Search

During the CalNex study (15 May to 16 June 2010) a large suite of instruments was operated at the Los Angeles area ground supersite to characterize the sources and atmospheric processing of atmospheric pollution. The thermal-desorption proton-transfer-reaction mass-spectrometer (TD-PTR-MS) was deployed to an urban area for the first time and detected 691 organic ions in aerosol samples, the mean total concentration of which was estimated as 3.3 μg m−3. Based on comparison to total organic aerosol (OA) measurements, we estimate that approximately 50% of the OA mass at this site was directly measured by the TD-PTR-MS. Based on correlations with aerosol mass spectrometer (AMS) OA components, the ions were grouped to represent hydrocarbon-like OA (HOA), local OA (LOA), semi-volatile oxygenated OA (SV-OOA), and low volatility oxygenated OA (LV-OOA). Mass spectra and thermograms of the ion groups are mostly consistent with the assumed sources and/or photochemical origin of the OA components. The mass spectra of ions representing the primary components HOA and LOA included the highest m/z, consistent with their higher resistance to thermal decomposition, and they were volatilized at lower temperatures (~ 150 °C). Photochemical ageing weakens C-C bond strengths (also resulting in chemical fragmentation), and produces species of lower volatility (through the addition of functional groups). Accordingly the mass spectra of ions representing the oxidized OA components (SV-OOA, and LV-OOA) lack the highest masses and they are volatilized at higher temperatures (250–300 °C). Chemical parameters like mean carbon number (nC), mean carbon oxidation state (OSC), and the atomic ratios O / C and H / C of the ion groups are consistent with the expected sources and photochemical processing of the aerosol components. Our data suggest that chemical fragmentation gains importance over functionalization as photochemical age of OA increases. Surprisingly, the photochemical age of OA decreases during the daytime hours, demonstrating the importance of rapid production of new (photochemically young) SV-OOA during daytime. The PTR detects higher organic N concentrations than the AMS, the reasons for which are not well understood and cannot be explained by known artifacts related to PTR or the AMS. The median atomic N / C ratio (6.4%) of the ion group representing LV-OOA is a factor 2 higher than N / C of any other ion group. This suggests a multiphase chemical source involving ammonium ions is contributing to LV-OOA.

Measurements of CH4 mixing ratio, vertical gradients and turbulent fluxes were carried out in a tropical forest (Reserva Biológica Cuieiras), about 60 km north of Manaus, Brazil. The methane mixing ratio and flux measurements were performed at a height of 53 m (canopy height 35 m). In addition, vertical CH4 gradients were measured within the canopy using custom made air samplers at levels of 2, 16 and 36 m above ground. The methane gradients within the canopy reveal that there is a continuous methane source at the surface. No clear evidence for aerobic methane emission from the canopy was found. The methane fluxes above the canopy are small but consistently upwards with a maximum early in the morning. The measured fluxes are in agreement with the observed CH4 gradient in the canopy. In the morning hours, a strong canopy venting peak is observed for both CH4 and CO2, but for CO2 this peak is then superimposed by photosynthetic uptake, whereas the peak lasts longer for CH4. Monthly averaged diurnal cycles of the CH4 mixing ratio show a decrease during daytime and increase during nighttime. The magnitude of the difference in CH4 mixing ratio between day and night gradually increases throughout the wet season. The fluxes required to explain the nighttime increase are in agreement with the nighttime fluxes measured above the canopy, which implies that the CH4 increase in the nighttime boundary layer originates from local sources.

Emissions of methyl chloride and several C2–C5 hydrocarbons from dry leaf litter at temperatures in the range 20–100 °C are reported for different plant species. The emission rates of ethane, ethene, propane, propene, n-pentane and methyl chloride increased with temperature. Hydrocarbon emission rates up to 0.88 ng gdw−1 h−1 were measured at 20 °C, while methyl chloride emission rates between 0.03 and 0.85 ng gdw−1 h−1 were observed at this temperature. At 70 °C emission rates increased up to 650 ng gdw−1 h−1 for C2–C5 hydrocarbons and up to 18 μg gdw−1 h−1 for methyl chloride. The Arrhenius relation can be used to describe the temperature dependence of methyl chloride emissions, while for hydrocarbon emissions deviations from this relation were observed. The emissions were not due to enzymatic activity, which was indicated by emission rates that continuously increased with increasing temperature, and activation energies higher than 50 kJ mol−1. At constant temperature, the emission rate of both methyl chloride and hydrocarbons from dry leaf litter decreased in time. At high temperatures (80–100 °C) this was noticeable on a timescale of hours, while at low temperatures (20–30 °C) the decrease was very slow and only visible on a timescale of months. Emission of methyl chloride from leaf litter might be significant for its global budget, while temperature induced hydrocarbon emissions from leaf litter are likely insignificant.

