Detection of RO2 radicals and other products from cyclohexene ozonolysis with NH4+ and acetate chemical ionization mass spectrometry

The performance of the novel ammonium chemical ionization time of flight mass spectrometer (NH4+-CI3-TOF) utilizing NH4+ adduct ion chemistry to measure first generation oxidized product molecules (OMs) as well as highly oxidized organic molecules (HOMs) was investigated for the first time. The gas-phase ozonolysis of cyclohexene served as a first test system. Experiments have been carried out in the TROPOS free-jet flow system at close to atmospheric conditions. Product ion signals were simultaneously observed by the NH4+-CI3-TOF and the acetate chemical ionization atmospheric pressure interface time of flight mass spectrometer (acetate-CI-APITOF). Both instruments are in remarkable good agreement within a factor of two for HOMs. For OMs not containing an OOH group the acetate technique can considerably underestimate OM concentrations by 2-3 orders of magnitude. First steps of cyclohexene ozonolysis generate ten different main products, detected with the ammonium-CI3-TOF, comprising 93% of observed OMs. The remaining 7% are distributed over several minor products that can be attributed to HOMs, predominately to highly oxidized RO2 radicals. Summing up, observed ammonium-CI3-TOF products yield 5.6 x le molecules cm" in excellent agreement with the amount of reacted cyclohexene of 4.5 x 10(9) molecules cm(-3) for reactant concentrations of [O-3] = 2.25 x 10(12) molecules cm(-3) and [cyclohexene] = 2.0 x 10(12) molecules cm(-3) and a reaction time of 7.9 s. NH4+ adduct ion chemistry is a promising CIMS technology for achieving carbon-closure due to the unique opportunity for complete detection of the whole product distribution including also peroxy radicals, and consequently, for a much better understanding of oxidation processes.Peer reviewe

NH4+ Association and Proton Transfer Reactions With a Series of Organic Molecules

In this study, we present reactions of NH4+ with a series of analytes (A): acetone (C3H6O), methyl vinyl ketone (C4H6O), methyl ethyl ketone (C4H8O) and eight monoterpene isomers (C10H16) using a Selective Reagent Ionization Time-of-Flight Mass Spectrometer (SRI-ToF-MS). We studied the ion-molecule reactions at collision energies of 55 meV and 80 meV. The ketones, having a substantially lower proton affinity than NH3, produce only cluster ions NH4+(A) in detectable amounts at 55 meV. At 80 meV, no cluster ions were detected meaning that these adduct ions are formed by strongly temperature dependent association reactions. Bond energies of cluster ions and proton affinities for most monoterpenes are not known and were estimated by high level quantum chemical calculations. The calculations reveal monoterpene proton affinities, which range from slightly smaller to substantially higher than the proton affinity of NH3. Proton affinities and cluster bond energies allow to group the monoterpenes as a function of the enthalpy for the dissociation reaction . We find that this enthalpy can be used to predict the NH4+-A cluster ion yield. The present study explains product ion formation involving NH4+ ion chemistry. This is of importance for chemical ionization mass spectrometry (CIMS) utilizing NH4+ as well as NH4+(H2O) as reagent ions to quantitatively detect atmospherically important organic compounds in real-time.Peer reviewe

Accretion Product Formation from Self- and Cross-Reactions of RO2 Radicals in the Atmosphere

Hydrocarbons are emitted into the Earth's atmosphere in very large quantities by human and biogenic activities. Their atmospheric oxidation processes almost exclusively yield RO2 radicals as reactive intermediates whose atmospheric fate is not yet fully unraveled. Herein, we show that gas-phase reactions of two RO2 radicals produce accretion products composed of the carbon backbone of both reactants. The rates for accretion product formation are very high for RO2 radicals bearing functional groups, competing with those of the corresponding reactions with NO and HO2. This pathway, which has not yet been considered in the modelling of atmospheric processes, can be important, or even dominant, for the fate of RO2 radicals in all areas of the atmosphere. Moreover, the vapor pressure of the formed accretion products can be remarkably low, characterizing them as an effective source for the secondary organic aerosol.Peer reviewe

Carbonyl sulfide (COS) as a tracer for canopy photosynthesis, transpiration and stomatal conductance: potential and limitations

The theoretical basis for the link between the leaf exchange of carbonyl sulfide (COS), carbon dioxide (CO2) and water vapour (H2O) and the assumptions that need to be made in order to use COS as a tracer for canopy net photosynthesis, transpiration and stomatal conductance, are reviewed. The ratios of COS to CO2 and H2O deposition velocities used to this end are shown to vary with the ratio of the internal to ambient CO2 and H2O mole fractions and the relative limitations by boundary layer, stomatal and internal conductance for COS. It is suggested that these deposition velocity ratios exhibit considerable variability, a finding that challenges current parameterizations, which treat these as vegetation-specific constants. COS is shown to represent a better tracer for CO2 than H2O. Using COS as a tracer for stomatal conductance is hampered by our present poor understanding of the leaf internal conductance to COS. Estimating canopy level CO2 and H2O fluxes requires disentangling leaf COS exchange from other ecosystem sources/sinks of COS. We conclude that future priorities for COS research should be to improve the quantitative understanding of the variability in the ratios of COS to CO2 and H2O deposition velocities and the controlling factors, and to develop operational methods for disentangling ecosystem COS exchange into contributions by leaves and other sources/sinks. To this end, integrated studies, which concurrently quantify the ecosystem-scale CO2, H2O and COS exchange and the corresponding component fluxes, are urgently needed

