scholarly journals Measurements of volatile organic compounds over West Africa

2010 ◽  
Vol 10 (12) ◽  
pp. 5281-5294 ◽  
Author(s):  
J. G. Murphy ◽  
D. E. Oram ◽  
C. E. Reeves
Keyword(s):  
Boundary Layer ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Marine Boundary Layer ◽  
Deep Convection ◽  
Proton Transfer Reaction ◽  
Oxidation Products ◽  
High Time Resolution ◽  
Airborne Measurements ◽  
Volatile Organic

Abstract. In this paper we describe measurements of volatile organic compounds (VOC) made using a Proton Transfer Reaction Mass Spectrometer (PTR-MS) aboard the UK Facility for Atmospheric Airborne Measurements during the African Monsoon Multidisciplinary Analyses (AMMA) campaign. Observations were made during approximately 85 h of flying time between 17 July and 17 August 2006, above an area between 4° N and 18° N and 3° W and 4° E, encompassing ocean, mosaic forest, and the Sahel desert. High time resolution observations of counts at mass to charge (m/z) ratios of 42, 59, 69, 71, and 79 were used to calculate mixing ratios of acetonitrile, acetone, isoprene, the sum of methyl vinyl ketone and methacrolein, and benzene respectively using laboratory-derived humidity-dependent calibration factors. Strong spatial associations between vegetation and isoprene and its oxidation products were observed in the boundary layer, consistent with biogenic emissions followed by rapid atmospheric oxidation. Acetonitrile, benzene, and acetone were all enhanced in airmasses which had been heavily influenced by biomass burning. Benzene and acetone were also elevated in airmasses with urban influence from cities such as Lagos, Cotonou, and Niamey. The observations provide evidence that both deep convection and mixing associated with fair-weather cumulus were responsible for vertical redistribution of VOC emitted from the surface. Profiles over the ocean showed a depletion of acetone in the marine boundary layer, but no significant decrease for acetonitrile.

scholarly journals Measurements of volatile organic compounds over West Africa

2010 ◽  
Vol 10 (2) ◽  
pp. 3861-3892 ◽  
Author(s):  
J. G. Murphy ◽  
D. E. Oram ◽  
C. E. Reeves
Keyword(s):  
Boundary Layer ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Marine Boundary Layer ◽  
Deep Convection ◽  
Proton Transfer Reaction ◽  
Oxidation Products ◽  
High Time Resolution ◽  
Airborne Measurements ◽  
Volatile Organic

Abstract. In this paper we describe measurements of volatile organic compounds (VOCs) made using a Proton Transfer Reaction Mass Spectrometer (PTR-MS) aboard the UK Facility for Atmospheric Airborne Measurements during the African Monsoon Multidisciplinary Analyses (AMMA) campaign. Observations were made during approximately 85 h of flying time between 17 July and 17 August 2006, above an area between 4° N and 18° N and 3° W and 4° E, encompassing ocean, mosaic forest, and the Sahel desert. High time resolution observations of counts at mass to charge (m/z) ratios of 42, 59, 69, 71, and 79 were used to calculate mixing ratios of acetonitrile, acetone, isoprene, the sum of methyl vinyl ketone and methacrolein, and benzene, respectively using laboratory-derived humidity-dependent calibration factors. Strong spatial associations between vegetation and isoprene and its oxidation products were observed in the boundary layer, consistent with biogenic emissions followed by rapid atmospheric oxidation. Acetonitrile, benzene, and acetone were all enhanced in airmasses which had been heavily influenced by biomass burning. Benzene and acetone were also elevated in airmasses with urban influence from cities such as Lagos, Cotonou, and Niamey. The observations provide evidence that both deep convection and mixing associated with fair-weather cumulus were responsible for vertical redistribution of VOCs emitted from the surface. Profiles over the ocean showed a depletion of acetone in the marine boundary layer, but no significant decrease for acetonitrile.

scholarly journals A compact PTR-ToF-MS instrument for airborne measurements of volatile organic compounds at high spatiotemporal resolution

2014 ◽  
Vol 7 (11) ◽  
pp. 3763-3772 ◽  
Author(s):  
M. Müller ◽  
T. Mikoviny ◽  
S. Feil ◽  
S. Haidacher ◽  
G. Hanel ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Proton Transfer Reaction ◽  
Horizontal Resolution ◽  
Resolving Power ◽  
Spatiotemporal Resolution ◽  
Airborne Measurements ◽  
New Instrument ◽  
Volatile Organic ◽  
Tof Ms

