Ambient total OH reactivity was measured at the Finnish boreal forest station SMEAR II in Hyytiälä (Latitude 61&deg;51' N; Longitude 24&deg;17' E) in July and August 2010 using the Comparative Reactivity Method (CRM). The CRM – total OH reactivity method – is a direct, in-situ determination of the total loss rate of hydroxyl radicals (OH) caused by all reactive species in air. During the intensive field campaign HUMPPA-COPEC 2010 (<b>H</b>yytiälä <b>U</b>nited <b>M</b>easurements of <b>P</b>hotochemistry and <b>P</b>articles in <b>A</b>ir – <b>C</b>omprehensive <b>O</b>rganic <b>P</b>recursor <b>E</b>mission and <b>C</b>oncentration study) the total OH reactivity was monitored both inside (18 m) and directly above the forest canopy (24 m) for the first time. The comparison between these two total OH reactivity measurements, absolute values and the temporal variation have been analyzed here. Stable boundary layer conditions during night and turbulent mixing in the daytime induced low and high short-term variability, respectively. The impact on total OH reactivity from biogenic emissions and associated photochemical products was measured under "normal" and "stressed" (i.e. prolonged high temperature) conditions. The advection of biomass burning emissions to the site caused a marked change in the total OH reactivity vertical profile. By comparing the OH reactivity contribution from individually measured compounds and the directly measured total OH reactivity, the size of any unaccounted for or "missing" sink can be deduced for various atmospheric influences. For "normal" boreal conditions a missing OH reactivity of 58%, whereas for "stressed" boreal conditions a missing OH reactivity of 89% was determined. Various sources of not quantified OH reactive species are proposed as possible explanation for the high missing OH reactivity

The procedure for spectra interpretation and quantitative analysis is described through the context of an algorithm in which contributions of background and analyte absorption to the infrared spectrum are apportioned by the superposition of lineshapes constrained by laboratory measurements.

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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.

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Outdoor aerosols are transported indoors, where their component concentrations depend on aerosol size, physiochemical properties, indoor sources and losses, and cross-environment gradients of temperature and relative humidity. We explored these dependencies by measuring real-time outdoor and indoor non-refractory, submicron (PM ) aerosol component mass concentrations in a mixed-use laboratory space with an Aerodyne mini-aerosol mass spectrometer (AMS) and black carbon (BC) with an aethalometer. The median indoor/outdoor (I/O) ratios were 0.60 for sulfate, 0.25 for nitrate, 0.52 for ammonium, 0.73 for organics, and 0.61 for BC. Positive matrix factorization (PMF) on organic aerosol data identified hydrocarbon-like (HOA), cooking (COA), and oxygenated (OOA) factors. By assuming sulfate was nonvolatile, lost only by mechanical processes, and without indoor sources, the transformations of other components i due to partitioning changes or indoor sources were parameterized by normalizing their I/O ratios by sulfate's I/O ratio, that is, (I/O) . Component-specific behavior was quantified by regressions of (I/O) to outdoor-to-indoor temperature differences. Nitrate and HOA strongly and OOA weakly showed losses with increasing temperatures indoors vs. outdoors, and HOA likely had an indoor source. To our knowledge, this is the first reported deployment of an AMS to analyze real-time indoor aerosol composition and outdoor-to-indoor transformation.

Three flights from the Ice in Clouds Experiment–Tropical (ICE-T) field campaign examined the onset of ice near the ascending cloud tops of tropical maritime cumuli as they cooled from 0° to −14°C. Careful quantitative analysis of ice number concentrations included manual scrutiny of particle images and corrections for possible particle-shattering artifacts. The novel use of the Wyoming Cloud Radar documented the stage of cloud development and tops relative to the aircraft sampling, complemented the manual estimates of graupel concentrations, and provided new clear evidence of graupel movement through the rime-splintering zone. Measurements of ice-nucleating particles (INPs) provided an estimate of primary initiated ice. The data portray a dynamically complex picture of hydrometeor transport contributing to, and likely resulting from, the rime-splintering process. Hundreds per liter of supercooled raindrops ascended within the updrafts as the cloud tops reached 0°C and contributed in part to the 0.1 L−1 graupel detected soon after the cloud tops cooled to −5°C. Rime splintering could thus be initiated upon first ascent of the cloud top through that zone and arguably contributed to the 1 L−1 or more graupel observed above it. Graupel ascending/descending into, or balanced within, the rime-splintering zone were found. In wider, less isolated clouds with dying updrafts and tops near −14°C, ice particle concentrations sometimes reached 100 L−1. Future 3D numerical modeling will be required to evaluate if rime splintering alone can explain the difference of three to four orders of magnitude in the observed INPs and the graupel observed at −5°C and colder.