Accretion Product Formation from Ozonolysis and OH Radical Reaction of alpha-Pinene : Mechanistic Insight and the Influence of Isoprene and Ethylene

alpha-Pinene (C10H16) represents one of the most important biogenic emissions in the atmosphere. Its oxidation products can significantly contribute to the secondary organic aerosol (SOA) formation. Here, we report on the formation mechanism of C-19 and C-20 accretion products from alpha-pinene oxidation, which are believed to be efficient SOA precursors. Measurements have been performed in a free-jet flow system. Detection of RO2 radicals and accretion products was carried out by recent mass spectrometric techniques using different ionization schemes. Observed C-10-RO2 radicals from alpha-pinene ozonolysis were O,O-C10H15(O-2)(x)O-2 with x = 0, 1, 2, 3 and from the OH radical reaction HO-C10H16(O-2)(alpha)O-2 with alpha = 0, 1, 2. All detected C 20 accretion products can be explained via the accretion reaction RO2 + R'O-2 -> ROOR' + O-2 starting from the measured C-10-RO2 radicals. We speculate that C-19 accretion products are formed in an analogous way assuming CH2O elimination. Addition of isoprene (C5H8), producing C-5-RO2 radicals, leads to C-15 accretion products formed via cross-reactions with C-10-RO2 radicals. This process is competing with the formation of C-19/C-20 products from the pure alpha-pinene oxidation. A similar behavior has been observed for ethylene additives that form C-12 accretion products. In the atmosphere, a complex accretion product spectrum from self- and cross-reactions of available RO2 radicals can be expected. Modeling atmospheric conditions revealed that C-19/C-20 product formation is only reduced by a factor of 1.2 or 3.6 in isoprene-dominated environments assuming a 2- or 15-fold isoprene concentration over alpha-pinene, respectively, as present in different forested areas.Peer reviewe

First oxidation products from the reaction of hydroxyl radicals with isoprene for pristine environmental conditions

Isoprene, C5H8, inserts about half of the non-methane carbon flux of biogenic origin into the atmosphere. Its degradation is primarily initiated by the reaction with hydroxyl radicals. Here we show experimentally the formation of reactive intermediates and corresponding closedshell products from the reaction of hydroxyl radicals with isoprene for low nitric oxide and low hydroperoxy radical conditions. Detailed product analysis is achieved by mass spectrometric techniques. Quantum chemical calculations support the usefulness of applied ionization schemes. Observed peroxy radicals are the isomeric HO-C5H8O2 radicals and their isomerization products HO-C5H8(O-2)O-2, bearing most likely an additional hydroperoxy group, and in traces HO-C5H8(O-2)(2)O-2 with two hydroperoxy groups. Main closed-shell products from unimolecular peroxy radical reactions are hydroperoxy aldehydes, C5H8O3, and smaller yield products with the composition C5H8O4 and C4H8O5. Detected signals of C10H18O4, C10H18O6, and C5H10O2 stand for products arising from peroxy radical self- and cross-reactions.Peer reviewe

Global Budget of Methanol: Constraints from Atmospheric Observations

We use a global three-dimensional model simulation of atmospheric methanol to examine the consistency between observed atmospheric concentrations and current understanding of sources and sinks. Global sources in the model include 128 Tg yr−1 from plant growth, 38 Tg yr−1 from atmospheric reactions of CH3O2 with itself and other organic peroxy radicals, 23 Tg yr−1 from plant decay, 13 Tg yr−1 from biomass burning and biofuels, and 4 Tg yr−1 from vehicles and industry. The plant growth source is a factor of 3 higher for young than from mature leaves. The atmospheric lifetime of methanol in the model is 7 days; gas-phase oxidation by OH accounts for 63% of the global sink, dry deposition to land 26%, wet deposition 6%, uptake by the ocean 5%, and aqueous-phase oxidation in clouds less than 1%. The resulting simulation of atmospheric concentrations is generally unbiased in the Northern Hemisphere and reproduces the observed correlations of methanol with acetone, HCN, and CO in Asian outflow. Accounting for decreasing emission from leaves as they age is necessary to reproduce the observed seasonal variation of methanol concentrations at northern midlatitudes. The main model discrepancy is over the South Pacific, where simulated concentrations are a factor of 2 too low. Atmospheric production from the CH3O2 self-reaction is the dominant model source in this region. A factor of 2 increase in this source (to 50–100 Tg yr−1) would largely correct the discrepancy and appears consistent with independent constraints on CH3O2 concentrations. Our resulting best estimate of the global source of methanol is 240 Tg yr−1. More observations of methanol concentrations and fluxes are needed over tropical continents. Better knowledge is needed of CH3O2 concentrations in the remote troposphere and of the underlying organic chemistry.Earth and Planetary Science

Distinct pathways for zinc metabolism in the terrestrial slug Arion vulgaris

In most organisms, the concentration of free Zn is controlled by metallothioneins (MTs). In contrast, no significant proportions of Zn are bound to MTs in the slug, Arion vulgaris. Instead, this species possesses cytoplasmic low-molecular-weight Zn (LMW Zn) binding compound that divert these metal ions into pathways uncoupled from MT metabolism. Zn is accumulated in the midgut gland calcium cells of Arion vulgaris, where they associate with a low-molecular-weight ligand with an apparent molecular mass of ~ 2,000 Da. Mass spectrometry of the semi-purified LMW Zn binding compound combining an electrospray ion source with a differential mobility analyser coupled to a time-of-flight mass spectrometer revealed the presence of four Zn-containing ion signals, which arise from disintegration of one higher MW complex resulting in an ion-mobility diameter of 1.62 nm and a molecular mass of 837 Da. We expect that the novel Zn ion storage pathway may be shared by many other gastropods, and particularly species that possess Cd-selective MT isoforms or variants with only very low affinity to Zn

Detection of Plant Volatiles after Leaf Wounding and Darkening by Proton Transfer Reaction ‘‘Time-of-Flight’’ Mass Spectrometry (PTR-TOF)

Peer reviewe