The short-chain non-methane hydrocarbons (NMHC) are mostly emitted into the atmosphere by anthropogenic processes. Recent studies have pointed out a tight linkage between the atmospheric mole fractions of the NMHC ethane to the atmospheric growth rate of methane. Consequently, atmospheric NMHC are valuable indicators for tracking changes in anthropogenic emissions, photochemical ozone production, and greenhouse gases. This study investigates the 1950–2010 Northern Hemisphere atmospheric C2-C5 NMHC ethane, propane, i-butane, n-butane, i-pentane, and n-pentane. Atmospheric mole fractions of these trace gases were constructed from (a) air samples of these trace gases from air samples extracted from three firn boreholes in 2008 and 2009 at the North Greenland Eemian Ice Drilling (NEEM) site using state of the art models of trace gas transport in firn, and by (b) considering eight years of ambient NMHC monitoring data from five Arctic sites within the NOAA Global Monitoring Division (GMD) Cooperative Air Sampling Network. Results indicate that these NMHC increased by ~ 40–120% after 1950, peaked around 1980 (with the exception of ethane, which peaked approximately 10 years earlier), and have since dramatically decreased to be now back close to 1950 levels. The earlier peak time of ethane versus the C3-C5 NMHC suggests that different processes and emissions mitigation measures contributed to the decline in these NMHC. The 60 yr record also illustrates notable increases in the ratios of the isomeric iso-/n-butane and iso-/n-pentane ratios. Comparison of the reconstructed NMHC histories with 1950–2000 volatile organic compounds (VOC) emissions data and with other recently published ethane trend analyses from ambient air Pacific transect data showed (a) better agreement with North America and Western Europe emissions than with total Northern Hemisphere emissions data, and (b) better agreement with other Greenland firn air data NMHC history reconstructions than with the Pacific region trends. These analyses emphasize that for NMHC, having atmospheric lifetimes on the order of < 2 months, the Greenland firn air records are primarily a representation of Western Europe and North America emission histories.

PTRwid is a fast and user friendly tool that has been developed to process data from proton-transfer-reaction time-of-flight mass spectrometers (PTR-TOF-MS) that use HTOF (high-resolution time-of-flight) mass spectrometers from Tofwerk AG (Switzerland). PTRwid is designed for a comprehensive evaluation of whole laboratory or field-based studies. All processing runs autonomously, and entire laboratory or field campaigns can, in principle, be processed with a few mouse clicks. Unique features of PTRwid include (i) an autonomous and accurate mass scale calibration, (ii) the computation of a "unified mass list" that – in addition to a uniform data structure – provides a robust method to determine the precision of attributed peak masses, and (iii) fast data analysis due to well considered choices in data processing.

Intensive measurements of submicron aerosol particles and their chemical composition were performed with an Aerosol Chemical Speciation Monitor (ACSM) at the Cabauw Experimental Site for Atmospheric Research (CESAR) in Cabauw, NL. The campaign lasted nearly one year from July 2012 to June 2013 as part of the ACTRIS project. Including black carbon data an average particulate mass concentration of 9.50 μg m−3 was obtained during the whole campaign with dominant contributions from ammonium nitrate (45 %), organic aerosol (OA, 29 %), and ammonium sulfate (19 %). 12 exceedances of the World Health Organization (WHO) PM2.5 daily mean limit (25 μg m−3) were observed at this rural site using PM1 instrumentation only. Ammonium nitrate and OA represented the largest contributors to total particulate matter during periods of exceedance.Source apportionment of OA was performed season-wise by Positive Matrix Factorization (PMF) using the Multilinear Engine 2 (ME-2) controlled via the source finder (SoFi). Primary organic aerosols were attributed mainly to traffic (8–16 % contribution to total OA, averaged season-wise) and biomass burning (0–23 %). Secondary organic aerosols (SOA, 61–84 %) dominated the organic fraction during the whole campaign, particularly on days with high mass loadings. A SOA factor which is attributed to humic-like substances (HULIS) was identified as a highly oxidized background aerosol in Cabauw. This shows the importance of atmospheric ageing processes for aerosol concentration at this rural site. Due to the large secondary fraction, the reduction of particulate mass at this rural site is challenging on a local scale.

