Carsten Warneke

Biomass burning as a source of formaldehyde, acetaldehyde, methanol, acetone, acetonitrile, and hydrogen cyanide

Using a novel experimental technique, based on proton transfer reaction mass spectrometry, from measurements of emissions from laboratory scale biomass burning experiments, we have estimated the source strengths of several potential HOx producing gases: formaldehyde, acetaldehyde, methanol and acetone. The derived global average emissions are 5–13; 3.8–10; 1.5-4; 2.3-6.1 Tg y−1, respectively. The resulting global average HOx production from photochemical decay of these gases is 3 × 109 molecules cm−2 s−1. Although relatively small in a global context, these emissions are significant for the photochemistry in fresh fire plumes. From our measurements are also estimated global source strengths from biomass burning for CH3CN and HCN of 0.4-1.0; 0.2-0.6 Tg y−1 respectively. The biomass burning emissions of CH3CN may well dominate the global source of this compound, which thus might well be a unique tracer for biomass burning. Some discrepancies between experimental studies must, however, be resolved.

An Atmospheric Chemistry Interpretation of Mass Scans Obtained from a Proton Transfer Mass Spectrometer Flown over the Tropical Rainforest of Surinam

Data on a variety of organic gases are presented, obtained with a protontransfer mass spectrometer (PTR-MS) operated during the March 1998 LBA/CLAIREairborne measurement campaign, between 60 and 12500 m over the rainforest inSurinam (2° N–5° N, 54° W–57° W). The instrumentcan detect molecules with a proton affinity greater than water, includingalkenes, dialkenes, carbonyls, alcohols, and nitriles. Many such molecules areemitted from the rainforest (e.g., isoprene) or formed from the oxidation ofprimary emissions (e.g., methylvinylketone (MVK) and methacrolein (MACR)).From a comparison with modelled data; the variation with altitude; previouslyreported biogenic emissions and the time and location of the measurement,possible and probable identities for the significant masses encountered in therange 33–140 amu have been deduced.The main observed protonated masses, postulated identities and observedaverage boundary layer mixing ratios over the rainforest were: 33 methanol(1.1 nmol/mol); 42 acetonitrile (190 pmol/mol); 43 multiple possibilities (5.9nmol/mol), 45 acetaldehyde (1.7 nmol/mol), 47 formic acid (not quantified);59 acetone (2.9 nmol/mol), 61 acetic acid (not quantified), 63 dimethylsulphide (DMS) (289 pmol/mol), 69 isoprene (1.7 nmol/mol), 71 MVK + MACR (1.3nmol/mol), 73 methyl ethyl ketone (1.8 nmol/mol), 75 hydroxyacetone (606pmol/mol), 83 C5 isoprene hydroxy carbonylsC5H8O2, methyl furan, and cis 3-hexen-1-ol(732 pmol/mol), 87 C5 carbonyls and methacrylic acid, 95 possibly2-vinyl furan (656 pmol/mol), 97 unknown (305 pmol/mol), 99 cis hexenal (512pmol/mol) and 101 isoprene C5 hydroperoxides (575 pmol/mol). Somespecies agreed well with those derived from an isoprene only photochemicalmodel (e.g., mass 71 MVK + MACR) while others did not and were observed athigher than previously reported mixing ratios (e.g., mass 59 acetone, mass 63DMS). Monoterpenes were not detected above the detection limit of 300pmol/mol. Several species postulated are potentially important sources ofHOx in the free troposphere, e.g., methanol, acetone, methyl ethylketone, methyl vinyl ketone and methacrolein.

Isoprene and Its Oxidation Products Methyl Vinyl Ketone, Methacrolein, and Isoprene Related Peroxides Measured Online over the Tropical Rain Forest of Surinam in March 1998

Airborne measurements of volatile organic compounds (VOC) were performed overthe tropical rainforest in Surinam (0–12 km altitude,2°–7° N, 54°–58° W) using the proton transferreaction mass spectrometry (PTR-MS) technique, which allows online monitoringof compounds like isoprene, its oxidation products methyl vinyl ketone,methacrolein, tentatively identified hydroxy-isoprene-hydroperoxides, andseveral other organic compounds. Isoprene volume mixing ratios (VMR) variedfrom below the detection limit at the highest altitudes to about 7 nmol/molin the planetary boundary layer shortly before sunset. Correlations betweenisoprene and its product compounds were made for different times of day andaltitudes, with the isoprene-hydroperoxides showing the highest correlation.Model calculated mixing ratios of the isoprene oxidation products using adetailed hydrocarbon oxidation mechanism, as well as the intercomparisonmeasurement with air samples collected during the flights in canisters andlater analysed with a GC-FID, showed good agreement with the PTR-MSmeasurements, in particular at the higher mixing ratios.Low OH concentrations in the range of 1–3 × 105molecules cm-3 averaged over 24 hours were calculated due to lossof OH and HO2 in the isoprene oxidation chain, thereby stronglyenhancing the lifetime of gases in the forest boundary layer.

