Despite the known biochemical production of a range of aromatic compounds by plants and the presence of benzenoids in floral scents, the emissions of only a few benzenoid compounds have been reported ...from the biosphere to the atmosphere. Here, using evidence from measurements at aircraft, ecosystem, tree, branch and leaf scales, with complementary isotopic labeling experiments, we show that vegetation (leaves, flowers, and phytoplankton) emits a wide variety of benzenoid compounds to the atmosphere at substantial rates. Controlled environment experiments show that plants are able to alter their metabolism to produce and release many benzenoids under stress conditions. The functions of these compounds remain unclear but may be related to chemical communication and protection against stress. We estimate the total global secondary organic aerosol potential from biogenic benzenoids to be similar to that from anthropogenic benzenoids (~10 Tg y(-1)), pointing to the importance of these natural emissions in atmospheric physics and chemistry.
The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which ...vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH sub(3)) and sulfuric acid (H sub(2)SO sub(4)). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH sub(3)-H sub(2)SO sub(4) clusters over a wide range of atmospherically relevant environmental conditions. We covered NH sub(3) in the range from < 2 to 1400 pptv, H sub(2)SO sub(4) from 3.3 x 10 super(6) to 1.4 x 10 super(9) cm super(-3) (0.1 to 56 pptv), and a temperature range from -25 to +20 degree C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH sub(3) and H sub(2)SO sub(4), and then grew to larger clusters containing more than 50 molecules of NH sub(3) and H sub(2)SO sub(4), corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH sub(3)-H sub(2)SO sub(4) clusters is primarily determined by the ratio of gas-phase concentrations NH sub(3) / H sub(2)SO sub(4), as well as by temperature. Pure binary H sub(2)O-H sub(2)SO sub(4) clusters (observed as clusters of only H sub(2)SO sub(4)) only form at NH sub(3) / H sub(2)SO sub(4) < 0.1 to 1. For larger values of NH sub(3) / H sub(2)SO sub(4), the composition of NH sub(3)-H sub(2)SO sub(4) clusters was characterized by the number of NH sub(3) molecules m added for each added H sub(2)SO sub(4) molecule n ( Delta m/ Delta n), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Delta m/ Delta n saturated between 1 and 1.4 for NH sub(3) / H sub(2)SO sub(4) > 10. Positively charged clusters grew on average by Delta m/ Delta n = 1.05 and were only observed at sufficiently high NH sub(3) / H sub(2)SO sub(4). The H sub(2)SO sub(4) molecules of these clusters are partially neutralized by NH sub(3), in close resemblance to the acid-base bindings of ammonium bisulfate. Supported by model simulations, we substantiate previous evidence for acid-base reactions being the essential mechanism behind the formation of these clusters under atmospheric conditions and up to sizes of at least 2 nm. Our results also suggest that electrically neutral NH sub(3)-H sub(2)SO sub(4) clusters, unobservable in this study, have generally the same composition as ionic clusters for NH sub(3) / H sub(2)SO sub(4) > 10. We expect that NH sub(3)-H sub(2)SO sub(4) clusters form and grow also mostly by Delta m/ Delta n > 1 in the atmosphere's boundary layer, as NH sub(3) / H sub(2)SO sub(4) is mostly larger than 10. We compared our results from CLOUD with APi-TOF measurements of NH sub(3)-H sub(2)SO sub(4) anion clusters during new-particle formation in the Finnish boreal forest. However, the exact role of NH sub(3)-H sub(2)SO sub(4) clusters in boundary layer particle formation remains to be resolved.
