to the development of a number of highly sensitive analytical techniques. Recent work has indicated that the laser-induced fluorescence of the OH molecules method based on the fluorescence assay by gas expansion technique (LIF-FAGE) for the measurement of atmospheric OH in some environments may be influenced by artificial OH generated within the instrument, and a chemical method to remove this interference was implemented in a LIF-FAGE system by . While it is not clear whether other LIF-FAGE instruments suffer from the same interference, we have applied this method to our LIF-FAGE HORUS (Hydroxyl Radical Measurement Unit based on fluorescence Spectroscopy) system, and developed and deployed an inlet pre-injector (IPI) to determine the chemical zero level in the instrument via scavenging the ambient OH radical.We describe and characterise this technique in addition to its application at field sites in forested locations in Finland, Spain and Germany. Ambient measurements show that OH generated within the HORUS instrument is a non-negligible fraction of the total OH signal, which can comprise 30 to 80 % during daytime and 60 to 100 % during the night. The contribution of the background OH varied greatly between measurement sites and was likely related to the type and concentration of volatile organic compounds (VOCs) present at each particular location. Two inter-comparisons in contrasting environments between the HORUS instrument and two different chemical ionisation mass spectrometers (CIMS) are described to demonstrate the efficacy of IPI and the necessity of the chemical zeroing method for our LIF-FAGE instrument in such environments.

Abstract. This paper describes the background, instrumentation, goals, and the regional influences on the HUMPPA-COPEC intensive field measurement campaign, conducted at the Boreal forest research station SMEAR II (Station for Measuring Ecosystem-Atmosphere Relation) in Hyytiälä, Finland from 12 July-12 August 2010. The prevailing meteorological conditions during the campaign are examined and contrasted with those of the past six years. Back trajectory analyses show that meteorological conditions at the site in 2010 were characterized by a higher proportion of southerly flow than in the other years studied. As a result the summer Correspondence to: J. Williams (jonathan.williams@mpic.de) of 2010 was anomalously warm and high in ozone making the campaign relevant for the analysis of possible future climates. A comprehensive land use analysis, provided on both 5 and 50 km scales, shows that the main vegetation types surrounding the site on both the regional and local scales are: coniferous forest (Scots pine and/or Norway spruce); mixed forest (Birch and conifers); and woodland scrub (e.g. Willows, Aspen); indicating that the campaign results can be taken as representative of the Boreal forest ecosystem. In addition to the influence of biogenic emissions, the measurement site was occasionally impacted by sources other than vegetation. Specific tracers have been used here to identify the time periods when such sources have impacted the site namely: biomass burning (acetonitrile and CO), urbanPublished by Copernicus Publications on behalf of the European Geosciences Union. 10600 J. Williams et al.: An overview of meteorological and chemical influences anthropogenic pollution (pentane and SO 2 ) and the nearby Korkeakoski sawmill (enantiomeric ratio of chiral monoterpenes). None of these sources dominated the study period, allowing the Boreal forest summertime emissions to be assessed and contrasted with various other source signatures.

Abstract. Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.

Abstract. We present an automated dynamic chamber system which is optimised for continuous unattended flux measurements of multiple non-reactive and reactive trace gases on grassland ecosystems. Main design features of our system are (a) highly transparent chamber walls consisting of chemically inert material, (b) individual purging flow units for each chamber, and (c) a movable lid for automated opening and closing of the chamber. The purging flow rate was chosen high enough to keep the mean residence time of the chamber air below one minute. This guarantees a proven efficient mixing of the chamber volume and a fast equilibration after lid closing. The dynamic chamber system is able to measure emission as well as deposition fluxes of trace gases. For the latter case, the modification of the turbulent transport by the chamber (compared to undisturbed ambient conditions) is quantitatively described by a bulk resistance concept.Beside a detailed description of the design and functioning of the system, results of field applications at two grassland sites are presented. In the first experiment, fluxes of five trace gases (CO 2 , H 2 O, NO, NO 2 , O 3 ) were measured simultaneously on small grassland plots.It showed that the dynamic chamber system is able to detect the characteristic diurnal cycles with a sufficient temporal resolution. The results also demonstrated the importance of considering the chemical source/sink in the chamber due to gas phase reactions for the reactive compounds of the NO-NO 2 -O 3 triad. In a second field experiment, Correspondence to: L. Pape (llehmann@mpch-mainz.mpg.de) chamber flux measurements of CO 2 and methanol were compared to simultaneous independent eddy covariance flux measurements on the field scale. The fluxes obtained with the two methods showed a very good agreement indicating a minimal disturbance of the chambers on the physiological activity of the enclosed vegetation.