Abstract. Herein, we report on the development of a compact proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) for airborne measurements of volatile organic compounds (VOCs). The new instrument resolves isobaric ions with a mass resolving power (m/Δm) of ~1000, provides accurate m/z measurements (Δm < 3 mDa), records full mass spectra at 1 Hz and thus overcomes some of the major analytical deficiencies of quadrupole-MS-based airborne instruments. 1 Hz detection limits for biogenic VOCs (isoprene, α total monoterpenes), aromatic VOCs (benzene, toluene, xylenes) and ketones (acetone, methyl ethyl ketone) range from 0.05 to 0.12 ppbV, making the instrument well-suited for fast measurements of abundant VOCs in the continental boundary layer. The instrument detects and quantifies VOCs in locally confined plumes (< 1 km), which improves our capability of characterizing emission sources and atmospheric processing within plumes. A deployment during the NASA 2013 DISCOVER-AQ mission generated high vertical- and horizontal-resolution in situ data of VOCs and ammonia for the validation of satellite retrievals and chemistry transport models.

scholarly journals Missing OH reactivity in the global marine boundary layer

2020 ◽  
Vol 20 (6) ◽  
pp. 4013-4029 ◽  
Author(s):  
Alexander B. Thames ◽  
William H. Brune ◽  
David O. Miller ◽  
Hannah M. Allen ◽  
Eric C. Apel ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Limit Of Detection ◽  
Chemical Species ◽  
Volatile Organic ◽  
The Mean ◽  
The Difference

Abstract. The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime, influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although the calculated OH reactivity was below the limit of detection for the ATom instrument used to measure OH reactivity throughout much of the free troposphere, the instrument was able to measure the OH reactivity in and just above the marine boundary layer. The mean measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom deployments was 1.9 s−1, which is 0.5 s−1 larger than the mean calculated OH reactivity. The missing OH reactivity, the difference between the measured and calculated OH reactivity, varied between 0 and 3.5 s−1, with the highest values over the Northern Hemisphere Pacific Ocean. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions.

scholarly journals Missing OH Reactivity in the Global Marine Boundary Layer

2019 ◽  
Author(s):  
Alexander B. Thames ◽  
William H. Brune ◽  
David O. Miller ◽  
Hannah M. Allen ◽  
Eric C. Apel ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Limit Of Detection ◽  
Chemical Species ◽  
Four Seasons ◽  
Volatile Organic ◽  
The Difference

Abstract. The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime, influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although the calculated OH reactivity was below the OH reactivity instrument's limit-of-detection for much of the free troposphere, the OHR instrument was able to measure the OH reactivity in and just above the marine boundary layer. The average measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom phases was 1.9 s−1, which 0.5 s−1 larger than the average calculated OH reactivity. Concurrently, missing OH reactivity, the difference between the measured and calculated OH reactivity, was measured to be ~ 0.5–2.0 s−1 at some locations in the tropics and midlatitudes. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions.

scholarly journals Direct ecosystem fluxes of volatile organic compounds from oil palms in South-East Asia

2011 ◽  
Vol 11 (17) ◽  
pp. 8995-9017 ◽  
Author(s):  
P. K. Misztal ◽  
E. Nemitz ◽  
B. Langford ◽  
C. F. Di Marco ◽  
G. J. Phillips ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Canopy Temperature ◽  
Proton Transfer Reaction ◽  
Oxidation Products ◽  
Palm Trees ◽  
Volatile Organic ◽  
Resistance Approach ◽  
Oil Palms ◽  
Malaysian Borneo

Abstract. This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs) from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS), measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84 %) of all emitted BVOCs measured, at up to 30 mg m−2 h−1 over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) exhibited clear deposition of 1 mg m−2 h−1, with a small average canopy resistance of 230 s m−1. Approximately 15 % of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m−2 h−1, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m−2 h−1 was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. Consistent with Karl et al. (2010), we also propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions.

scholarly journals Surface and boundary layer exchanges of volatile organic compounds, nitrogen oxides and ozone during the GABRIEL campaign