We present the first eddy covariance flux measurements of volatile organic compounds (VOCs) using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) above a ponderosa pine ...forest in Colorado, USA. The high mass resolution of the PTR-TOF-MS enabled the identification of chemical sum formulas. During a 30 day measurement period in August and September 2010, 649 different ion mass peaks were detected in the ambient air mass spectrum (including primary ions and mass calibration compounds). Eddy covariance with the vertical wind speed was calculated for all ion mass peaks. On a typical day, 17 ion mass peaks, including protonated parent compounds, their fragments and isotopes as well as VOC-H+-water clusters, showed a significant flux with daytime average emissions above a reliable flux threshold of 0.1 mg compound m−2 h−1. These ion mass peaks could be assigned to seven compound classes. The main flux contributions during daytime (10:00–18:00 LT) are attributed to the sum of 2-methyl-3-buten-2-ol (MBO) and isoprene (50%), methanol (12%), the sum of acetic acid and glycolaldehyde (10%) and the sum of monoterpenes (10%). The total MBO + isoprene flux was composed of 10% isoprene and 90% MBO. There was good agreement between the light- and temperature dependency of the sum of MBO and isoprene observed for this work and those of earlier studies. The above canopy flux measurements of the sum of MBO and isoprene and the sum of monoterpenes were compared to emissions calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN 2.1). The best agreement between MEGAN 2.1 and measurements was reached using emission factors determined from site-specific leaf cuvette measurements. While the modeled and measured MBO + isoprene fluxes agree well, the emissions of the sum of monoterpenes is underestimated by MEGAN 2.1. This is expected as some factors impacting monoterpene emissions, such as physical damage of needles and branches due to storms, are not included in MEGAN 2.1. After a severe hailstorm event, 22 ion mass peaks (attributed to six compound classes plus some unknown compounds) showed an elevated flux for the two following days. The sum of monoterpene emissions was 4–23 times higher compared to emissions prior to the hailstorm while MBO emissions remained unchanged. The monoterpene emission (in mg compound m−2) during this measurement period is underestimated by 40% if the effect of this disturbance source is not considered.
Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa) during the BEACHON-ROCS field ...study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser-Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and likely points to an offset in calibration, rather than a difference in the ability to measure the sum of terpenes. The contribution of isoprene relative to MBO inferred from PTR-MS and PTR-TOF-MS was smaller than 12% while GC-MS data suggested an average of 21% of isoprene relative to MBO. This comparison demonstrates that the current capability of VOC measurements to account for OH reactivity associated with the measured VOCs is within 20%.
Eddy covariance (EC) is the preferable technique for flux measurements since it is the only direct flux determination method. It requires a continuum of high time resolution measurements (e.g. 5-20 ...Hz). For volatile organic compounds (VOC) soft ionization via proton transfer reaction has proven to be a quantitative method for real time mass spectrometry; here we use a proton transfer reaction time of flight mass spectrometer (PTR-TOF) for 10 Hz EC measurements of full mass spectra up to
315. The mass resolution of the PTR-TOF enabled the identification of chemical formulas and separation of oxygenated and hydrocarbon species exhibiting the same nominal mass. We determined 481 ion mass peaks from ambient air concentration above a managed, temperate mountain grassland in Neustift, Stubai Valley, Austria. During harvesting we found significant fluxes of 18 compounds distributed over 43 ions, including protonated parent compounds, as well as their isotopes and fragments and VOC-H
- water clusters. The dominant BVOC fluxes were methanol, acetaldehyde, ethanol, hexenal and other C
leaf wound compounds, acetone, acetic acid, monoterpenes and sequiterpenes. The smallest reliable fluxes we determined were less than 0.1 nmol m
s
, as in the case of sesquiterpene emissions from freshly cut grass. Terpenoids, including mono- and sesquiterpenes, were also deposited to the grassland before and after the harvesting. During cutting, total VOC emission fluxes up to 200 nmolC m
s
were measured. Methanol emissions accounted for half of the emissions of oxygenated VOCs and a third of the carbon of all measured VOC emissions during harvesting.
We present the results of laboratory measurements of the ion-ion recombination coefficient at different temperatures, relative humidities and concentrations of ozone and sulfur dioxide. The ...experiments were carried out using the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at CERN, the walls of which are made of conductive material, making it possible to measure small ions. We produced ions in the chamber using a 3.5 GeV c-1 beam of positively charged pions ( pi +) generated by the CERN Proton Synchrotron (PS). When the PS was switched off, galactic cosmic rays were the only ionization source in the chamber. The range of the ion production rate varied from 2 to 100 cm-3 s-1, covering the typical range of ionization throughout the troposphere. The temperature ranged from -55 to 20 degree C, the relative humidity (RH) from 0 to 70 %, the SO2 concentration from 0 to 40 ppb, and the ozone concentration from 200 to 700 ppb. The best agreement of the retrieved ion-ion recombination coefficient with the commonly used literature value of 1.6 10-6 cm3 s-1 was found at a temperature of 5 degree C and a RH of 40 % (1.5 plus or minus 0.6) 10-6 cm3 s-1. At 20 degree C and 40 % RH, the retrieved ion-ion recombination coefficient was instead (2.3 plus or minus 0.7) 10-6 cm3 s-1. We observed no dependency of the ion-ion recombination coefficient on ozone concentration and a weak variation with sulfur dioxide concentration. However, we observed a more than fourfold increase in the ion-ion recombination coefficient with decreasing temperature. We compared our results with three different models and found an overall agreement for temperatures above 0 degree C, but a disagreement at lower temperatures. We observed a strong increase in the recombination coefficient for decreasing relative humidities, which has not been reported previously.
Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the ...troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a ponderosa pine forest during the summer 2010 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen – Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptv (parts per trillion by volume) and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Since primary reaction partners for peroxy radicals are either measured (NO) or underpredicted (HO2 and RO2, i.e., self-reaction), missing sources are the most likely explanation for this result. A close comparison of model output with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (~120 and 50 pptv min−1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within forests. We conclude that a similar mechanism may underlie many such observations.
We present simultaneous fast, in-situ measurements of formaldehyde and glyoxal from two rural campaigns, BEARPEX 2009 and BEACHON-ROCS, both located in Pinus Ponderosa forests with emissions ...dominated by biogenic volatile organic compounds (VOCs). Despite considerable variability in the formaldehyde and glyoxal concentrations, the ratio of glyoxal to formaldehyde, RGF, displayed a very regular diurnal cycle over nearly 2 weeks of measurements. The only deviations in RGF were toward higher values and were the result of a biomass burning event during BEARPEX 2009 and very fresh anthropogenic influence during BEACHON-ROCS. Other rapid changes in glyoxal and formaldehyde concentrations have hardly any affect on RGF and could reflect transitions between low and high NO regimes. The trend of increased RGF from both anthropogenic reactive VOC mixtures and biomass burning compared to biogenic reactive VOC mixtures is robust due to the short timescales over which the observed changes in RGF occurred. Satellite retrievals, which suggest higher RGF for biogenic areas, are in contrast to our observed trends. It remains important to address this discrepancy, especially in view of the importance of satellite retrievals and in situ measurements for model comparison. In addition, we propose that RGF represents a useful metric for biogenic or anthropogenic reactive VOC mixtures and, in combination with absolute concentrations of glyoxal and formaldehyde, furthermore represents a useful metric for the extent of anthropogenic influence on overall reactive VOC processing via NOx. In particular, RGF yields information about not simply the VOCs dominating reactivity in an airmass, but the VOC processing itself that is directly coupled to ozone and secondary organic aerosol production.
We present a detailed analysis of OH observations from the BEACHON (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2 O, Organics and Nitrogen)-ROCS (Rocky Mountain Organic Carbon ...Study) 2010 field campaign at the Manitou Forest Observatory (MFO), which is a 2-methyl-3-butene-2-ol (MBO) and monoterpene (MT) dominated forest environment. A comprehensive suite of measurements was used to constrain primary production of OH via ozone photolysis, OH recycling from HO2 , and OH chemical loss rates, in order to estimate the steady-state concentration of OH. In addition, the University of Washington Chemical Model (UWCM) was used to evaluate the performance of a near-explicit chemical mechanism. The diurnal cycle in OH from the steady-state calculations is in good agreement with measurement. A comparison between the photolytic production rates and the recycling rates from the HO2 + NO reaction shows that recycling rates are ~20 times faster than the photolytic OH production rates from ozone. Thus, we find that direct measurement of the recycling rates and the OH loss rates can provide accurate predictions of OH concentrations. More importantly, we also conclude that a conventional OH recycling pathway (HO2 + NO) can explain the observed OH levels in this non-isoprene environment. This is in contrast to observations in isoprene-dominated regions, where investigators have observed significant underestimation of OH and have speculated that unknown sources of OH are responsible. The highly-constrained UWCM calculation under-predicts observed HO2 by as much as a factor of 8. As HO2 maintains oxidation capacity by recycling to OH, UWCM underestimates observed OH by as much as a factor of 4. When the UWCM calculation is constrained by measured HO2 , model calculated OH is in better agreement with the observed OH levels. Conversely, constraining the model to observed OH only slightly reduces the model-measurement HO2 discrepancy, implying unknown HO2 sources. These findings demonstrate the importance of constraining the inputs to, and recycling within, the ROx radical pool (OH + HO2 + RO2 ).
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