Numerous volatile organic compounds (VOCs) exist in Earth’s atmosphere, most of which originate from biogenic emissions. Despite VOCs’ critical role in tropospheric chemistry, studies for evaluating their atmosphere-ecosystem exchange (emission and deposition) have been limited to a few dominant compounds owing to a lack of appropriate measurement techniques. Using a high–mass resolution proton transfer reaction–time of flight–mass spectrometer and an absolute value eddy-covariance method, we directly measured 186 organic ions with net deposition, and 494 that have bidirectional flux. This observation of active atmosphere-ecosystem exchange of the vast majority of detected VOCs poses a challenge to current emission, air quality, and global climate models, which do not account for this extremely large range of compounds. This observation also provides new insight for understanding the atmospheric VOC budget.

During summer 2010, a proton transfer reaction – time of flight – mass spectrometer (PTR-TOF-MS) and a quadrupole proton transfer reaction mass spectrometer (PTR-MS) were deployed simultaneously for one month in an orange orchard in the Central Valley of California to collect continuous data suitable for eddy covariance (EC) flux calculations. The high time resolution (5 Hz) and high mass resolution (up to 5000 m/1m) data from the PTRTOF- MS provided the basis for calculating the concentration and flux for a wide range of volatile organic compounds (VOC). Throughout the campaign, 664 mass peaks were detected in mass-to-charge ratios between 10 and 1278. Here we present PTR-TOF-MS EC fluxes of the 27 ion species for which the vertical gradient was simultaneously measured by PTR-MS. These EC flux data were validated through spectral analysis (i.e., co-spectrum, normalized co-spectrum, and ogive). Based on inter-comparison of the two PTR instruments, no significant instrumental biases were found in either mixing ratios or fluxes, and the data showed agreement within 5% on average for methanol and acetone. For the measured biogenic volatile organic compounds (BVOC), the EC fluxes from PTR-TOF-MS were in agreement with the qualitatively inferred flux directions from vertical gradient measurements by PTR-MS. For the 27 selected ion species reported here, the PTR-TOF-MS measured total (24 h) mean net flux of 299 μg Cm−2 h−1. The dominant BVOC emissions from this site were monoterpenes (m/z 81.070 +m/z 137.131 +m/z 95.086, 34 %, 102 μg Cm−2 h−1) and methanol (m/z 33.032, 18 %, 72 μgCm−2 h−1). The next largest fluxes were detected at the following masses (attribution in parenthesis): m/z 59.048 (mostly acetone, 12.2 %, 36.5 μgCm−2 h−1), m/z 61.027 (mostly acetic acid, 11.9 %, 35.7 μg Cm−2 h−1), m/z 93.069 (para-cymene + toluene, 4.1 %, 12.2 μgCm−2 h−1), m/z 45.033 (acetaldehyde, 3.8 %, 11.5 μgCm−2 h−1), m/z 71.048 (methylvinylketone + methacrolein, 2.4 %, 7.1 μgCm−2 h−1), and m/z 69.071 (isoprene + 2-methyl- 3-butene-2-ol, 1.8 %, 5.3 μg Cm−2 h−1). Low levels of emission and/or deposition (

Methyl chloride (CH(3)Cl) is the most abundant natural chlorine containing compound in the atmosphere, and responsible for a significant fraction of stratospheric ozone destruction. Understanding the global CH(3)Cl budget is therefore of great importance. However, the strength of the individual sources and sinks is still uncertain. Leaf litter is a potentially important source of methyl chloride, but factors controlling the emissions are unclear. This study investigated CH(3)Cl emissions from leaf litter of twelve halophyte species. The emissions were not due to biological activity, and emission rates varied between halophyte species up to two orders of magnitude. For all species, the CH(3)Cl emission rates increased with temperature following the Arrhenius relation. Activation energies were similar for all investigated plant species, indicating that even though emissions vary largely between plant species, their response to changing temperatures is similar. The chloride and methoxyl group contents of the leaf litter samples were determined, but those parameters were not significantly correlated to the CH(3)Cl emission rate.