2008 ◽  
Vol 8 (20) ◽  
pp. 6223-6243 ◽  
Author(s):  
L. Ganzeveld ◽  
G. Eerdekens ◽  
G. Feig ◽  
H. Fischer ◽  
H. Harder ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Residual Layer ◽  
Oxidation Products ◽  
Emission Flux ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Isoprene Oxidation ◽  
Isoprene Oxidation Products

Abstract. We present an evaluation of sources, sinks and turbulent transport of nitrogen oxides, ozone and volatile organic compounds (VOC) in the boundary layer over French Guyana and Suriname during the October 2005 GABRIEL campaign by simulating observations with a single-column chemistry and climate model (SCM) along a zonal transect. Simulated concentrations of O3 and NO as well as NO2 photolysis rates over the forest agree well with observations when a small soil-biogenic NO emission flux was applied. This suggests that the photochemical conditions observed during GABRIEL reflect a pristine tropical low-NOx regime. The SCM uses a compensation point approach to simulate nocturnal deposition and daytime emissions of acetone and methanol and produces daytime boundary layer mixing ratios in reasonable agreement with observations. The area average isoprene emission flux, inferred from the observed isoprene mixing ratios and boundary layer height, is about half the flux simulated with commonly applied emission algorithms. The SCM nevertheless simulates too high isoprene mixing ratios, whereas hydroxyl concentrations are strongly underestimated compared to observations, which can at least partly explain the discrepancy. Furthermore, the model substantially overestimates the isoprene oxidation products methlyl vinyl ketone (MVK) and methacrolein (MACR) partly due to a simulated nocturnal increase due to isoprene oxidation. This increase is most prominent in the residual layer whereas in the nocturnal inversion layer we simulate a decrease in MVK and MACR mixing ratios, assuming efficient removal of MVK and MACR. Entrainment of residual layer air masses, which are enhanced in MVK and MACR and other isoprene oxidation products, into the growing boundary layer poses an additional sink for OH which is thus not available for isoprene oxidation. Based on these findings, we suggest pursuing measurements of the tropical residual layer chemistry with a focus on the nocturnal depletion of isoprene and its oxidation products.

scholarly journals A novel Whole Air Sample Profiler (WASP) for the quantification of volatile organic compounds in the boundary layer

2013 ◽  
Vol 6 (10) ◽  
pp. 2703-2712 ◽  
Author(s):  
J. E. Mak ◽  
L. Su ◽  
A. Guenther ◽  
T. Karl
Keyword(s):  
Boundary Layer ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Flow Rate ◽  
Gas Analysis ◽  
Oxidation Products ◽  
Outer Diameter ◽  
Sampling System ◽  
Important Region ◽  
Volatile Organic

Abstract. The emission and fate of reactive volatile organic compounds (VOCs) is of inherent interest to those studying chemical biosphere–atmosphere interactions. In-canopy VOC observations are obtainable using tower-based samplers, but the lack of suitable sampling systems for the full boundary layer has limited the availability of data characterizing the vertical structure of such gases above the canopy height and still in the boundary layer. This is an important region where many reactive VOCs are oxidized or otherwise removed. Here we describe an airborne sampling system designed to collect a vertical profile of air into a 3/8 in. OD (outer diameter) tube 150 m in length. The inlet ram air pressure is used to flow sampled air through the tube, which results in a varying flow rate based on aircraft speed and altitude. Since aircraft velocity decreases during ascent, it is necessary to account for the variable flow rate into the tube. This is accomplished using a reference gas that is pulsed into the air stream so that the precise altitude of the collected air can be reconstructed post-collection. The pulsed injections are also used to determine any significant effect from diffusion/mixing within the sampling tube, either during collection or subsequent extraction for gas analysis. This system has been successfully deployed, and we show some measured vertical profiles of isoprene and its oxidation products methacrolein and methyl vinyl ketone from a mixed canopy near Columbia, Missouri.

scholarly journals Direct ecosystem fluxes of volatile organic compounds from oil palms in South-East Asia