PROTON TRANSFER REACTION MASS SPECTROMETRY (PTR-MS) : PROPANOL IN HUMAN BREATH

Abstract Proton transfer reaction mass spectrometry (PTR-MS) based on reactions of H 3 O + ions has been used to measure the concentrations of propanol in 46 healthy persons, yielding an average concentration of about 150 ppb. That the measurements were not obscured by other components of the same mass as propanol was proven by comparison of PTR-MS data with separate selected-ion flow-drift tube (SIFDT) investigations of the energy dependences of reactions of H 3 O + and H 3 O + ·H 2 O with isopropanol, n -propanol, acetic acid and methyl formate.

High acetone concentrations throughout the 0-12 km altitude range over the tropical rainforest in Surinam

Airborne measurements of acetone were performed overthe tropical rainforest in Surinam(2°–7° N, 54°–58° W, 0–12 kmaltitude) during the LBA-CLAIRE campaign in March1998, using a novel proton transfer reaction massspectrometer (PTR-MS) that enables the on-linemonitoring of volatile organic compounds (VOC) with ahigher proton affinity than water. The measuredacetone volume mixing ratios ranged from ∼0.1 nmol/molup to ∼8 nmol/mol with an overall average of 2.6nmol/mol and a standard deviation of 1.0 nmol/mol. Theobserved altitude profile and correlations with CO,acetonitrile, propane and wind direction are discussedwith respect to potential acetone sources. No linearcorrelation between acetone and CO mixing ratios wasobserved, at variance with results of previousmeasurement campaigns. The mean acetone/CO ratio(0.022) was substantially higher than typical valuesfound before. The abundance of acetone appears to beinfluenced, but not dominated, by biomass burning,thus suggesting large emissions of acetone and/oracetone precursors, such as possibly 2-propanol, fromliving plants or decaying litter in the rainforest.

PTR-MS real time monitoring of the emission of volatile organic compounds during postharvest aging of berryfruit

Abstract A novel method, based on proton transfer reaction-mass spectrometry (PTR-MS) was used to monitor the postharvest aging of strawberries, blackberries, raspberries, blueberries, and white and red currants by real time detection of volatile organic compounds (VOCs) in the headspace of the fruits. The observed intensities of emission for the different identified compounds, and their ratios as well as their rate of evolution, showed definite, berry-specific, behaviour. Very high sensitivity (sub-ppb level) combined with real time detection of a large variety of compounds makes PTR-MS very promising for studies dealing with quality assessment and preservation of fruits.

Proton-transfer-reaction mass spectrometry (PTR-MS): on-line monitoring of volatile organic compounds at volume mixing ratios of a few pptv

A system for on-line measurements of trace compounds in air with concentrations as low as a few pptv has been developed on the basis of proton transfer reactions. The sensitivity of this system is demonstrated by means of calibration data of benzene and data on the diurnal variation of C9-alkylbenzene and its 13C-isotope in ambient air. First on-line data on the concentrations of volatile organic compounds obtained during plane flights are presented.

Variability‐lifetime relationship for organic trace gases: A novel aid to compound identification and estimation of HO concentrations

In this study we report aircraft-borne measurements of organic species made during March 1998 in Surinam, an unpolluted region on the northeast coast of South America Measurements included the following: CO by tunable diode laser; a wide variety of organics including acetone, acetonitrile, and isoprene by proton transfer mass spectrometry (PTR-MS); and nonmethane hydrocarbon measurements by gas chromatography-flame ionization detection. Here we compare the standard deviation of the natural logarithm of the mixing ratio (Sigma_1nX) to the estimated lifetime of these species. This relationship has been used to support identification of masses measured by the PTR-MS; ascertain the consistency and quality of hydrocarbon measurement data; and to provide information concerning sinks of important trace species. A selection of the data is used to indirectly determine an average HO concentration of 2.0 X 10(5) molecules cm(-3) along the back trajectory for air encountered during the Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE) measurement campaign between 0-1 km over the tropical rain forest. The lower than expected HO concentration derived could have been caused by significant atmospheric or oceanic photochemical production of acetone and MEK along the back trajectory.

Final Report for SERDP Project RC-1649: Advanced Chemical Measurements of Smoke from DoD-prescribed Burns

Abstract : Project RC-1649, Advanced Chemical Measurement of Smoke from DoD-prescribed Burns was undertaken to use advanced instrumental techniques to study in detail the particulate and vapor-phase chemical composition of the smoke that results from prescribed fires used as a land management tool on DoD bases, particularly bases in the southeastern U.S. The statement of need (SON) called for (1) improving characterization of fuel consumption and (2) improving characterization of air emissions under both flaming and smoldering conditions with respect to ... volatile organic compounds, heavy metals, and reactive gases. The measurements and fuels were from several bases throughout the southeast (Camp Lejeune, Ft. Benning, and Ft. Jackson) and were carried out in collaboration and conjunction with projects 1647 (models) and 1648 (particulates, SW bases).