A series of 12 high volume air samples collected from the S2 firn core during the North Greenland Eemian Ice Drilling (NEEM) 2009 campaign have been measured for mixing ratio and stable carbon isotope composition of the chlorofluorocarbon CFC- 12 (CCl2F2). While the mixing ratio measurements compare favorably to other firn air studies, the isotope results show extreme 13C depletion at the deepest measurable depth (65 m), to values lower than 13C=−80‰vs. VPDB (the international stable carbon isotope scale), compared to present day surface tropospheric measurements near −40 ‰. Firn air modeling was used to interpret these measurements. Reconstructed atmospheric time series indicate even larger depletions (to −120‰) near 1950AD, with subsequent rapid enrichment of the atmospheric reservoir of the compound to the present day value. Mass-balance calculations show that this change must have been caused by a large change in the isotopic composition of anthropogenic CFC-12 emissions, probably due to technological changes in the CFC production process over the last 80 yr. Propagating the mass-balance calculations into the future demonstrates that as emissions decrease to zero, isotopic fractionation by the stratospheric sinks will lead to continued 13C enrichment in atmospheric CFC-12.

Observations of aerosol chemical composition in Cabauw, the Netherlands, are presented for two intensive measurement periods in May 2008 and March 2009. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and is compared to observations from aerosol size distribution measurements as well as composition measurements with a Monitor for AeRosol and GAses (MARGA) based instrument and a Thermal-desorption Proton-transfer-reaction Mass-spectrometer (TD-PTR-MS). An overview of the data is presented and the data quality is discussed. In May 2008 enhanced pollution was observed with organics contributing 40% to the PM1 mass. In contrast the observed average mass loading was lower in March 2009 and a dominance of ammonium nitrate (42%) was observed. The semi-volatile nature of ammonium nitrate is evidenced in the diurnal cycles with maximum concentrations observed in the morning hours in May 2008 and little diurnal variation observed in March 2009. Size dependent composition data from AMS measurements are presented and show a dominance of organics in the size range below 200 nm. © 2011 Author(s).

The chlorofluorocarbons CFC-11 (CFCl3) and CFC-12 (CF2Cl2) are stable atmospheric compounds that are produced at the earth's surface, but removed only at high altitudes in the stratosphere by photolytic reactions. Their removal liberates atomic chlorine that then catalytically destroys stratospheric ozone. For such long-lived compounds, isotope effects in the stratospheric removal reactions have a large effect on their global isotope budgets. We have demonstrated a photolytic isotope fractionation for stable carbon isotopes of CFC-11 and CFC-12 in laboratory experiments using broadband UV-C (190–230 nm) light. 13C/12C isotope fractionations (ε) range from (−23.8±0.9) to (−17.7±0.4) ‰ for CFC-11 and (−66.2±3.1) to (−51.0±2.9) permil for CFC-12 between 203 and 288 K, a temperature range relevant to conditions in the troposphere and stratosphere. These results suggest that CFCs should become strongly enriched in 13C with decreasing mixing ratio in the stratosphere, similar to what has been recently observed for CFC chlorine isotopes. In conjunction with the strong variations in CFC emissions before and after the Montréal Protocol, the stratospheric enrichments should also lead to a significant temporal increase in the 13C content of the CFCs at the surface over the past decades, which should be recorded in atmospheric air archives such as firn air.