2011 ◽  
Vol 11 (4) ◽  
pp. 12671-12724 ◽  
Author(s):  
P. K. Misztal ◽  
E. Nemitz ◽  
B. Langford ◽  
C. F. Di Marco ◽  
G. J. Phillips ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Canopy Temperature ◽  
Proton Transfer Reaction ◽  
Oxidation Products ◽  
Palm Trees ◽  
Volatile Organic ◽  
Resistance Approach ◽  
Oil Palms ◽  
Malaysian Borneo

Abstract. This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs) from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS), measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84%) of all emitted BVOCs measured, at up to 30 mg m−2 h−1 over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) exhibited clear deposition, with a small average canopy resistance of 230 s m−1. Approximately 15% of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m−2 h−1, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m−2 h−1 was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. We propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions.

scholarly journals Surface and boundary layer exchanges of volatile organic compounds, nitrogen oxides and ozone during the GABRIEL Campaign

2008 ◽  
Vol 8 (3) ◽  
pp. 11909-11965 ◽  
Author(s):  
L. Ganzeveld ◽  
G. Eerdekens ◽  
G. Feig ◽  
H. Fischer ◽  
H. Harder ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Residual Layer ◽  
Oxidation Products ◽  
Emission Flux ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Isoprene Oxidation ◽  
Isoprene Oxidation Products

Abstract. We present an evaluation of sources, sinks and turbulent transport of nitrogen oxides, ozone and volatile organic compounds (VOC) in the boundary layer over French Guyana and Suriname during the October 2005 GABRIEL campaign by simulating observations with a single-column chemistry and climate model (SCM) along a zonal transect. Simulated concentrations of O3 and NO as well as NO2 photolysis rates over the forest agree well with observations when a small soil-biogenic NO emission flux was applied. This suggests that the photochemical conditions observed during GABRIEL reflect a pristine tropical low-NOx regime. The SCM uses a compensation point approach to simulate nocturnal deposition and daytime emissions of acetone and methanol and produces daytime boundary layer mixing ratios in reasonable agreement with observations. The area average isoprene emission flux, inferred from the observed isoprene mixing ratios and boundary layer height, is about half the flux simulated with commonly applied emission algorithms. The SCM nevertheless simulates too high isoprene mixing ratios, whereas hydroxyl concentrations are strongly underestimated compared to observations, which can at least partly explain the discrepancy. Furthermore, the model substantially overestimates the isoprene oxidation products methlyl vinyl ketone (MVK) and methacrolein (MACR) partly due to a simulated nocturnal increase due to isoprene oxidation. This increase is most prominent in the residual layer whereas in the nocturnal inversion layer we simulate a decrease in MVK and MACR mixing ratios, assuming efficient removal of MVK and MACR. Entrainment of residual layer air masses, which are enhanced in MVK and MACR and other isoprene oxidation products, into the growing boundary layer poses an additional sink for OH which is thus not available for isoprene oxidation. Based on these findings, we suggest pursuing measurements of the tropical residual layer chemistry with a focus on the nocturnal depletion of isoprene and its oxidation products.

scholarly journals First Eddy Covariance Flux Measurements of Semi Volatile Organic Compounds with the PTR3-TOF-MS

2021 ◽  
Author(s):  
Lukas Fischer ◽  
Martin Breitenlechner ◽  
Eva Canaval ◽  
Wiebke Scholz ◽  
Marcus Striednig ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Eddy Covariance ◽  
Organic Compounds ◽  
Proton Transfer Reaction ◽  
Oxidation Products ◽  
Concentration Data ◽  
Single Digit ◽  
Volatile Organic ◽  
Flux Measurements ◽  
Tof Ms

Abstract. We present first eddy covariance flux measurements with the PTR3-TOF-MS, a novel proton-transfer-reaction mass-spectrometer (PTR-MS). During three weeks in spring 2016 the instrument recorded 10 Hz BVOC data on top of the SMEAR II tower in Hyytiälä, Finland. Flux and concentration data of isoprene, monoterpenes and sesquiterpenes were compared to the literature. Due to the improved instrument sensitivity and a customized “wall less” inlet design we could detect a number of fluxes of semi-volatile and low volatile organic compounds (SVOC and LVOC) with less than single digit picomol/m2/s values for the first time. These compounds include sesquiterpene oxidation products and diterpenes. Daytime diterpene fluxes were in the range of 0.05 to 0.15 picomol/m2/s, which amounts to about 0.25 % to 0.5 % of the daytime sesquiterpene flux above canopy.

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