The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3(-))-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 ± 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H2O or D2O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.

Boreal forests emit a large amount of monoterpenes into the atmosphere. Traditionally these emissions are assumed to originate as evaporation from large storage pools. Thus, their diurnal cycle would depend mostly on temperature. However, there is indication that a significant part of the monoterpene emission would originate directly from de novo synthesis. By applying 13 CO2 fumigation and analyzing the isotope fractions with proton transfer reaction mass spectrometry (PTR-MS) and classical GC-MS, we determined the fractions of monoterpene emissions originating from de novo biosynthesis in Pinus sylvestris (58%), Picea abies (33.5%), Larix decidua (9.8%) and Betula pendula (100%). Application of the observed split between de novo and pool emissions from P. sylvestris in a hybrid emission algorithm resulted in a better description of ecosystem scale monoterpene emissions from a boreal Scots pine forest stand.

Abstract. Proton transfer reaction mass spectrometry (PTR-MS) is a technique for online measurements of atmospheric concentrations, or volume mixing ratios, of volatile organic compounds (VOCs). This paper gives a detailed description of our measurement, calibration, and volume mixing ratio calculation methods, which have been designed for longterm stand-alone field measurements by PTR-MS. The PTR-MS instrument has to be calibrated regularly with a gas standard to ensure the accuracy needed in atmospheric VOC measurements. We introduce a novel method for determining an instrument specific relative transmission curve using information obtained from a calibration. This curve enables consistent mixing ratio calculation for VOCs not present in a calibration gas standard. Our method proved to be practical, systematic, and sensitive enough to capture changes in the transmission over time. We also propose a new approach to considering the abundance of H 3 O + H 2 O ions in mixing ratio calculation. The approach takes into account the difference in the transmission efficiencies for H 3 O + and H 3 O + H 2 O ions. To illustrate the functionality of our measurement, calibration, and calculation methods, we present a one-month period of ambient mixing ratio data measured in a boreal forest ecosystem at the SMEAR II station in southern Finland. During the measurement period 27 March-26 April 2007, the hourly averages of the mixing ratios were 0.051-0.57 ppbv for formaldehyde, 0.19-3.1 ppbv for methanol, 0.038-0.39 ppbv for benzene, and 0.020-1.3 ppbv Correspondence to: R. Taipale (risto.taipale@helsinki.fi) for monoterpenes. The detection limits for the hourly averages were 0.020, 0.060, 0.0036, and 0.0092 ppbv, respectively.

A B S T R A C T Atmosphere-surface exchange represents one mechanism by which atmospheric particle mass and number size distributions are modified. Deposition velocities (v d ) exhibit a pronounced dependence on surface type, due in part to turbulence structure (as manifest in friction velocity), with minima of approximately 0.01 and 0.2 cm s −1 over grasslands and 0.1-1 cm s −1 over forests. However, as noted over 20 yr ago, observations over forests generally do not support the pronounced minimum of deposition velocity (v d ) for particle diameters of 0.1-2 μm as manifest in theoretical predictions. Closer agreement between models and observations is found over less-rough surfaces though those data also imply substantially higher surface collection efficiencies than were originally proposed and are manifest in current models. We review theorized dependencies for particle fluxes, describe and critique model approaches and innovations in experimental approaches, and synthesize common conclusions of experimental and modelling studies. We end by proposing a number of research avenues that should be pursued in to facilitate further insights and development of improved numerical models of atmospheric particles.

Abstract.We measured the fluxes of several hydrocarbon species above a Scots pine (Pinus sylvestris) stand using disjunct eddy covariance technique with proton transfer reaction -mass spectrometry. The measurements were conducted during four days in July at SMEAR II research station in Hyytiälä, Finland. Compounds which showed significant emission fluxes were methanol, acetaldehyde, acetone, and monoterpenes. A stochastic Lagrangian transport model with simple chemical degradation was applied to assess the sensitivity of the above canopy fluxes to chemistry. According to the model, the chemical degradation had a minor effect on the fluxes measured in this study but may have a major effect on the vertical flux profiles of more reactive compounds, such as sesquiterpenes. The monoterpene fluxes derived using M81 and M137 had a systematic difference with the latter one being higher. These fluxes followed the traditional exponential temperature dependent emission algorithm but were considerably higher than the fluxes measured before at the same site. The normalized monoterpene emission potentials at 30 • C, obtained using the temperature dependence coefficient of 0.09 • C −1 , were 2.0 µg g −1 dw h −1 and 2.5 µg g −1 dw h −1 , for fluxes derived using M81 and M137.

Abstract. In order to investigate the negative ions in the boreal forest we have performed measurements to chemically characterise the composition of negatively charged clusters containing highly oxygenated molecules (HOMs). Additionally, we compared this information with the chemical composition of the neutral gas-phase molecules detected in the ambient atmosphere during the same period. The chemical composition of the ions was retrieved using an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF-MS) while the gas-phase neutral molecules (mainly sulfuric acid and HOMs) were characterised using the same mass spectrometer coupled to a nitrate-based chemical ionisation unit (CI-APi-TOF). Overall, we divided the identified HOMs in two classes: HOMs containing only carbon, hydrogen and oxygen and nitrogen-containing HOMs or organonitrates (ONs). During the day, among the ions, in addition to the well-known pure sulfuric acid clusters, we found a large number of HOMs clustered with nitrate (NO Finally, diurnal profiles of the negative ions were consistent with the neutral compounds revealing that ONs peak during the day while HOMs are more abundant at night-time. However, during the day, a large fraction of the negative charge is taken up by the pure sulfuric acid clusters causing differences between ambient ions and neutral compounds (i.e. less available charge for HOM and ON).

Abstract. Emission rates and concentrations of biogenic volatile organic compounds (BVOCs) were measured at a Mediterranean coastal site at Castelporziano, approximately 25 km south-west of Rome, between 7 May and 3 June 2007, as part of the ACCENT-VOCBAS field campaign on biosphere-atmosphere interactions. Concentrations and emission rates were measured using the disjunct eddy covariance (DEC) method utilizing three different proton transfer reaction mass spectrometers (PTR-MS) so allowing a comparison between the instruments. The high resolution data from the PTR-MS instruments considerably enhances the original BEMA measurements of the mid 1990s.Depending on the measurement period, the volume mixing ratios were in the range 1.6-3.5 ppbv for methanol, 0.44-1.3 ppbv for acetaldehyde, 0.96-2.1 ppbv for acetone, 0.10-0.14 ppbv for isoprene, and 0.13-0.30 ppbv for monoterpenes. A diurnal cycle in mixing ratios was apparent with daytime maxima for methanol, acetaldehyde, acetone, and isoprene. The fluxes ranged from 370-440 µg m −2 h −1 for methanol, 180-360 µg m −2 h −1 for acetaldehyde, 180-450 µg m −2 h −1 for acetone, 71-290 µg m −2 h −1 for isoprene, and 240-860 µg m −2 h −1 for monoterpenes. From the measured flux data (7 May-3 June) an average basal emission rate for the Macchia vegetation was calculated

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