We present setup, testing and initial results from a new automated system for stable carbon isotope ratio measurements on C2 to C6 atmospheric hydrocarbons. The inlet system allows analysis of trace gases from air samples ranging from a few liters for urban samples and samples with high mixing ratios, to many tens of liters for samples from remote unpolluted regions with very low mixing ratios. The centerpiece of the sample preparation is the separation trap, which is used to separate CO2 and methane from the compounds of interest. The main features of the system are (i) the capability to sample up to 300 l of air, (ii) long term (since May 2009) operational δ13C accuracy levels in the range 0.3–0.8‰ (1- σ), and (iii) detection limits of order 1.5–2.5 ngC (collected amount of substance) for all reported compounds. The first application of this system was the analysis of 21 ambient air samples taken during 48 h in August 2009 in Utrecht, the Netherlands. Results obtained are generally in good agreement with those from similar urban ambient air studies. Short sample intervals allowed by the design of the instrument help to illustrate the complex diurnal behavior of hydrocarbons in an urban environment, where diverse sources, dynamical processes, and chemical reactions are present.

We present a novel analytical approach to measure the chemical composition of organic aerosol. The new instrument combines proton-transfer-reaction mass-spectrometry (PTR-MS) with a collection-thermal-desorption aerosol sampling technique. For secondary organic aerosol produced from the reaction of ozone with isoprenoids in a laboratory reactor, the TD-PTR-MS instrument detected typically 80% of the mass that was measured with a scanning mobility particle sizer (SMPS). The first field deployment of the instrument was the EUCAARI-IOP campaign at the CESAR tall tower site in the Netherlands. For masses with low background values (~30% of all masses) the detection limit of aerosol compounds was below 0.2 ng/m3 which corresponds to a sampled compound mass of 35 pg. Comparison of thermograms from ambient samples and from chamber-derived secondary organic aerosol shows that, in general, organic compounds from ambient aerosol samples desorb at much higher temperatures than chamber samples. This suggests that chamber aerosol is not a good surrogate for ambient aerosol and therefore caution is advised when extrapolating results from chamber experiments to ambient conditions.

For the first time a high mass resolution thermal desorption proton transfer reaction mass spectrometer (hr-TD-PTR-MS) was deployed in the field to analyze the composition of the organic fraction of aerosols. We report on measurements from the remote Mt. Sonnblick observatory in the Austrian alps (3108 m a.s.l.) during a 7 week period in summer 2009. A total of 638 mass peaks in the range 18–392 Da were detected and quantified in aerosols. An empirical formula was tentatively attributed to 464 of these compounds by custom-made data analysis routines which consider compounds containing C, H, O, N, and S atoms. Most of the other (unidentified) compounds must contain other elements – most likely halogenated compounds. The mean total concentration of all detected compounds was 1.1 μg m−3. Oxygenated hydrocarbons constitute the bulk of the aerosol mass (75%) followed by organic nitrogen compounds (9%), inorganic compounds (mostly NH3, 8%), unidentified/halogenated (3.8%), hydrocarbons (2.7%), and organic sulfur compounds (0.8%). The measured O/C ratios are lower than expected and suggest a significant effect from charring. A significant part of the organic nitrogen compounds is non volatile. Organic carbon concentrations measured with TD-PTR-MS were about 25% lower than measurements on high volume filter samples.

Long term methane flux measurements have been mostly performed with plant or soil enclosure techniques on specific components of an ecosystem. New fast response methane analyzers make it possible to use the eddy covariance (EC) technique instead. The EC technique is advantageous because it allows continuous flux measurements integrating over a larger and more representative area including the complete ecosystem, and allows fluxes to be observed as environmental conditions change naturally without disturbance. We deployed the closed-path Fast Methane analyzer (FMA) from Los Gatos Research Ltd and demonstrate its performance for EC measurements at a Ponderosa pine plantation at the Blodgett Forest site in central California. The fluctuations of the CH4 concentration measured at 10 Hz appear to be small and their standard deviation is comparable to the magnitude of the signal noise (±5 ppbv). Consequently, the power spectra typically have a white noise signature at the high frequency end (a slope of +1). Nevertheless, in the frequency range important for turbulent exchange, the cospectra of CH4 compare very well with all other scalar cospectra confirming the quality of the FMA measurements are good for the EC technique. We furthermore evaluate the complications of combined open and closed-path measurements when applying the Webb-Pearman-Leuning (WPL) corrections (Webb et al., 1980) and the consequences of a phase lag between the water vapor and methane signal inside the closed path system. The results of diurnal variations of CH4 concentrations and fluxes are summarized and compared to the monthly results of process-based model calculations

Multiple field studies have suggested chemistry within a forest canopy is poorly understood due to inadequate detection and quantification of reactive biogenic emissions, such as terpenes. To measure emission rates of terpenes at Blodgett Forest, a coniferous forest in the Sierra Nevada mountains of California, we placed enclosures over branches of the dominant species at the site – Ponderosa pine, manzanita, and ceanothus – in the summer of 2005. Zero air, with ambient CO2 concentrations, flowed through the chamber system and volatile organic compound (VOC) emission measurements were made by proton transfer reaction mass spectrometry (PTR-MS), solid phase microextraction (SPME) on fibers followed by direct injection into a gas chromatograph with an ion trap mass spectrometer (GC-ITMS), and by in situ GC with a flame ionization detector (GC-FID). We show that previously undetected sesquiterpenes and methyl chavicol significantly contribute to the total reactive biogenic emission profile from this field site.

We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten- 2-ol (MBO), a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72– 10.2μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

Monoterpenes, primarily emitted by terrestrial vegetation, can influence atmospheric ozone chemistry, and can form precursors for secondary organic aerosol. The short-term emissions of monoterpenes have been well studied and understood, but their long-term variability, which is particularly important for atmospheric chemistry, has not. This understanding is crucial for the understanding of future changes. In this study, two algorithms of terrestrial biogenic monoterpene emissions, the first one based on the short-term volatilization of monoterpenes, as commonly used for temperature-dependent emissions, and the second one based on long-term production of monoterpenes (linked to photosynthesis) combined with emissions from storage, were compared and evaluated with measurements from a Ponderosa pine plantation (Blodgett Forest, California). The measurements were used to parameterize the long-term storage of monoterpenes, which takes place in specific storage organs and which determines the temporal distribution of the emissions over the year. The difference in assumptions between the first (emission-based) method and the second (production-based) method, which causes a difference in upscaling from instantaneous to daily emissions, requires roughly a doubling of emission capacities to bridge the gap to production capacities. The sensitivities to changes in temperature and light were tested for the new methods, the temperature sensitivity was slightly higher than that of the short-term temperature dependent algorithm. Applied on a global scale, the first algorithm resulted in annual total emissions of 29.6 Tg C a−1, the second algorithm resulted in 31.8 Tg C a−1 when applying the correction factor 2 between emission capacities and production capacities. However, the exact magnitude of such a correction is spatially varying and hard to determine as a global average

International audience; The recently reported finding that plant matter and living plants produce significant amounts of the important greenhouse gas methane under aerobic conditions has led to an intense scientific and public controversy. Whereas some studies question the up-scaling method that was used to estimate the global source strength, others have suggested that experimental artifacts could have caused the reported signals, and in fact one study has recently reported the absence of CH4 emissions from plants based on an isotope labeling experiment. Here we show ? using several independent experimental analysis techniques ? that dry and detached fresh plant matter, as well as several structural plant components, emit significant amounts of methane upon irradiation with UV light and/or heating. Emissions from UV irradiation are almost instantaneous, indicating a direct photochemical process. Long-time irradiation experiments demonstrate that the size of the CH4 producing reservoir is large, exceeding potential interferences from degassing or desorption processes by several orders of magnitude. A dry leaf of a pure 13C plant produces 13CH4 at a similar rate as dry leaves of non-labeled plants produce non-labeled methane.

Measurements of organic carbon compounds in both the gas and particle phases measured upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m−3 from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketene and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.

International audience; Monoterpene fluxes have been measured over an 11 month period from June 2003 to April 2004. During all seasons ambient air temperature was the environmental factor most closely related to the measured emission rates. The monoterpene flux was modeled using a basal emission rate multiplied by an exponential function of a temperature, following the typical practice for modelling temperature dependent biogenic emissions. A basal emission of 1.0 ?mol h?1 m?2 (at 30°C, based on leaf area) and a temperature dependence (?) of 0.12°C?1 reproduced measured summer emissions well but underestimated spring and winter measured emissions by 60?130%. The total annual monoterpene emission may be underestimated by ~50% when using a model optimized to reproduce monoterpene emissions in summer. The long term dataset also reveals an indirect connection between non-stomatal ozone and monoterpene flux beyond the dependence on temperature that has been shown for both fluxes.